Contents

1 Hydrogen sulfide 1
1.1 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4.1 Production of thioorganic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4.2 Alkali metal sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4.3 Analytical chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4.4 Precursor to metal sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4.5 Miscellaneous applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.5 Removal from fuel gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.6 Removal from water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.7 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.7.1 Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.7.2 Incidents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.7.3 Suicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.8 Function in the body . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.9 Involvement in diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.9.1 Hydrogen sulfide deficiency after heart attack . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.9.2 Other diseases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.10 Induced hypothermia and suspended animation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.11 Participant in the sulfur cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.12 Mass extinctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.13 Life adapted to hydrogen sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.14 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.15 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.16 Additional resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.17 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

2 Alkene 15
2.1 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.1 Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.1.2 Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

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2.2 Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

2.3 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3.1 Addition reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.3.2 Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3.3 Metal complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3.4 Reaction overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4.1 Industrial methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.4.2 Elimination reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.4.3 Synthesis from carbonyl compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.4.4 Synthesis from alkenes: olefin metathesis and hydrovinylation . . . . . . . . . . . . . . . . 23
2.4.5 From alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.4.6 Rearrangements and related reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.5 Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.5.1 IUPAC names . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.5.2 Cis-trans notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.5.3 E,Z notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.5.4 Groups containing C=C double bonds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.7 Nomenclature links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

3 Alkane 28
3.1 Structure classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.2 Isomerism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.3 Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3.1 Linear alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3.2 Branched alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.3.3 Cyclic alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3.4 Trivial names . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.4 Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.4.1 Table of alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.4.2 Boiling point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.4.3 Melting points . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.4.4 Conductivity and solubility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.4.5 Molecular geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.4.6 Bond lengths and bond angles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.4.7 Conformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.4.8 Spectroscopic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.5 Chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.5.1 Reactions with oxygen (combustion reaction) . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.5.2 Reactions with halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
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3.5.3 Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.5.4 Isomerization and reformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.5.5 Other reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.6 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.6.1 Occurrence of alkanes in the Universe . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.6.2 Occurrence of alkanes on Earth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
3.6.3 Biological occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.6.4 Ecological relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.7 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.7.1 Petroleum refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.7.2 Fischer-Tropsch . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.7.3 Laboratory preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.8 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.9 Environmental transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.10 Hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.11 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.12 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.13 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

4 Methane 49
4.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2 Properties and bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.3 Chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.3.1 Acid-base reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.3.2 Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.3.3 Reactions with halogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.4.1 Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.4.2 Chemical feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.5 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.5.1 Biological routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.5.2 Serpentinization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.5.3 Industrial routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.5.4 Laboratory synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.6 Occurrence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.6.1 Alternative sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.6.2 Atmospheric methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
4.6.3 Clathrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.7 Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.8 Extraterrestrial methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.10 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
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4.11 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.12 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

5 Ethane 67
5.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.2 Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.2.1 Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.2.2 Ethane barrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.3 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.5 Health and safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.6 Atmospheric and extraterrestrial ethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.8 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
5.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

6 Propane 73
6.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6.2 Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.3 Properties and reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
6.3.1 Energy content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.3.2 Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.4 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.4.1 Domestic and industrial fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.4.2 Refrigeration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
6.4.3 Motor fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.4.4 Improvised Explosive Device . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.4.5 Other uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6.5 Propane risks and alternate gas fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.6 Retail cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.6.1 United States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82

7 Butane 83
7.1 Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.2 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.3 Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
7.4 Effects and health issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
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7.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

8 Pentane 86
8.1 Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.2 Industrial uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.3 Laboratory use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.4 Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8.5 Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
8.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87

9 Engine knocking 88
9.1 Normal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
9.2 Abnormal combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
9.3 Pre-ignition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
9.4 Causes of pre-ignition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
9.5 Detonation induced pre-ignition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.6 Knock detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.7 Knock prediction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
9.9 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
9.10 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

10 Octane rating 93
10.1 Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
10.1.1 The problem: pre-ignition and knocking . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
10.1.2 Isooctane as a reference standard . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
10.2 Measurement methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
10.2.1 Research Octane Number (RON) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
10.2.2 Motor Octane Number (MON) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
10.2.3 Anti-Knock Index (AKI) or (R+M)/2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
10.2.4 Difference between RON, MON, and AKI . . . . . . . . . . . . . . . . . . . . . . . . . . 95
10.2.5 Observed Road Octane Number (RdON) . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
10.2.6 Aviation gasoline octane ratings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
10.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
10.4 Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
10.5 Regional variations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
10.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
10.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
10.8 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
10.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102

11 Cetane number 103

vi CONTENTS

11.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103

11.2 Typical values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
11.3 Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
11.4 Alternative fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
11.5 Chemical relevance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
11.6 Measuring cetane number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
11.6.1 Ignition Quality Tester (IQT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
11.6.2 Fuel ignition tester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
11.6.3 Cetane index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
11.6.4 Industry standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
11.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
11.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
11.9 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
11.10External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105

12 Flash point 106

12.1 Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
12.2 Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
12.3 Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
12.4 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
12.5 Standardization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
12.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
12.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

13 Autoignition temperature 110

13.1 Autoignition equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
13.2 Autoignition point of selected substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
13.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
13.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
13.5 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

14 Fire point 112

14.1 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
14.2 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

15 Pour point 113

15.1 Measuring the pour point of petroleum products . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
15.1.1 Manual Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
15.1.2 Automatic Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
15.2 Measuring the pour point of crude oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
15.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
15.4 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
15.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
CONTENTS vii

16 Smoke point 115

16.1 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
16.2 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

17 API gravity 117

17.1 History of development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
17.2 API gravity formulas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
17.3 Using API gravity to calculate barrels of crude oil per metric ton . . . . . . . . . . . . . . . . . . . 118
17.4 Measurement of API gravity from its density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
17.5 Direct Measurement of API gravity (Hydrometer method) . . . . . . . . . . . . . . . . . . . . . . 118
17.6 Classifications or grades . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
17.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
17.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
17.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

18 Light crude oil 120

18.1 Varying standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
18.2 Examples of light crude oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
18.3 U.S. price . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
18.3.1 Trading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
18.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
18.5 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121

19 Heavy crude oil 122

19.1 Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
19.2 Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
19.3 Environmental impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
19.4 Geological origin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
19.5 Chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
19.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
19.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
19.8 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

20 Furnace 127
20.1 Household furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
20.1.1 Categories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
20.1.2 Heat distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
20.1.3 Furnace types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
20.2 Metallurgical furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
20.3 Industrial process furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
20.3.1 Radiant section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
20.3.2 Convection section . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
20.3.3 Radiant Coil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
viii CONTENTS

20.3.4 Burner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137

20.3.5 Sootblower . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
20.3.6 Stack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
20.3.7 Insulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
20.3.8 Foundations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
20.3.9 Access Doors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
20.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
20.5 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
20.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
20.7 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141

21 Chemical reactor 142

21.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
21.2 Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
21.2.1 CSTR (Continuous Stirred-Tank Reactor) . . . . . . . . . . . . . . . . . . . . . . . . . . 143
21.2.2 PFR (Plug Flow Reactor) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
21.2.3 Semi-batch reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
21.2.4 Catalytic reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
21.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
21.4 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
21.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147

22 Catalysis 148
22.1 Technical perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
22.2 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
22.3 General principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
22.3.1 Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
22.3.2 Typical mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
22.3.3 Reaction energetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
22.3.4 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
22.4 Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
22.4.1 Heterogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
22.4.2 Homogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
22.4.3 Enzymes and biocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
22.5 Significance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
22.5.1 Energy processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
22.5.2 Bulk chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
22.5.3 Fine chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
22.5.4 Food processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
22.5.5 Environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
22.6 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
22.7 Inhibitors, poisons and promoters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
CONTENTS ix

22.8 Current market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156

22.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
22.10References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
22.11External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

23 Catalytic converter 160

23.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
23.2 Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
23.3 Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
23.3.1 Two-way . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
23.3.2 Three-way . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
23.3.3 Diesel engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
23.3.4 Lean burn spark-ignition engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
23.4 Installation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
23.5 Damage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
23.6 Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
23.7 Negative aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
23.7.1 Warm-up period . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
23.7.2 Environmental impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
23.8 Theft . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
23.9 Diagnostics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
23.10See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
23.11References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
23.12Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
23.13External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169

24 BTEX 170
24.1 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
24.2 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170

25 Alkylation 171
25.1 Alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
25.1.1 Nucleophilic alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
25.1.2 Electrophilic alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
25.1.3 Carbene alkylating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
25.2 In biology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
25.3 Oil refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
25.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
25.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
25.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
25.7 Text and image sources, contributors, and licenses . . . . . . . . . . . . . . . . . . . . . . . . . . 175
25.7.1 Text . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
x CONTENTS

25.7.2 Images . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181

25.7.3 Content license . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
Chapter 1

Hydrogen sulfide

Hydrogen sulfide is a chemical compound with the formula H

2S. It is a colorless gas with the characteristic foul odor of rotten eggs; it is heavier than air, very poisonous, corrosive,
flammable, and explosive.
Hydrogen sulfide often results from the bacterial breakdown of organic matter in the absence of oxygen gas, such as
in swamps and sewers; this process is commonly known as anaerobic digestion. H
2S also occurs in volcanic gases, natural gas, and in some sources of well water. It is also present in natural halite
type rock salts, most notably in Himalayan Black Salt, which is mostly harvested from the mineral-rich "Salt Range"
mountains of Pakistan. The human body produces small amounts of H
2S and uses it as a signaling molecule.
Dissolved in water, hydrogen sulfide is known as hydrosulfuric acid or sulfhydric acid, a weak acid.
Swedish chemist Carl Wilhelm Scheele is credited with having discovered hydrogen sulfide in 1777.
The British English spelling of this compound is hydrogen sulphide, but this spelling is not recommended by the
International Union of Pure and Applied Chemistry nor the Royal Society of Chemistry.
Hydrogen sulfide under high pressure has recently been demonstrated to undergo superconducting transition at 190K,
the highest temperature superconductor known to date. [7]

1.1 Properties

Hydrogen sulfide is slightly heavier than air; a mixture of H

2S and air is explosive. Hydrogen sulfide and oxygen burn with a blue flame to form sulfur dioxide (SO
2) and water. In general, hydrogen sulfide acts as a reducing agent.
At high temperature or in the presence of catalysts, sulfur dioxide can be made to react with hydrogen sulfide to form
elemental sulfur and water. This is exploited in the Claus process, the main way to convert hydrogen sulfide into
elemental sulfur.
Hydrogen sulfide is slightly soluble in water and acts as a weak acid, giving the hydrosulfide ion HS− (pKₐ = 6.9 in 0.01-
0.1 mol/litre solutions at 18 °C). A solution of hydrogen sulfide in water, known as sulfhydric acid or hydrosulfuric
acid, is initially clear but over time turns cloudy. This is due to the slow reaction of hydrogen sulfide with the oxygen
dissolved in water, yielding elemental sulfur, which precipitates out. The sulfide dianion S2− exists only in strongly
alkaline aqueous solutions; it is exceptionally basic with a pKₐ > 14.
Hydrogen sulfide reacts with metal ions to form metal sulfides, which may be considered the salts of hydrogen sulfide.
Some ores are sulfides. Metal sulfides often have a dark color. Lead(II) acetate paper is used to detect hydrogen
sulfide because it turns grey in the presence of the gas as lead(II) sulfide is produced. Reacting metal sulfides with
strong acid liberates hydrogen sulfide.
If gaseous hydrogen sulfide is put into contact with concentrated nitric acid, it explodes.
Hydrogen sulfide reacts with alcohols to form thiols, an important class of organosulfur compounds.

1
2 CHAPTER 1. HYDROGEN SULFIDE

1.2 Production
Hydrogen sulfide is most commonly obtained by its separation from sour gas, which is natural gas with high content
of H
2S. It can also be produced by reacting hydrogen gas with molten elemental sulfur at about 450 °C. Hydrocarbons
can replace hydrogen in this process.[8]
Sulfate-reducing (resp. sulfur-reducing) bacteria generate usable energy under low-oxygen conditions by using sul-
fates (resp. elemental sulfur) to oxidize organic compounds or hydrogen; this produces hydrogen sulfide as a waste
product.
The standard lab preparation is to react ferrous sulfide (FeS) with a strong acid in a Kipp generator:

FeS + 2 HCl → FeCl2 + H2 S

A less well-known and more convenient alternative is to react aluminium sulfide with water:[9]

6 H2 O + Al2 S3 → 3 H2 S + 2 Al(OH)3

This gas is also produced by heating sulfur with solid organic compounds and by reducing sulfurated organic com-
pounds with hydrogen.
Hydrogen sulfide production can be costly because of the dangers involved in production.
Water heaters can aid the conversion of sulfate in water to hydrogen sulfide gas. This is due to providing a warm
environment sustainable for sulfur bacteria and maintaining the reaction which interacts between sulfate in the water
and the water heater anode, which is usually made from magnesium metal.[10]

1.3 Occurrence
Small amounts of hydrogen sulfide occur in crude petroleum, but natural gas can contain up to 90%. Volcanoes and
some hot springs (as well as cold springs) emit some H
2S, where it probably arises via the hydrolysis of sulfide minerals, i.e. MS + H
2O → MO + H
2S. Hydrogen sulfide can be present naturally in well water, often as a result of the action of sulfate-reducing bacteria.
Hydrogen Sulfide is created by the human body in small doses through bacterial breakdown of proteins containing
sulfur in the intestinal tract, it is also produced in the mouth and is a cause for Halitosis.[11]
A portion of global H
2S emissions are due to human activity. By far the largest industrial route to H
2S occurs in petroleum refineries: The hydrodesulfurization process liberates sulfur from petroleum by the action of
hydrogen. The resulting H
2S is converted to elemental sulfur by partial combustion via the Claus process, which is a major source of elemental
sulfur. Other anthropogenic sources of hydrogen sulfide include coke ovens, paper mills (using the sulfate method),
and tanneries. H
2S arises from virtually anywhere where elemental sulfur comes in contact with organic material, especially at high
temperatures.
In 2011 it was reported that increased concentration of H
2S, possibly due to oil field practices, was observed in the Bakken formation crude and presented challenges such as
“health and environmental risks, corrosion of wellbore, added expense with regard to materials handling and pipeline
equipment, and additional refinement requirements”.[12]
Besides living near a gas and oil drilling operations, ordinary citizens can be exposed to hydrogen sulfide by being
near waste water treatment facilities, landfills and farms with manure storage. Exposure occurs through breathing
contaminated air or drinking contaminated water.[13]

1.4 Uses
1.4. USES 3

Deposit of sulfur on a rock, caused by volcanic gases

1.4.1 Production of thioorganic compounds

Several organosulfur compounds are produced using hydrogen sulfide. These include methanethiol, ethanethiol, and
thioglycolic acid.

1.4.2 Alkali metal sulfides

Upon combining with alkali metal bases, hydrogen sulfide converts to alkali hydrosulfides such as sodium hydrosulfide
and sodium sulfide, which are used in the degradation of biopolymers. The depilation of hides and the delignification
of pulp by the Kraft process both are effected by alkali sulfides.

1.4.3 Analytical chemistry

For well over a century, hydrogen sulfide was important in analytical chemistry, in the qualitative inorganic analysis of
metal ions. In these analyses, heavy metal (and nonmetal) ions (e.g., Pb(II), Cu(II), Hg(II), As(III)) are precipitated
from solution upon exposure to H
2S. The components of the resulting precipitate redissolve with some selectivity.
For small-scale laboratory use in analytic chemistry, the use of thioacetamide has superseded H
2S as a source of sulfide ions.

1.4.4 Precursor to metal sulfides

As indicated above, many metal ions react with hydrogen sulfide to give the corresponding metal sulfides. This
conversion is widely exploited. For example, gases or waters contaminated by hydrogen sulfide can be cleaned
4 CHAPTER 1. HYDROGEN SULFIDE

with metal sulfides. In the purification of metal ores by flotation, mineral powders are often treated with hydro-
gen sulfide to enhance the separation. Metal parts are sometimes passivated with hydrogen sulfide. Catalysts used
in hydrodesulfurization are routinely activated with hydrogen sulfide, and the behavior of metallic catalysts used in
other parts of a refinery is also modified using hydrogen sulfide.

1.4.5 Miscellaneous applications

Hydrogen sulfide is used to separate deuterium oxide, or heavy water, from normal water via the Girdler Sulfide
process.
Scientists from the University of Exeter discovered that cell exposure to small amounts of hydrogen sulfide gas have
shown to prevent mitochondrial damage. When the cell is stressed with disease, enzymes are drawn into the cell to
produce small amounts of hydrogen sulfide This study could have further implications on preventing strokes, heart
disease and arthritis.[14]
Hydrogen sulfide may have anti-aging properties by blocking destructive chemicals within the cell, bearing similar
properties to resveratrol, an antioxidant found in red wine.[15]
Hydrogen sulfide under high pressure has recently been demonstrated to undergo superconducting transition at 190K
-- the highest among all known superconductors to date . [16]

1.5 Removal from fuel gases

Hydrogen sulfide is commonly found in natural gas, biogas, and LPG. It can be removed in a number of ways.

• Reaction with iron oxide

Gas is pumped through a container of hydrated iron(III) oxide, which combines with hydro-
gen sulfide.

Fe
2O
3(s) + H
2O(l) + 3 H
2S(g) → Fe
2S
3(s) + 4 H
2O(l)

In order to regenerate iron(III) oxide, the container must be taken out of service, flooded with
water and aerated.

2 Fe
2S
3(s) + 3 O
2(g) + 2 H
2O(l) → 2 Fe
2O
3(s) + 2 H
2O(l) + 6 S(s)

On completion of the regeneration reaction the container is drained of water and can be
returned to service. The advantage of this system is that it is completely passive during the
extraction phase.[17]

• Hydrodesulfurization
1.6. REMOVAL FROM WATER 5

Hydrodesulfurization is a more complex method of removing sulfur from fuels.

• Filtration through impregnated activated carbon

A gas stream containing hydrogen sulfide can be purified by passing it through a suitably
designed filter containing an impregnated activated carbon. This method is typically used for
odor abatement at municipal sewage works and for the purification of landfill biogas, prior to
its use in combined heat and power (CHP) engines, or injection into the gas grid.

• Treatment by plasma

Plasma dissociation of hydrogen sulfide is a new method of treatment which utilizes plasma
to dissociate hydrogen sulfide into hydrogen gas and elemental sulfur.

1.6 Removal from water

Hydrogen sulfide can be removed effectively from drinking water and there are a number of processes designed for
this purpose. However, the preferred method can change according to the level of concentration in water. Drinking
water should be checked for hydrogen sulfide levels, especially if using ground water due to low dissolved oxygen
levels.[18]

• Continuous Chlorination

For levels up to 75 mg/L Chlorine is used in the purification process as an oxidizing chemical to react with hydrogen
sulfide. This reaction yields insoluble solid sulfur. Usually the chlorine used is in the form of sodium hypochlorite.[19]

• Aeration

For concentrations of hydrogen sulfide less than 2mg/L aeration is an ideal treatment process. Oxygen is added to a
water and a reaction between oxygen and hydrogen sulfide react to produce odorless sulfate[20]

1.7 Safety
Hydrogen sulfide is a highly toxic and flammable gas (flammable range: 4.3–46%). Being heavier than air, it tends to
accumulate at the bottom of poorly ventilated spaces. Although very pungent at first, it quickly deadens the sense of
smell, so victims may be unaware of its presence until it is too late. For safe handling procedures, a hydrogen sulfide
material safety data sheet (MSDS) should be consulted.[21]

1.7.1 Toxicity
Hydrogen sulfide is considered a broad-spectrum poison, meaning that it can poison several different systems in the
body, although the nervous system is most affected. The toxicity of H
2S is comparable with that of hydrogen cyanide or carbon monoxide.[22] It forms a complex bond with iron in the
mitochondrial cytochrome enzymes, thus preventing cellular respiration.
Since hydrogen sulfide occurs naturally in the body, the environment and the gut, enzymes exist in the body capable of
detoxifying it by oxidation to (harmless) sulfate.[23] Hence, low levels of hydrogen sulfide may be tolerated indefinitely.
At some threshold level, believed to average around 300–350 ppm, the oxidative enzymes become overwhelmed.
Many personal safety gas detectors, such as those used by utility, sewage and petrochemical workers, are set to alarm
at as low as 5 to 10 ppm and to go into high alarm at 15 ppm.
A diagnostic clue of extreme poisoning by H
2S is the discoloration of copper coins in the pockets of the victim. Treatment involves immediate inhalation of amyl
nitrite, injections of sodium nitrite or administration of 4-dimethylaminophenol in combination with inhalation of
6 CHAPTER 1. HYDROGEN SULFIDE

pure oxygen, administration of bronchodilators to overcome eventual bronchospasm, and in some cases hyperbaric
oxygen therapy (HBOT).[22] HBOT has clinical and anecdotal support.[24][25][26]
Exposure to lower concentrations can result in eye irritation, a sore throat and cough, nausea, shortness of breath,
and fluid in the lungs (pulmonary edema).[22] These effects are believed to be due to the fact that hydrogen sulfide
combines with alkali present in moist surface tissues to form sodium sulfide, a caustic.[27] These symptoms usually
go away in a few weeks.
Long-term, low-level exposure may result in fatigue, loss of appetite, headaches, irritability, poor memory, and
dizziness. Chronic exposure to low level H
2S (around 2 ppm) has been implicated in increased miscarriage and reproductive health issues among Russian and
Finnish wood pulp workers,[28] but the reports have not (as of circa 1995) been replicated.
Short-term, high-level exposure can induce immediate collapse, with loss of breathing and a high probability of death.
If death does not occur, high exposure to hydrogen sulfide can lead to cortical pseudolaminar necrosis, degeneration
of the basal ganglia and cerebral edema.[22] Although respiratory paralysis may be immediate, it can also be delayed
up to 72 hours.[29]

• 0.00047 ppm or 0.47 ppb is the odor threshold, the point at which 50% of a human panel can detect the
presence of an odor without being able to identify it.[30]

• 0.0047 ppm is the recognition threshold, the concentration at which 50% of humans can detect the characteristic
odor of hydrogen sulfide,[30] normally described as resembling “a rotten egg”.

• 10 ppm is the OSHA permissible exposure limit (PEL) (8 hour time-weighted average).[11]

• 10–20 ppm is the borderline concentration for eye irritation.

• 20 ppm is the acceptable ceiling concentration established by OSHA.[11]

• 50 ppm is the acceptable maximum peak above the ceiling concentration for an 8 hour shift, with a maximum
duration of 10 minutes.[11]

• 50–100 ppm leads to eye damage.

• At 100–150 ppm the olfactory nerve is paralyzed after a few inhalations, and the sense of smell disappears,
often together with awareness of danger.[31][32]

• 320–530 ppm leads to pulmonary edema with the possibility of death.[22]

• 530–1000 ppm causes strong stimulation of the central nervous system and rapid breathing, leading to loss of
breathing.

• 800 ppm is the lethal concentration for 50% of humans for 5 minutes exposure (LC50).

• Concentrations over 1000 ppm cause immediate collapse with loss of breathing, even after inhalation of a
single breath.

1.7.2 Incidents
Hydrogen sulfide was used by the British Army as a chemical weapon during World War I. It was not considered to
be an ideal war gas, but, while other gases were in short supply, it was used on two occasions in 1916.[33]
In 1975, a hydrogen sulfide release from an oil drilling operation in Denver City, Texas, killed nine people and
caused the state legislature to focus on the deadly hazards of the gas. State Representative E L Short took the lead in
endorsing an investigation by the Texas Railroad Commission and urged that residents be warned “by knocking on
doors if necessary” of the imminent danger stemming from the gas. One may die from the second inhalation of the
gas, and a warning itself may be too late.[34]
A dump of toxic waste containing hydrogen sulfide is believed to have caused 17 deaths and thousands of illnesses in
Abidjan, on the West African coast, in the 2006 Côte d'Ivoire toxic waste dump.
In 2014, Levels of Hydrogen Sulfide as high as 83 ppm have been detected at a recently built mall in Thailand called
Siam Square One at the Siam Square area. Shop tenants at the mall reported health complications such as sinus
1.8. FUNCTION IN THE BODY 7

inflammation, breathing difficulties and eye irritation. After investigation it was determined that the large amount of
gas originated from imperfect treatment and disposal of waste water in the building.[35]
In November 2014, a substantial amount of hydrogen sulfide gas shrouded the central, eastern and south-eastern parts
of Moscow. Residents living in the area were urged to stay indoors by the emergencies ministry. Although the exact
source of the gas was not known, blame had been placed on a Moscow oil refinery.[36]

1.7.3 Suicides
The gas, produced by mixing certain household ingredients, was used in a suicide wave in 2008 in Japan.[37] The
wave prompted staff at Tokyo’s suicide prevention center to set up a special hot line during "Golden Week", as they
received an increase in calls from people wanting to kill themselves during the annual May holiday.[38]
As of 2010, this phenomenon has occurred in a number of US cities, prompting warnings to those arriving at the
site of the suicide.[39] These first responders, such as emergency services workers or family members are at risk of
death from inhaling lethal quantities of the gas, or by fire.[40][41] Local governments have also initiated campaigns to
prevent such suicides.

1.8 Function in the body

Hydrogen sulfide is produced in small amounts by some cells of the mammalian body and has a number of biological
signaling functions. (Only two other such gases are currently known: nitric oxide (NO) and carbon monoxide (CO).)
The gas is produced from cysteine by the enzymes cystathionine beta-synthase and cystathionine gamma-lyase. It acts
as a relaxant of smooth muscle and as a vasodilator[42] and is also active in the brain, where it increases the response
of the NMDA receptor and facilitates long term potentiation,[43] which is involved in the formation of memory.
Eventually the gas is converted to sulfite in the mitochondria by thiosulfate reductase, and the sulfite is further oxidized
to thiosulfate and sulfate by sulfite oxidase. The sulfates are excreted in the urine.[44]
Due to its effects similar to nitric oxide (without its potential to form peroxides by interacting with superoxide),
hydrogen sulfide is now recognized as potentially protecting against cardiovascular disease.[42] The cardioprotective
role effect of garlic is caused by catabolism of the polysulfide group in allicin to H
2S, a reaction that could depend on reduction mediated by glutathione.[45]
Though both nitric oxide (NO) and hydrogen sulfide have been shown to relax blood vessels, their mechanisms of
action are different: while NO activates the enzyme guanylyl cyclase, H
2S activates ATP-sensitive potassium channels in smooth muscle cells. Researchers are not clear how the vessel-
relaxing responsibilities are shared between nitric oxide and hydrogen sulfide. However there exists some evidence
to suggest that nitric oxide does most of the vessel-relaxing work in large vessels and hydrogen sulfide is responsible
for similar action in smaller blood vessels.[46]
Recent findings suggest strong cellular crosstalk of NO and H
2S,[47] demonstrating that the vasodilatatory effects of these two gases are mutually dependent. Additionally, H
2S reacts with intracellular S-nitrosothiols to form the smallest S-nitrosothiol (HSNO), and a role of hydrogen sulfide
in controlling the intracellular S-nitrosothiol pool has been suggested.[48]
Like nitric oxide, hydrogen sulfide is involved in the relaxation of smooth muscle that causes erection of the penis,
presenting possible new therapy opportunities for erectile dysfunction.[49][50]

1.9 Involvement in diseases

1.9.1 Hydrogen sulfide deficiency after heart attack

A hydrogen sulfide (H2S) deficiency can be detrimental to the vascular function after an acute myocardial infarction
(AMI).[51] AMIs can lead to cardiac dysfunction through two distinct changes; increased oxidative stress via free
radical accumulation and decreased NO bioavailability.[52] Free radical accumulation occurs due to increased electron
transport uncoupling at the active site of endothelial nitric oxide synthase (eNOS), an enzyme involved in converting
L-arginine to NO.[51][52] During an AMI, oxidative degradation of tetrahydrobiopterin (BH4), a cofactor in NO
8 CHAPTER 1. HYDROGEN SULFIDE

production, limits BH4 availability and limits NO productionby eNOS.[52] Instead, eNOS reacts with oxygen, another
cosubstrates involved in NO production. The products of eNOS are reduced to superoxides, increasing free radical
production and oxidative stress within the cells.[51] A H2S deficiency impairs eNOS activity by limiting Akt activation
and inhibiting Akt phosphorylation of the eNOSS1177 activation site.[51][53] Instead, Akt activity is increased to
phosphorylate the eNOST495 inhibition site, downregulating eNOS production of NO.[51][53]
H2S therapy uses a H2S donor, such as diallyl trisulfide (DATS), to increase the supply of H2S to an AMI patient.
H2S donors reduce myocardial injury and reperfusion complications.[51] Increased H2S levels within the body will
react with oxygen to produce sulfane sulfur, a storage intermediate for H2S.[51] H2S pools in the body attracts oxygen
to react with excess H2S and eNOS to increase NO production.[51] With increased use of oxygen to produce more
NO, less oxygen is available to react with eNOS to produce superoxides during an AMI, ultimately lowering the
accumulation of reactive oxygen species (ROS).[51] Furthermore, decreased accumulation of ROS lowers oxidative
stress in vascular smooth muscle cells, decreasing oxidative degeneration of BH4.[52] Increased BH4 cofactor con-
tributes to increased production of NO within the body.[52] Higher concentrations of H2S directly increase eNOS
activity through Akt activation to increase phosphorylation of the eNOSS1177 activation site, and decrease phospho-
rylation of the eNOST495 inhibition site.[51][53] This phosphorylation process upregulates eNOS activity, catalyzing
more conversion of L-arginine to NO.[51][53] Increased NO production enables soluble guanylyl cyclase (sGC) ac-
tivity, leading to an increased conversion of guanosine triphosphate (GTP) to 3’,5’-cyclic guanosine monophosphate
(cGMP).[54] In H2S therapy immediately following an AMI, increased cGMP triggers an increase in protein kinase G
(PKG) activity.[55] PKG reduces intracellular Ca2+ in vascular smooth muscle to increase smooth muscle relaxation
and promote blood flow.[55] PKG also limits smooth muscle cell proliferation, reducing intima thickening following
AMI injury, ultimately decreasing myocardial infarct size.[51][54]

1.9.2 Other diseases

In Alzheimer’s disease the brain’s hydrogen sulfide concentration is severely decreased.[56] In a certain rat model of
Parkinson’s disease, the brain’s hydrogen sulfide concentration was found to be reduced, and administering hydro-
gen sulfide alleviated the condition.[57] In trisomy 21 (Down syndrome) the body produces an excess of hydrogen
sulfide.[44] Hydrogen sulfide is also involved in the disease process of type 1 diabetes. The beta cells of the pancreas
in type 1 diabetes produce an excess of the gas, leading to the death of these cells and to a reduced production of
insulin by those that remain.[46]

1.10 Induced hypothermia and suspended animation

In 2005, it was shown that mice can be put into a state of suspended animation-like hypothermia by applying a low
dosage of hydrogen sulfide (81 ppm H
2S) in the air. The breathing rate of the animals sank from 120 to 10 breaths per minute and their temperature fell
from 37 °C to just 2 °C above ambient temperature (in effect, they had become cold-blooded). The mice survived
this procedure for 6 hours and afterwards showed no negative health consequences.[58] In 2006 it was shown that the
blood pressure of mice treated in this fashion with hydrogen sulfide did not significantly decrease.[59]
A similar process known as hibernation occurs naturally in many mammals and also in toads, but not in mice. (Mice
can fall into a state called clinical torpor when food shortage occurs). If the H
2S-induced hibernation can be made to work in humans, it could be useful in the emergency management of severely
injured patients, and in the conservation of donated organs. In 2008, hypothermia induced by hydrogen sulfide for
48 hours was shown to reduce the extent of brain damage caused by experimental stroke in rats.[60]
As mentioned above, hydrogen sulfide binds to cytochrome oxidase and thereby prevents oxygen from binding, which
leads to the dramatic slowdown of metabolism. Animals and humans naturally produce some hydrogen sulfide in their
body; researchers have proposed that the gas is used to regulate metabolic activity and body temperature, which would
explain the above findings.[61]
Two recent studies cast doubt that the effect can be achieved in larger mammals. A 2008 study failed to reproduce
the effect in pigs, concluding that the effects seen in mice were not present in larger mammals.[62] Likewise a paper
by Haouzi et al. noted that there is no induction of hypometabolism in sheep, either.[63]
At the February 2010 TED conference, Mark Roth announced that hydrogen sulfide induced hypothermia in humans
had completed Phase I clinical trials.[64] The clinical trials commissioned by the company he helped found, Ikaria,
were however withdrawn or terminated by August 2011.[65][66]
1.11. PARTICIPANT IN THE SULFUR CYCLE 9

1.11 Participant in the sulfur cycle

Main article: Sulfur cycle

Hydrogen sulfide is a central participant in the sulfur cycle, the biogeochemical cycle of sulfur on Earth.
In the absence of oxygen, sulfur-reducing and sulfate-reducing bacteria derive energy from oxidizing hydrogen or
organic molecules by reducing elemental sulfur or sulfate to hydrogen sulfide. Other bacteria liberate hydrogen sulfide
from sulfur-containing amino acids; this gives rise to the odor of rotten eggs and contributes to the odor of flatulence.

Sludge from a pond; the black color is due to metal sulfides

As organic matter decays under low-oxygen (or hypoxic) conditions (such as in swamps, eutrophic lakes or dead
zones of oceans), sulfate-reducing bacteria will use the sulfates present in the water to oxidize the organic matter,
producing hydrogen sulfide as waste. Some of the hydrogen sulfide will react with metal ions in the water to produce
metal sulfides, which are not water soluble. These metal sulfides, such as ferrous sulfide FeS, are often black or brown,
leading to the dark color of sludge.
Several groups of bacteria can use hydrogen sulfide as fuel, oxidizing it to elemental sulfur or to sulfate by using
dissolved oxygen, metal oxides (e.g., Fe oxyhydroxides and Mn oxides) or nitrate as oxidant.[67]
The purple sulfur bacteria and the green sulfur bacteria use hydrogen sulfide as electron donor in photosynthesis,
thereby producing elemental sulfur. (In fact, this mode of photosynthesis is older than the mode of cyanobacteria,
algae, and plants, which uses water as electron donor and liberates oxygen.)

1.12 Mass extinctions

Main article: Anoxic event
Hydrogen sulfide has been implicated in several mass extinctions that have occurred in the Earth’s past. In particular,
a buildup of hydrogen sulfide in the atmosphere may have caused the Permian-Triassic extinction event 252 million
10 CHAPTER 1. HYDROGEN SULFIDE

A hydrogen sulfide bloom (green) stretching for about 150km along the coast of Namibia. As oxygen-poor water reaches the coast,
bacteria in the organic-matter rich sediment produce hydrogen sulfide which is toxic to fish. (The image is taken from a bird’s eye
view)

years ago.[68]
Organic residues from these extinction boundaries indicate that the oceans were anoxic (oxygen-depleted) and had
species of shallow plankton that metabolized H
2S. The formation of H
2S may have been initiated by massive volcanic eruptions, which emitted carbon dioxide and methane into the atmo-
sphere, which warmed the oceans, lowering their capacity to absorb oxygen that would otherwise oxidize H
2S. The increased levels of hydrogen sulfide could have killed oxygen-generating plants as well as depleted the ozone
layer, causing further stress. Small H
2S blooms have been detected in modern times in the Dead Sea and in the Atlantic ocean off the coast of Namibia.[68]

1.13 Life adapted to hydrogen sulfide

High levels of hydrogen sulfide are lethal to most animals, but a few highly specialized species (extremophiles) do
thrive in habitats that are rich in this chemical.[69]
Freshwater springs rich in hydrogen sulfide are mainly home to invertebrates, but also include a small number of fish:
Cyprinodon bobmilleri (a pupfish from Mexico), Limia sulphurophilia (a poeciliid from the Dominican Republic),
Gambusia eurystoma (a poeciliid from Mexico), and a few Poecilia (poeciliids from Mexico).[69][70]
In the deep sea, hydrothermal vents and cold seeps with high levels of hydrogen sulfide are home to a number of
extremely specialized lifeforms, ranging from bacteria to fish.[71] Because of the absence of light at these depths,
these ecosystems rely on chemosynthesis rather than photosynthesis.[72]

1.14 See also

• Amine gas treating
1.15. REFERENCES 11

• Sewer gas

• Induced hypothermia

• Jenkem

• Gasotransmitters

1.15 References
[1] “Hydrogen Sulfide - PubChem Public Chemical Database”. The PubChem Project. USA: National Center for Biotechnology
Information.

[2] Perrin, D.D., Ionisation Constants of Inorganic Acids and Bases in Aqueous Solution, 2nd Ed., Pergamon Press: Oxford,
1982.

[3] Bruckenstein, S.; Kolthoff, I.M., in Kolthoff, I.M.; Elving, P.J. Treatise on Analytical Chemistry, Vol. 1, pt. 1; Wiley, NY,
1959, pp. 432-433.

[4] Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN 0-07-049439-8

[5] Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin Company. p. A23. ISBN 0-618-94690-X.

[6] Hydrogen sulfide: Overview, National Pollutant Inventory, Australia

[7] Drozdov, A. “Conventional superconductivity at 190 K at high pressures”. arxiv. Retrieved 1 September 2014.

[8] Jacques Tournier-Lasserve “Hydrogen Sulfide” in Ullmann’s Encyclopedia of Chemical Industry

[9] McPherson, William (1913). Laboratory manual. Boston: Ginn and Company. p. 445.

[10] “Why Does My Water Smell Like Rotten Eggs? Hydrogen Sulfide and Sulfur Bacteria in Well Water”. Minnesota Depart-
ment of Health. Minnesota Department of Health. Retrieved 1 December 2014.

[11] Agency for Toxic Substances and Disease Registry (July 2006). “Toxicological Profile For Hydrogen Sulfide”. p. 154.
Retrieved 2012-06-20.

[12] Holubnyak et al, SPE 141434-MS

[13] “HYDROGEN SULFIDE”. Agency for Toxic Substances and Disease Registry.

[14] Stampler, Laura. “A Stinky Compound May Protect Against Cell Damage, Study Finds”. Time. Time. Retrieved 1
December 2014.

[15] Khan, Natasha. “Rotten Egg Gas Seen Offering Promise of Extending Life”. Bloomberg. Bloomberg. Retrieved 1 De-
cember 2014.

[16] Drozdov, A. “Conventional superconductivity at 190 K at high pressures”. arxiv. Retrieved 1 September 2014.

[17] “Marcab Co Inc”. Marcab Co Inc. Retrieved 2013-12-19.

[18] Lemley, Ann T.; Schwartz, John J.; Wagenet, Linda P. “Hydrogen Sulfide in Household Drinking Water”. Cornell Univer-
sity.

[19] “Hydrogen Sulfide (Rotten Egg Odor) in Pennsylvania Groundwater Wells”. Penn State. Penn State College of Agricultural
Sciences. Retrieved 1 December 2014.

[20] McFarland, Mark L.; Provin, T. L. “Hydrogen Sulfide in Drinking Water Treatment Causes and Alternatives”. Texas A&M
University. Retrieved 1 December 2014.

[21] Iowa State University, Department of Chemistry MSDS. “Hydrogen Sulfide Material Safety Data Sheet”. Retrieved 2009-
03-14.

[22] Lindenmann J, Matzi V, Neuboeck N, Ratzenhofer-Komenda B, Maier A, Smolle-Juettner FM (December 2010). “Severe
hydrogen sulphide poisoning treated with 4-dimethylaminophenol and hyperbaric oxygen”. Diving and Hyperbaric Medicine
: the Journal of the South Pacific Underwater Medicine Society 40 (4): 213–7. PMID 23111938. Retrieved 2013-06-07.
12 CHAPTER 1. HYDROGEN SULFIDE

[23] S. Ramasamy, S. Singh, P. Taniere, M. J. S. Langman, M. C. Eggo (2006). “Sulfide-detoxifying enzymes in the human
colon are decreased in cancer and upregulated in differentiation”. Am. J. Physiol. Gastrointest. Liver Physiol. 291 (2):
G288–G296. doi:10.1152/ajpgi.00324.2005. PMID 16500920. Retrieved 2007-10-20.

[24] Gerasimon G, Bennett S, Musser J, Rinard J (May 2007). “Acute hydrogen sulfide poisoning in a dairy farmer”. Clin
Toxicol (Phila) 45 (4): 420–3. doi:10.1080/15563650601118010. PMID 17486486. Retrieved 2008-07-22.

[25] Belley R, Bernard N, Côté M, Paquet F, Poitras J (July 2005). “Hyperbaric oxygen therapy in the management of two
cases of hydrogen sulfide toxicity from liquid manure”. CJEM 7 (4): 257–61. PMID 17355683. Retrieved 2008-07-22.

[26] Hsu P, Li H-W, Lin Y-T (1987). “Acute hydrogen sulfide poisoning treated with hyperbaric oxygen”. J. Hyperbaric Med
2 (4): 215–221. ISSN 0884-1225. Retrieved 2008-07-22.

[27] Lewis, R.J. Sax’s Dangerous Properties of Industrial Materials. 9th ed. Volumes 1-3. New York, NY: Van Nostrand
Reinhold, 1996

[28] Hemminki K., Niemi M.L. (1982) Int. Arch. Occup. Environ. Health 51 (1): 55-63.

[29] “The chemical suicide phenomenon”. Firerescue1.com. 2011-02-07. Retrieved 2013-12-19.

[30] Iowa State University Extension (May 2004). “The Science of Smell Part 1: Odor perception and physiological response”.
PM 1963a. Retrieved 2012-06-20.

[31] USEPA; Health and Environmental Effects Profile for Hydrogen Sulfide p.118-8 (1980) ECAO-CIN-026A

[32] Zenz, C., O.B. Dickerson, E.P. Horvath. Occupational Medicine. 3rd ed. St. Louis, MO., 1994, p.886

[33] Foulkes, Charles Howard (2001) [First published Blackwood & Sons, 1934]. “Gas!" The story of the special brigade.
Published by Naval & Military P. p. 105. ISBN 1-84342-088-0.

[34] Howard Swindle, “The Deadly Smell of Success”. Texas Monthly, June 1975. June 1975. Retrieved December 14, 2010.

[35] “Do not breathe: Dangerous, toxic gas found at Siam Square One”. Coconuts Bangkok. Coconuts Media. Retrieved 20
November 2014.

[36] “Russian capital Moscow shrouded in noxious gas”. BBC News Europe. British Broadcasting Corporation. Retrieved 1
December 2014.

[37] “Dangerous Japanese ‘Detergent Suicide’ Technique Creeps Into U.S”. Wired.com (Wired (magazine)). March 13, 2009.

[38] Namiki, Noriko (2008-05-22). “Terrible Twist in Japan Suicide Spates - ABC News”. Abcnews.go.com. Retrieved 2013-
12-19.

[39] See e.g. http://info.publicintelligence.net/LARTTAChydrogensulfide.pdf , http://info.publicintelligence.net/MAchemicalsuicide.

pdf , http://info.publicintelligence.net/illinoisH2Ssuicide.pdf , http://info.publicintelligence.net/NYhydrogensulfide.pdf
, http://info.publicintelligence.net/KCTEWhydrogensulfide.pdf

[40]

[41] Scoville, Dean (April 2011). “Chemical Suicides - Article - POLICE Magazine”. Policemag.com. Retrieved 2013-12-19.

[42] Lefer, David J. (November 2007). “A new gaseous signaling molecule emerges: Cardioprotective role of hydrogen sulfide”.
PNAS 104 (46): 17907–17908. Bibcode:2007PNAS..10417907L. doi:10.1073/pnas.0709010104. PMC 2084269. PMID
17991773. Retrieved 2008-09-26.

[43] Kimura, Hideo (2002). “Hydrogen sulfide as a neuromodulator”. Molecular Neurobiology 26 (1): 13–19. doi:10.1385/MN:
26:1:013. PMID 12392053.

[44] Kamoun, Pierre (July 2004). “H2 S, a new neuromodulator”. Médecine/Sciences 20 (6–7): 697–700. doi:10.1051/medsci/2004206-
7697. PMID 15329822.

[45] Benavides, Gloria A; Giuseppe L Squadrito, Robert W Mills, Hetal D Patel, T Scott Isbell, Rakesh P Patel, Victor
M Darley-Usmar, Jeannette E Doeller, David W Kraus (2007-11-13). “Hydrogen sulfide mediates the vasoactivity of
garlic”. Proceedings of the National Academy of Sciences of the United States of America 104 (46): 17977–17982.
Bibcode:2007PNAS..10417977B. doi:10.1073/pnas.0705710104. PMC 2084282. PMID 17951430.

[46] "Toxic Gas, Lifesaver", Scientific American, March 2010

1.15. REFERENCES 13

[47] Coletta, C.; Papapetropoulos, A.; Erdelyi, K.; Olah, G.; Modis, K.; Panopoulos, P.; Asimakopoulou, A.; Gero, D.; Sharina,
I.; Martin, E.; Szabo, C. (2012). “Hydrogen sulfide and nitric oxide are mutually dependent in the regulation of angiogenesis
and endothelium-dependent vasorelaxation”. Proceedings of the National Academy of Sciences 109 (23): 9161–9166.
doi:10.1073/pnas.1202916109. PMC 3384190. PMID 22570497.

[48] Filipovic, M. R.; Miljkovic, J. L.; Nauser, T.; Royzen, M.; Klos, K.; Shubina, T.; Koppenol, W. H.; Lippard, S. J.;
Ivanović-Burmazović, I. (2012). “Chemical Characterization of the SmallestS-Nitrosothiol, HSNO; Cellular Cross-talk of
H2S andS-Nitrosothiols”. Journal of the American Chemical Society 134 (29): 12016–12027. doi:10.1021/ja3009693.
PMC 3408084. PMID 22741609.

[49] Roberta d'Emmanuele di Villa Biancaa, Raffaella Sorrentinoa, Pasquale Maffiaa, Vincenzo Mironeb, Ciro Imbimbob,
Ferdinando Fuscob, Raffaele De Palmad, Louis J. Ignarroe und Giuseppe Cirino (2009). “Hydrogen sulfide as a mediator
of human corpus cavernosum smooth-muscle relaxation”. PNAS 106 (11): 4513–8. Bibcode:2009PNAS..106.4513D.
doi:10.1073/pnas.0807974105. PMC 2657379. PMID 19255435.

[50] “Hydrogen Sulfide: Potential Help for ED”. WebMD. March 2, 2009.

[51] King, Adrienne; Polhemus, Bhushan, Otsuka, Kondo, Nicholson, Bradley, Islam, Calvert, Tao, Dugas, Kelley, Elrod,
Huang, Wang, Lefer (January 2014). “Hydrogen sulfide cytoprotective signaling is endothelial nitric oxide synthase-nitric
oxide dependent”. PNAS 111 (Early Edition): 1–6. doi:10.1073/pnas.1321871111.

[52] Alp, Nicholas; Channon (2003). “Regulation of endothelial nitric oxide synthase by tetrahydrobiopterin in vascular dis-
ease”. Journal of the American Heart Association 24: 413–420. doi:10.1161/01.ATV0000110785.96039.f6 (inactive
2014-03-19).

[53] Coletta, Ciro; Papapetropoulos, Erdelyi, Olah, Modis, Panopoulos, Asimakopoulou, Gero, Sharina, Martin, Szabo (April
2012). “Hydrogen sulfide and nitric oxide are mutually dependent in the regulation of angiogenesis and endothelium-
dependent vasorelaxation”. PNAS 109 (23): 9161–9166. Bibcode:2012PNAS..109.9161C. doi:10.1073/pnas.1202916109.
PMC 3384190. PMID 22570497.

[54] Boerth, N. J.; Dey, Cornwell, Lincoln (1997). “Cyclic GMP-dependent protein kinase regulates vascular smooth muscle
cell phenotype”. Journal of Vascular Research 34 (4): 245–259. doi:10.1159/000159231. PMID 9256084.

[55] Lincoln, T. M.; Cornwell, Taylor (March 1990). “cGMP-dependent protein kinase mediates the reduction of Ca2+ by
cAMP in vascular smooth muscle cells”. American Journal of Physiology 258 (3): C399–C407. PMID 2156436.

[56] Eto, Ko; Takashi Asada; Kunimasa Arima; Takao Makifuchi; Hideo Kimura (2002-05-24). “Brain hydrogen sulfide is
severely decreased in Alzheimer’s disease”. Biochemical and Biophysical Research Communications 293 (5): 1485–1488.
doi:10.1016/S0006-291X(02)00422-9. PMID 12054683.

[57] Hu, L. F.; Lu, M.; Tiong, C. X.; Dawe, G. S.; Hu, G.; Bian, J. S. (2010). “Neuroprotective effects of hydrogen sulfide on
Parkinson’s disease rat models”. Aging cell 9 (2): 135–146. doi:10.1111/j.1474-9726.2009.00543.x. PMID 20041858.

[58] Mice put in 'suspended animation', BBC News, 21 April 2005

[59] Gas induces 'suspended animation', BBC News, 9 October 2006

[60] Florian B, Vintilescu R, Balseanu AT, Buga A-M, Grisk O, Walker LC, Kessler C, Popa-Wagner A (2008). “Long-
term hypothermia reduces infarct volume in aged rats after focal ischemia”. Neuroscience Letters 438 (2): 180–185.
doi:10.1016/j.neulet.2008.04.020. PMID 18456407.

[61] Mark B. Roth and Todd Nystul. Buying Time in Suspended Animation. Scientific American, 1 June 2005

[62] Li, Jia; Zhang, Gencheng; Cai, Sally; Redington, Andrew N (January 2008). “Effect of inhaled hydrogen sulfide on
metabolic responses in anesthetized, paralyzed, and mechanically ventilated piglets”. Pediatric Critical Care Medicine 9 (1):
110–112. doi:10.1097/01.PCC.0000298639.08519.0C. PMID 18477923. Retrieved 2008-02-07. H2 S does not appear
to have hypometabolic effects in ambiently cooled large mammals and conversely appears to act as a hemodynamic and
metabolic stimulant.

[63] Haouzi P, Notet V, Chenuel B, Chalon B, Sponne I, Ogier V et al. (2008). “H2 S induced hypometabolism in mice is
missing in sedated sheep”. Respir Physiol Neurobiol 160 (1): 109–15. doi:10.1016/j.resp.2007.09.001. PMID 17980679.

[64] “Mark Roth: Suspended animation is within our grasp”.

[65] “IK-1001 (Sodium Sulfide (Na2S) for Injection) in Subjects With Acute ST-Segment Elevation Myocardial Infarction”.
ClinicalTrials.gov. 2010-11-04. This study has been withdrawn prior to enrollment. ( Company decision. Non-safety
related )
14 CHAPTER 1. HYDROGEN SULFIDE

[66] “Reduction of Ischemia-Reperfusion Mediated Cardiac Injury in Subjects Undergoing Coronary Artery Bypass Graft
Surgery”. ClinicalTrials.gov. 2011-08-03. This study has been terminated. ( Study Terminated - Company decision )

[67] Jørgensen, B. B. & D. C. Nelson (2004) Sulfide oxidation in marine sediments: Geochemistry meets microbiology, pp.
36–81. In J. P. Amend, K. J. Edwards, and T. W. Lyons (eds.) Sulfur Biogeochemistry - Past and Present. Geological
Society of America.

[68] “Impact From the Deep” in the October 2006 issue of Scientific American.

[69] Tobler; Riesch; García de León; Schlupp; & Plath (2008). Two endemic and endangered fishes, Poecilia sulphuraria
(Alvarez, 1948) and Gambusia eurystoma Miller, 1975 (Poeciliidae, Teleostei) as only survivors in a small sulphidic habitat.
Journal of Fish Biology 72: 523–533.

[70] Palacios, Arias-Rodriguez, Plath, Eifert, Lerp, Lamboj, Voelker, & Tobler (2013). The Rediscovery of a Long Described
Species Reveals Additional Complexity in Speciation Patterns of Poeciliid Fishes in Sulfide Springs. PLoS ONE 8(8): e71069.

[71] Bernardino; Levin; Thurber; & Smith (2012). Comparative Composition, Diversity and Trophic Ecology of Sediment Macro-
fauna at Vents, Seeps and Organic Falls. PLoS ONE 7(4): e33515.

[72] Marine Sociaty of Australia: Hydrothermal Vents. Retrieved 28 December 2014.

1.16 Additional resources

• “Hydrogen Sulfide”, Committee on Medical and Biological Effects of Environmental Pollutants, University
Park Press, 1979, Baltimore. ISBN 0-8391-0127-9

• Siefers, Andrea (2010). A novel and cost-effective hydrogen sulfide removal technology using tire derived rubber
particles (MS thesis). Iowa State University. Retrieved 8 February 2013.

1.17 External links

• International Chemical Safety Card 0165
• Concise International Chemical Assessment Document 53

• National Pollutant Inventory - Hydrogen sulfide fact sheet

• NIOSH Pocket Guide to Chemical Hazards

• NACE (National Association of Corrosion Epal)

Chapter 2

Alkene

This article is about the chemical compound. For the material, see Olefin fiber.
Not to be confused with Alkane or Alkyne.
In organic chemistry, an alkene, olefin, or olefine is an unsaturated hydrocarbon containing at least one carbon–

A 3D model of ethylene, the simplest alkene.

carbon double bond.[1] The simplest acyclic alkenes, with only one double bond and no other functional groups, known
as mono-enes, form a homologous series of hydrocarbons with the general formula C H₂ .[2] They have two hydrogen
atoms less than the corresponding alkane (with the same number of carbon atoms).
The simplest alkene is ethylene (C2 H4 ), which has the International Union of Pure and Applied Chemistry (IUPAC)
name ethene. In the petrochemical industry alkenes are often called olefins. For bridged alkenes, Bredt’s rule states
that a double bond cannot be placed at the bridgehead of a bridged ring system, unless the rings are large enough (8 or
more atoms). Aromatic compounds are often drawn as cyclic alkenes, but their structure and properties are different

15
16 CHAPTER 2. ALKENE

and they are not considered to be alkenes.[2]

2.1 Structure

2.1.1 Bonding

Ethylene (ethene), showing the pi bond in green.

Like a single covalent bond, double bonds can be described in terms of overlapping atomic orbitals, except that,
unlike a single bond (which consists of a single sigma bond), a carbon–carbon double bond consists of one sigma
bond and one pi bond. This double bond is stronger than a single covalent bond (611 kJ/mol for C=C vs. 347 kJ/mol
for C–C)[1] and also shorter with an average bond length of 1.33 Angstroms (133 pm).
Each carbon of the double bond uses its three sp² hybrid orbitals to form sigma bonds to three atoms. The unhy-
bridized 2p atomic orbitals, which lie perpendicular to the plane created by the axes of the three sp² hybrid orbitals,
2.2. PHYSICAL PROPERTIES 17

combine to form the pi bond. This bond lies outside the main C–C axis, with half of the bond on one side and half
on the other.
Rotation about the carbon–carbon double bond is restricted because it involves breaking the pi bond, which requires
a large amount of energy (264 kJ/mol in ethylene). As a consequence, substituted alkenes may exist as one of two
isomers, called cis or trans isomers. More complex alkenes may be named using the E-Z notation, used to describe
molecules having three or four different substituents (side groups). For example, of the isomers of butene, the two
methyl groups of (Z)-but-2-ene (aka cis−2-butene) face the same side of the double bond, and in (E)-but2-ene (aka
trans−2-butene) the methyl groups face the opposite side. These two isomers of butene are slightly different in their
chemical and physical properties.
It is certainly not impossible to twist a double bond. In fact, a 90° twist requires an energy approximately equal to
half the strength of a pi bond. The misalignment of the p orbitals is less than expected because pyramidalization
takes place (See: pyramidal alkene). trans-Cyclooctene is a stable strained alkene and the orbital misalignment is
only 19° with a dihedral angle of 137° (normal 120°) and a degree of pyramidalization of 18°. This explains the
dipole moment of 0.8 D for this compound (cis-isomer 0.4 D) where a value of zero is expected.[3] The trans isomer
of cycloheptene is only stable at low temperatures.

2.1.2 Shape

As predicted by the VSEPR model of electron pair repulsion, the molecular geometry of alkenes includes bond
angles about each carbon in a double bond of about 120°. The angle may vary because of steric strain introduced by
nonbonded interactions created by functional groups attached to the carbons of the double bond. For example, the
C-C-C bond angle in propylene is 123.9°.

2.2 Physical properties

The physical properties of alkenes are comparable with those of alkanes. The main differences between the two are
that the acidity levels of alkenes are much higher than the ones in alkanes. The physical state depends on molecular
mass. The simplest alkenes, ethene, propene and butene are gases. Linear alkenes of approximately five to sixteen
carbons are liquids, and higher alkenes are waxy solids.

2.3 Reactions

Alkenes are relatively stable compounds, but are more reactive than alkanes due to the presence of a carbon–carbon
pi-bond. It is also attributed to the presence of pi-electrons in the molecule. The majority of the reactions of alkenes
involve the rupture of this pi bond, forming new single bonds.
Alkenes serve as a feedstock for the petrochemical industry because they can participate in a wide variety of reactions.

2.3.1 Addition reactions

Alkenes react in many addition reactions, which occur by opening up the double-bond. Most addition reactions
to alkenes follow the mechanism of electrophilic addition. Examples of addition reactions are hydrohalogenation,
halogenation, halohydrin formation, oxymercuration, hydroboration, dichlorocarbene addition, Simmons–Smith re-
action, catalytic hydrogenation, epoxidation, radical polymerization and hydroxylation.
18 CHAPTER 2. ALKENE

Hydrogenation

Hydrogenation of alkenes produces the corresponding alkanes. The reaction is carried out under pressure at a tem-
perature of 200 °C in the presence of a metallic catalyst. Common industrial catalysts are based on platinum, nickel
or palladium. For laboratory syntheses, Raney nickel (an alloy of nickel and aluminium) is often employed. The
simplest example of this reaction is the catalytic hydrogenation of ethylene to yield ethane:

CH2 =CH2 + H2 → CH3 -CH3

Hydration

Hydration, the addition of water across the double bond of alkenes, yields alcohols. The reaction is catalyzed by
strong acids such as sulfuric acid. This reaction is carried out on an industrial scale to make ethanol.

CH2 =CH2 + H2 O → CH3 -CH2 OH

Alkenes can also be converted into alcohols via the oxymercuration–demercuration reaction or hydroboration–oxidation
reaction.

Halogenation

In electrophilic halogenation the addition of elemental bromine or chlorine to alkenes yields vicinal dibromo- and
dichloroalkanes (1,2-dihalides or ethylene dihalides), respectively. The decoloration of a solution of bromine in
water with dichloromethylene as catalyst is an analytical test for the presence of alkenes:

CH2 =CH2 + Br2 → BrCH2 -CH2 Br

It is also used as a quantitative test of unsaturation, expressed as the bromine number of a single compound or mixture.
The reaction works because the high electron density at the double bond causes a temporary shift of electrons in the
Br-Br bond causing a temporary induced dipole. This makes the Br closest to the double bond slightly positive and
therefore an electrophile.

Hydrohalogenation

Hydrohalogenation is the addition of hydrohalic acids such as HCl or HI to alkenes to yield the corresponding
haloalkanes.

CH3 -CH=CH2 + HI → CH3 -CHI-CH2 -H

If the two carbon atoms at the double bond are linked to a different number of hydrogen atoms, the halogen is found
preferentially at the carbon with fewer hydrogen substituents (Markovnikov’s rule). The use of radical initiators or
other chemicals can lead to the opposite product result, but the reactive-intermediate structures and mechanisms are
different. Hydrobromic acid in particular is prone to forming radicals in the presence of various impurities or even
atmospheric oxygen, leading to the reversal of the Markovnikov result:[4]

CH3 -CH=CH2 + HBr → CH3 -CHH-CH2 -Br

Halohydrin formation

Alkenes react with water and halogens to form halohydrins by an addition reaction. Markovnikov regiochemistry and
anti stereochemistry occur.

CH2 =CH2 + X2 + H2 O → XCH2 -CH2 OH + HX

2.3. REACTIONS 19

Oxidation

Alkenes are oxidized with a large number of oxidizing agents. In the presence of oxygen, alkenes burn with a bright
flame to produce carbon dioxide and water. Catalytic oxidation with oxygen or the reaction with percarboxylic acids
yields epoxides. Reaction with ozone in ozonolysis leads to the breaking of the double bond, yielding two aldehydes
or ketones. Reaction with concentrated, hot KMnO4 (or other oxidizing salts) in an acidic solution will yield ketones
or carboxylic acids.

R1 -CH=CH-R2 + O3 → R1 -CHO + R2 -CHO + H2 O

This reaction can be used to determine the position of a double bond in an unknown alkene.
The oxidation can be stopped at the vicinal diol rather than full cleavage of the alkene by using milder (dilute,lower
temperature) KMnO4 or with osmium tetroxide or other oxidants.

Photooxygenation

In the presence of an appropriate photosensitiser, such as methylene blue and light, alkenes can undergo reactions
with reactive oxygen species generated by the photosensitiser, such as hydroxyl radicals, singlet oxygen or superoxide
ion. These reactive photochemical intermediates are generated in what are known as Type I, Type II, and Type III
processes, respectively. These various alternative processes and reactions can be controlled by choice of specific
reaction conditions, leading to a wide range of different products. A common example is the [4+2] cycloaddition of
singlet oxygen with a diene such as cyclopentadiene to yield an endoperoxide:

Another example is the Schenck ene reaction, in which singlet oxygen reacts with an allylic structure to give a trans-
posed allyl peroxide:

hυ / Sens O
O2 O
R R
20 CHAPTER 2. ALKENE

2.3.2 Polymerization
Main article: polyolefin

Polymerization of alkenes is a reaction that yields polymers of high industrial value at great economy, such as the plas-
tics polyethylene and polypropylene. Polymers from alkene monomers are referred to in a general way as polyolefins
or in rare instances as polyalkenes. A polymer from alpha-olefins is called a polyalphaolefin (PAO). Polymerization
can proceed via either a free-radical or an ionic mechanism, converting the double to a single bond and forming
single bonds to join the other monomers. Polymerization of conjugated dienes such as buta-1,3-diene or isoprene
(2-methylbuta-1,3-diene) results in largely 1,4-addition with possibly some 1,2-addition of the diene monomer to a
growing polymer chain.

2.3.3 Metal complexation

Structure of bis(cyclooctadiene)nickel(0), a metal–alkene complex

Alkenes are ligands in transition metal alkene complexes. The two carbon centres bond to the metal using the C-
C pi- and pi* orbitals. Mono- and diolefins are often used as ligands in stable complexes. Cyclooctadiene and
norbornadiene are popular chelating agents, and even ethylene itself is sometimes used as a ligand, for example,
in Zeise’s salt. In addition, metal–alkene complexes are intermediates in many metal-catalyzed reactions including
hydrogenation, hydroformylation, and polymerization.

2.3.4 Reaction overview

2.4 Synthesis

2.4.1 Industrial methods

Alkenes are produced by hydrocarbon cracking. Raw materials are mostly natural gas condensate components (prin-
cipally ethane and propane) in the US and Mideast and naphtha in Europe and Asia. Alkanes are broken apart at
high temperatures, often in the presence of a zeolite catalyst, to produce a mixture of primarily aliphatic alkenes and
lower molecular weight alkanes. The mixture is feedstock and temperature dependent, and separated by fractional
distillation. This is mainly used for the manufacture of small alkenes (up to six carbons).[1]
Related to this is catalytic dehydrogenation, where an alkane loses hydrogen at high temperatures to produce a cor-
responding alkene.[1] This is the reverse of the catalytic hydrogenation of alkenes.
2.4. SYNTHESIS 21

Cracking of n-octane to give pentane + propene

Dehydrogenation of butane to give butadiene and isomers of butene

This process is also known as reforming. Both processes are endothermic and are driven towards the alkene at high
temperatures by entropy.
Catalytic synthesis of higher α-alkenes (of the type RCH=CH2 ) can also be achieved by a reaction of ethylene with
the organometallic compound triethylaluminium in the presence of nickel, cobalt, or platinum.

2.4.2 Elimination reactions

One of the principal methods for alkene synthesis in the laboratory is the elimination of alkyl halides, alcohols, and
similar compounds. Most common is the β-elimination via the E2 or E1 mechanism,[5] but α-eliminations are also
known.
The E2 mechanism provides a more reliable β-elimination method than E1 for most alkene syntheses. Most E2
eliminations start with an alkyl halide or alkyl sulfonate ester (such as a tosylate or triflate). When an alkyl halide
is used, the reaction is called a dehydrohalogenation. For unsymmetrical products, the more substituted alkenes
(those with fewer hydrogens attached to the C=C) tend to predominate (see Zaitsev’s rule). Two common methods
of elimination reactions are dehydrohalogenation of alkyl halides and dehydration of alcohols. A typical example
is shown below; note that if possible, the H is anti to the leaving group, even though this leads to the less stable
Z-isomer.[6]

An example of an E2 Elimination

Alkenes can be synthesized from alcohols via dehydration, in which case water is lost via the E1 mechanism. For
example, the dehydration of ethanol produces ethene:

CH3 CH2 OH + H2 SO4 → H2 C=CH2 + H3 O+ + HSO4 −

An alcohol may also be converted to a better leaving group (e.g., xanthate), so as to allow a milder syn-elimination
such as the Chugaev elimination and the Grieco elimination. Related reactions include eliminations by β-haloethers
(the Boord olefin synthesis) and esters (ester pyrolysis).
Alkenes can be prepared indirectly from alkyl amines. The amine or ammonia is not a suitable leaving group, so
the amine is first either alkylated (as in the Hofmann elimination) or oxidized to an amine oxide (the Cope reaction)
22 CHAPTER 2. ALKENE

to render a smooth elimination possible. The Cope reaction is a syn-elimination that occurs at or below 150 °C, for
example:[7]

Synthesis of cyclooctene via Cope elimination

The Hofmann elimination is unusual in that the less substituted (non-Saytseff) alkene is usually the major product.
Alkenes are generated from α-halo sulfones in the Ramberg-Bäcklund reaction, via a three-membered ring sulfone
intermediate.

2.4.3 Synthesis from carbonyl compounds

Another important method for alkene synthesis involves construction of a new carbon–carbon double bond by coupling
of a carbonyl compound (such as an aldehyde or ketone) to a carbanion equivalent. Such reactions are sometimes
called olefinations. The most well-known of these methods is the Wittig reaction, but other related methods are
known.
The Wittig reaction involves reaction of an aldehyde or ketone with a Wittig reagent (or phosphorane) of the type
Ph3 P=CHR to produce an alkene and Ph3 P=O. The Wittig reagent is itself prepared easily from triphenylphosphine
and an alkyl halide. The reaction is quite general and many functional groups are tolerated, even esters, as in this
example:[8]

A typical example of the Wittig reaction

Related to the Wittig reaction is the Peterson olefination. This uses a less accessible silicon-based reagent in place
of the phosphorane, but it allows for the selection of E or Z products. If an E-product is desired, another alternative
is the Julia olefination, which uses the carbanion generated from a phenyl sulfone. The Takai olefination based on
an organochromium intermediate also delivers E-products. A titanium compound, Tebbe’s reagent, is useful for the
synthesis of methylene compounds; in this case, even esters and amides react.
A pair of carbonyl compounds can also be reductively coupled together (with reduction) to generate an alkene. Sym-
metrical alkenes can be prepared from a single aldehyde or ketone coupling with itself, using Ti metal reduction
(the McMurry reaction). If two different ketones are to be coupled, a more complex, indirect method such as the
Barton–Kellogg reaction may be used.
A single ketone can also be converted to the corresponding alkene via its tosylhydrazone, using sodium methoxide
(the Bamford–Stevens reaction) or an alkyllithium (the Shapiro reaction).
2.5. NOMENCLATURE 23

2.4.4 Synthesis from alkenes: olefin metathesis and hydrovinylation

Main article: Olefin metathesis

Alkenes can be prepared by exchange with other alkenes, in a reaction known as olefin metathesis. Frequently, loss
of ethene gas is used to drive the reaction towards a desired product. In many cases, a mixture of geometric isomers
is obtained, but the reaction tolerates many functional groups. The method is particularly effective for the preparation
of cyclic alkenes, as in this synthesis of muscone:

Ring-closing metathesis used in synthesis of muscone

Transition metal catalyzed hydrovinylation is another important alkene synthesis process starting from alkene itself.[9]
In general, it involves the addition of a hydrogen and a vinyl group (or an alkenyl group) across a double bond. The
hydrovinylation reaction was first reported by Alderson, Jenner, and Lindsey by using rhodium and ruthenium salts,
other metal catalysts commonly employed nowadays included iron, cobalt, nickel, and palladium. The addition can be
done highly regio- and stereo-selectively, the choices of metal centers, ligands, substrates and counterions often play
very important role.[10][11][12] Recent studies showed that the use of N-heterocyclic carbene with Ni can be useful for
the selective preparations of functionalized geminal olefins or 1,1-disubstituted alkenes.[13][14]

2.4.5 From alkynes

Reduction of alkynes is a useful method for the stereoselective synthesis of disubstituted alkenes. If the cis-alkene
is desired, hydrogenation in the presence of Lindlar’s catalyst (a heterogeneous catalyst that consists of palladium
deposited on calcium carbonate and treated with various forms of lead) is commonly used, though hydroboration
followed by hydrolysis provides an alternative approach. Reduction of the alkyne by sodium metal in liquid ammonia
gives the trans-alkene.[15]

Synthesis of cis- and trans-alkenes from alkynes

For the preparation multisubstituted alkenes, carbometalation of alkynes can give rise to a large variety of alkene
derivatives.

2.4.6 Rearrangements and related reactions

Alkenes can be synthesized from other alkenes via rearrangement reactions. Besides olefin metathesis (described
above), a large number of pericyclic reactions can be used such as the ene reaction and the Cope rearrangement.
In the Diels-Alder reaction, a cyclohexene derivative is prepared from a diene and a reactive or electron-deficient
alkene.

2.5 Nomenclature
24 CHAPTER 2. ALKENE

H
Cope rearrangement of divinylcyclobutane to cyclooctadiene

2.5.1 IUPAC names

To form the root of the IUPAC names for alkenes, simply change the -an- infix of the parent to -en-. For example,
CH3 -CH3 is the alkane ethANe. The name of CH2 =CH2 is therefore ethENe.
In higher alkenes, where isomers exist that differ in location of the double bond, the following numbering system is
used:

1. Number the longest carbon chain that contains the double bond in the direction that gives the carbon atoms of
the double bond the lowest possible numbers.

2. Indicate the location of the double bond by the location of its first carbon.

3. Name branched or substituted alkenes in a manner similar to alkanes.

4. Number the carbon atoms, locate and name substituent groups, locate the double bond, and name the main
chain.

Naming substituted hex-1-enes

2.5.2 Cis-trans notation

Main article: Cis-trans isomerism

In the specific case of disubstituted alkenes where the two carbons have one substituent each, Cis-trans notation may
be used. If both substituents are on the same side of the bond, it is defined as (cis-). If the substituents are on either
side of the bond, it is defined as (trans-).
2.6. SEE ALSO 25

1 4 4

2 3 2 3

cis-but-2-ene trans-but-2-ene
The difference between cis- and trans- isomers

2.5.3 E,Z notation

Main article: E-Z notation

When an alkene has more than one substituent (especially necessary with 3 or 4 substituents), the double bond geome-
try is described using the labels E and Z. These labels come from the German words “entgegen,” meaning “opposite,”
and “zusammen,” meaning “together.” Alkenes with the higher priority groups (as determined by CIP rules) on the
same side of the double bond have these groups together and are designated Z. Alkenes with the higher priority groups
on opposite sides are designated E. A mnemonic to remember this: Z notation has the higher priority groups on “ze
zame zide.”

The difference between E and Z isomers

2.5.4 Groups containing C=C double bonds

IUPAC recognizes two names for hydrocarbon groups containing carbon–carbon double bonds, the vinyl group and
the allyl group. .[2]

2.6 See also

• Alpha-olefin

• Cycloalkene
26 CHAPTER 2. ALKENE

• Arenes

• Diene

• Dendralene

• Radialene

• Annulene

• Polyene

• Nitroalkene

2.7 Nomenclature links

• Rule A-3. Unsaturated Compounds and Univalent Radicals IUPAC Blue Book.

• Rule A-4. Bivalent and Multivalent Radicals IUPAC Blue Book.

• Rules A-11.3, A-11.4, A-11.5 Unsaturated monocyclic hydrocarbons and substituents IUPAC Blue Book.

• Rule A-23. Hydrogenated Compounds of Fused Polycyclic Hydrocarbons IUPAC Blue Book.

2.8 References
[1] Wade, L.G. (Sixth Ed., 2006). Organic Chemistry. Pearson Prentice Hall. p. 279. ISBN 1-4058-5345-X. Check date
values in: |date= (help)

[2] Moss, G. P.; Smith, P. A. S.; Tavernier, D. (1995). “Glossary of Class Names of Organic Compounds and Reactive
Intermediates Based on Structure (IUPAC Recommendations 1995)". Pure and Applied Chemistry 67 (8–9): 1307–1375.
doi:10.1351/pac199567081307.

[3] Barrows, Susan E.; Eberlein, Thomas H. (2005). “Understanding Rotation about a C=C Double Bond”. J. Chem. Educ.
82 (9): 1329. Bibcode:2005JChEd..82.1329B. doi:10.1021/ed082p1329.

[4] Streiwieser, A.; Heathcock, C.H.; Kosower, E.M. (1992). “11.6.G. Alkenes: Reacttions: Free Radical Additions”. Intro-
duction to Organic Chemistry (4th ed.). New York: Macmillan. p. 288.

[5] Saunders, W. H. (1964). Patai, Saul, ed. The Chemistry of Alkenes. Wiley Interscience. pp. 149–150.

[6] Cram, D.J.; Greene, Frederick D.; Depuy, C. H. (1956). “Studies in Stereochemistry. XXV. Eclipsing Effects in the E2
Reaction1”. Journal of the American Chemical Society 78 (4): 790–796. doi:10.1021/ja01585a024.

[7] Bach, R.D.; Andrzejewski, Denis; Dusold, Laurence R. (1973). “Mechanism of the Cope elimination”. J. Org. Chem. 38
(9): 1742–3. doi:10.1021/jo00949a029.

[8] Snider, Barry B.; Matsuo, Y; Snider, BB (2006). “Synthesis of ent-Thallusin”. Org. Lett. 8 (10): 2123–6. doi:10.1021/ol0605777.
PMC 2518398. PMID 16671797.
2.8. REFERENCES 27

[9] Vogt, D. (2010). “Cobalt-Catalyzed Asymmetric Hydrovinylation”. Angew. Chem. Int. Ed. 49 (40): 7166–8. doi:10.1002/anie.201003133.
PMID 20672269.

[10] Grutters, M. M. P. Muller, C. Vogt, D. (2006). “Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene”. J. Am.
Chem. Soc. 128 (23): 7414–5. doi:10.1021/ja058095y. PMID 16756275.

[11] Hilt, G. Danz, M. Treutwein, J. (2009). “Cobalt-Catalyzed 1,4-Hydrovinylation of Styrenes and 1-Aryl-1,3-butadienes”.
Org. Lett. 11 (15): 3322–5. doi:10.1021/ol901064p. PMID 19583205.

[12] Sharma, R. K. RajanBabu, T. V. (2010). “Asymmetric Hydrovinylation of Unactivated Linear 1,3-Dienes”. J. Am. Chem.
Soc. 132 (10): 3295–7. doi:10.1021/ja1004703. PMC 2836389. PMID 20163120.

[13] Ho, C.-Y., He, L. (2010). “Catalytic Intermolecular Tail-to-Tail Hydroalkenylation of Styrenes with alpha-Olefins: Re-
gioselective Migratory Insertion Controlled by a Nickel/N-Heterocyclic Carbene”. Angew. Chem. Int. Ed. 49 (48):
9182–9186. doi:10.1002/anie.201001849. PMID 20853303.

[14] Ho, C.-Y., He, L. (2012). “Shuffle Off the Classic Beta-Si Elimination by Ni-NHC Cooperation: Implication for C–C
Forming Reactions Involving Ni-Alkyl-Beta-Silanes”. Chem. Commun. 48 (10): 1481–1483. doi:10.1039/c1cc14593b.
PMID 22116100.

[15] Zweifel, George S.; Nantz, Michael H. (2007). Modern Organic Synthesis: An Introduction. New York: W. H. Freeman &
Co. p. 366. ISBN 0-7167-7266-3.
Chapter 3

Alkane

Not to be confused with Alkene, Alkyne, or Alkaline.

In organic chemistry, an alkane, or paraffin (a historical name that also has other meanings), is a saturated

Chemical structure of methane, the simplest alkane

28
3.1. STRUCTURE CLASSIFICATION 29

hydrocarbon. Alkanes consist only of hydrogen and carbon atoms and all bonds are single bonds.[1] Alkanes (techni-
cally, always acyclic) have the general chemical formula C H₂ ₊₂. Alkanes belong to a homologous series of organic
compounds in which the members differ by a molecular mass of 14.03u (mass of a methanediyl group, —CH2 —,
one carbon atom of mass 12.01u, and two hydrogen atoms of mass ≈1.01u each). There are two main commercial
sources: crude oil[2] and natural gas.
Each carbon atom has 4 bonds (either C-H or C-C bonds), and each hydrogen atom is joined to a carbon atom (H-C
bonds). A series of linked carbon atoms is known as the carbon skeleton or carbon backbone. The number of carbon
atoms is used to define the size of the alkane (e.g., C2 -alkane).
An alkyl group, generally abbreviated with the symbol R, is a functional group or side-chain that, like an alkane,
consists solely of single-bonded carbon and hydrogen atoms, for example a methyl or ethyl group.
The simplest possible alkane (the parent molecule) is methane, CH4 . There is no limit to the number of carbon atoms
that can be linked together, the only limitation being that the molecule is acyclic, is saturated, and is a hydrocarbon.
Saturated oils and waxes are examples of larger alkanes where the number of carbons in the carbon backbone is
greater than 10.
Alkanes are not very reactive and have little biological activity. All alkanes are colourless and odourless. Alkanes
can be viewed as a molecular tree upon which can be hung the more biologically active/reactive portions (functional
groups) of the molecule.

3.1 Structure classification

Saturated hydrocarbons can be:

• linear (general formula C

nH
2n + 2) wherein the carbon atoms are joined in a snake-like structure

• branched (general formula C

nH
2n + 2, n > 3) wherein the carbon backbone splits off in one or more directions

• cyclic (general formula C

nH
2n, n > 2) wherein the carbon backbone is linked so as to form a loop.

According to the definition by IUPAC, the former two are alkanes, whereas the third group is called cycloalkanes.[3]
Saturated hydrocarbons can also combine any of the linear, cyclic (e.g., polycyclic) and branching structures, and they
are still alkanes (no general formula) as long as they are acyclic (i.e., having no loops).They also have single covalent
bonds between their carbons.

3.2 Isomerism
Alkanes with more than three carbon atoms can be arranged in various different ways, forming structural isomers. The
simplest isomer of an alkane is the one in which the carbon atoms are arranged in a single chain with no branches. This
isomer is sometimes called the n-isomer (n for “normal”, although it is not necessarily the most common). However
the chain of carbon atoms may also be branched at one or more points. The number of possible isomers increases
rapidly with the number of carbon atoms. For example:[4]

• C1 : methane only

• C2 : ethane only

• C3 : propane only

• C4 : 2 isomers: n-butane and isobutane

30 CHAPTER 3. ALKANE

Different C4 -alkanes and -cycloalkanes (left to right): n-butane and isobutane are the two C4 H10 isomers; cyclobutane and
methylcyclopropane are the two C4 H8 isomers.
Bicyclo[1.1.0]butane is the only C4 H6 compound and has no isomer; tetrahedrane (not shown) is the only C4 H4 compound and has
also no isomer.

• C5 : 3 isomers: pentane, isopentane, and neopentane

• C6 : 5 isomers: hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane
• C12 : 355 isomers
• C32 : 27,711,253,769 isomers
• C60 : 22,158,734,535,770,411,074,184 isomers, many of which are not stable.

Branched alkanes can be chiral. For example 3-methylhexane and its higher homologues are chiral due to their
stereogenic center at carbon atom number 3. In addition to these isomers, the chain of carbon atoms may form one
3.3. NOMENCLATURE 31

or more loops. Such compounds are called cycloalkanes.

3.3 Nomenclature
Main article: IUPAC nomenclature of organic chemistry

The IUPAC nomenclature (systematic way of naming compounds) for alkanes is based on identifying hydrocarbon
chains. Unbranched, saturated hydrocarbon chains are named systematically with a Greek numerical prefix denoting
the number of carbons and the suffix "-ane”.[5]
In 1866, August Wilhelm von Hofmann suggested systematizing nomenclature by using the whole sequence of vowels
a, e, i, o and u to create suffixes -ane, -ene, -ine (or -yne), -one, -une, for the hydrocarbons C H₂ ₊₂, C H₂ , C H₂ -₂,
C H₂ -₄, C H₂ -₆.[6] Now, the first three name hydrocarbons with single, double and triple bonds;[7] "-one” represents
a ketone; "-ol” represents an alcohol or OH group; "-oxy-" means an ether and refers to oxygen between two carbons,
so that methoxy-methane is the IUPAC name for dimethyl ether.
It is difficult or impossible to find compounds with more than one IUPAC name. This is because shorter chains
attached to longer chains are prefixes and the convention includes brackets. Numbers in the name, referring to which
carbon a group is attached to, should be as low as possible, so that 1- is implied and usually omitted from names
of organic compounds with only one side-group. Symmetric compounds will have two ways of arriving at the same
name.

3.3.1 Linear alkanes

Straight-chain alkanes are sometimes indicated by the prefix n- (for normal) where a non-linear isomer exists. Al-
though this is not strictly necessary, the usage is still common in cases where there is an important difference in
properties between the straight-chain and branched-chain isomers, e.g., n-hexane or 2- or 3-methylpentane.
The members of the series (in terms of number of carbon atoms) are named as follows:

methane, CH4 - one carbon and four hydrogen

ethane, C2 H6 - two carbon and six hydrogen
propane, C3 H8 - three carbon and 8 hydrogen
butane, C4 H10 - four carbon and 10 hydrogen
pentane, C5 H12 - five carbon and 12 hydrogen
hexane, C6 H14 - six carbon and 14 hydrogen

The first four names were derived from methanol, ether, propionic acid and butyric acid, respectively. Alkanes with
five or more carbon atoms are named by adding the suffix -ane to the appropriate numerical multiplier prefix[8] with
elision of any terminal vowel (-a or -o) from the basic numerical term. Hence, pentane, C5 H12 ; hexane, C6 H14 ;
heptane, C7 H16 ; octane, C8 H18 ; etc. The prefix is generally Greek, however alkanes with a carbon atom count
ending in nine, for example nonane, use the Latin prefix non-. For a more complete list, see List of alkanes.

3.3.2 Branched alkanes

Simple branched alkanes often have a common name using a prefix to distinguish them from linear alkanes, for
example n-pentane, isopentane, and neopentane.
IUPAC naming conventions can be used to produce a systematic name.
The key steps in the naming of more complicated branched alkanes are as follows:[9]

• Identify the longest continuous chain of carbon atoms

• Name this longest root chain using standard naming rules

32 CHAPTER 3. ALKANE

Ball-and-stick model of isopentane (common name) or 2-methylbutane (IUPAC systematic name)

• Name each side chain by changing the suffix of the name of the alkane from "-ane” to "-yl”

• Number the root chain so that the sum of the numbers assigned to each side group will be as low as possible

• Number and name the side chains before the name of the root chain

• If there are multiple side chains of the same type, use prefixes such as “di-" and “tri-" to indicate it as such,
and number each one.

• Add side chain names in alphabetical (disregarding “di-" etc. prefixes) order in front of the name of the root
chain

3.3.3 Cyclic alkanes

Main article: Cycloalkane

So-called cyclic alkanes are, in the technical sense, not alkanes, but cycloalkanes. They are hydrocarbons just like
alkanes, but contain one or more rings.
Simple cycloalkanes have a prefix “cyclo-" to distinguish them from alkanes. Cycloalkanes are named as per their
acyclic counterparts with respect to the number of carbon atoms, e.g., cyclopentane (C5 H10 ) is a cycloalkane with 5
carbon atoms just like pentane (C5 H12 ), but they are joined up in a five-membered ring. In a similar manner, propane
and cyclopropane, butane and cyclobutane, etc.
Substituted cycloalkanes are named similar to substituted alkanes — the cycloalkane ring is stated, and the substituents
are according to their position on the ring, with the numbering decided by Cahn-Ingold-Prelog rules.[8]
3.4. PHYSICAL PROPERTIES 33

3.3.4 Trivial names

The trivial (non-systematic) name for alkanes is paraffins. Together, alkanes are known as the paraffin series. Trivial
names for compounds are usually historical artifacts. They were coined before the development of systematic names,
and have been retained due to familiar usage in industry. Cycloalkanes are also called naphthenes.
It is almost certain that the term paraffin stems from the petrochemical industry. Branched-chain alkanes are called
isoparaffins. The use of the term “paraffin” is a general term and often does not distinguish between pure compounds
and mixtures of isomers, i.e., compounds with the same chemical formula, e.g., pentane and isopentane.

Examples

The following trivial names are retained in the IUPAC system:

• isobutane for 2-methylpropane

• isopentane for 2-methylbutane

• neopentane for 2,2-dimethylpropane.

3.4 Physical properties

All alkanes are colourless and odourless.[10][11]

3.4.1 Table of alkanes

3.4.2 Boiling point

Melting (blue) and boiling (orange) points of the first 16 n-alkanes in °C.

Alkanes experience inter-molecular van der Waals forces. Stronger inter-molecular van der Waals forces give rise to
greater boiling points of alkanes.[12]
There are two determinants for the strength of the van der Waals forces:

• the number of electrons surrounding the molecule, which increases with the alkane’s molecular weight
34 CHAPTER 3. ALKANE

• the surface area of the molecule

Under standard conditions, from CH4 to C4 H10 alkanes are gaseous; from C5 H12 to C17 H36 they are liquids; and
after C18 H38 they are solids. As the boiling point of alkanes is primarily determined by weight, it should not be
a surprise that the boiling point has almost a linear relationship with the size (molecular weight) of the molecule.
As a rule of thumb, the boiling point rises 20–30 °C for each carbon added to the chain; this rule applies to other
homologous series.[12]
A straight-chain alkane will have a boiling point higher than a branched-chain alkane due to the greater surface area
in contact, thus the greater van der Waals forces, between adjacent molecules. For example, compare isobutane (2-
methylpropane) and n-butane (butane), which boil at −12 and 0 °C, and 2,2-dimethylbutane and 2,3-dimethylbutane
which boil at 50 and 58 °C, respectively.[12] For the latter case, two molecules 2,3-dimethylbutane can “lock” into
each other better than the cross-shaped 2,2-dimethylbutane, hence the greater van der Waals forces.
On the other hand, cycloalkanes tend to have higher boiling points than their linear counterparts due to the locked
conformations of the molecules, which give a plane of intermolecular contact.

3.4.3 Melting points

The melting points of the alkanes follow a similar trend to boiling points for the same reason as outlined above.
That is, (all other things being equal) the larger the molecule the higher the melting point. There is one significant
difference between boiling points and melting points. Solids have more rigid and fixed structure than liquids. This
rigid structure requires energy to break down. Thus the better put together solid structures will require more energy
to break apart. For alkanes, this can be seen from the graph above (i.e., the blue line). The odd-numbered alkanes
have a lower trend in melting points than even numbered alkanes. This is because even numbered alkanes pack well
in the solid phase, forming a well-organized structure, which requires more energy to break apart. The odd-number
alkanes pack less well and so the “looser” organized solid packing structure requires less energy to break apart.[13]
The melting points of branched-chain alkanes can be either higher or lower than those of the corresponding straight-
chain alkanes, again depending on the ability of the alkane in question to pack well in the solid phase: This is
particularly true for isoalkanes (2-methyl isomers), which often have melting points higher than those of the linear
analogues.

3.4.4 Conductivity and solubility

Alkanes do not conduct electricity, nor are they substantially polarized by an electric field. For this reason they
do not form hydrogen bonds and are insoluble in polar solvents such as water. Since the hydrogen bonds between
individual water molecules are aligned away from an alkane molecule, the coexistence of an alkane and water leads to
an increase in molecular order (a reduction in entropy). As there is no significant bonding between water molecules
and alkane molecules, the second law of thermodynamics suggests that this reduction in entropy should be minimized
by minimizing the contact between alkane and water: Alkanes are said to be hydrophobic in that they repel water.
Their solubility in nonpolar solvents is relatively good, a property that is called lipophilicity. Different alkanes are,
for example, miscible in all proportions among themselves.
The density of the alkanes usually increases with increasing number of carbon atoms, but remains less than that of
water. Hence, alkanes form the upper layer in an alkane-water mixture.

3.4.5 Molecular geometry

The molecular structure of the alkanes directly affects their physical and chemical characteristics. It is derived from
the electron configuration of carbon, which has four valence electrons. The carbon atoms in alkanes are always
sp3 hybridized, that is to say that the valence electrons are said to be in four equivalent orbitals derived from the
combination of the 2s orbital and the three 2p orbitals. These orbitals, which have identical energies, are arranged
spatially in the form of a tetrahedron, the angle of cos−1 (−⅓) ≈ 109.47° between them.
3.4. PHYSICAL PROPERTIES 35

sp3 -hybridization in methane.

3.4.6 Bond lengths and bond angles

An alkane molecule has only C – H and C – C single bonds. The former result from the overlap of a sp3 -orbital of
carbon with the 1s-orbital of a hydrogen; the latter by the overlap of two sp3 -orbitals on different carbon atoms. The
bond lengths amount to 1.09×10−10 m for a C – H bond and 1.54×10−10 m for a C – C bond.
The spatial arrangement of the bonds is similar to that of the four sp3 -orbitals—they are tetrahedrally arranged,
with an angle of 109.47° between them. Structural formulae that represent the bonds as being at right angles to one
another, while both common and useful, do not correspond with the reality.

3.4.7 Conformation

Main article: Alkane stereochemistry

The structural formula and the bond angles are not usually sufficient to completely describe the geometry of a
molecule. There is a further degree of freedom for each carbon – carbon bond: the torsion angle between the atoms
or groups bound to the atoms at each end of the bond. The spatial arrangement described by the torsion angles of the
molecule is known as its conformation.
Ethane forms the simplest case for studying the conformation of alkanes, as there is only one C – C bond. If one
looks down the axis of the C – C bond, one will see the so-called Newman projection. The hydrogen atoms on both
36 CHAPTER 3. ALKANE

The tetrahedral structure of methane.

the front and rear carbon atoms have an angle of 120° between them, resulting from the projection of the base of the
tetrahedron onto a flat plane. However, the torsion angle between a given hydrogen atom attached to the front carbon
and a given hydrogen atom attached to the rear carbon can vary freely between 0° and 360°. This is a consequence of
the free rotation about a carbon – carbon single bond. Despite this apparent freedom, only two limiting conformations
are important: eclipsed conformation and staggered conformation.
The two conformations, also known as rotamers, differ in energy: The staggered conformation is 12.6 kJ/mol lower
in energy (more stable) than the eclipsed conformation (the least stable).
This difference in energy between the two conformations, known as the torsion energy, is low compared to the thermal
energy of an ethane molecule at ambient temperature. There is constant rotation about the C-C bond. The time taken
for an ethane molecule to pass from one staggered conformation to the next, equivalent to the rotation of one CH3 -
group by 120° relative to the other, is of the order of 10−11 seconds.
The case of higher alkanes is more complex but based on similar principles, with the antiperiplanar conformation
always being the most favored around each carbon-carbon bond. For this reason, alkanes are usually shown in a zigzag
arrangement in diagrams or in models. The actual structure will always differ somewhat from these idealized forms,
as the differences in energy between the conformations are small compared to the thermal energy of the molecules:
Alkane molecules have no fixed structural form, whatever the models may suggest.
3.4. PHYSICAL PROPERTIES 37

Newman projections of the two conformations of ethane: eclipsed on the left, staggered on the right.

Ball-and-stick models of the two rotamers of ethane

3.4.8 Spectroscopic properties

Virtually all organic compounds contain carbon – carbon and carbon – hydrogen bonds, and so show some of the
features of alkanes in their spectra. Alkanes are notable for having no other groups, and therefore for the absence of
other characteristic spectroscopic features of different functional group like -OH, -CHO, -COOH etc.

Infrared spectroscopy

The carbon–hydrogen stretching mode gives a strong absorption between 2850 and 2960 cm−1 , while the carbon–
carbon stretching mode absorbs between 800 and 1300 cm−1 . The carbon–hydrogen bending modes depend on the
nature of the group: methyl groups show bands at 1450 cm−1 and 1375 cm−1 , while methylene groups show bands at
1465 cm−1 and 1450 cm−1 . Carbon chains with more than four carbon atoms show a weak absorption at around 725
cm−1 .
38 CHAPTER 3. ALKANE

NMR spectroscopy

The proton resonances of alkanes are usually found at δH = 0.5 – 1.5. The carbon-13 resonances depend on the
number of hydrogen atoms attached to the carbon: δC = 8 – 30 (primary, methyl, -CH3 ), 15 – 55 (secondary,
methylene, -CH2 -), 20 – 60 (tertiary, methyne, C-H) and quaternary. The carbon-13 resonance of quaternary carbon
atoms is characteristically weak, due to the lack of Nuclear Overhauser effect and the long relaxation time, and can
be missed in weak samples, or samples that have not been run for a sufficiently long time.

Mass spectrometry

Alkanes have a high ionization energy, and the molecular ion is usually weak. The fragmentation pattern can be
difficult to interpret, but, in the case of branched chain alkanes, the carbon chain is preferentially cleaved at tertiary
or quaternary carbons due to the relative stability of the resulting free radicals. The fragment resulting from the loss
of a single methyl group (M−15) is often absent, and other fragment are often spaced by intervals of fourteen mass
units, corresponding to sequential loss of CH2 -groups.

3.5 Chemical properties

Alkanes are only weakly reactive with ionic and other polar substances. The acid dissociation constant (pKₐ) values
of all alkanes are above 60, hence they are practically inert to acids and bases (see: carbon acids). This inertness is
the source of the term paraffins (with the meaning here of “lacking affinity”). In crude oil the alkane molecules have
remained chemically unchanged for millions of years.
However redox reactions of alkanes, in particular with oxygen and the halogens, are possible as the carbon atoms are
in a strongly reduced condition; in the case of methane, the lowest possible oxidation state for carbon (−4) is reached.
Reaction with oxygen (if present in sufficient quantity to satisfy the reaction stoichiometry) leads to combustion
without any smoke, producing carbon dioxide and water. Free radical halogenation reactions occur with halogens,
leading to the production of haloalkanes. In addition, alkanes have been shown to interact with, and bind to, certain
transition metal complexes in (See: carbon-hydrogen bond activation).
Free radicals, molecules with unpaired electrons, play a large role in most reactions of alkanes, such as cracking
and reformation where long-chain alkanes are converted into shorter-chain alkanes and straight-chain alkanes into
branched-chain isomers.
In highly branched alkanes, the bond angle may differ significantly from the optimal value (109.5°) in order to allow
the different groups sufficient space. This causes a tension in the molecule, known as steric hindrance, and can
substantially increase the reactivity.

3.5.1 Reactions with oxygen (combustion reaction)

All alkanes react with oxygen in a combustion reaction, although they become increasingly difficult to ignite as the
number of carbon atoms increases. The general equation for complete combustion is:

CnH₂n₊₂ + (1.5n+0.5)O2 → (n+1)H2 O + nCO2

or CnH₂n₊₂ + ((3n+1)/2)O2 → (n+1)H2 O + nCO2

In the absence of sufficient oxygen, carbon monoxide or even soot can be formed, as shown below:

CnH₍₂n₊₂₎ + (n+0.5)O2 → (n+1)H2 O + nCO

CnH₍₂n₊₂₎ + (0.5n+0.5)O2 → (n+1)H2 O + nC

For example methane:

2CH4 + 3O2 → 2CO + 4H2 O

CH4 + 1.5O2 → CO + 2H2 O
3.5. CHEMICAL PROPERTIES 39

See the alkane heat of formation table for detailed data. The standard enthalpy change of combustion, Δ H o , for
alkanes increases by about 650 kJ/mol per CH2 group. Branched-chain alkanes have lower values of Δ H o than
straight-chain alkanes of the same number of carbon atoms, and so can be seen to be somewhat more stable.

3.5.2 Reactions with halogens

Main article: Free radical halogenation

Alkanes react with halogens in a so-called free radical halogenation reaction. The hydrogen atoms of the alkane are
progressively replaced by halogen atoms. Free-radicals are the reactive species that participate in the reaction, which
usually leads to a mixture of products. The reaction is highly exothermic, and can lead to an explosion.
These reactions are an important industrial route to halogenated hydrocarbons. There are three steps:

• Initiation the halogen radicals form by homolysis. Usually, energy in the form of heat or light is required.
• Chain reaction or Propagation then takes place—the halogen radical abstracts a hydrogen from the alkane
to give an alkyl radical. This reacts further.
• Chain termination where step the radicals recombine.

Experiments have shown that all halogenation produces a mixture of all possible isomers, indicating that all hydrogen
atoms are susceptible to reaction. The mixture produced, however, is not a statistical mixture: Secondary and tertiary
hydrogen atoms are preferentially replaced due to the greater stability of secondary and tertiary free-radicals. An
example can be seen in the monobromination of propane:[12] [In the Figure below, the Statistical Distribution should
be 25% and 75%]

Monobromination of propane

3.5.3 Cracking
Main article: Cracking (chemistry)

Cracking breaks larger molecules into smaller ones. This can be done with a thermal or catalytic method. The
thermal cracking process follows a homolytic mechanism with formation of free-radicals. The catalytic cracking
process involves the presence of acid catalysts (usually solid acids such as silica-alumina and zeolites), which promote
a heterolytic (asymmetric) breakage of bonds yielding pairs of ions of opposite charges, usually a carbocation and
the very unstable hydride anion. Carbon-localized free-radicals and cations are both highly unstable and undergo
processes of chain rearrangement, C-C scission in position beta (i.e., cracking) and intra- and intermolecular hydrogen
transfer or hydride transfer. In both types of processes, the corresponding reactive intermediates (radicals, ions) are
permanently regenerated, and thus they proceed by a self-propagating chain mechanism. The chain of reactions is
eventually terminated by radical or ion recombination.

3.5.4 Isomerization and reformation

Dragan and his colleague were the first to report about isomerization in alkanes.[14] Isomerization and reformation
are processes in which straight-chain alkanes are heated in the presence of a platinum catalyst. In isomerization,
40 CHAPTER 3. ALKANE

the alkanes become branched-chain isomers. In other words, it does not lose any carbons or hydrogens, keeping the
same molecular weight.[14] In reformation, the alkanes become cycloalkanes or aromatic hydrocarbons, giving off
hydrogen as a by-product. Both of these processes raise the octane number of the substance. Butane is the most
common alkane that is put under the process of isomerization, as it makes many branched alkanes with high octane
numbers.[14]

3.5.5 Other reactions

Alkanes will react with steam in the presence of a nickel catalyst to give hydrogen. Alkanes can be chlorosulfonated
and nitrated, although both reactions require special conditions. The fermentation of alkanes to carboxylic acids is of
some technical importance. In the Reed reaction, sulfur dioxide, chlorine and light convert hydrocarbons to sulfonyl
chlorides. Nucleophilic Abstraction can be used to separate an alkane from a metal. Alkyl groups can be transferred
from one compound to another by transmetalation reactions.

3.6 Occurrence

3.6.1 Occurrence of alkanes in the Universe

Alkanes form a small portion of the atmospheres of the outer gas planets such as Jupiter (0.1% methane, 0.0002%
ethane), Saturn (0.2% methane, 0.0005% ethane), Uranus (1.99% methane, 0.00025% ethane) and Neptune (1.5%
methane, 1.5 ppm ethane). Titan (1.6% methane), a satellite of Saturn, was examined by the Huygens probe, which
indicated that Titan’s atmosphere periodically rains liquid methane onto the moon’s surface.[15] Also on Titan the
Cassini mission has imaged seasonal methane/ethane lakes near the polar regions of Titan. Methane and ethane have
also been detected in the tail of the comet Hyakutake. Chemical analysis showed that the abundances of ethane
and methane were roughly equal, which is thought to imply that its ices formed in interstellar space, away from the
Sun, which would have evaporated these volatile molecules.[16] Alkanes have also been detected in meteorites such
as carbonaceous chondrites.

3.6.2 Occurrence of alkanes on Earth

Traces of methane gas (about 0.0002% or 1745 ppb) occur in the Earth’s atmosphere, produced primarily by methanogenic
microorganisms, such as Archaea in the gut of ruminants.[17]
The most important commercial sources for alkanes are natural gas and oil.[12] Natural gas contains primarily methane
and ethane, with some propane and butane: oil is a mixture of liquid alkanes and other hydrocarbons. These hydro-
carbons were formed when marine animals and plants (zooplankton and phytoplankton) died and sank to the bottom
of ancient seas and were covered with sediments in an anoxic environment and converted over many millions of
years at high temperatures and high pressure to their current form. Natural gas resulted thereby for example from the
following reaction:

C6 H12 O6 → 3CH4 + 3CO2

These hydrocarbon deposits, collected in porous rocks trapped beneath impermeable cap rocks, comprise commercial
oil fields. They have formed over millions of years and once exhausted cannot be readily replaced. The depletion of
these hydrocarbons reserves is the basis for what is known as the energy crisis.
Methane is also present in what is called biogas, produced by animals and decaying matter, which is a possible
renewable energy source.
Alkanes have a low solubility in water, so the content in the oceans is negligible; however, at high pressures and low
temperatures (such as at the bottom of the oceans), methane can co-crystallize with water to form a solid methane
clathrate (methane hydrate). Although this cannot be commercially exploited at the present time, the amount of
combustible energy of the known methane clathrate fields exceeds the energy content of all the natural gas and oil
deposits put together. Methane extracted from methane clathrate is therefore a candidate for future fuels.
3.6. OCCURRENCE 41

Methane and ethane make up a tiny proportion of Jupiter's atmosphere

3.6.3 Biological occurrence

Acyclic alkanes occur in nature in various ways.

Bacteria and archaea

Certain types of bacteria can metabolize alkanes: they prefer even-numbered carbon chains as they are easier to
degrade than odd-numbered chains.
On the other hand, certain archaea, the methanogens, produce large quantities of methane by the metabolism of
carbon dioxide or other oxidized organic compounds. The energy is released by the oxidation of hydrogen:

CO2 + 4H2 → CH4 + 2H2 O

Methanogens are also the producers of marsh gas in wetlands, and release about two billion tonnes of methane per
year—the atmospheric content of this gas is produced nearly exclusively by them. The methane output of cattle and
other herbivores, which can release up to 150 liters per day, and of termites, is also due to methanogens. They also
produce this simplest of all alkanes in the intestines of humans. Methanogenic archaea are, hence, at the end of the
carbon cycle, with carbon being released back into the atmosphere after having been fixed by photosynthesis. It is
probable that our current deposits of natural gas were formed in a similar way.
42 CHAPTER 3. ALKANE

Extraction of oil, which contains many different hydrocarbons including alkanes

Fungi and plants

Alkanes also play a role, if a minor role, in the biology of the three eukaryotic groups of organisms: fungi, plants and
animals. Some specialized yeasts, e.g., Candida tropicale, Pichia sp., Rhodotorula sp., can use alkanes as a source of
carbon and/or energy. The fungus Amorphotheca resinae prefers the longer-chain alkanes in aviation fuel, and can
cause serious problems for aircraft in tropical regions.[18]
In plants, the solid long-chain alkanes are found in the plant cuticle and epicuticular wax of many species, but are
only rarely major constituents.[19] They protect the plant against water loss, prevent the leaching of important min-
erals by the rain, and protect against bacteria, fungi, and harmful insects. The carbon chains in plant alkanes are
usually odd-numbered, between twenty-seven and thirty-three carbon atoms in length[19] and are made by the plants
by decarboxylation of even-numbered fatty acids. The exact composition of the layer of wax is not only species-
dependent, but changes also with the season and such environmental factors as lighting conditions, temperature or
humidity.[19]
More volatile short-chain alkanes are also produced by and found in plant tissues. The Jeffrey pine is noted for
producing exceptionally high levels of n-heptane in its resin, for which reason its distillate was designated as the
zero point for one octane rating. Floral scents have also long been known to contain volatile alkane components,
and n-nonane is a significant component in the scent of some roses.[20] Emission of gaseous and volatile alkanes
such as ethane, pentane, and hexane by plants has also been documented at low levels, though they are not generally
considered to be a major component of biogenic air pollution.[21]
Edible vegetable oils also typically contain small fractions of biogenic alkanes with a wide spectrum of carbon num-
bers, mainly 8 to 35, usually peaking in the low to upper 20s, with concentrations up to dozens of milligrams per
kilogram (parts per million by weight) and sometimes over a hundred for the total alkane fraction.[22]

Animals

Alkanes are found in animal products, although they are less important than unsaturated hydrocarbons. One exam-
ple is the shark liver oil, which is approximately 14% pristane (2,6,10,14-tetramethylpentadecane, C19 H40 ). They
3.7. PRODUCTION 43

Methanogenic archaea in the gut of this cow are responsible for some of the methane in Earth’s atmosphere.

are important as pheromones, chemical messenger materials, on which insects depend for communication. In some
species, e.g. the support beetle Xylotrechus colonus, pentacosane (C25 H52 ), 3-methylpentaicosane (C26 H54 ) and
9-methylpentaicosane (C26 H54 ) are transferred by body contact. With others like the tsetse fly Glossina morsitans
morsitans, the pheromone contains the four alkanes 2-methylheptadecane (C18 H38 ), 17,21-dimethylheptatriacontane
(C39 H80 ), 15,19-dimethylheptatriacontane (C39 H80 ) and 15,19,23-trimethylheptatriacontane (C40 H82 ), and acts by
smell over longer distances. Waggle-dancing honey bees produce and release two alkanes, tricosane and pentacosane.[23]

3.6.4 Ecological relations

One example, in which both plant and animal alkanes play a role, is the ecological relationship between the sand
bee (Andrena nigroaenea) and the early spider orchid (Ophrys sphegodes); the latter is dependent for pollination on
the former. Sand bees use pheromones in order to identify a mate; in the case of A. nigroaenea, the females emit a
mixture of tricosane (C23 H48 ), pentacosane (C25 H52 ) and heptacosane (C27 H56 ) in the ratio 3:3:1, and males are
attracted by specifically this odor. The orchid takes advantage of this mating arrangement to get the male bee to
collect and disseminate its pollen; parts of its flower not only resemble the appearance of sand bees, but also produce
large quantities of the three alkanes in the same ratio as female sand bees. As a result numerous males are lured to
the blooms and attempt to copulate with their imaginary partner: although this endeavor is not crowned with success
for the bee, it allows the orchid to transfer its pollen, which will be dispersed after the departure of the frustrated
male to different blooms.

3.7 Production

3.7.1 Petroleum refining

As stated earlier, the most important source of alkanes is natural gas and crude oil.[12] Alkanes are separated in an
oil refinery by fractional distillation and processed into many different products.
44 CHAPTER 3. ALKANE

Early spider orchid (Ophrys sphegodes)

3.7.2 Fischer-Tropsch

The Fischer-Tropsch process is a method to synthesize liquid hydrocarbons, including alkanes, from carbon monoxide
and hydrogen. This method is used to produce substitutes for petroleum distillates.

3.7.3 Laboratory preparation

There is usually little need for alkanes to be synthesized in the laboratory, since they are usually commercially avail-
able. Also, alkanes are generally non-reactive chemically or biologically, and do not undergo functional group in-
terconversions cleanly. When alkanes are produced in the laboratory, it is often a side-product of a reaction. For
example, the use of n-butyllithium as a strong base gives the conjugate acid, n-butane as a side-product:
3.8. APPLICATIONS 45

An oil refinery at Martinez, California.

C4 H9 Li + H2 O → C4 H10 + LiOH

However, at times it may be desirable to make a portion of a molecule into an alkane like functionality (alkyl group)
using the above or similar methods. For example, an ethyl group is an alkyl group; when this is attached to a hydroxy
group, it gives ethanol, which is not an alkane. To do so, the best-known methods are hydrogenation of alkenes:

RCH=CH2 + H2 → RCH2 CH3 (R = alkyl)

Alkanes or alkyl groups can also be prepared directly from alkyl halides in the Corey-House-Posner-Whitesides
reaction. The Barton-McCombie deoxygenation[24][25] removes hydroxyl groups from alcohols e.g.

S
S
Cl R1 Bu SnH
R OH R 3
R H
- HCl O R1 AIBN

and the Clemmensen reduction[26][27][28][29] removes carbonyl groups from aldehydes and ketones to form alkanes or
alkyl-substituted compounds e.g.:

3.8 Applications
The applications of a certain alkane can be determined quite well according to the number of carbon atoms. The
first four alkanes are used mainly for heating and cooking purposes, and in some countries for electricity generation.
46 CHAPTER 3. ALKANE

Methane and ethane are the main components of natural gas; they are normally stored as gases under pressure. It is,
however, easier to transport them as liquids: This requires both compression and cooling of the gas.
Propane and butane can be liquefied at fairly low pressures, and are well known as liquified petroleum gas (LPG).
Propane, for example, is used in the propane gas burner and as a fuel for cars,[30] butane in disposable cigarette
lighters. The two alkanes are used as propellants in aerosol sprays.
From pentane to octane the alkanes are reasonably volatile liquids. They are used as fuels in internal combustion
engines, as they vaporise easily on entry into the combustion chamber without forming droplets, which would impair
the uniformity of the combustion. Branched-chain alkanes are preferred as they are much less prone to premature
ignition, which causes knocking, than their straight-chain homologues. This propensity to premature ignition is mea-
sured by the octane rating of the fuel, where 2,2,4-trimethylpentane (isooctane) has an arbitrary value of 100, and
heptane has a value of zero. Apart from their use as fuels, the middle alkanes are also good solvents for nonpolar
substances.
Alkanes from nonane to, for instance, hexadecane (an alkane with sixteen carbon atoms) are liquids of higher viscosity,
less and less suitable for use in gasoline. They form instead the major part of diesel and aviation fuel. Diesel fuels are
characterized by their cetane number, cetane being an old name for hexadecane. However, the higher melting points
of these alkanes can cause problems at low temperatures and in polar regions, where the fuel becomes too thick to
flow correctly.
Alkanes from hexadecane upwards form the most important components of fuel oil and lubricating oil. In the latter
function, they work at the same time as anti-corrosive agents, as their hydrophobic nature means that water cannot
reach the metal surface. Many solid alkanes find use as paraffin wax, for example, in candles. This should not be
confused however with true wax, which consists primarily of esters.
Alkanes with a chain length of approximately 35 or more carbon atoms are found in bitumen, used, for example, in
road surfacing. However, the higher alkanes have little value and are usually split into lower alkanes by cracking.
Some synthetic polymers such as polyethylene and polypropylene are alkanes with chains containing hundreds of
thousands of carbon atoms. These materials are used in innumerable applications, and billions of kilograms of these
materials are made and used each year.

3.9 Environmental transformations

When released in the environment, alkanes don't undergo rapid biodegradation, because they have no functional
groups (like hydroxyl or carbonyl) that are needed by most organisms in order to metabolize the compound.
However, some bacteria can metabolize some alkanes (especially those linear and short), by oxidizing the terminal
carbon atom. The product is an alcohol, that could be next oxidized to an aldehyde, and finally to a carboxylic acid.
The resulting fatty acid could be metabolized through the fatty acid degradation pathway.

3.10 Hazards

Methane is explosive when mixed with air (1 – 8% CH4 ). Other lower alkanes can also form explosive mixtures with
air. The lighter liquid alkanes are highly flammable, although this risk decreases with the length of the carbon chain.
Pentane, hexane, heptane, and octane are classed as dangerous for the environment and harmful.
Considerations for detection /risk control:

• Methane is lighter than air (possibility of accumulation under roofs)

• Ethane is slightly heavier than air (possibility of pooling at ground levels / pits)

• Propane is heavier than air (possibility of pooling at ground levels / pits)

• Butane is heavier than air (possibility of pooling at ground levels / pits)

3.11. SEE ALSO 47

3.11 See also

• Alkene

• Alkyne

• Cycloalkane

3.12 References
[1] “Alkane - Definition and More from the Free Merriam-Webster Dictionary”. merriam-webster.com. Retrieved 3 October
2014.

[2] Arora, A. (2006). Hydrocarbons (Alkanes, Alkenes And Alkynes). Discovery Publishing House Pvt. Limited. ISBN
9788183561426.

[3] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”) (1997). Online corrected version: (2006–)
"alkanes".

[4] On-Line Encyclopedia of Integer Sequences (sequence A000602 in OEIS)

[5] IUPAC, Commission on Nomenclature of Organic Chemistry (1993). “R-2.2.1: Hydrocarbons”. A Guide to IUPAC
Nomenclature of Organic Compounds (Recommendations 1993). Blackwell Scientific. ISBN 0-632-03488-2. Retrieved
12 February 2007.

[6] Alkane Nomenclature

[7] Thus, the ending "-diene” is applied in some cases where von Hofmann had "-ine”

[8] William Reusch. “Nomenclature - Alkanes”. Virtual Textbook of Organic Chemistry.

[9] William Reusch. “Examples of the IUPAC Rules in Practice”. Virtual Textbook of Organic Chemistry.

[10]

[11] “13. Hydrocarbons | Textbooks”. textbook.s-anand.net. Retrieved 3 October 2014.

[12] R. T. Morrison, R. N. Boyd (1992). Organic Chemistry (6th ed.). New Jersey: Prentice Hall. ISBN 0-13-643669-2.

[13] Boese R, Weiss HC, Blaser D (1999). “The melting point alternation in the short-chain n-alkanes: Single-crystal X-ray anal-
yses of propane at 30 K and of n-butane to n-nonane at 90 K”. Angew Chemie Int Ed 38: 988–992. doi:10.1002/(SICI)1521-
3773(19990401)38:7<988::AID-ANIE988>3.3.CO;2-S.

[14] Asinger, Friedrich. Paraffins; Chemistry and Technology. Oxford: Pergamon Press, 1967. Print.

[15] Emily Lakdawalla. “Titan: Arizona in an Icebox?". Archived from the original on 6 April 2008. Retrieved 21 January
2004.

[16] Mumma, M.J.; Disanti, M.A., dello Russo, N., Fomenkova, M., Magee-Sauer, K., Kaminski, C.D., and D.X. Xie (1996).
“Detection of Abundant Ethane and Methane, Along with Carbon Monoxide and Water, in Comet C/1996 B2 Hyakutake:
Evidence for Interstellar Origin”. Science 272 (5266): 1310–4. Bibcode:1996Sci...272.1310M. doi:10.1126/science.272.5266.1310.
PMID 8650540.

[17] Janssen, P. H.; Kirs, M. (2008). “Structure of the Archaeal Community of the Rumen”. Appl Environ Microbiol 74 (12):
3619–3625. doi:10.1128/AEM.02812-07. PMC 2446570. PMID 18424540.

[18] Hendey, N. I. (1964). “Some observations on Cladosporium resinae as a fuel contaminant and its possible role in the corro-
sion of aluminium alloy fuel tanks”. Transactions of the British Mycological Society 47 (7): 467–475. doi:10.1016/s0007-
1536(64)80024-3.

[19] EA Baker (1982) Chemistry and morphology of plant epicuticular waxes. pp139-165. In “The Plant Cuticle”. edited by
DF Cutler, KL Alvin and CE Price. Academic Press, London. ISBN 0-12-199920-3

[20] Kim, HyunJung; Kim, NamSun; Lee, DongSun (2000). “Determination of floral fragrances of Rosa hybrida using solid-
phase trapping-solvent extraction and gas chromatography-mass spectrometry.”. Journal of Chromatography, A 902 (2):
389–404. doi:10.1016/S0021-9673(00)00863-3.
48 CHAPTER 3. ALKANE

[21] Kesselmeier, J.; Staudt, N. (1999). “Biogenic Volatile Organic Compounds (VOC): An Overview on Emission, Physiology
and Ecology”. Journal of Atmospheric Chemistry 33: 22–38.

[22] Moreda, W.; Perez-Camino, M.C; Cert, A. (2001). “Gas and liquid chromatography of hydrocarbons in edible vegetable
oils”. Journal of Chromatography A 936: 159–171. doi:10.1016/s0021-9673(01)01222-5.

[23] Thom, et al. (21 August 2007). “The Scent of the Waggle Dance”. PLoS Biology 5 (9): e228. doi:10.1371/journal.pbio.0050228.
PMC 1994260. PMID 17713987.

[24] Barton, D. H. R.; McCombie, S. W. (1975). “A new method for the deoxygenation of secondary alcohols”. J. Chem. Soc.,
Perkin Trans. 1 (16): 1574–1585. doi:10.1039/P19750001574.

[25] Crich, David; Quintero, Leticia (1989). “Radical chemistry associated with the thiocarbonyl group”. Chem. Rev. 89 (7):
1413–1432. doi:10.1021/cr00097a001.

[26] Martin, E. L. Org. React. 1942, 1, 155. (Review)

[27] Buchanan, J. G. St. C.; Woodgate, P. D. Quart. Rev. 1969, 23, 522, (Review).

[28] Vedejs, E. Org. React. 1975, 22, 401, (Review).

[29] Yamamura, S.; Nishiyama, S. Comp. Org. Syn. 1991, 8, 309-313, (Review).

[30] Using propane as a fuel

3.13 Further reading

• Virtual Textbook of Organic Chemistry
Chapter 4

Methane

Methane (/ˈmɛθeɪn/ or /ˈmiːθeɪn/) is a chemical compound with the chemical formula CH

4 (one atom of carbon and four atoms of hydrogen). It is the simplest alkane and the main component of natural gas.
The relative abundance of methane makes it an attractive fuel, though capturing and storing it poses challenges due to
its gaseous state found at normal conditions. In its natural state, methane is found both below ground, and under the
sea floor, where it often finds its way to the surface and in the atmosphere of Earth where it is known as atmospheric
methane.[4]

4.1 History

In November 1776, methane was first scientifically identified by Italian physicist Alessandro Volta in the marshes
of Lake Maggiore straddling Italy and Switzerland, having been inspired to search for the substance after reading a
paper written by Benjamin Franklin about “flammable air”.[5] Volta captured the gas rising from the marsh, and by
1778 had isolated the pure gas.[6] He also demonstrated means to ignite the gas with an electric spark.[6]

4.2 Properties and bonding

Methane is a tetrahedral molecule with four equivalent C-H bonds. Its electronic structure is described by four
bonding molecular orbitals (MOs) resulting from the overlap of the valence orbitals on C and H. The lowest energy
MO is the result of the overlap of the 2s orbital on carbon with the in-phase combination of the 1s orbitals on the four
hydrogen atoms. Above this level in energy is a triply degenerate set of MOs that involve overlap of the 2p orbitals
on carbon with various linear combinations of the 1s orbitals on hydrogen. The resulting “three-over-one” bonding
scheme is consistent with photoelectron spectroscopic measurements.
At room temperature and standard pressure, methane is a colorless, odorless gas.[7] The familiar smell of natural gas
as used in homes is a safety measure achieved by the addition of an odorant, usually blends containing tert-butylthiol.
Methane has a boiling point of −161 °C (−257.8 °F) at a pressure of one atmosphere.[8] As a gas it is flammable over
a range of concentrations (4.4–17%) in air at standard pressure.

4.3 Chemical reactions

Main reactions with methane are: combustion, steam reforming to syngas, and halogenation. In general, methane re-
actions are difficult to control. Partial oxidation to methanol, for example, is challenging because the reaction typically
progresses all the way to carbon dioxide and water even with incomplete amounts of oxygen. The enzymes methane
monooxygenase can produce methanol from methane, but they cannot be used for industrial scale reactions.[9]

49
50 CHAPTER 4. METHANE

4.3.1 Acid-base reactions

Like other hydrocarbons, methane is a very weak acid. Its pKa in DMSO is estimated to be 56.[10] It cannot be
deprotonated in solution, but the conjugate base with methyllithium is known.
A variety of positive ions derived from methane have been observed, mostly as unstable species in low-pressure gas
mixtures. These include methenium or methyl cation CH+
3, methane cation CH+
4, and methanium or protonated methane CH+
5. Some of these have been detected in outer space. Methanium can also be produced as diluted solutions from
methane with super acids. Cations with higher charge, such as CH2+
6 and CH3+
7, have been studied theoretically and conjectured to be stable.[11]
Despite the strength of its C-H bonds, there is intense interest in catalysts that facilitate C–H bond activation in
methane (and other low alkanes).[12]

4.3.2 Combustion

Methane’s heat of combustion is 55.5 MJ/kg.[13] Combustion of methane is a multiple step reaction. The following
equations are part of the process, with the net result being:
CH4 + 2 O2 → CO2 + 2 H2 O (ΔH = −891 k J/mol (at standard conditions))

1. CH4 + M* → CH3 + H + M

2. CH4 + O2 → CH3 + HO2

3. CH4 + HO2 → CH3 + 2 OH

4. CH4 + OH → CH3 + H2 O

5. O2 + H → O + OH

6. CH4 + O → CH3 + OH

7. CH3 + O2 → CH2 O + OH

8. CH2 O + O → CHO + OH

9. CH2 O + OH → CHO + H2 O

10. CH2 O + H → CHO + H2

11. CHO + O → CO + OH

12. CHO + OH → CO + H2 O

13. CHO + H → CO + H2

14. H2 + O → H + OH

15. H2 + OH → H + H2 O

16. CO + OH → CO2 + H

17. H + OH + M → H2 O + M*

18. H + H + M → H2 + M*

19. H + O2 + M → HO2 + M*
4.4. USES 51

The species M* signifies an energetic third body, from which energy is transferred during a molecular collision.
Formaldehyde (HCHO or H
2CO) is an early intermediate (reaction 7). Oxidation of formaldehyde gives the formyl radical (HCO; reactions
8–10), which then give carbon monoxide (CO) (reactions 11, 12 & 13). Any resulting H2 oxidizes to H2 O or other
intermediates (reaction 14, 15). Finally, the CO oxidizes, forming CO2 (reaction 16). In the final stages (reactions 17–
19), energy is transferred back to other third bodies. The overall speed of reaction is a function of the concentration
of the various entities during the combustion process. The higher the temperature, the greater the concentration of
radical species and the more rapid the combustion process.[14]

4.3.3 Reactions with halogens

Methane reacts with halogens given appropriate conditions as follows:

X2 + UV → 2 X•
X• + CH4 → HX + CH3 •
CH3 • + X2 → CH3 X + X•

where X is a halogen: fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). This mechanism for this process is called
free radical halogenation. It is initiated with UV light or some other radical initiator. A chlorine atom is generated
from elemental chlorine, which abstracts a hydrogen atom from methane, resulting in the formation of hydrogen
chloride. The resulting methyl radical, CH3 •, can combine with another chlorine molecule to give methyl chloride
(CH3 Cl) and a chlorine atom. This chlorine atom can then react with another methane (or methyl chloride) molecule,
repeating the chlorination cycle.[15] Similar reactions can produce dichloromethane (CH2 Cl2 ), chloroform (CHCl3 ),
and, ultimately, carbon tetrachloride (CCl4 ), depending upon reaction conditions and the chlorine to methane ratio.

4.4 Uses
Methane is used in industrial chemical processes and may be transported as a refrigerated liquid (liquefied natural gas,
or LNG). While leaks from a refrigerated liquid container are initially heavier than air due to the increased density
of the cold gas, the gas at ambient temperature is lighter than air. Gas pipelines distribute large amounts of natural
gas, of which methane is the principal component.

4.4.1 Fuel
Natural gas

Main article: natural gas

Methane is important for electrical generation by burning it as a fuel in a gas turbine or steam generator. Compared to
other hydrocarbon fuels, burning methane produces less carbon dioxide for each unit of heat released. At about 891
kJ/mol, methane’s heat of combustion is lower than any other hydrocarbon but the ratio of the heat of combustion
(891 kJ/mol) to the molecular mass (16.0 g/mol, of which 12.0 g/mol is carbon) shows that methane, being the
simplest hydrocarbon, produces more heat per mass unit (55.7 kJ/g) than other complex hydrocarbons. In many
cities, methane is piped into homes for domestic heating and cooking purposes. In this context it is usually known
as natural gas, which is considered to have an energy content of 39 megajoules per cubic meter, or 1,000 BTU per
standard cubic foot.
Methane in the form of compressed natural gas is used as a vehicle fuel and is claimed to be more environmentally
friendly than other fossil fuels such as gasoline/petrol and diesel.[16] Research into adsorption methods of methane
storage for use as an automotive fuel has been conducted.[17]

Liquefied natural gas

Main article: Liquefied natural gas

52 CHAPTER 4. METHANE

Liquefied natural gas or LNG is natural gas (predominantly methane, CH4 ) that has been converted to liquid form
for ease of storage or transport.
Liquefied natural gas takes up about 1/600th the volume of natural gas in the gaseous state. It is odorless, colorless,
non-toxic and non-corrosive. Hazards include flammability after vaporization into a gaseous state, freezing and
asphyxia.
The liquefaction process involves removal of certain components, such as dust, acid gases, helium, water, and heavy
hydrocarbons, which could cause difficulty downstream. The natural gas is then condensed into a liquid at close to
atmospheric pressure (maximum transport pressure set at around 25 kPa or 3.6 psi) by cooling it to approximately
−162 °C (−260 °F).
LNG achieves a higher reduction in volume than compressed natural gas (CNG) so that the energy density of LNG is
2.4 times greater than that of CNG or 60% of that of diesel fuel.[18] This makes LNG cost efficient to transport over
long distances where pipelines do not exist. Specially designed cryogenic sea vessels (LNG carriers) or cryogenic
road tankers are used for its transport.
LNG, when it is not highly refined for special uses, is principally used for transporting natural gas to markets, where
it is regasified and distributed as pipeline natural gas. It is also used in LNG-fueled road vehicles as is beginning to be
seen with some trucks in commercial operation, which have been achieving payback periods of approximately four
years on the higher initial investment required in LNG equipment on the trucks and LNG infrastructure to support
fueling.[19] However, it remains more common to design vehicles to use compressed natural gas. As of 2002, the
relatively higher cost of LNG production and the need to store LNG in more expensive cryogenic tanks had slowed
widespread commercial use.[20]

Power to gas

Main article: Power to gas

Power to gas is a technology which converts electrical power to a gas fuel. The method is used to convert carbon
dioxide and water to methane, (see natural gas) using electrolysis and the Sabatier reaction. The excess power or off
peak power generated by wind generators or solar arrays could theoretically be used for load balancing in the energy
grid.

Liquid methane rocket fuel

In a highly refined form, liquid methane is used as a rocket fuel.[21]

While investigations of methane use have existed for decades, no production methane engines have yet been used on
orbital spaceflights.[22] This is changing, and liquid methane has recently been selected for the active development of
a variety of bipropellant rocket engines.
Since the 1990s, a number of Russian rockets have been proposed to use liquid methane.[23][24] One 1990s Russian
engine proposal was the RD-192, a methane/LOX variant of the RD-191.[24]
In 2005, US companies, Orbitech and XCOR Aerospace, developed a demonstration liquid oxygen/liquid methane
rocket engine and a larger 7,500 pounds-force (33 kN)-thrust engine in 2007 for potential use as the CEV lunar return
engine, before the CEV program was later cancelled.[25][26][27]
More recently the American private space company SpaceX announced in 2012 an initiative to develop liquid methane
rocket engines,[28] including, initially, the very large Raptor rocket engine.[29]
Raptor is being designed to produce 4.4 meganewtons (1,000,000 lbf) of thrust with a vacuum specific impulse (I )
of 363 seconds and a sea-level I of 321 seconds,[30] and is expected to begin component-level testing in 2014.[31]
In February 2014, the Raptor engine design was revealed to be of the highly efficient and theoretically more reliable
full-flow staged combustion cycle type, where both propellant streams—oxidizer and fuel—will be completely in
the gas phase before they enter the combustion chamber. Prior to 2014, only two full-flow rocket engines have
ever progressed sufficiently to be tested on test stands, but neither engine completed development or flew on a flight
vehicle.[30]
In October 2013, the China Aerospace Science and Technology Corporation, a state-owned contractor for the Chinese
space program, announced that it had completed a first ignition test on a new LOX methane rocket engine. No engine
4.5. PRODUCTION 53

size was provided.[32]

In September 2014, another American private space company—Blue Origin announced work on a large methane
rocket engine. The new engine, the Blue Engine 4, or BE-4, has been designed to produce 2,400 kilonewtons (550,000
lbf) of thrust. While initially planned to be used exclusively on a Blue Origin proprietary launch vehicle, it will now
be used on a new United Launch Alliance (ULA) engine on an new launch vehicle that is a successor to the Atlas V.
ULA expects the first flight of the new launch vehicle no earlier than 2019.[33]
One advantage of methane is that it is abundant in many parts of the solar system and it could potentially be harvested
on the surface of another solar-system body (in particular, using In Situ Resource Utilization on Mars[34] and Titan),
providing fuel for a return journey.[21][35]
By 2013, NASA’s Project Morpheus had developed a small restartable LOX methane rocket engine with 5,000
pounds-force (22 kN) thrust and a specific impulse of 321 seconds suitable for inspace applications including landers.
Small LOX methane thrusters 5–15 pounds-force (22–67 N) were also developed suitable for use in a Reaction
Control System (RCS).[36][37]
SpaceNews is reporting in early 2015 that the French space agency CNES is working with Germany and a few other
governments and will propose a LOX/methane engine on a reusable launch vehicle by mid-2015, with flight testing
unlikely before approximately 2026.[38]

4.4.2 Chemical feedstock

Although there is great interest in converting methane into useful or more easily liquefied compounds, the only prac-
tical processes are relatively unselective. In the chemical industry, methane is converted to synthesis gas, a mixture
of carbon monoxide and hydrogen, by steam reforming. This endergonic process (requiring energy) utilizes nickel
catalysts and requires high temperatures, around 700–1100 °C:

CH4 + H2 O → CO + 3 H2

Related chemistries are exploited in the Haber-Bosch Synthesis of ammonia from air, which is reduced with natural
gas to a mixture of carbon dioxide, water, and ammonia.
Methane is also subjected to free-radical chlorination in the production of chloromethanes, although methanol is a
more typical precursor.[39]

4.5 Production

4.5.1 Biological routes

Main article: methanogenesis

Naturally occurring methane is mainly produced by the process of methanogenesis. This multistep process is used
by microorganisms as an energy source. The net reaction is:

CO2 + 8 H+ + 8 e− → CH4 + 2 H2 O

The final step in the process is catalyzed by the enzyme methyl-coenzyme M reductase. Methanogenesis is a form of
anaerobic respiration used by organisms that occupy landfill, ruminants (e.g., cattle), and the guts of termites.
It is uncertain if plants are a source of methane emissions.[40][41][42]

4.5.2 Serpentinization

Methane could also be produced by a non-biological process called serpentinization[lower-alpha 1] involving water, carbon
dioxide, and the mineral olivine, which is known to be common on Mars.[43]
54 CHAPTER 4. METHANE

4.5.3 Industrial routes

Methane can be produced by hydrogenating carbon dioxide through the Sabatier process. Methane is also a side
product of the hydrogenation of carbon monoxide in the Fischer-Tropsch process. This technology is practiced on a
large scale to produce longer chain molecules than methane.
Natural gas is so abundant that the intentional production of methane is relatively rare. The only large scale facility
of this kind is the Great Plains Synfuels plant, started in 1984 in Beulah, North Dakota as a way to develop abundant
local resources of low grade lignite, a resource which is otherwise very hard to transport for its weight, ash content,
low calorific value and propensity to spontaneous combustion during storage and transport.
An adaptation of the Sabatier methanation reaction may be used via a mixed catalyst bed and a reverse water gas shift
in a single reactor to produce methane from the raw materials available on Mars, utilizing water from the Martian
subsoil and carbon dioxide in the Martian atmosphere.[34]
4.6. OCCURRENCE 55

4.5.4 Laboratory synthesis

Methane can also be produced by the destructive distillation of acetic acid in the presence of soda lime or similar.
Acetic acid is decarboxylated in this process. Methane can also be prepared by reaction of aluminium carbide with
water or strong acids.

4.6 Occurrence
Methane was discovered and isolated by Alessandro Volta between 1776 and 1778 when studying marsh gas from
Lake Maggiore. It is the major component of natural gas, about 87% by volume. The major source of methane
is extraction from geological deposits known as natural gas fields, with coal seam gas extraction becoming a major
source (see Coal bed methane extraction, a method for extracting methane from a coal deposit, while enhanced coal
bed methane recovery is a method of recovering methane from non-mineable coal seams). It is associated with other
hydrocarbon fuels, and sometimes accompanied by helium and nitrogen. The gas at shallow levels (low pressure)
forms by anaerobic decay of organic matter and reworked methane from deep under the Earth’s surface. In general,
sediments buried deeper and at higher temperatures than those that contain oil generate natural gas.
It is generally transported in bulk by pipeline in its natural gas form, or LNG carriers in its liquefied form; few
countries transport it by truck.

4.6.1 Alternative sources

Testing Australian sheep for exhaled methane production (2001), CSIRO

Apart from gas fields, an alternative method of obtaining methane is via biogas generated by the fermentation of or-
ganic matter including manure, wastewater sludge, municipal solid waste (including landfills), or any other biodegrad-
able feedstock, under anaerobic conditions. Rice fields also generate large amounts of methane during plant growth.
Methane hydrates/clathrates (ice-like combinations of methane and water on the sea floor, found in vast quantities)
are a potential future source of methane. Cattle belch methane accounts for 16% of the world’s annual methane
emissions to the atmosphere.[44] One study reported that the livestock sector in general (primarily cattle, chickens,
and pigs) produces 37% of all human-induced methane.[45] Early research has found a number of medical treatments
56 CHAPTER 4. METHANE

and dietary adjustments that help slightly limit the production of methane in ruminants.[46][47] A more recent study, in
2009, found that at a conservative estimate, at least 51% of global greenhouse gas emissions were attributable to the
life cycle and supply chain of livestock products, meaning all meat, dairy, and by-products, and their transportation.[48]
Many efforts are underway to reduce livestock methane production and trap the gas to use as energy.[49]
Paleoclimatology research published in Current Biology suggests that flatulence from dinosaurs may have warmed the
Earth.[50]

4.6.2 Atmospheric methane

Main article: Atmospheric methane

Methane is created near the Earth’s surface, primarily by microorganisms by the process of methanogenesis. It

2011 methane concentration in the upper troposphere[51]

is carried into the stratosphere by rising air in the tropics. Uncontrolled build-up of methane in the atmosphere is
naturally checked – although human influence can upset this natural regulation – by methane’s reaction with hydroxyl
radicals formed from singlet oxygen atoms and with water vapor. It has a net lifetime of about 10 years,[52] and is
primarily removed by conversion to carbon dioxide and water.
Methane also affects the degradation of the ozone layer.[53][54]
In addition, there is a large (but unknown) amount of methane in methane clathrates in the ocean floors as well as the
Earth’s crust. Most methane is the result of biological process called methanogenesis.
In 2010, methane levels in the Arctic were measured at 1850 nmol/mol, a level over twice as high as at any time in
the 400,000 years prior to the industrial revolution. Historically, methane concentrations in the world’s atmosphere
have ranged between 300 and 400 nmol/mol during glacial periods commonly known as ice ages, and between 600 to
700 nmol/mol during the warm interglacial periods. Recent research suggests that the Earth’s oceans are a potentially
important new source of Arctic methane.[55]
A Bristol University study published in Nature claims that methane under the Antarctic Ice Sheet may yet play an
important role globally. Researchers believe these sub-ice environments to be biologically active, in that microbes are
converting organic carbon to carbon dioxide and methane.[56] Possible adverse effects projected as the gas escapes
into the atmosphere are estimated to have the potential of a sixty trillion dollar impact on the world economy.[57]
The IPCC Fifth Assessment Report determined that methane in the Earth’s atmosphere is an important greenhouse gas
with a global warming potential of 34 compared to CO2 over a 100-year period (although accepted figures probably
represent an underestimate[58][59] ). This means that a methane emission will have 34 times the effect on temperature
of a carbon dioxide emission of the same mass over the following 100 years. And methane has 33 times the effect
4.7. SAFETY 57

when accounted for aerosol interactions.[60]

Methane has a large effect for a brief period (a net lifetime of 8.4 years in the atmosphere), whereas carbon dioxide
has a small effect for a long period (over 100 years). Because of this difference in effect and time period, the global
warming potential of methane over a 20-year time period is 72. The Earth’s atmospheric methane concentration has
increased by about 150% since 1750, and it accounts for 20% of the total radiative forcing from all of the long-lived
and globally mixed greenhouse gases (these gases don't include water vapor which is by far the largest component of
the greenhouse effect).[61] Usually, excess methane from landfills and other natural producers of methane is burned
so CO2 is released into the atmosphere instead of methane, because methane is a more effective greenhouse gas.
Recently, methane emitted from coal mines has been successfully utilized to generate electricity.

4.6.3 Clathrates
Methane is essentially insoluble in water, but it can be trapped in ice forming a similar solid. Significant deposits of
methane clathrate have been found under sediments on the ocean floors of Earth at large depths.
Arctic methane release from permafrost and methane clathrates is an expected consequence and further cause of
global warming.[62][63][64]

4.7 Safety
Methane is not toxic, yet it is extremely flammable and may form explosive mixtures with air. Methane is violently
reactive with oxidizers, halogen, and some halogen-containing compounds. Methane is also an asphyxiant and may
displace oxygen in an enclosed space. Asphyxia may result if the oxygen concentration is reduced to below about 16%
by displacement, as most people can tolerate a reduction from 21% to 16% without ill effects. The concentration of
methane at which asphyxiation risk becomes significant is much higher than the 5–15% concentration in a flammable
or explosive mixture. Methane off-gas can penetrate the interiors of buildings near landfills and expose occupants to
significant levels of methane. Some buildings have specially engineered recovery systems below their basements to
actively capture this gas and vent it away from the building.
Methane gas explosions are responsible for many deadly mining disasters.[65] A methane gas explosion was the cause
of the Upper Big Branch coal mine disaster in West Virginia on April 5, 2010, killing 25.[66]

4.8 Extraterrestrial methane

Methane has been detected or is believed to exist on all planets of the solar system, as well as on most of the larger
moons. In most cases, it is believed to have been created by abiotic processes. Possible exceptions are Mars and
Titan.

• Mercury – the tenuous atmosphere contains trace amounts of methane.[67]

• Venus – the atmosphere contains a large amount of methane from 60 km (37 mi) to the surface according to
data collected by the Pioneer Venus Large Probe Neutral Mass Spectrometer[68]
• Moon – traces are outgassed from the surface[69]

• Mars – the Martian atmosphere contains 10 nmol/mol methane.[70] The source of methane on Mars has not been
determined. Recent research suggests that methane may come from volcanoes, fault lines, or methanogens,[71]
or that it may be a byproduct of electrical discharges from dust devils and dust storms,[72] or that it may be
the result of UV radiation.[73] In January 2009, NASA scientists announced that they had discovered that the
planet often vents methane into the atmosphere in specific areas, leading some to speculate this may be a sign
of biological activity going on below the surface.[74] Analysis of observations made by a Weather Research and
Forecasting model for Mars (MarsWRF) and related Mars general circulation model (MGCM) suggests that it
is potentially possible to isolate methane plume source locations to within tens of kilometers, which is within the
roving capabilities of future Mars rovers.[75] The Curiosity rover, which landed on Mars in August 2012, is able
to make measurements that distinguish between different isotopologues of methane;[76] but even if the mission
58 CHAPTER 4. METHANE

Methane (CH4 ) on Mars - potential sources and sinks.

is to determine that microscopic Martian life is the source of the methane, the life forms likely reside far below
the surface, outside of the rover’s reach.[77] Curiosity’s Sample Analysis at Mars (SAM) instrument is capable
of tracking the presence of methane over time to determine if it is constant, variable, seasonal, or random,
providing further clues about its source.[78] The first measurements with the Tunable Laser Spectrometer (TLS)
indicated that there is less than 5 ppb of methane at the landing site at the point of the measurement.[79][80][81][82]
The Mars Trace Gas Mission orbiter planned to launch in 2016 would further study the methane,[83][84] as well
as its decomposition products such as formaldehyde and methanol. Alternatively, these compounds may instead
be replenished by volcanic or other geological means, such as serpentinization.[43] On July 19, 2013, NASA
scientists reported finding “not much methane” (i.e., “an upper limit of 2.7 parts per billion of methane”) around
the Gale Crater area where the Curiosity rover landed in August 2012.[85][86][87] On September 19, 2013,
NASA scientists, on the basis of further measurements by Curiosity, reported no detection of atmospheric
methane with a measured value of 0.18±0.67 ppbv corresponding to an upper limit of only 1.3 ppbv (95%
confidence limit) and, as a result, conclude that the probability of current methanogenic microbial activity
on Mars is reduced.[88][89][90] On 16 December 2014, NASA reported the Curiosity rover detected a “tenfold
spike”, likely localized, in the amount of methane in the Martian atmosphere. Sample measurements taken “a
dozen times over 20 months” showed increases in late 2013 and early 2014, averaging “7 parts of methane per
billion in the atmosphere.” Before and after that, readings averaged around one-tenth that level.[91][92]

• Saturn – the atmosphere contains 4500 ± 2000 ppm methane[93]

• Enceladus – the atmosphere contains 1.7% methane[94]

• Iapetus
• Titan – the atmosphere contains 1.6% methane and thousands of methane lakes have been detected on
the surface.[95] In the upper atmosphere the methane is converted into more complex molecules including
acetylene, a process that also produces molecular hydrogen. There is evidence that acetylene and hydrogen
are recycled into methane near the surface. This suggests the presence either of an exotic catalyst, or
an unfamiliar form of methanogenic life.[96] An apparent lake of liquid methane has been spotted by
the Cassini-Huygens probe, causing researchers to speculate about the possibility of life on Titan.[97]
4.8. EXTRATERRESTRIAL METHANE 59

Methane measurements in the atmosphere of Mars by the Curiosity rover.

Methane showers, probably prompted by changing seasons, have also been observed.[98] On October 24,
2014, methane was found in polar clouds on Titan.[99][100]

Polar clouds, made of methane, on Titan (left) compared with polar clouds on Earth (right).

• Uranus – the atmosphere contains 2.3% methane[101]

• Ariel – methane is believed to be a constituent of Ariel’s surface ice
• Miranda
• Oberon – about 20% of Oberon’s surface ice is composed of methane-related carbon/nitrogen compounds
• Titania – about 20% of Titania’s surface ice is composed of methane-related organic compounds
• Umbriel – methane is a constituent of Umbriel’s surface ice
• Neptune – the atmosphere contains 1.5 ± 0.5% methane[102]
60 CHAPTER 4. METHANE

• Triton – Triton has a tenuous nitrogen atmosphere with small amounts of methane near the surface.[103][104]
• Pluto – spectroscopic analysis of Pluto’s surface reveals it to contain traces of methane[105][106]
• Charon – methane is believed present on Charon, but it is not completely confirmed[107]
• Eris – infrared light from the object revealed the presence of methane ice[108]
• Halley’s Comet
• Comet Hyakutake – terrestrial observations found ethane and methane in the comet[109]
• Extrasolar planets – methane was detected on extrasolar planet HD 189733b; this is the first detection of
an organic compound on a planet outside the solar system. Its origin is unknown, since the planet’s high
temperature (700 °C) would normally favor the formation of carbon monoxide instead.[110] Research indicates
that meteoroids slamming against exoplanet atmospheres could add organic gases such as methane, making the
exoplanets look as though they are inhabited by life, even if they are not.[111]
• Interstellar clouds[112]

4.9 See also

• 2007 Zasyadko mine disaster
• Abiogenic petroleum origin
• Aerobic methane production
• Anaerobic digestion
• Anaerobic respiration
• Arctic methane release
• Biogas
• Coal Oil Point seep field
• Energy density
• Global Methane Initiative
• Greenhouse gas
• Halomethane, halogenated methane derivatives.
• Industrial gas
• Lake Kivu (more general: limnic eruption)
• List of alkanes
• Methanation
• Methane clathrate, ice that contains methane.
• Methane (data page)
• Methane on Mars: atmosphere
• Methane on Mars: climate
• Methanogen, archaea that produce methane.
• Methanogenesis, microbes that produce methane.
• Methanotroph, bacteria that grow with methane.
• Methyl group, a functional group related to methane.
• Organic gas
• Thomas Gold
4.10. NOTES 61

4.10 Notes
[1] There are many serpentinization reactions. Olivine is a solid solution between forsterite and fayalite whose general formula
is (Fe,Mg)2 SiO4 . The reaction producing methane from olivine can be written as: Forsterite + Fayalite + Water + Carbonic
acid → Serpentine + Magnetite + Methane , or (in balanced form): 18 Mg2 SiO4 + 6 Fe2 SiO4 + 26 H2 O + CO2 → 12
Mg3 Si2 O5 (OH)4 + 4 Fe3 O4 + CH4

4.11 References
[1] “methane (CHEBI:16183)". Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. October 17,
2009. Retrieved October 10, 2011.

[2] “Gas Encyclopedia”. Retrieved November 7, 2013.

[3] “Safety Datasheet, Material Name: Methane” (PDF). USA: Metheson Tri-Gas Incorporated. December 4, 2009. Retrieved
December 4, 2011.

[4] Khalil, M. A. K. (1999). “Non-Co2 Greenhouse Gases in the Atmosphere”. Annual Review of Energy and the Environment
24: 645. doi:10.1146/annurev.energy.24.1.645.

[5] Volta, Alessandro (1777) Lettere del Signor Don Alessandro Volta … Sull' Aria Inflammabile Nativa delle Paludi [Letters
of Signor Don Alessandro Volta … on the flammable native air of the marshes], Milan, Italy: Guiseppe Marelli.

[6] “Methane”. BookRags. Retrieved January 26, 2012.

[7] Hensher, David A. and Button, Kenneth J. (2003). Handbook of transport and the environment. Emerald Group Publishing.
p. 168. ISBN 0-08-044103-3.

[8] Methane Phase change data. NIST Chemistry Webbook.

[9] Baik, Mu-Hyun; Newcomb, Martin; Friesner, Richard A.; Lippard, Stephen J. (2003). “Mechanistic Studies on the Hy-
droxylation of Methane by Methane Monooxygenase”. Chemical Reviews 103 (6): 2385–419. doi:10.1021/cr950244f.
PMID 12797835.

[10] Bordwell, Frederick G. (1988). “Equilibrium acidities in dimethyl sulfoxide solution”. Accounts of Chemical Research 21
(12): 456. doi:10.1021/ar00156a004.

[11] Rasul, G.; Surya Prakash, G. K.; Olah, G. A. (2011). “Comparative study of the hypercoordinate carbonium ions and
their boron analogs: A challenge for spectroscopists”. Chemical Physics Letters 517: 1. Bibcode:2011CPL...517....1R.
doi:10.1016/j.cplett.2011.10.020.

[12] Bernskoetter, W.H.; Schauer, C.K.; Goldberg, K.I.; Brookhart, M. (2009). “Characterization of a Rhodium(I) σ-Methane
Complex in Solution”. Science 326 (5952): 553–556. Bibcode:2009Sci...326..553B. doi:10.1126/science.1177485. PMID
19900892.

[13] Energy Content of some Combustibles (in MJ/kg). People.hofstra.edu. Retrieved on March 30, 2014.

[14] Drysdale, Dougal (2008). “Physics and Chemistry of Fire”. In Cote, Arthur E. Fire Protection Handbook 1 (20th ed.).
Quincy, MA: National Fire Protection Association. pp. 2–18. ISBN 978-0-87765-758-3.

[15] March, Jerry (1968). Advance Organic Chemistry: Reactions, Mechanisms and Structure. New York: McGraw-Hill Book
Company. pp. 533–534.

[16] Cornell, Clayton B. (April 29, 2008). “Natural Gas Cars: CNG Fuel Almost Free in Some Parts of the Country”. Com-
pressed natural gas is touted as the 'cleanest burning' alternative fuel available, since the simplicity of the methane molecule
reduces tailpipe emissions of different pollutants by 35 to 97%. Not quite as dramatic is the reduction in net greenhouse-gas
emissions, which is about the same as corn-grain ethanol at about a 20% reduction over gasoline

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66 CHAPTER 4. METHANE

4.12 External links

• Methane at The Periodic Table of Videos (University of Nottingham)

• Methane thermodynamics
• International Chemical Safety Card 0291

• Methane Hydrates

• Safety data for methane

• Catalytic conversion of methane to more useful chemicals and fuels

• CDC – Handbook for Methane Control in Mining

Chapter 5

Ethane

This article is about the chemical compound. For the emergency service protocol, see ETHANE.

Ethane (/ˈɛθeɪn/ or /ˈiːθeɪn/) is a chemical compound with chemical formula C2 H6 . At standard temperature and
pressure, ethane is a colorless, odorless gas. Ethane is isolated on an industrial scale from natural gas, and as a
byproduct of petroleum refining. Its chief use is as petrochemical feedstock for ethylene production.

5.1 History
Ethane was first synthesised in 1834 by Michael Faraday, applying electrolysis of a potassium acetate solution. He
mistook the hydrocarbon product of this reaction for methane, and did not investigate it further.[4] During the period
1847–1849, in an effort to vindicate the radical theory of organic chemistry, Hermann Kolbe and Edward Frankland
produced ethane by the reductions of propionitrile (ethyl cyanide)[5] and ethyl iodide[6] with potassium metal, and,
as did Faraday, by the electrolysis of aqueous acetates. They, however, mistook the product of these reactions for
methyl radical, rather than the dimer of methyl, ethane. This error was corrected in 1864 by Carl Schorlemmer, who
showed that the product of all these reactions was in fact ethane.[7]
The name ethane is derived from the IUPAC nomenclature of organic chemistry. “Eth-" refers to the presence of 2
carbon atoms, and "-ane” refers to the presence of a single bond between them.

5.2 Chemistry
In the laboratory, ethane may be conveniently prepared by Kolbe electrolysis. In this technique, an aqueous solution
of an acetate salt is electrolysed. At the anode, acetate is oxidized to produce carbon dioxide and methyl radicals,
and the highly reactive methyl radicals combine to produce ethane: −

CH3 COO− → CH3 • + CO2 + e−

CH3 • + •CH3 → C2 H6

Another method, the oxidation of acetic anhydride by peroxides, is conceptually similar.

The chemistry of ethane also involves chiefly free radical reactions. Ethane can react with the halogens, especially
chlorine and bromine, by free radical halogenation. This reaction proceeds through the propagation of the ethyl
radical:

C2 H5 • + Cl2 → C2 H5 Cl + Cl•
Cl• + C2 H6 → C2 H5 • + HCl

Because halogenated ethanes can undergo further free radical halogenation, this process results in a mixture of several
halogenated products. In the chemical industry, more selective chemical reactions are used for the production of any
particular two-carbon haloalkane.

67
68 CHAPTER 5. ETHANE

5.2.1 Combustion
The complete combustion of ethane releases 1559.7 kJ/mol, or 51.9 kJ/g, of heat, and produces carbon dioxide and
water according to the chemical equation

2 C2 H6 + 7 O2 → 4 CO2 + 6 H2 O + 3120 kJ

Combustion occurs by a complex series of free-radical reactions. Computer simulations of the chemical kinetics of
ethane combustion have included hundreds of reactions. An important series of reaction in ethane combustion is the
combination of an ethyl radical with oxygen, and the subsequent breakup of the resulting peroxide into ethoxy and
hydroxyl radicals.

C2 H5 • + O2 → C2 H5 OO•
C2 H5 OO• + HR → C2 H5 OOH + •R
C2 H5 OOH → C2 H5 O• + •OH

The principal carbon-containing products of incomplete ethane combustion are single-carbon compounds such as
carbon monoxide and formaldehyde. One important route by which the carbon-carbon bond in ethane is broken to
yield these single-carbon products is the decomposition of the ethoxy radical into a methyl radical and formaldehyde,
which can in turn undergo further oxidation.

C2 H5 O• → CH3 • + CH2 O

Some minor products in the incomplete combustion of ethane include acetaldehyde, methane, methanol, and ethanol.
At higher temperatures, especially in the range 600–900 °C, ethylene is a significant product. It arises via reactions
like

C2 H5 • + O2 → C2 H4 + •OOH

Similar reactions (although with species other than oxygen as the hydrogen abstractor) are involved in the production
of ethylene from ethane in steam cracking.

5.2.2 Ethane barrier

Rotating a molecular substructure about a twistable bond usually requires energy. The minimum energy to produce
a 360-degree bond rotation is called the rotational barrier.
Ethane gives a classic, simple example of such a rotational barrier, sometimes called the “ethane barrier.” Among the
earliest experimental evidence of this barrier (see diagram at left) was obtained by modelling the entropy of ethane.[8]
The three hydrogens at each end are free to pinwheel about the central carbon-carbon bond, provided that there is
sufficient energy to overcome the barrier. The physical origin of the barrier is still not completely settled,[9] although
the overlap (exchange) repulsion [10] between the hydrogens on opposing ends of the molecule is perhaps the strongest
candidate, with the stabilizing effect of hyperconjugation on the staggered conformation contributing as well.[11]
However, theoretical methods that use an appropriate starting point (orthogonal orbitals) find that hyperconjugation
is the most important factor in the origin of ethane rotation barrier.[12]
As far back as 1890–1891 ethane was suggested to prefer a staggered conformation with the two ends of the molecule
askew from each other.[13][14][15]

5.3 Production
After methane, ethane is the second-largest component of natural gas. Natural gas from different gas fields varies
in ethane content from less than 1% to over 6% by volume. Prior to the 1960s, ethane and larger molecules were
typically not separated from the methane component of natural gas, but simply burnt along with the methane as a fuel.
Today, however, ethane is an important petrochemical feedstock, and it is separated from the other components of
5.4. USES 69

Ethane barrier to rotation about the carbon-carbon bond. The curve is potential energy as a function of rotational angle.

natural gas in most well-developed gas fields. Ethane can also be separated from petroleum gas, a mixture of gaseous
hydrocarbons that arises as a byproduct of petroleum refining. Economics of building and running processing plants
can change, however. If the relative value of sending the unprocessed natural gas to a consumer exceeds the value of
extracting ethane, then the plant may not be run. This can cause operational issues managing the changing quality of
the gas in downstream systems.
Ethane is most efficiently separated from methane by liquefying it at cryogenic temperatures. Various refrigeration
strategies exist: the most economical process presently in wide use employs turboexpansion, and can recover over 90%
of the ethane in natural gas. In this process, chilled gas expands through a turbine; as it expands, its temperature drops
to about −100 °C. At this low temperature, gaseous methane can be separated from the liquefied ethane and heavier
hydrocarbons by distillation. Further distillation then separates ethane from the propane and heavier hydrocarbons.

5.4 Uses
The chief use of ethane is in the chemical industry in the production of ethene (ethylene) by steam cracking. When
diluted with steam and briefly heated to very high temperatures (900 °C or more), heavy hydrocarbons break down
into lighter hydrocarbons, and saturated hydrocarbons become unsaturated. Ethane is favored for ethene production
because the steam cracking of ethane is fairly selective for ethene, while the steam cracking of heavier hydrocarbons
yields a product mixture poorer in ethene, and richer in heavier alkenes (olefins) such as propene (propylene) and
butadiene, and in aromatic hydrocarbons.
Experimentally, ethane is under investigation as a feedstock for other commodity chemicals. Oxidative chlorination
of ethane has long appeared to be a potentially more economical route to vinyl chloride than ethene chlorination.
Many processes for carrying out this reaction have been patented, but poor selectivity for vinyl chloride and corrosive
reaction conditions (specifically, a hydrochloric acid-containing reaction mixture at temperatures greater than 500
70 CHAPTER 5. ETHANE

°C) have discouraged the commercialization of most of them. Presently, INEOS operates a 1000 t/a (tonnes per
annum) ethane-to-vinyl chloride pilot plant at Wilhelmshaven in Germany.
Similarly, the Saudi Arabian firm SABIC has announced construction of a 30,000 tonnes per annum plant to produce
acetic acid by ethane oxidation at Yanbu. This economic viability of this process may rely on the low cost of ethane
near Saudi oil fields, and it may not be competitive with methanol carbonylation elsewhere in the world.
Ethane can be used as a refrigerant in cryogenic refrigeration systems. On a much smaller scale, in scientific research,
liquid ethane is used to vitrify water-rich samples for electron microscopy (cryo-electron microscopy). A thin film
of water, quickly immersed in liquid ethane at −150 °C or colder, freezes too quickly for water to crystallize. This
rapid freezing does not disrupt the structure of soft objects present in the liquid state, as the formation of ice crystals
can do.

5.5 Health and safety

At room temperature, ethane is a flammable gas. When mixed with air at 3.0%–12.5% by volume, it forms an
explosive mixture.
Some additional precautions are necessary where ethane is stored as a cryogenic liquid. Direct contact with liquid
ethane can result in severe frostbite. In addition, the vapors evaporating from liquid ethane are, until they warm to
room temperature, heavier than air and can creep along the ground or gather in low places, and if they encounter an
ignition source, can flash back to the body of ethane from which they evaporated.
Containers recently emptied of ethane may contain insufficient oxygen to support life. Beyond this asphyxiation
hazard, ethane poses no known acute or chronic toxicological risk. It is not a carcinogen.[16]

5.6 Atmospheric and extraterrestrial ethane

A photograph of Titan's northern latitudes. The dark features appear to be hydrocarbon lakes, but further images will be needed to
see if the dark spots remain the same (as they would if they were lakes)
5.7. REFERENCES 71

Ethane occurs as a trace gas in the Earth’s atmosphere, currently having a concentration at sea level of 0.5 ppb,[17]
though its pre-Industrial concentration is likely to have been lower since a significant proportion of the ethane in
today’s atmosphere may have originated as fossil fuels. Although ethane is a greenhouse gas, it is much less abundant
than methane and also less efficient relative to mass. It has also been detected as a trace component in the atmospheres
of all four giant planets, and in the atmosphere of Saturn's moon Titan.[18]
Atmospheric ethane results from the Sun’s photochemical action on methane gas, also present in these atmospheres:
ultraviolet photons of shorter wavelengths than 160 nm can photo-dissociate the methane molecule into a methyl
radical and a hydrogen atom. When two methyl radicals recombine, the result is ethane:

CH4 → CH3 • + •H
CH3 • + •CH3 → C2 H6

In the case of Titan, it was once widely hypothesized that ethane produced in this fashion rained back onto the
moon’s surface, and over time had accumulated into hydrocarbon seas or oceans covering much of the moon’s surface.
Infrared telescopic observations cast significant doubt on this hypothesis, and the Huygens probe, which landed on
Titan in 2005, failed to observe any surface liquids, although it did photograph features that could be presently dry
drainage channels. In December 2007 the Cassini probe found at least one lake at Titan’s south pole, now called
Ontario Lacus because of the lake’s similar area to Lake Ontario on Earth (approximately 20,000 km2 ). Further
analysis of infrared spectroscopic data presented in July 2008[19] provided stronger evidence for the presence of
liquid ethane in Ontario Lacus.
In 1996, ethane was detected in Comet Hyakutake,[20] and it has since been detected in some other comets. The
existence of ethane in these distant solar system bodies may implicate ethane as a primordial component of the solar
nebula from which the sun and planets are believed to have formed.
In 2006, Dale Cruikshank of NASA/Ames Research Center (a New Horizons co-investigator) and his colleagues
announced the spectroscopic discovery of ethane on Pluto's surface.[21]

5.7 References
[1] “Ethane – Compound Summary”. PubChem Compound. USA: National Center for Biotechnology Information. 16 Septem-
ber 2004. Retrieved 7 December 2011.

[2] Lide, D. R., ed. (2005). CRC Handbook of Chemistry and Physics (86th ed.). Boca Raton (FL): CRC Press. p. 3.22.
ISBN 0-8493-0486-5.

[3] Lide, D. R., ed. (2005). CRC Handbook of Chemistry and Physics (86th ed.). Boca Raton (FL): CRC Press. p. 8.88.
ISBN 0-8493-0486-5.

[4] Faraday, Michael (1834). “Experimental researches in electricity: Seventh series”. Philosophical Transactions 124: 77–
122. doi:10.1098/rstl.1834.0008.

[5] Kolbe, Hermann; Frankland, Edward (1849). “On the products of the action of potassium on cyanide of ethyl”. Journal
of the Chemical Society 1: 60–74. doi:10.1039/QJ8490100060.

[6] Frankland, Edward (1850). “On the isolation of the organic radicals”. Journal of the Chemical Society 2 (3): 263–296.
doi:10.1039/QJ8500200263.

[7] Schorlemmer, Carl (1864). Annalen der Chemie 132: 234.

[8] Kemp, J. D. and Pitzer, K. S., J. Am. Chem. Soc., 1937, 59, 276-279

[9] Ercolani, G. (2005). “Determination of the Rotational Barrier in Ethane by Vibrational Spectroscopy and Statistical Ther-
modynamics”. J. Chem. Educ. 82 (11): 1703–1708. Bibcode:2005JChEd..82.1703E. doi:10.1021/ed082p1703.

[10] Pitzer, R. M. (1983). “The Barrier to Internal Rotation in Ethane”. Acc. Chem. Res. 16 (6): 207–210. doi:10.1021/ar00090a004.

[11] Mo, Y.; Wu, W.; Song, L.; Lin, M.; Zhang, Q.; Gao, J. (2004). “The Magnitude of Hyperconjugation in Ethane: A Perspec-
tive from Ab Initio Valence Bond Theory”. Angew. Chem. Int. Ed. 43 (15): 1986–1990. doi:10.1002/anie.200352931.

[12] Pophristic, V.; Goodman, L. (2001) Hyperconjugation not steric repulsion leads to the staggered structure of ethane.
Nature, 411, 565-568. Schreiner, P. R. (2002) Teaching the Right Reasons: Lessons from the Mistaken Origin of the
Rotational Barrier in Ethane. Angewandte Chemie International Edition, 41, 3579-3581.
72 CHAPTER 5. ETHANE

[13] Bischoff, CA, (1890), Chem. Ber. 23, 623

[14] Bischoff, CA, (1891a), Chem. Ber. 24, 1074, 1086

[15] Bischoff, CA, (1891b), Chem. Ber. 26, 1452

[16] Daniel Vallero (June 7, 2010). Environmental Biotechnology: A Biosystems Approach. Academic Press. p. 641.

[17] Trace gases. Atmosphere.mpg.de. Retrieved on 2011-12-08.

[18] Brown, Bob; et al. (2008). “NASA Confirms Liquid Lake on Saturn Moon”.

[19] Brown, R. H.; Soderblom, L. A.; Soderblom, J. M.; Clark, R. N.; Jaumann, R.; Barnes, J. W.; Sotin, C.; Buratti, B. et al.
(2008). “The identification of liquid ethane in Titan’s Ontario Lacus”. Nature 454 (7204): 607–10. Bibcode:2008Natur.454..607B.
doi:10.1038/nature07100. PMID 18668101.

[20] Mumma, Michael J. et al. (1996). “Detection of Abundant Ethane and Methane, Along with Carbon Monoxide and Water,
in Comet C/1996 B2 Hyakutake: Evidence for Interstellar Origin”. Science 272 (5266): 1310–1314. Bibcode:1996Sci...272.1310M.
doi:10.1126/science.272.5266.1310. PMID 8650540.

[21] A. Stern (November 1, 2006). “Making Old Horizons New”. The PI’s Perspective. Johns Hopkins University Applied
Physics Laboratory. Retrieved 2007-02-12.

5.8 Further reading

• Kolbe, Hermann (1850). “Researches on the electrolysis of organic compounds”. Journal of the Chemical
Society 2 (2): 157–184. doi:10.1039/QJ8500200157.

5.9 External links

• International Chemical Safety Card 0266
• Market-Driven Evolution of Gas Processing Technologies for NGLs

• Staggered and eclipsed ethane

Chapter 6

Propane

Not to be confused with propene.

Propane (/ˈproʊpeɪn/) is a three-carbon alkane with the molecular formula C

3H
8, normally a gas, but compressible to a transportable liquid. A by-product of natural gas processing and petroleum
refining, it is commonly used as a fuel for engines, oxy-gas torches, portable stoves, and residential central heating.
Propane is one of a group of liquefied petroleum gases (LP gases). The others include butane, propylene, butadiene,
butylene, isobutylene and mixtures thereof.
Propane containing too much propene (also called propylene) is not suited for most vehicle fuels. HD-5 is a specifi-
cation that establishes a maximum concentration of 5% propene in propane. Propane and other LP gas specifications
are established in ASTM D-1835.[3] All propane fuels include an odorant, almost always ethanethiol, so that people
can easily smell the gas in case of a leak. Propane as HD-5 was originally intended for use as vehicle fuel. HD-5 is
currently being used in all propane applications.

6.1 History

Propane was first identified as a volatile component in gasoline by Walter O. Snelling of the U.S. Bureau of Mines
in 1910. The volatility of these lighter hydrocarbons caused them to be known as “wild” because of the high vapor
pressures of unrefined gasoline. On March 31, the New York Times reported on Snelling’s work with liquefied gas
and that “a steel bottle will carry enough gas to light an ordinary home for three weeks.”[4]
It was during this time that Snelling, in cooperation with Frank P. Peterson, Chester Kerr, and Arthur Kerr, created
ways to liquefy the LP gases during the refining of natural gasoline. Together they established American Gasol Co.,
the first commercial marketer of propane. Snelling had produced relatively pure propane by 1911, and on March
25, 1913, his method of processing and producing LP gases was issued patent #1,056,845.[5] A separate method of
producing LP gas through compression was created by Frank Peterson and patented in 1912.
The 1920s saw increased production of LP gas, with the first year of recorded production totaling 223,000 US gallons
(840 m3 ) in 1922. In 1927, annual marketed LP gas production reached 1 million US gallons (3,800 m3 ), and by
1935, the annual sales of LP gas had reached 56 million US gallons (210,000 m3 ). Major industry developments
in the 1930s included the introduction of railroad tank car transport, gas odorization, and the construction of local
bottle-filling plants. The year 1945 marked the first year that annual LP gas sales reached a billion gallons. By 1947,
62% of all U.S. homes had been equipped with either natural gas or propane for cooking.[5]
In 1950, 1,000 propane-fueled buses were ordered by the Chicago Transit Authority, and by 1958, sales in the U.S.
had reached 7 billion US gallons (26,000,000 m3 ) annually. In 2004 it was reported to be a growing $8-billion to
$10-billion industry with over 15 billion US gallons (57,000,000 m3 ) of propane being used annually in the U.S.[6]
The "prop-" root found in “propane” and names of other compounds with three-carbon chains was derived from
"propionic acid".[7]

73
74 CHAPTER 6. PROPANE

6.2 Sources
Propane is produced as a by-product of two other processes, natural gas processing and petroleum refining. The
processing of natural gas involves removal of butane, propane, and large amounts of ethane from the raw gas, in
order to prevent condensation of these volatiles in natural gas pipelines. Additionally, oil refineries produce some
propane as a by-product of cracking petroleum into gasoline or heating oil. The supply of propane cannot easily be
adjusted to meet increased demand, because of the by-product nature of propane production. About 90% of U.S.
propane is domestically produced. The United States imports about 10% of the propane consumed each year, with
about 70% of that coming from Canada via pipeline and rail. The remaining 30% of imported propane comes to the
United States from other sources via ocean transport.
After it is produced, North American propane is stored in huge salt caverns. Examples of these are Fort Saskatchewan,
Alberta; Mont Belvieu, Texas and Conway, Kansas. These salt caverns were hollowed out in the 1940s,[8] and they
can store 80,000,000 barrels (13,000,000 m3 ) or more of propane. When the propane is needed, much of it is shipped
by pipelines to other areas of the United States. Propane is also shipped by truck, ship, barge, and railway to many
U.S. areas.[9]

6.3 Properties and reactions

Propane undergoes combustion reactions in a similar fashion to other alkanes. In the presence of excess oxygen,
propane burns to form water and carbon dioxide.

C
3H
8+5O
2 → 3 CO
2+4H
2O + heat
propane + oxygen → carbon dioxide + water

When not enough oxygen is present for complete combustion, incomplete combustion occurs, allowing carbon
monoxide and/or soot (carbon) to be formed as well:

2C
3H
8+9O
2 → 4 CO
2 + 2 CO + 8 H
2O + heat
propane + oxygen → carbon dioxide + carbon monoxide + water

C
3H
8+2O
2→3C+4H
2O + heat
propane + oxygen → soot + water

Unlike natural gas, propane is heavier than air (1.5 times as dense). In its raw state, propane sinks and pools at the
floor. Liquid propane will flash to a vapor at atmospheric pressure and appears white due to moisture condensing
from the air.
When properly combusted, propane produces about 50 MJ/kg of heat.[10] The gross heat of combustion of one normal
cubic meter of propane is around 91 megajoules.[11]
Propane is nontoxic; however, when abused as an inhalant, it poses a mild asphyxiation risk through oxygen depri-
vation. Commercial products contain hydrocarbons beyond propane, which may increase risk. Commonly stored
6.4. USES 75

under pressure at room temperature, propane and its mixtures expand and cool when released and may cause mild
frostbite.
Propane combustion is much cleaner than gasoline combustion, though not as clean as natural gas combustion. The
presence of C–C bonds, plus the multiple bonds of propylene and butylene, create organic exhausts besides carbon
dioxide and water vapor during typical combustion. These bonds also cause propane to burn with a visible flame.

6.3.1 Energy content

The enthalpy of combustion of propane gas where all products return to standard state, for example where water
returns to its liquid state at standard temperature, (known as higher heating value) is (−2219.2 ± 0.5) kJ/mol, or
(50.33 ± 0.01) MJ/kg.[10] The enthalpy of combustion of propane gas where products do not return to standard state,
for example where the hot gases including water vapor exit a chimney, (known as lower heating value) is −2043.455
kJ/mol.[12] The lower heat value is the amount of heat available from burning the substance where the combustion
products are vented to the atmosphere. For example, the heat from a fireplace when the flu is open.

6.3.2 Density
The density of liquid propane at 25 °C (77 °F) is 0.493 g/cm3 , which is equivalent to 4.11 pounds per U.S. liquid
gallon or 493 kg/m3 . Propane expands at 1.5% per 10 °F. Thus, liquid propane has a density of approximately 4.2
pounds per gallon (504 kg/m3 ) at 60 °F (15.6 °C).

6.4 Uses
Propane is a popular choice for barbecues and portable stoves because the low boiling point of −42 °C (−44 °F)
makes it vaporize as soon as it is released from its pressurized container. Therefore, no carburetor or other vaporizing
device is required; a simple metering nozzle suffices. Propane powers some locomotives, buses, forklifts, taxis and
ice resurfacing machines and is used for heat and cooking in recreational vehicles and campers. Since it can be
transported easily, it is a popular fuel for home heat and backup electrical generation in sparsely populated areas that
do not have natural gas pipelines.
Propane is generally stored and transported in steel cylinders as a liquid with a vapor space above the liquid. The
vapor pressure in the cylinder is a function of temperature. When gaseous propane is drawn at a high rate, the latent
heat of vaporisation required to create the gas will cause the bottle to cool. (This is why water often condenses on
the sides of the bottle and then freezes). In addition, the lightweight, high-octane compounds vaporize before the
heavier, low-octane ones. Thus, the ignition properties change as the cylinder empties. For these reasons, the liquid
is often withdrawn using a dip tube. Propane is used as fuel in furnaces for heat, in cooking, as an energy source for
water heaters, laundry dryers, barbecues, portable stoves, and motor vehicles.
Commercially available “propane” fuel, or LPG, is not pure. Typically in the United States and Canada, it is primarily
propane (at least 90%), with the rest mostly ethane, propylene, butane, and odorants including ethyl mercaptan.[13][14]
This is the HD-5 standard, (Heavy Duty-5% maximum allowable propylene content, and no more than 5% butanes
and ethane) defined by the American Society for Testing and Materials by its Standard 1835 for internal combustion
engines. Not all products labeled “LPG” conform to this standard however. In Mexico, for example, gas labeled
“LPG” may consist of 60% propane and 40% butane. “The exact proportion of this combination varies by country,
depending on international prices, on the availability of components and, especially, on the climatic conditions that
favor LPG with higher butane content in warmer regions and propane in cold areas”.[15]

6.4.1 Domestic and industrial fuel

Propane use is growing rapidly in non-industrialized areas of the world. Propane has completely replaced wood and
other traditional fuel sources, now it’s commonly known as 'cooking gas’. The “propane” sold outside North America
is actually a mixture of propane and butane. The warmer the country, the higher the butane content, commonly
50/50 and sometimes reaching 75% butane. Usage is calibrated to the different-sized nozzles found in non-U.S.
grills. Americans who take their grills overseas — such as military personnel — can find U.S.-specification propane
at AAFES military post exchanges.
76 CHAPTER 6. PROPANE

A 20 lb (9.1 kg) steel propane cylinder. This cylinder is fitted with an overfill prevention device (OPD) valve, as evidenced by the
trilobular handwheel.

North American industries using propane include glass makers, brick kilns, poultry farms and other industries that
need portable heat.
In rural areas of North America, as well as northern Australia and some parts of southern India propane is used to
heat livestock facilities, in grain dryers, and other heat-producing appliances. When used for heating or grain drying
it is usually stored in a large, permanently placed cylinder which is recharged by a propane-delivery truck. As of
2007, 9.7 million American households use propane as their primary heating fuel.[16]
6.4. USES 77

Domestic spherical steel pressure vessel for propane storage in the United States, designed in the 1980s, with pressure regulator.

In North America, local delivery trucks with an average cylinder size of 3,000 US gallons (11,000 L), fill up large
cylinders that are permanently installed on the property, or other service trucks exchange empty cylinders of propane
with filled cylinders. Large tractor-trailer trucks, with an average cylinder size of 10,000 US gallons (38,000 L),
transport the propane from the pipeline or refinery to the local bulk plant. The bobtail and transport are not unique
to the North American market, though the practice is not as common elsewhere, and the vehicles are generally called
tankers. In many countries, propane is delivered to consumers via small or medium-sized individual cylinders, while
empty cylinders are removed for refilling at a central location.
78 CHAPTER 6. PROPANE

A local delivery truck, behind the pickup truck

Retail sale of propane in the United States

6.4.2 Refrigeration

Propane is also instrumental in providing off-the-grid refrigeration, usually by means of a gas absorption refrigerator.
Blends of pure, dry “isopropane” (R-290a) (isobutane/propane mixtures) and isobutane (R-600a) have negligible
ozone depletion potential and very low Global Warming Potential (having a value of 3.3 times the GWP of car-
6.4. USES 79

bon dioxide) and can serve as a functional replacement for R-12, R-22, R-134a, and other chlorofluorocarbon or
hydrofluorocarbon refrigerants in conventional stationary refrigeration and air conditioning systems.[17]

In motor vehicles

Such substitution is widely prohibited or discouraged in motor vehicle air conditioning systems, on the grounds that
using flammable hydrocarbons in systems originally designed to carry non-flammable refrigerant presents a significant
risk of fire or explosion.[18][19][20][21][22][23][24][25]
Vendors and advocates of hydrocarbon refrigerants argue against such bans on the grounds that there have been very
few such incidents relative to the number of vehicle air conditioning systems filled with hydrocarbons.[26][27]

6.4.3 Motor fuel

Main article: Autogas

Propane is also being used increasingly for vehicle fuels. In the U.S., over 190,000 on-road vehicles use propane, and
over 450,000 forklifts use it for power. It is the third most popular vehicle fuel in the world,[28] behind gasoline and
Diesel fuel. In other parts of the world, propane used in vehicles is known as autogas. In 2007, approximately 13
million vehicles worldwide use autogas.[28]
The advantage of propane in cars is its liquid state at a moderate pressure. This allows fast refill times, affordable fuel
cylinder construction, and price ranges typically just over half that of gasoline. Meanwhile it is noticeably cleaner
(both in handling, and in combustion), results in less engine wear (due to carbon deposits) without diluting engine
oil (often extending oil-change intervals), and until recently was a relative bargain in North America. Octane rating
of propane is relatively high at 110. In the United States the propane fueling infrastructure is the most developed
of all alternative vehicle fuels. Many converted vehicles have provisions for topping off from “barbecue bottles”.
Purpose-built vehicles are often in commercially owned fleets, and have private fueling facilities. A further saving
for propane fuel vehicle operators, especially in fleets, is that pilferage is much more difficult than with gasoline or
Diesel fuels.
Propane is also used as fuel for small engines, especially those used indoors or in areas with insufficient fresh air and
ventilation to carry away the more toxic exhaust of an engine running on gasoline or Diesel fuel. More recently, there
have been lawn care products like string trimmers, lawn mowers and leaf blowers intended for outdoor use, but fueled
by propane to reduce air pollution.

6.4.4 Improvised Explosive Device

• Propane and propane cylinders have been used in attacks and attempted attacks against schools and terrorist
targets such as the Columbine High School massacre, 2012 Brindisi school bombing, the Discovery Commu-
nications headquarters hostage crisis and in car bombs.

6.4.5 Other uses

• Propane is the primary flammable gas in blowtorch for soldering or brazing.

• Propane is used as a feedstock for the production of base petrochemicals in steam cracking.

• Propane is the primary fuel for hot air balloons.

• It is used in semiconductor manufacture to deposit silicon carbide.

• Propane is commonly used in theme parks and in the movie industry as an inexpensive, high-energy fuel for
explosions and other special effects.

• Propane is used as a propellant, relying on the expansion of the gas to fire the projectile. It does not ignite the
gas. The use of a liquefied gas gives more shots per cylinder, compared to a compressed gas.

• Propane is used as a propellant for many household aerosol sprays, including shaving creams and air fresheners.
80 CHAPTER 6. PROPANE

6.5 Propane risks and alternate gas fuels

Propane is denser than air. If a leak in a propane fuel system occurs, the gas will have a tendency to sink into
any enclosed area and thus poses a risk of explosion and fire. The typical scenario is a leaking cylinder stored in a
basement; the propane leak drifts across the floor to the pilot light on the furnace or water heater, and results in an
explosion or fire. This property makes propane generally unsuitable as a fuel for boats.
Propane is bought and stored in a liquid form (LPG), and thus fuel energy can be stored in a relatively small space.
Compressed Natural Gas (CNG), largely methane, is another gas used as fuel, but it cannot be liquefied by compres-
sion at normal temperatures, as these are well above its critical temperature. As a gas, very high pressure is required
to store useful quantities. This poses the hazard that, in an accident, just as with any compressed gas cylinder (such
as a CO2 cylinder used for a soda concession) a CNG cylinder may burst with great force, or leak rapidly enough to
become a self-propelled missile. Therefore, CNG is much less efficient to store, due to the large cylinder volume
required. An alternative means of storing natural gas is as a cryogenic liquid in an insulated container as Liquefied
Natural Gas (LNG). This form of storage is at low pressure and is around 3.5 times as efficient as storing it as CNG.
Unlike propane, if a spill occurs, CNG will evaporate and dissipate harmlessly because it is lighter than air. Propane
is much more commonly used to fuel vehicles than is natural gas because the equipment required costs less. Propane
requires just 1,220 kilopascals (177 psi) of pressure to keep it liquid at 37.8 °C (100 °F).[29]

6.6 Retail cost

6.6.1 United States

As of October 2013, the retail cost of propane was approximately $2.37 per gallon, or roughly $25.95 per 1 million
BTUs.[30] This means that filling a 500-gallon propane tank, which is what households that use propane as their main
source of energy usually require, costs $948 (80% of 500 gallons or 400 gallons), a 7.5% increase on the 2012–2013
winter season average US price.[31] However, propane costs per gallon change significantly from one state to another:
the Energy Information Administration quotes a $2.995 per gallon average on the East Coast for October 2013,[32]
while the figure for the Midwest was $1.860 for the same period.[33]

6.7 See also

• Blau gas

• Dimethyl ether

• National Propane Gas Association

• Isopropyl alcohol

• Propargyl alcohol

6.8 References
[1] “Propane – Compound Summary”. PubChem Compound. USA: National Center for Biotechnology Information. 27 March
2005. Identification and Related Records. Retrieved 8 December 2011.

[2] Record of Propane in the GESTIS Substance Database from the IFA

[3] ASTM D-1835

[4] “GAS PLANT IN STEEL BOTTLE.; Dr. Snelling’s Process Gives Month’s Supply in Liquid Form.”. The New York Times.
April 1, 1912. p. 9. Retrieved 2007-12-22.

[5] National Propane Gas Association. “The History of Propane”. Retrieved 2007-12-22.

[6] Propane Education and Research Council. “Fact Sheet – The History of Propane”. Retrieved 2007-12-22.
6.8. REFERENCES 81

[7] “Online Etymology Dictionary entry for propane”. Etymonline.com. Retrieved 2010-10-29.

[8] Argonne National Laborator (1999). “Salt Cavern Information Center”. Retrieved 2007-12-22.

[9] Propane Education and Research Council. “History of Propane”. Retrieved 22 May 2012.

[10] Propane. NIST Standard Reference Data referring to Pittam, D. A.; Pilcher, G. (1972). “Measurements of heats of
combustion by flame calorimetry. Part 8.—Methane, ethane, propane, n-butane and 2-methylpropane”. Journal of the
Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases 68: 2224. doi:10.1039/f19726802224.
and Rossini, F.D. (1934). “Calorimetric determination of the heats of combustion of ethane, propane, normal butane, and
normal pentane”. J. Res. NBS 12: 735–750.

[11] Bossel, Ulf (2003) Well-to-Wheel Studies, Heating Values, and the Energy Conservation Principle, Proceedings of Fuel
Cell Forum.

[12] Ҫengel, Yunus A.; Boles, Michael A. (2006). Thermodynamics: An Engineering Approach (Fifth ed.). McGrawHill. p.
925. ISBN 9780072884951.

[13] Amerigas. “Amerigas Material Safety Data Sheet for Odorized Propane”. Retrieved 2011-10-24.

[14] Suburban Propane. “Suburban Propane Material Safety Data Sheet for Commercial Odorized Propane”. Retrieved 2011-
10-24.

[15] Mexican Ministry of Energy. “Liquefied Petroleum Gas Market Outlook 2008 – 2017”. Mexican Ministry of Energy.
Retrieved 2012-05-17.

[16] Sloan, Michael and Meyer, Richard. “2009 Propane Market Outlook”. Propane Education and Research Council. Re-
trieved 28 May 2012.

[17] “European Commission on retrofit refrigerants for stationary applications” (PDF). Retrieved 2010-10-29.

[18] “U.S. EPA hydrocarbon-refrigerants FAQ”. Epa.gov. Retrieved 2010-10-29.

[19] Compendium of hydrocarbon-refrigerant policy statements, October 2006. vasa.org.au

[20] “MACS bulletin: hydrocarbon refrigerant usage in vehicles” (PDF). Retrieved 2010-10-29.

[21] “Society of Automotive Engineers hydrocarbon refrigerant bulletin”. Sae.org. 2005-04-27. Retrieved 2010-10-29.

[22] “Shade Tree Mechanic on hydrocarbon refrigerants”. Shadetreemechanic.com. 2005-04-27. Retrieved 2010-10-29.

[23] “Saskatchewan Labour bulletin on hydrocarbon refrigerants in vehicles”. Labour.gov.sk.ca. 2010-06-29. Retrieved 2010-
10-29.

[24] VASA on refrigerant legality & advisability. vasa.org.au

[25] “Queensland (Australia) government warning on hydrocarbon refrigerants”. Energy.qld.gov.au. Retrieved 2010-10-29.

[26] “New South Wales (Australia) Parliamentary record, 16 October 1997”. Parliament.nsw.gov.au. 1997-10-16. Retrieved
2010-10-29.

[27] “New South Wales (Australia) Parliamentary record, 29 June 2000”. Parliament.nsw.gov.au. Retrieved 2010-10-29.

[28] Propane Education & Research Council. “Autogas”. PERC. Retrieved 2012-05-17.

[29] “Propane Vapor Pressure”. The Engineering ToolBox. 2005. Retrieved 2008-07-28.

[30] US Energy Information Administration (November 12, 2013). “Heating Oil and Propane Prices”.

[31] Propane Deal (November 12, 2013). “Current Propane Prices”.

[32] US Energy Information Administration (November 12, 2013). “East Coast Heating Oil and Propane Prices”.

[33] US Energy Information Administration (November 12, 2013). “Midwest Heating Oil and Propane Prices”.
82 CHAPTER 6. PROPANE

6.9 External links

• Canadian Propane Association

• Direct synthesis of propane from synthesis gas (syngas)

• International Chemical Safety Card 0319

• National Propane Gas Association (U.S.)

• NIOSH Pocket Guide to Chemical Hazards

• Propane Education & Research Council (U.S.)

• Propane Properties Explained Descriptive Breakdown of Propane Characteristics

• UKLPG: Propane and Butane in the UK

• US Energy Information Administration

• World LP Gas Association (WLPGA)
Chapter 7

Butane

Butane (/ˈbjuːteɪn/) is an organic compound with the formula C4 H10 that is an alkane with four carbon atoms. Butane
is a gas at room temperature and atmospheric pressure. The term may refer to either of two structural isomers, n-
butane or isobutane (or “methylpropane”), or to a mixture of these isomers. In the IUPAC nomenclature, however,
“butane” refers only to the n-butane isomer (which is the isomer with the unbranched structure). Butanes are highly
flammable, colorless, easily liquefied gases. The name butane comes from the roots but- (from butyric acid) and -ane.

7.1 Isomers
Rotation about the central C-C bond produces two different conformations (trans and gauche) for n-butane.[4]

7.2 Reactions
When oxygen is plentiful, butane burns to form carbon dioxide and water vapor; when oxygen is limited, carbon
(soot) or carbon monoxide may also be formed.
When there is sufficient oxygen:

2 C4 H10 + 13 O2 → 8 CO2 + 10 H2 O

When oxygen is limited:

2 C4 H10 + 9 O2 → 8 CO + 10 H2 O

The maximum adiabatic flame temperature of butane with air is 2,243 K (1,970 °C; 3,578 °F).
n-Butane is the feedstock for DuPont's catalytic process for the preparation of maleic anhydride:

2 CH3 CH2 CH2 CH3 + 7 O2 → 2 C2 H2 (CO)2 O + 8 H2 O

n-Butane, like all hydrocarbons, undergoes free radical chlorination providing both 1-chloro- and 2-chlorobutanes, as
well as more highly chlorinated derivatives. The relative rates of the chlorination is partially explained by the differing
bond dissociation energies, 425 and 411 kJ/mol for the two types of C-H bonds.

7.3 Uses
Normal butane is mainly used for gasoline blending, as a fuel gas, either alone or in a mixture with propane, and as a
feedstock for the manufacture of ethylene and butadiene, a key ingredient of synthetic rubber. Isobutane is primarily
used by refineries to enhance (increase) the octane number of motor gasoline.[5][6][7][8]

83
84 CHAPTER 7. BUTANE

When blended with propane and other hydrocarbons, it may be referred to commercially as LPG, for liquified
petroleum gas. It is used as a petrol component, as a feedstock for the production of base petrochemicals in steam
cracking, as fuel for cigarette lighters and as a propellant in aerosol sprays such as deodorants.[9]
Very pure forms of butane, especially isobutane, can be used as refrigerants and have largely replaced the ozone
layer-depleting halomethanes, for instance in household refrigerators and freezers. The system operating pressure
for butane is lower than for the halomethanes, such as R-12, so R-12 systems such as in automotive air conditioning
systems, when converted to butane will not function optimally.
Butane is also used as lighter fuel for a common lighter or butane torch and is sold bottled as a fuel for cooking and
camping. In this form it is often mixed with small amounts of hydrogen sulfide and mercaptans which will give the
unburned gas an offensive smell easily detected by the human nose. In this way, butane leaks can easily be identified.
Both hydrogen sulfide and mercaptans, while considered poisons, have low boiling points and quickly vaporize when
not under pressure. Most commercially available butane also contains a certain amount of contaminant oil which can
be removed through filtration but which will otherwise leave a deposit at the point of ignition and may eventually
block the uniform flow of gas.
Cordless hair irons are usually powered by butane cartridges.[10]

7.4 Effects and health issues

Inhalation of butane can cause euphoria, drowsiness, narcosis, asphyxia, cardiac arrhythmia, fluctuations in blood
pressure, temporary memory loss and frostbite, and can result in death from asphyxiation and ventricular fibrillation.
Butane is the most commonly misused volatile substance in the UK, and was the cause of 52% of solvent related
deaths in 2000.[11] By spraying butane directly into the throat, the jet of fluid can cool rapidly to −20 °C (−4 °F) by
expansion, causing prolonged laryngospasm.[12] "Sudden sniffer’s death" syndrome, first described by Bass in 1970,[13]
is the most common single cause of solvent related death, resulting in 55% of known fatal cases.[12]
A small amount of nitrogen dioxide, a toxic gas, results from burning butane gas, along with any combustion in the
earths atmosphere, and represents a human health hazard from home heaters and stoves.[14]

7.5 See also

• Isobutane

• Dimethyl ether

• Volatile substance abuse

• Butane (data page)

• Butanone

• n-Butanol

• Liquefied petroleum gas

• Industrial gas

• Butane torch

7.6 References
[1] PubChem 7843

[2] W. B. Kay. “Pressure-Volume-Temperature Relations for n-Butane”. Standard Oil Company.

[3] “Safety Data Sheet, Material Name: N-Butane” (PDF). USA: Matheson Tri-Gas Incorporated. 5 February 2011. Retrieved
11 December 2011.
7.7. EXTERNAL LINKS 85

[4] Roman M. Balabin (2009). “Enthalpy Difference between Conformations of Normal Alkanes: Raman Spectroscopy Study
of n-Pentane and n-Butane”. J. Phys. Chem. A 113 (6): 1012–9. doi:10.1021/jp809639s. PMID 19152252.

[5] MarkWest Energy Partners, L.P. Form 10-K. Sec.gov

[6] Copano Energy, L.L.C. Form 10-K. Sec.gov. Retrieved on 2012-12-03.

[7] Targa Resources Partners LP Form10-k. Sec.gov. Retrieved on 2012-12-03.

[8] Crosstex Energy, L.P. FORM 10-K. Sec.gov

[9] A Primer on Gasoline Blending. An EPRINC Briefing Memorandum

[10] FAA: Hazardous Materials p. 4

[11] Field-Smith M, Bland JM, Taylor JC, et al. “Trends in death Associated with Abuse of Volatile Substances 1971–2004”.
Department of Public Health Sciences. London: St George’s Medical School.

[12] Ramsey J, Anderson HR, Bloor K, et al. (1989). “An introduction to the practice, prevalence and chemical toxicology of
volatile substance abuse”. Hum Toxicol 8 (4): 261–269. doi:10.1177/096032718900800403. PMID 2777265.

[13] Bass M. (1970). “Sudden sniffing death”. JAMA 212 (12): 2075–2079. doi:10.1001/jama.1970.03170250031004. PMID
5467774.

[14] Ghosn, Marwan; Flouty, Roula; Saliba, Najat A. (2005). “Emission of Nitrogen Dioxide from Butane Gas Heaters and
Stoves Indoors”. American Journal of Applied Sciences 2 (3): 707. doi:10.3844/ajassp.2005.707.710.

7.7 External links

• International Chemical Safety Card 0232

• NIOSH Pocket Guide to Chemical Hazards

Chapter 8

Pentane

Pentane is an organic compound with the formula C5 H12 — that is, an alkane with five carbon atoms. The term
may refer to any of three structural isomers, or to a mixture of them: in the IUPAC nomenclature, however, pen-
tane means exclusively the n-pentane isomer; the other two being called isopentane (methylbutane) and neopentane
(dimethylpropane). Cyclopentane is not an isomer of pentane.
Pentanes are components of some fuels and are employed as specialty solvents in the laboratory. Their properties are
very similar to those of butanes and hexanes.

8.1 Isomers

8.2 Industrial uses

Pentanes are some of the primary blowing agents used in the production of polystyrene foam and other foams. Usually,
a mixture of n-, i-, and increasingly cyclopentane is used for this purpose.
Because of its low boiling point, low cost, and relative safety, pentane is used as a working medium in geothermal
power stations. It is added into some refrigerant blends as well.
Pentanes are also used as an active ingredient in some pesticides.[3]

8.3 Laboratory use

Pentanes are relatively inexpensive and are the most volatile alkanes that are liquid at room temperature, so they are
often used in the laboratory as solvents that can be conveniently evaporated. However, because of their nonpolarity
and lack of functionality, they can only dissolve non-polar and alkyl-rich compounds. Pentanes are miscible with
most common nonpolar solvents such as chlorocarbons, aromatics, and ethers. They are also often used in liquid
chromatography.

8.4 Physical properties

The boiling points of the pentane isomers range from about 9 to 36 °C. As is the case for other alkanes, the more
branched isomers tend to have lower boiling points.
The same trend normally holds for the melting points of alkane isomers, and indeed that of isopentane is 30 °C lower
than that of n-pentane. However, the melting point of neopentane, the most heavily branched of the three, is 100
°C higher that of isopentane. The anomalously high melting point of neopentane has been attributed to the better
solid-state packing assumed to be possible with its tetrahedral molecule; but this explanation has been challenged on
account of it having a lower density than the other two isomers.[2]

86
8.5. REACTIONS 87

The branched isomers are more stable (have lower heat of formation and heat of combustion) than normal pentane.
The difference is 1.8 kcal/mol for isopentane, and 5 kcal/mol for neopentane.[4]
Rotation about two central single C-C bonds of n-pentane produces four different conformations.[5]

8.5 Reactions
Like other alkanes, pentanes are under standard room temperature and conditions largely unreactive - however, with
sufficient activation energy (i.e. an open flame), they get readily oxidized to form carbon dioxide and water:

C5 H12 + 8 O2 → 5 CO2 + 6 H2 O + heat/ energy

Like other alkanes, pentanes undergo free radical chlorination:

C5 H12 + Cl2 → C5 H11 Cl + HCl

Such reactions are unselective; with n-pentane, the result is a mixture of the 1-, 2-, and 3-chloropentanes, as well as
more highly chlorinated derivatives. Other radical halogenations can also occur.

8.6 References
[1] Record of n-Pentane in the GESTIS Substance Database from the IFA, accessed on 19 April 2011

[2] James Wei (1999), Molecular Symmetry, Rotational Entropy, and Elevated Melting Points. Ind. Eng. Chem. Res., volume
38 issue 12, pp. 5019–5027 doi:10.1021/ie990588m

[3] Milne, ed., G.W.A. (2005). Gardner’s Commercially Important Chemicals: Synonyms, Trade Names, and Properties. Hobo-
ken, New Jersey: John Wiley & Sons, Inc. p. 477. ISBN 978-0-471-73518-2.

[4] From the values listed at Standard enthalpy change of formation (data table).

[5] Roman M. Balabin (2009). “Enthalpy Difference between Conformations of Normal Alkanes: Raman Spectroscopy Study
of n-Pentane and n-Butane”. J. Phys. Chem. A 113 (6): 1012–9. doi:10.1021/jp809639s. PMID 19152252.

8.7 External links

• International Chemical Safety Card 0534 at ILO.org

• NIOSH Pocket Guide to Chemical Hazards at CDC.gov

• Phytochemical data for pentane at Ars-grin.gov
Chapter 9

Engine knocking

“Pinging” redirects here. For other uses, see Ping (disambiguation).

Knocking (also called knock, detonation, spark knock, pinging or pinking) in spark-ignition internal combustion
engines occurs when combustion of the air/fuel mixture in the cylinder does not start off correctly in response to
ignition by the spark plug, but one or more pockets of air/fuel mixture explode outside the envelope of the normal
combustion front.
The fuel-air charge is meant to be ignited by the spark plug only, and at a precise point in the piston’s stroke. Knock
occurs when the peak of the combustion process no longer occurs at the optimum moment for the four-stroke cycle.
The shock wave creates the characteristic metallic “pinging” sound, and cylinder pressure increases dramatically.
Effects of engine knocking range from inconsequential to completely destructive.
Knocking should not be confused with pre-ignition – they are two separate events. However, pre-ignition is usually
followed by knocking.

9.1 Normal combustion

Under ideal conditions the common internal combustion engine burns the fuel/air mixture in the cylinder in an orderly
and controlled fashion. The combustion is started by the spark plug some 10 to 40 crankshaft degrees prior to top dead
center (TDC), depending on many factors including engine speed and load. This ignition advance allows time for the
combustion process to develop peak pressure at the ideal time for maximum recovery of work from the expanding
gases.[1]
The spark across the spark plug’s electrodes forms a small kernel of flame approximately the size of the spark plug
gap. As it grows in size, its heat output increases, which allows it to grow at an accelerating rate, expanding rapidly
through the combustion chamber. This growth is due to the travel of the flame front through the combustible fuel air
mix itself, and due to turbulence which rapidly stretches the burning zone into a complex of fingers of burning gas
that have a much greater surface area than a simple spherical ball of flame would have. In normal combustion, this
flame front moves throughout the fuel/air mixture at a rate characteristic for the particular mixture. Pressure rises
smoothly to a peak, as nearly all the available fuel is consumed, then pressure falls as the piston descends. Maximum
cylinder pressure is achieved a few crankshaft degrees after the piston passes TDC, so that the force applied on the
piston (from the increasing pressure applied to the top surface of the piston) can give its hardest push precisely when
the piston’s speed and mechanical advantage on the crank shaft gives the best recovery of force from the expanding
gases, thus maximizing torque transferred to the crank shaft.[1][2]

9.2 Abnormal combustion

Main article: cool flame

When unburned fuel/air mixture beyond the boundary of the flame front is subjected to a combination of heat and

88
9.2. ABNORMAL COMBUSTION 89

pressure for a certain duration (beyond the delay period of the fuel used), detonation may occur. Detonation is
characterized by an instantaneous, explosive ignition of at least one pocket of fuel/air mixture outside of the flame
front. A local shockwave is created around each pocket and the cylinder pressure may rise sharply beyond its design
limits.
If detonation is allowed to persist under extreme conditions or over many engine cycles, engine parts can be damaged
or destroyed. The simplest deleterious effects are typically particle wear caused by moderate knocking, which may
further ensue through the engine’s oil system and cause wear on other parts before being trapped by the oil filter.
Severe knocking can lead to catastrophic failure in the form of physical holes punched through the piston or cylinder
head (i.e., rupture of the combustion chamber), either of which depressurizes the affected cylinder and introduces
large metal fragments, fuel, and combustion products into the oil system. Hypereutectic pistons are known to break
easily from such shock waves.[2]
Detonation can be prevented by any or all of the following techniques:

• the use of a fuel with high octane rating, which increases the combustion temperature of the fuel and reduces
the proclivity to detonate;

• enriching the air–fuel ratio which alters the chemical reactions during combustion, reduces the combustion
temperature and increases the margin above detonation;

• reducing peak cylinder pressure;

• decreasing the manifold pressure by reducing the throttle opening, boost pressure or

• reducing the load on the engine.

Because pressure and temperature are strongly linked, knock can also be attenuated by controlling peak combustion
chamber temperatures by compression ratio reduction, exhaust gas recirculation, appropriate calibration of the en-
gine’s ignition timing schedule, and careful design of the engine’s combustion chambers and cooling system as well
as controlling the initial air intake temperature.
The addition of certain materials such as lead and thallium will suppress detonation extremely well when certain fuels
are used. The addition of tetraethyllead (TEL), a soluble organolead compound added to gasoline was common until
it was discontinued for reasons of toxic pollution. Lead dust added to the intake charge will also reduce knock with
various hydrocarbon fuels. Manganese compounds are also used to reduce knock with petrol fuel.
Knock is less common in cold climates. As an aftermarket solution, a water injection system can be employed to
reduce combustion chamber peak temperatures and thus suppress detonation. Steam (water vapor) will suppress
knock even though no added cooling is supplied.
Certain chemical changes must first occur for knock to happen, hence fuels with certain structures tend to knock
easier than others. Branched chain paraffins tend to resist knock while straight chain paraffins knock easily. It has
been theorized that lead, steam, and the like interfere with some of the various oxidative changes that occur during
combustion and hence the reduction in knock.
Turbulence, as stated, has very important effect on knock. Engines with good turbulence tend to knock less than
engines with poor turbulence. Turbulence occurs not only while the engine is inhaling but also when the mixture
is compressed and burned. During compression/expansion “squish” turbulence is used to violently mix the air/fuel
together as it is ignited and burned which reduces knock greatly by speeding up burning and cooling the unburnt
mixture. One example of this is all modern side valve or flathead engines. A considerable portion of the head space
is made to come in close proximity of the piston crown, making for much turbulence near TDC. In the early days of
side valve heads this was not done and a much lower compression ratio had to be used for any given fuel. Also such
engines were sensitive to ignition advance and had less power.[2]
Knocking is more or less unavoidable in diesel engines, where fuel is injected into highly compressed air towards the
end of the compression stroke. There is a short lag between the fuel being injected and combustion starting. By this
time there is already a quantity of fuel in the combustion chamber which will ignite first in areas of greater oxygen
density prior to the combustion of the complete charge. This sudden increase in pressure and temperature causes the
distinctive diesel 'knock' or 'clatter', some of which must be allowed for in the engine design.
Careful design of the injector pump, fuel injector, combustion chamber, piston crown and cylinder head can reduce
knocking greatly, and modern engines using electronic common rail injection have very low levels of knock. Engines
using indirect injection generally have lower levels of knock than direct injection engine, due to the greater dispersal
90 CHAPTER 9. ENGINE KNOCKING

of oxygen in the combustion chamber and lower injection pressures providing a more complete mixing of fuel and
air. Diesels actually do not suffer exactly the same “knock” as gasoline engines since the cause is known to be only
the very fast rate of pressure rise, not unstable combustion. Diesel fuels are actually very prone to knock in gasoline
engines but in the diesel engine there is no time for knock to occur because the fuel is only oxidized during the
expansion cycle. In the gasoline engine the fuel is slowly oxidizing all the while it is being compressed before the
spark. This allows for changes to occur in the structure/makeup of the molecules before the very critical period of
high temp/pressure.[2]
An unconventional engine that makes use of detonation to improve efficiency and decrease pollutants is the Bourke
engine.

9.3 Pre-ignition
Pre-ignition (or preignition) in a spark-ignition engine is a technically different phenomenon from engine knocking,
and describes the event wherein the air/fuel mixture in the cylinder ignites before the spark plug fires. Pre-ignition is
initiated by an ignition source other than the spark, such as hot spots in the combustion chamber, a spark plug that
runs too hot for the application, or carbonaceous deposits in the combustion chamber heated to incandescence by
previous engine combustion events.
The phenomenon is also referred to as 'after-run', or 'run-on' or sometimes dieseling, when it causes the engine to
carry on running after the ignition is shut off. This effect is more readily achieved on carbureted gasoline engines,
because the fuel supply to the carburetor is typically regulated by a passive mechanical float valve and fuel delivery
can feasibly continue until fuel line pressure has been relieved, provided the fuel can be somehow drawn past the
throttle plate. The occurrence is rare in modern engines with throttle-body or electronic fuel injection, because the
injectors will not be permitted to continue delivering fuel after the engine is shut off, and any occurrence may indicate
the presence of a leaking (failed) injector.[3]
In the case of highly supercharged or high compression multi-cylinder engines particularly ones that use methanol
(or other fuels prone to pre-ignition) pre-ignition can quickly melt or burn pistons since the power generated by other
still functioning pistons will force the overheated ones along no matter how early the mix pre-ignites. Many engines
have suffered such failure where improper fuel delivery is present. Often one injector may clog while the others carry
on normally allowing mild detonation in one cylinder that leads to serious detonation, then pre-ignition.[4]
The challenges associated with pre-ignition have increased in recent years with the development of highly boosted
and “downspeeded” spark ignition engines. The reduced engine speeds allow more time for autoignition chemistry
to complete thus promoting the possibility of pre-ignition and so called “mega-knock”. Under these circumstances,
there is still significant debate as to the sources of the pre-ignition event.[5]
Pre-ignition and engine knock both sharply increase combustion chamber temperatures. Consequently, either ef-
fect increases the likelihood of the other effect occurring, and both can produce similar effects from the operator’s
perspective, such as rough engine operation or loss of performance due to operational intervention by a powertrain-
management computer. For reasons like these, a person not familiarized with the distinction might describe one by
the name of the other. Given proper combustion chamber design, pre-ignition can generally be eliminated by proper
spark plug selection, proper fuel/air mixture adjustment, and periodic cleaning of the combustion chambers.[1]

9.4 Causes of pre-ignition

Causes of pre-ignition include the following:[3]

• Carbon deposits form a heat barrier and can be a contributing factor to pre-ignition. Other causes include: An
overheated spark plug (too hot a heat range for the application). Glowing carbon deposits on a hot exhaust
valve (which may mean the valve is running too hot because of poor seating, a weak valve spring or insufficient
valve lash)

• A sharp edge in the combustion chamber or on top of a piston (rounding sharp edges with a grinder can
eliminate this cause)

• Sharp edges on valves that were reground improperly (not enough margin left on the edges)
9.5. DETONATION INDUCED PRE-IGNITION 91

• A lean fuel mixture

• An engine that is running hotter than normal due to a cooling system problem (low coolant level, slipping fan
clutch, inoperative electric cooling fan or other cooling system problem)

• Auto-ignition of engine oil droplets[5]

• Insufficient oil in the engine

9.5 Detonation induced pre-ignition

Because of the way detonation breaks down the boundary layer of protective gas surrounding components in the
cylinder, such as the spark plug electrode, these components can start to get very hot over sustained periods of
detonation and glow. Eventually this can lead to the far more catastrophic pre-Ignition as described above.
While it is not uncommon for an automobile engine to continue on for thousands of miles with mild detonation,
pre-ignition can destroy an engine in just a few strokes of the piston.

9.6 Knock detection

Due to the large variation in fuel quality, a large number of engines now contain mechanisms to detect knocking
and adjust timing or boost pressure accordingly in order to offer improved performance on high octane fuels while
reducing the risk of engine damage caused by knock while running on low octane fuels.
An early example of this is in turbo charged Saab H engines, where a system called Automatic Performance Control
was used to reduce boost pressure if it caused the engine to knock.[6]
Various monitoring devices are commonly utilized by tuners as a method of seeing and listening to the engine in order
to ascertain if a tuned vehicle is safe under load or used to re-tune a vehicle safely.

9.7 Knock prediction

Since the avoidance of knocking combustion is so important to development engineers, a variety of simulation tech-
nologies have been developed which can identify engine design or operating conditions in which knock might be
expected to occur. This then enables engineers to design ways to mitigate knocking combustion whilst maintaining
a high thermal efficiency.
Since the onset of knock is sensitive to the in-cylinder pressure, temperature and autoignition chemistry associated
with the local mixture compositions within the combustion chamber, simulations which account for all of these aspects
[7]
have thus proven most effective in determining knock operating limits and enabling engineers to determine the
most appropriate operating strategy.

9.8 References
[1] Jack Erjavec (2005). Automotive technology: a systems approach. Cengage Learning. p. 630. ISBN 1-4018-4831-1.

[2] H.N. Gupta (2006). Fundamentals of Internal Combustion Engines. PHI Learning. pp. 169–173. ISBN 81-203-2854-X.

[3] Daniel Hall (2007). Automotive Engineering. Global Media. p. 32. ISBN 81-904575-0-0.

[4] Barry Hollembeak (2004). Automotive fuels & emissions. Cengage Learning. p. 165. ISBN 1-4018-3904-5.

[5] “solutions for pre-ignition (“mega-knock”), misfire, extinction, flame propagation and conventional “knock”. cmcl innova-
tions, UK. Retrieved 12 June 2010.

[6] “Turbocharger with a brain”. Popular Science 221 (1): 85. July 1982.

[7] “Advanced simulation technologies”. cmcl innovations, UK. Retrieved 12 June 2010.
92 CHAPTER 9. ENGINE KNOCKING

9.9 Further reading

• Modeling of in-cylinder pressure oscillations under knocking conditions: A general approach based on the
damped wave equation, FUEL Journal, DOI:10.1016/j.fuel.2012.07.066, ISSN 0016-2361, Feb., 2013.
• Experimental Evaluation of Reduced Kinetic Models for the Simulation of Knock in SI Engines, SAE Technical
Paper n. 2011-24-0033, DOI: 10.4271/2011-24-0033, ISSN 0148-7191, Sep., 2011.

• Modeling Pressure Oscillations Under Knocking Conditions: A Partial Differential Wave Equation Approach,
SAE Technical Paper n. 2010-01-2185, DOI 10.4271/2010-01-2185, ISSN 0148-7191, Oct., 2010.

• Predictive combustion simulations for “downsized” direct injection spark-ignition engines: solutions for pre-
ignition (“mega-knock”), misfire, extinction, flame propagation and conventional “knock”, cmcl innovations,
accessed June 2010.
• Engine Basics: Detonation and Pre-Ignition, Allen W. Cline, accessed June 2007.

• Experimental Investigation on the Use of Ion Current on SI Engines for Knock Detection, SAE Technical Paper
n. 2009-01-2745, DOI 10.4271/2009-01-2745, ISSN 0148-7191, Nov., 2009.

• Charles Fayette Taylor, Internal Combustion Engine In Theory And Practice, Second Edition, Revised, Volume
2, MIT Press, 1985, Chapter 2 on “Detonation and Preignition”, pp 34–85, ISBN 9780262700276.

9.10 External links

• Pre-ignition and Detonation by Bob Hewitt (Misterfixit) Accessed June 2007
• NACA - Combustion and knock in a spark-ignition engine

• NACA - Ionization in the knock zone of an internal combustion engine

• NACA - Interdependence of various types of autoignition and knock

• Avweb - Detonation myths

• Misterfixit - What is detonation?

• Gasoline FAQ
Chapter 10

Octane rating

Octane rating or octane number is a standard measure of the performance of an engine or aviation fuel. The higher
the octane number, the more compression the fuel can withstand before detonating (igniting). In broad terms, fuels
with a higher octane rating are used in high performance petrol engines that require higher compression ratios. In
contrast, fuels with lower octane numbers (but higher cetane numbers) are ideal for diesel engines, because diesel
engines (also referred to as compression-ignition engines) do not compress the fuel but rather compress only air and
then inject the fuel into the air heated up by compression. Petrol engines (also referred to as gasoline engines) rely
on ignition of air and fuel compressed together as a mixture without ignition, which is then ignited at the end of the
compression stroke using spark plugs. Therefore, high compressibility of the fuel matters mainly for petrol engines.
Use of petrol (gasoline) with lower octane numbers may lead to the problem of engine knocking.[1]

10.1 Principles

10.1.1 The problem: pre-ignition and knocking

Main article: Engine knocking

In a normal spark-ignition engine, the air-fuel mixture is heated due to being compressed and is then triggered to
burn rapidly by the spark plug and ignition system. If it is heated or compressed too much, then it will explode
when triggered, or even self-ignite before the ignition system sparks. This causes much higher pressures than engine
components are designed for and can cause a “knocking” or “pinging” sound. Knocking can cause major engine
damage if severe.
The most typically used engine management systems found in automobiles today have a knock sensor that monitors
if knock is being produced by the fuel being used. In modern computer controlled engines, the ignition timing will
be automatically altered by the engine management system to reduce the knock to an acceptable level.

10.1.2 Isooctane as a reference standard

Octanes are a family of hydrocarbon that are typical components of gasoline. They are colourless liquids that boil
around 125 °C (260 °F). One member of the octane family, isooctane, is used as a reference standard to benchmark
the tendency of gasoline/petrol or LPG fuels to resist self-ignition.
The octane rating of gasoline is measured in a test engine and is defined by comparison with the mixture of 2,2,4-
trimethylpentane (iso-octane) and heptane that would have the same anti-knocking capacity as the fuel under test:
the percentage, by volume, of 2,2,4-trimethylpentane in that mixture is the octane number of the fuel. For example,
petrol with the same knocking characteristics as a mixture of 90% iso-octane and 10% heptane would have an octane
rating of 90.[2] A rating of 90 does not mean that the petrol contains just iso-octane and heptane in these proportions
but that it has the same detonation resistance properties (generally, petrol sold for common use never consists solely
of iso-octane and heptane; it is a mixture of many hydrocarbons and often other additives). Because some fuels are
more knock-resistant than pure iso-octane, the definition has been extended to allow for octane numbers greater than

93
94 CHAPTER 10. OCTANE RATING

Isooctane (upper) has an octane rating of 100 whereas n-heptane has an octane rating of 0.

100.
Octane ratings are not indicators of the energy content of fuels. (See Effects below and Heat of combustion). They
are only a measure of the fuel’s tendency to burn in a controlled manner, rather than exploding in an uncontrolled
manner. Where the octane number is raised by blending in ethanol, energy content per volume is reduced. Ethanol
BTUs can be compared with gasoline BTUs in heat of combustion tables.
It is possible for a fuel to have a Research Octane Number (RON) more than 100, because iso-octane is not the most
knock-resistant substance available. Racing fuels, avgas, LPG and alcohol fuels such as methanol may have octane
ratings of 110 or significantly higher. Typical “octane booster” gasoline additives include MTBE, ETBE, isooctane
and toluene. Lead in the form of tetraethyllead was once a common additive, but its use for fuels for road vehicles
has been progressively phased-out worldwide, beginning in the 1970s.[3]

10.2 Measurement methods

10.2.1 Research Octane Number (RON)

The most common type of octane rating worldwide is the Research Octane Number (RON). RON is determined
by running the fuel in a test engine with a variable compression ratio under controlled conditions, and comparing the
results with those for mixtures of iso-octane and n-heptane.

10.2.2 Motor Octane Number (MON)

Another type of octane rating, called Motor Octane Number (MON), is determined at 900 rpm engine speed
instead of the 600 rpm for RON.[1] MON testing uses a similar test engine to that used in RON testing, but with a
preheated fuel mixture, higher engine speed, and variable ignition timing to further stress the fuel’s knock resistance.
Depending on the composition of the fuel, the MON of a modern pump gasoline will be about 8 to 12 octane lower
than the RON, but there is no direct link between RON and MON. Pump gasoline specifications typically require
both a minimum RON and a minimum MON.
10.2. MEASUREMENT METHODS 95

A US gas station pump offering five different (R+M)/2 octane ratings

10.2.3 Anti-Knock Index (AKI) or (R+M)/2

In most countries, including Australia, New Zealand and all of those in Europe, the “headline” octane rating shown on
the pump is the RON, but in Canada, the United States, Brazil, and some other countries, the headline number is the
average of the RON and the MON, called the Anti-Knock Index (AKI), and often written on pumps as (R+M)/2).
It may also sometimes be called the Posted Octane Number (PON).

10.2.4 Difference between RON, MON, and AKI

Because of the 8 to 12 octane number difference between RON and MON noted above, the AKI shown in Canada
and the United States is 4 to 6 octane numbers lower than elsewhere in the world for the same fuel. This difference
between RON and MON is known as the fuel’s Sensitivity,[4] and is not typically published for those countries that
use the Anti-Knock Index labelling system.
See the table in the following section for a comparison.

10.2.5 Observed Road Octane Number (RdON)

Another type of octane rating, called Observed Road Octane Number (RdON), is derived from testing gasolines
in real world multi-cylinder engines, normally at wide open throttle. It was developed in the 1920s and is still reliable
today. The original testing was done in cars on the road but as technology developed the testing was moved to chassis
dynamometers with environmental controls to improve consistency.[5]
96 CHAPTER 10. OCTANE RATING

10.2.6 Aviation gasoline octane ratings

Gasoline used in piston aircraft common in general aviation have slightly different methods of measuring the octane
of the fuel. Similar to AKI, it has two different ratings, although it is referred to only by the lower of the two. One
is referred to as the “aviation lean” rating and is the same as the MON of the fuel up to 100.[6] The second is the
“aviation rich” rating and corresponds to the octane rating of a test engine under forced induction operation common
in high-performance and military piston aircraft. This utilizes a supercharger, and uses a significantly richer fuel/air
ratio for improved detonation resistance.[4]
The most commonly used current fuel, 100LL, has an aviation lean rating of 100 octane, and an aviation rich rating
of 130.[7]

10.3 Examples
The RON/MON values of n-heptane and iso-octane are exactly 0 and 100, respectively, by the definition of octane
rating. The following table lists octane ratings for various other fuels.[8][9]

10.4 Effects
Higher octane ratings correlate to higher activation energies: the amount of applied energy required to initiate com-
bustion. Since higher octane fuels have higher activation energy requirements, it is less likely that a given compression
will cause uncontrolled ignition, otherwise known as autoignition or detonation.
The compression ratio is directly related to power and to thermodynamic efficiency of an internal combustion engine
(see Otto-cycle). Engines with higher compression ratios develop more area under the Otto-Cycle curve, thus they
extract more energy from a given quantity of fuel.
During the compression stroke of an internal combustion engine, as the air-fuel mix is compressed its temperature
rises.
A fuel with a higher octane rating is less prone to auto-ignition and can withstand a greater rise in temperature
during the compression stroke of an internal combustion engine without auto-igniting, thus allowing more power to
be extracted from the Otto-Cycle.
If during the compression stroke the air-fuel mix reaches a temperature greater than the auto-ignition temperature
of the fuel, the fuel self or auto-ignites. When auto-ignition occurs (before the piston reaches the top of its travel)
the up-rising piston is then attempting to squeeze the rapidly heating fuel charge. This will usually destroy an engine
quickly if allowed to continue.
There are two types of induction systems on internal combustion engines: normally aspirated engine (air is sucked in
using the engine’s pistons), or forced induction engines (see supercharged or turbocharged engines).
In the case of the normally aspirated engine, at the start of the compression stroke the cylinder air / fuel volume is very
low, this translates into a low starting pressure. As the piston travels upward, abnormally high cylinder pressures may
result in the mixture auto-igniting or detonating, which is why conservative compression ratios are used in consumer
vehicles. In a forced induction engine where at the start of the compression stroke the cylinder pressure is already
raised (having a greater volume of air/fuel) Exp. 202kPa (29.4Psi) the starting pressure or air / fuel volume would
be 2 times that of the normally aspirated engine. This would translate into an effective compression ratio of 20:1 vs.
10:1 for the normally aspirated. This is why many forced induction engines have compression ratios in the 8:1 range.
Many high-performance engines are designed to operate with a high maximum compression, and thus demand fuels
of higher octane. A common misconception is that power output or fuel efficiency can be improved by burning fuel
of higher octane than that specified by the engine manufacturer. The power output of an engine depends in part on
the energy density of the fuel being burnt. Fuels of different octane ratings may have similar densities, but because
switching to a higher octane fuel does not add more hydrocarbon content or oxygen, the engine cannot develop more
power.
However, burning fuel with a lower octane rating than that for which the engine is designed often results in a reduction
of power output and efficiency. Many modern engines are equipped with a knock sensor (a small piezoelectric
microphone), which sends a signal to the engine control unit, which in turn retards the ignition timing when detonation
10.5. REGIONAL VARIATIONS 97

is detected. Retarding the ignition timing reduces the tendency of the fuel-air mixture to detonate, but also reduces
power output and fuel efficiency. Because of this, under conditions of high load and high temperature, a given
engine may have a more consistent power output with a higher octane fuel, as such fuels are less prone to detonation.
Some modern high performance engines are actually optimized for higher than pump premium (93 AKI in the US).
The 2001 - 2007 BMW M3 with the S54 engine is one such car. Car and Driver magazine tested a car using a
dynamometer, and found that the power output increased as the AKI was increased up to approximately 96 AKI.
Most fuel filling stations have two storage tanks (even those offering 3 or 4 octane levels): those motorists who
purchase intermediate grade fuels are given a mixture of higher and lower octane fuels. “Premium” grade is fuel
of higher octane, and the minimum grade sold is fuel of lower octane. Purchasing 91 octane fuel (where offered)
simply means that more fuel of higher octane is blended with commensurately less fuel of lower octane, than when
purchasing a lower grade. The detergents and other additives in the fuel are often, but not always, identical.
The octane rating was developed by chemist Russell Marker at the Ethyl Corporation in 1926. The selection of n-
heptane as the zero point of the scale was due to its availability in high purity. Other isomers of heptane produced
from crude oil have greatly different ratings.

10.5 Regional variations

The selection of octane ratings available at the pump can vary greatly from region to region.

• Australia: “regular” unleaded fuel is 91 RON, “premium” unleaded with 95 RON is widely available, and
98 RON fuel is also reasonably common. Shell used to sell 100 RON petrol (5% ethanol content) from a
small number of service stations, most of which are located in major cities (stopped in August 2008).[22]
United Petroleum sells 100 RON unleaded fuel (10% ethanol content) at a small number of its service stations
(originally only two, but it has now expanded to 67 outlets nationwide).[23][24] All fuel in Australia is unleaded
except for some aviation fuels.

• Bahrain: 91 and 95 (RON), standard in all petrol station in the country and advertised as (Jayyid) for Regular
or 91 and (Mumtaz) for Premium or 95.

• China: 93 and 97 (RON) are commonly offered. In limited areas higher rating such as 99 RON is available.
In some rural areas it can be difficult to find fuel with over 93 RON.

• Chile: 93, 95 and 97 RON are standard at almost all gas stations thorough Chile. The three types are unleaded.

• Colombia: “Ecopetrol”, Colombia’s monopoly of refining and distribution of gasoline establishes a minimum
AKI of 81 octanes for “Corriente” gasoline [25] and minimum AKI of 87 octanes for “Extra” gasoline.[26] (85
RON corriente, and 91 RON for extra)

• Costa Rica: RECOPE, Costa Rica’s distribution monopoly, establishes the following ratings: Plus 91 (at least
91 RON) and Super (at least 95 RON).[27]

• Croatia: All fuel stations offer unleaded “Eurosuper BS” (abbreviation “BS” meaning “no sulfur content”) 95
RON fuel, many also offer “Eurosuper Plus BS” 98 RON.[28][29] Some companies offer 100 RON fuel instead
of 98.[30]

• Cyprus: All fuel stations offer unleaded 95 and 98 RON and a few offer 100 RON as well.

• Denmark: 95 and 98 RON are common choices. Some varieties of low percentage Ethanol mixtures are offered
at larger gas stations. E85 is being implemented but has yet to be finalized in the parliament.

• Ecuador: “Extra” with 87 and “Super” with 92 (RON) are available in all fuel stations. “Extra” is the most
commoly used. All fuels are unleaded.[31]
98 CHAPTER 10. OCTANE RATING

• Egypt: Egyptian Fuel Stations had 90 RON until July 2014 where the Government found no use for it. Leaving
only 92 RON and 95 RON. 80 RON is found in a very limited amount of fuel stations as they are used only
for extremely old cars that cannot cope with high octane fuel. 95 RON in used by limit due to its high price
(more than twice the price of 92 RON).[32]

• Finland: 95 and 98 (RON), advertised as such, at almost all gas stations. Most cars run on 95, but 98 is
available for vehicles that need higher octane fuel, or older models containing parts easily damaged by high
ethanol content. Shell offers V-Power, advertised as “over 99 octane”, instead of 98. In the beginning of 2011
95 RON was replaced by 95E10 containing 10% ethanol, and 98 RON by 98E5, containing 5% ethanol. ST1
also offers RE85 on some stations, which is 85% ethanol made from biodegradable waste (from which the
advertised name “ReFuel” comes). RE85 is only suitable for flexifuel cars that can run on high-percentage
ethanol.[33]

• Germany: “Super E10” 95 RON and “Super Plus E5” 98 RON are available practically everywhere. Big
suppliers such as Shell or Aral offer 100 RON gasoline (Shell V-Power, Aral Ultimate) at almost every fuel
station. “Normal” 91 RON is only rarely offered because lower production amounts make it more expensive
than “Super” 95 RON. Due to a new European Union law, gas stations are being required to offer a minimum
rate of the new mixture of “Super” 95 RON with up to 10% Ethanol branded as “Super E10”. Producers are
discontinuing “Super E5” 95 RON with <5% Ethanol so cars that are unable to use E10 must use 98 RON
petrol instead.

• Greece (Hellas): 95 RON (standard unleaded), 97+ & 100 RON unleaded offered by some companies (e.g.
EKO, Shell, BP). Also available Super LRP 96 RON for older (non-catalytic) vehicles.

• Hong Kong: only 98 RON is available in the market. There have been calls to re-introduce 95 RON, but the
calls have been rejected by all petrol station chains, citing that 95 RON was phased out because of market
forces.

• India: India’s ordinary and premium petrols are of 91 RON. The premium petrols are generally ordinary fuels
with additives, that do not really change the octane value. Two variants, “Speed 93” and “Speed 97”, were
launched, with RON values of 93 and 97. India’s economy-class vehicles usually have compression ratios
under 10:1, thus enabling them to use lower-octane petrol without engine knocking.

• Indonesia: Indonesia’s “Premium” petrol rated at 88 RON and being subsidized it cost only about US$0.65/liter.
Other options are “Pertamax” rated at 92 RON and the “Pertamax Plus” rated at RON 95. “Pertamax Racing
Fuel”, a bioethanol flexfuel rated at RON 100 (sold in gallon can container only). Total and Shell stations only
sell RON 92 and 95 gasoline.

• Ireland: 95 RON “unleaded” is the only petrol type available through stations, although E5 (99 RON) is be-
coming more commonplace.

• Italy: 95 RON is the only compulsory gasoline offered (verde, “green”), only a few fuel stations (Agip, IP,
IES, OMV) offer 98 RON as the premium type, many Shell and Tamoil stations close to the cities offer also
V-Power Gasoline rated at 100 RON. Recently Agip introduced “Blu Super+", a 100 RON gasoline.

• Israel: 95 RON & 98 RON are normally available at most petrol stations. 96 RON is also available at a large
number of gas stations but 95 RON is more preferred because it’s cheaper and performance differences aren't
very wide and noticeable. “Regular” fuel is 95 RON. All variants are unleaded.

• Japan: Since 1986, “regular” is >=89 RON, and “high octane” is >=96 RON, lead free. Those values are
defined in standard JIS K 2202. Sometimes “high octane” is sold under different names, such as “F-1”.

• Latvia: 95 RON and 98 RON widely available.

• Lebanon: 95 RON and 98 RON are widely available.

10.5. REGIONAL VARIATIONS 99

• Lithuania: 92 RON, 95 RON and 98 RON widely available. In “LUKOIL” gas stations E85 (bioethanol)
gasoline, 98E15 (15% of ethanol), 98E25 (25% of ethanol) are available.

• Malaysia: Had RON 92 until September 2009. Replaced with “regular” unleaded fuel Ron 95 RON, “pre-
mium” fuel is rated at 97 RON (but for Shell 97 RON is V-Power 97, and Shell’s V-Power Racing is rated at
min 97 RON.)[34]

• México: Pemex Magna (87 AKI) is sold as a “regular” fuel and is available at every station. And Pemex
Premium (92 AKI) is sold at almost all gas stations. Both variants are unleaded.

• Mongolia: 92 RON and 95 RON (advertised as A92 and A95 respectively) are available at nearly all stations
while slightly fewer stations offer 80 RON (advertised as A80). 98 RON (advertised as A98) is available in
select few stations.

• Montenegro: 95 RON is sold as a “regular” fuel. As a “premium” fuel, 98 RON is sold. Both variants are
unleaded.

• Netherlands: 95 RON “Euro” is sold at every station, whereas 98 RON “Super Plus” is being phased out in
favor of “premium” fuels, which are all 95 RON fuels with extra additives. Shell V-Power is a 97 RON (labelled
as 95 due to the legalities of only using 95 or 98 labelling), some independent tests have shown that one year
after introduction it was downgraded to 95 RON, whereas in neighboring Germany Shell V-Power consists of
the regular 100 RON fuel.

• New Zealand: 91 RON “Regular” and 95 RON “Premium” are both widely available. 98 RON is available
instead of 95 RON at some (BP, Mobil, Gull) service stations in larger urban areas.

• Philippines: A brand of Petron, Petron Blaze is rated at 100 RON (the only brand of gasoline in the Philippines
without an ethanol blend). Other “super premium” brands like Petron XCS, Caltex Gold, Shell V-Power are
rated at 95-97 RON, while Petron Xtra Unleaded, Caltex Silver, and Shell Super Unleaded are rated at 93
RON.

• Poland: Eurosuper 95 (RON 95) is sold in every gas station. Super Plus 98 (RON 98) is available in most sta-
tions, sometimes under brand (Orlen - Verva, BP - Ultimate, Shell - V-Power) and usually containing additives.
Shell offers V-Power Racing fuel which is rated RON 100.

• Portugal: 95 RON “Euro” is sold in every station and 98 RON “Super” being offered in almost every station.

• Russia and CIS countries: 80 RON (76 MON) is the minimum available, the standard is 92 RON and 95 RON.
98 RON is available on some stations but it’s usually quite expensive compared to the lower octane rating fuels.

• Saudi Arabia: Two types of fuel are available at all gas stations in Saudi Arabia. “Premium 91” (RON 91)
where the pumps are coloured green, and “Super Premium 95” (RON 95) where the pumps are coloured red.
While gas stations in Saudi Arabia are privatized, the prices are regulated by the authorities and have a fixed
at S.A.R. 0.45 (U.S. $0.12) and S.A.R. 0.60 (U.S. $0.16) per litre respectively. Prior to 2006, only Super
Premium RON 95 was available and the pumps weren't coloured in any specific order. The public didn't know
what Octane rating was, therefore big educating campaigns were spread, telling the people to use the “red gas”
only for high end cars, and save money on using the “green gas” for regular cars and trucks.

• Singapore: All four providers, Caltex, ExxonMobil, SPC and Shell have 3 grades of petrol. Typically, these
are 92, 95, and 98 RON. However, since 2009, Shell has removed 92 RON.

• South Africa: “regular” unleaded fuel is 95 RON in coastal areas. Inland (higher elevation) “regular” unleaded
fuel is 93 RON; once again most fuel stations optionally offer 95 RON.

• Spain: 95 RON “Euro” is sold in every station with 98 RON “Super” being offered in most stations. Many
stations around cities and highways offer other high-octane “premium” brands.
100 CHAPTER 10. OCTANE RATING

• Sri Lanka: In Ceypetco filling stations, 92 RON is the regular petrol and 95 RON is called 'Super Petrol',[35]
which comes at a premium price. In LIOC filling stations, 90 RON remains as regular petrol and 92 RON is
available as 'Premium Petrol'. The cost of premium petrol is lower than the cost of super petrol. (Sri Lanka
switched their regular petrol from 90 RON to 92 RON on January 1, 2014)

• Sweden: 95 RON, 98 RON and E85 are widely available.

• Taiwan: 92 RON, 95 RON and 98 RON are widely available at gas stations in Taiwan.

• Thailand: 91 RON and 95 RON are widely available. 91 RON benzine/petrol withdrawn on Jan 1st 2013 to
increase uptake of gasohol fuels.

• Trinidad and Tobago: 92 RON (Super) and 95 RON (Premium) are widely available.

• Turkey: 95 RON and 98 RON are widely available in gas stations. 92 RON (Regular) has been dropped in
2006.

• Ukraine: the standard gasoline is 95 RON, but 92 RON gasoline is also widely available and popular as a less
expensive replacement for 95 RON gasoline. 80 RON gasoline is available for old cars and motorcycles.

• United Kingdom: 'regular' petrol has an octane rating of 95 RON, with 97 RON fuel being widely available
as the Super Unleaded. Tesco and Shell both offer 99 RON fuel. In April 2006, BP started a public trial of
the super-high octane petrol BP Ultimate Unleaded 102, which as the name suggests, has an octane rating of
102 RON.[36] Although BP Ultimate Unleaded (with an octane rating of 97 RON) and BP Ultimate Diesel
are both widely available throughout the UK, BP Ultimate Unleaded 102 was available throughout the UK in
only 10 filling stations, and was priced at about two and half times more than their 97 RON fuel. In March
2010, BP stopped sales of Ultimate Unleaded 102, citing the closure of their specialty fuels manufacturing
facility.[37] Shell V-Power is also available, but in a 99 RON octane rating, and Tesco fuel stations also supply
the Greenergy produced 99 RON “Momentum99 ".

• United States: in the US octane rating is displayed in AKI. In most areas, the standard grades are 87, 89-90 and
91-94 AKI.[38] In the Rocky Mountain (high elevation) states, 85 AKI (90 RON) is the minimum octane, and
91 AKI (95 RON) is the maximum octane available in fuel.[39] The reason for this is that in higher-elevation
areas, a typical naturally aspirated engine draws in less air mass per cycle because of the reduced density of the
atmosphere. This directly translates to less fuel and reduced absolute compression in the cylinder, therefore
deterring knock. It is safe to fill a carbureted car that normally takes 87 AKI fuel at sea level with 85 AKI
fuel in the mountains, but at sea level the fuel may cause damage to the engine. A disadvantage to this strategy
is that most turbocharged vehicles are unable to produce full power, even when using the “premium” 91 AKI
fuel. In some east coast states, up to 94 AKI (98 RON) is available.[40] As of January, 2011, over 40 states
and a total of over 2500 stations offer ethanol-based E-85 fuel with 105 AKI.[41] Often, filling stations near US
racing tracks will offer higher octane levels such as 100 AKI .
• Venezuela: 91 RON and 95 RON gasoline is available nationwide, in all PDV gas stations. 95 RON petrol is
the most widely used in the country, although most cars in Venezuela would work with 91 RON gasoline. This
is because petrol prices are heavily subsidized by the government (0.$083 per gallon 95 RON,vs 0.$061 per
gallon 91 RON). All gasoline in Venezuela is unleaded.

• Vietnam: 92 is in every gas station and 95 is in the urban areas.

• Zimbabwe: 93 octane available with no other grades of fuels available, E10 which is an ethanol blend of fuel
at 10% ethanol is available the octane rating however is still to be tested and confirmed but it is assumed that
its around 95 Octane. E85 available from 3 outlets with an octane rating AKI index of between 102-105
depending on the base petrol the Ethanol is blended with.

10.6 See also

• Avgas
• Cetane number
10.7. REFERENCES 101

10.7 References
[1] Werner Dabelstein, Arno Reglitzky, Andrea Schütze and Klaus Reders “Automotive Fuels” in Ullmann’s Encyclopedia of
Industrial Chemistry 2007, Wiley-VCH, Weinheim.doi:10.1002/14356007.a16_719.pub2

[2] Kemp, Kenneth W.; Brown, Theodore; Nelson, John D. (2003). Chemistry: the central science. Englewood Cliffs, N.J:
Prentice Hall. p. 992. ISBN 0-13-066997-0.

[3] “Leaded Gas Phaseout”. U.S. EPA, Region 10. June 1995. Retrieved 2012-06-15.

[4] http://www.vintagebonanza.com/octane.htm

[5] http://www.runyard.org/jr/CFR/OctaneExplanation.htm

[6] http://www.txideafarm.com/unpublished_blend_paper.pdf

[7] http://www.aviation-fuel.com/pdfs/avgas100llspecsastmd910_2011.pdf

[8] Petroleum and Coal, Purdue

[9] Balaban, Alexandru T. (1983). “Topological Indices based on Topological Distances in Molecular Graphs” (PDF). Pure
and Applied Chemistry (IUPAC) 55 (2): 199–206. doi:10.1351/pac198855020199.

[10] Johnson Operation and Maintenance Manual, 1999

[11]

[12] Shell phases out V-Power Racing fuel (100 RON) – MRT

[13] Daniel, Ritchie (2012). "'Combustion performance of 2,5-dimethylfuran blends using dual-injection compared to direct-
injection in an SI engine'". Applied Energy 98: 59–68. doi:10.1016/j.apenergy.2012.02.073.

[14] Octane & Other Gasoline Basics

[15] Exxon Mobil Avgas product description

[16] Changes in Gasoline IV, sponsored by Renewable Fuels Foundation

[17] Energy Citations Database (ECD)

[18] BP Ultimate 102

[19] A. T. Balaban, L. B. Kier, and N. Josh, MATCH (Commun. Math. Chem.) 28 (1992) 13–27.

[20] Eyidogan, Muharrem (2010). "'Impact of alcohol–gasoline fuel blends on the performance and combustion characteristics
of an SI engine'". Fuel 89 (10): 2713–2720. doi:10.1016/j.fuel.2010.01.032.

[21] http://biofuel.org.uk/bioalcohols.html

[22] Shell V-Power

[23] http://www.unitedpetroleum.com.au/index.asp?pgID=65

[24] http://www.unitedpetroleum.com.au/distributor-premium100-locations.asp

[25] http://www.ecopetrol.com.co/contenido.aspx?catID=216&conID=37366

[26] http://www.ecopetrol.com.co/contenido.aspx?catID=216&conID=37367

[27] https://www.recope.go.cr/wp-content/uploads/2013/07/Manual_Productos.pdf

[28] http://www.ina.hr/default.aspx?id=204. Missing or empty |title= (help)

[29] http://www.lukoil.hr. Missing or empty |title= (help)

[30] http://www.crodux-derivati.hr/cijene-goriva/. Missing or empty |title= (help)

[31] http://www.arch.gob.ec/index.php/descargas/leyes-y-reglamentos/doc_download/292-norma-inen-935-2012.html

[32]

[33] VTT ja St1 kehittävät uutta vähäpäästöistä liikennepolttoainetta, VTT

102 CHAPTER 10. OCTANE RATING

[34] http://www.petrolworld.com/asia-headlines/malaysia-to-phase-out-ron-92-petrol-in-2009.html

[35] http://www.ceypetco.gov.lk/Ceypetco_Products.htm

[36] http://www.bp.com/liveassets/bp_internet/bp_ultimate/STAGING/brand_assets/downloads_pdfs/pq/bp_ultimate_uk_102_
final_press_release.pdf

[37] http://www.bp.com/sectiongenericarticle.do?categoryId=6621&contentId=7060376

[38] http://driving-tests.org/beginner-drivers/types-and-grades-of-fuel/

[39] http://www.aaa.com/aaa/006/EnCompass/2007/mar/mar_AutoTalk.htm

[40] Products – Retail Marketing

[41] Growth Energy Market Development

10.8 Further reading

• SAE standard J 1297 Alternative Automotive Fuels, Sept 2002

• Khoo, Kenny K. Understanding Octane and its Related Components. Yellowknife: Smithsonian Press, 2006.

10.9 External links

Octane ratings of some hydrocarbons

• Petroleum and Coal

• Gasoline Refining and Testing

Information in general

• Why are Octane levels important

• Gasoline FAQ
• How Octane Works at HowStuffWorks.com
Chapter 11

Cetane number

Cetane number or CN is an indicator of the combustion speed of diesel fuel. It is an inverse of the similar octane
rating for gasoline (petrol). The CN is an important factor in determining the quality of diesel fuel, but not the
only one; other measurements of diesel’s quality include (but are not limited to) energy content, density, lubricity,
cold-flow properties and sulphur content.[1]

11.1 Definition
Cetane number or CN is an inverse function of a fuel’s ignition delay, and the time period between the start of injection
and the first identifiable pressure increase during combustion of the fuel. In a particular diesel engine, higher cetane
fuels will have shorter ignition delay periods than lower Cetane fuels. Cetane numbers are only used for the relatively
light distillate diesel oils. For heavy (residual) fuel oil two other scales are used CCAI and CII.
In short, the higher the Cetane number the more easily the fuel will combust in a compression setting (such as a
diesel engine). The characteristic diesel “knock” occurs when fuel that has been injected into the cylinder ignites
after a delay causing a late shock wave. Minimizing this delay results in less unburned fuel in the cylinder and less
intense knock. Therefore higher-cetane fuel usually causes an engine to run more smoothly and quietly. This does
not necessarily translate into greater efficiency, although it may in certain engines.

11.2 Typical values

Generally, diesel engines operate well with a CN from 40 to 55. Fuels with higher cetane number have shorter ignition
delays, providing more time for the fuel combustion process to be completed. Hence, higher speed diesel engines
operate more effectively with higher cetane number fuels.
In Europe, diesel cetane numbers were set at a minimum of 38 in 1994 and 40 in 2000. The current standard for
diesel sold in European Union, Iceland, Norway and Switzerland is set in EN 590, with a minimum cetane index of
46 and a minimum cetane number of 51. Premium diesel fuel can have a cetane number as high as 60.[2]
In North America, most states adopt ASTM D975 as their diesel fuel standard and the minimum cetane number is
set at 40, with typical values in the 42-45 range. Premium diesels may or may not have higher cetane, depending on
the supplier. Premium diesel often use additives to improve CN and lubricity, detergents to clean the fuel injectors
and minimize carbon deposits, water dispersants, and other additives depending on geographical and seasonal needs..
California diesel fuel has a minimum cetane of 53.[3]

11.3 Additives
Alkyl nitrates (principally 2-ethylhexyl nitrate[4] ) and di-tert-butyl peroxide are used as additives to raise the cetane
number.

103
104 CHAPTER 11. CETANE NUMBER

11.4 Alternative fuels

Biodiesel from vegetable oil sources have been recorded as having a cetane number range of 46 to 52, and animal-fat
based biodiesels cetane numbers range from 56 to 60.[5] Dimethyl ether is a potential diesel fuel as it has a high cetane
rating (55-60) and can be produced as a biofuel.[6]

11.5 Chemical relevance

Cetane is the chemical compound with chemical formula n-C16 H34 , today named hexadecane according to IUPAC
rules. It is an unbranched alkane, a saturated hydrocarbon chain with no cycles. Cetane ignites very easily under
compression, so it was assigned a cetane number of 100, while alpha-methyl naphthalene was assigned a cetane
number of 0. All other hydrocarbons in diesel fuel are indexed to cetane as to how well they ignite under compression.
The cetane number therefore measures how quickly the fuel starts to burn (auto-ignites) under diesel engine conditions.
Since there are hundreds of components in diesel fuel, with each having a different cetane quality, the overall cetane
number of the diesel is the average cetane quality of all the components (strictly speaking high-cetane components
will have disproportionate influence, hence the use of high-cetane additives).

11.6 Measuring cetane number

Accurate measurements of the cetane number are rather difficult, as it requires burning the fuel in a rare diesel engine
called a Cooperative Fuel Research (CFR) engine, under standard test conditions. The operator of the CFR engine
uses a hand-wheel to increase the compression ratio (and therefore the peak pressure within the cylinder) of the
engine until the time between fuel injection and ignition is 2.407ms. The resulting cetane number is then calculated
by determining which mixture of cetane (hexadecane) and isocetane (2,2,4,4,6,8,8-heptamethylnonane) will result in
the same ignition delay.

11.6.1 Ignition Quality Tester (IQT)

Another reliable method of measuring the derived cetane number (DCN) of diesel fuel is the Ignition Quality Tester
(IQT). This instrument applies a simpler, more robust approach to CN measurement than the CFR. Fuel is injected
into a constant volume combustion chamber at approximately 575 °C and 310 psi. The time between the start of
injection and the recovery of the combustion chamber pressure to 310 psi is defined as the ignition delay. This
measured ignition delay is then used to calculate the DCN of the fuel. The fuel’s DCN is then calculated using an
empirical inverse relationship to ignition delay. Because of the reproducibility, material cost, and speed of the IQT,
this has been the definitive source for DCN measurements of fuels for since the late 2000s. [7] [8] [9]

11.6.2 Fuel ignition tester

Another reliable method of measuring the derived cetane number of diesel fuel is the Fuel Ignition Tester (FIT). This
instrument applies a simpler, more robust approach to CN measurement than the CFR. Fuel is injected into a constant
volume combustion chamber in which the ambient temperature is approximately 575 °C. The fuel combusts, and the
high rate of pressure change within the chamber defines the start of combustion. The ignition delay of the fuel can
then be calculated as the time difference between the start of fuel injection and the start of combustion. The fuel’s
derived cetane number can then be calculated using an empirical inverse relationship to ignition delay.

11.6.3 Cetane index

Another method that fuel-users control quality is by using the cetane index (CI), which is a calculated number based
on the density and distillation range of the fuel. There are various versions of this, depending on whether metric or
Imperial units are used, and how many distillation points are used. These days most oil companies use the '4-point
method', ASTM D4737, based on density, 10% 50% and 90% recovery temperatures. The '2-point method' is defined
in ASTM D976, and uses just density and the 50% recovery temperature. This 2-point method tends to overestimate
cetane index and is not recommended. Cetane index calculations can not account for cetane improver additives and
11.7. SEE ALSO 105

therefore do not measure total cetane number for additized diesel fuels. Diesel engine operation is primarily related
to the actual cetane number and the cetane index is simply an estimation of the base (unadditized) cetane number.

11.6.4 Industry standards

The industry standards for measuring cetane number are ASTM D-613 (ISO 5165) for the CFR engine, D-6890 for
the IQT, and D-7170 for the FIT.

11.7 See also

• NExBTL

• Octane rating

11.8 References
[1] Werner Dabelstein, Arno Reglitzky, Andrea Schütze and Klaus Reders “Automotive Fuels” in Ullmann’s Encyclopedia of
Industrial Chemistry, 2007, Wiley-VCH, Weinheim.doi:10.1002/14356007.a16_719.pub2

[2] bosch.de (German)

[3] http://www.arb.ca.gov/enf/fuels/dieselspecs.pdf

[4] dorfketal.com

[5] biodiesel.org

[6] Olah, G.A.; Goeppert, A.; Prakash, G.K. (2006). “11”. Beyond Oil and Gas: The Methanol Economy.

[7] Heyne, Kirby, Boehman, Energy & Fuels, 2009. DOI: 10.1021/ef900715m

[8] Stephen Dooley, Sang Hee Won, Joshua Heyne, Tanvir I. Farouk, Yiguang Ju, Frederick L. Dryer, Kamal Kumar, Xin
Hui, Chih-Jen Sung, Haowei Wang, Matthew A. Oehlschlaeger, Venkatesh Iyer, Suresh Iyer, Thomas A. Litzinger, Robert
J. Santoro, Tomasz Malewicki, Kenneth Brezinsky, The experimental evaluation of a methodology for surrogate fuel for-
mulation to emulate gas phase combustion kinetic phenomena, Combustion and Flame, 2012, http://dx.doi.org/10.1016/
j.combustflame.2011.11.002.

[9] Stephen Dooley, Sang Hee Won, Marcos Chaos, Joshua Heyne, Yiguang Ju, Frederick L. Dryer, Kamal Kumar, Chih-Jen
Sung, Haowei Wang, Matthew A. Oehlschlaeger, Robert J. Santoro, Thomas A. Litzinger, A jet fuel surrogate formulated
by real fuel properties, Combustion and Flame, 2010, http://dx.doi.org/10.1016/j.combustflame.2010.07.001.

11.9 Further reading

• John B. Heywood (1988). Internal Combustion Engine Fundamentals. McGraw Hill. ISBN 0-07-100499-8.
• Keith Owen, Trevor Coley SAE (1995). Automotive Fuels Reference Book. ISBN 1-56091-589-7.

11.10 External links

• Article by Bruce Hamilton
• Explanation of Cetane from BP
Chapter 12

Flash point

For other uses, see Flashpoint.

The flash point of a volatile material is the lowest temperature at which it can vaporize to form an ignitable mixture
in air. Measuring a flash point requires an ignition source. At the flash point, the vapor may cease to burn when the
ignition source is removed.
The flash point is not to be confused with the autoignition temperature (which does not require an ignition source) or
with the fire point (the temperature at which the vapor continues to burn after being ignited).
Neither the flash point nor the fire point is dependent on the temperature of the ignition source, which is much higher.

12.1 Liquids
The flash point is a descriptive characteristic that is used to distinguish flammable liquids (such as liquid fuel) from
combustible liquids.
It is also used to characterize the fire hazards of liquids. Liquids which have a flash point less than 37.8 or 60.5 °C
(100.0 or 140.9 °F), depending on the standard that is used, are called flammable — whereas liquids having a flash
point above that temperature are called combustible.[1]

12.2 Mechanism
Every liquid has a vapor pressure, which is a function of that liquid’s temperature. As the temperature increases, the
vapor pressure increases. As the vapor pressure increases, the concentration of vapor of the flammable liquid in the
air increases. Hence, temperature determines the concentration of vapor of the flammable liquid in the air.
A certain concentration of vapor in the air is necessary to sustain combustion, and that concentration is different for
each flammable liquid. The flash point of a flammable liquid is the lowest temperature at which there will be enough
flammable vapor to ignite when an ignition source is applied.

12.3 Measurement
There are two basic types of flash point measurement: open cup and closed cup.
In open cup devices the sample is contained in an open cup which is heated, and at intervals a flame is brought over
the surface. The measured flash point will actually vary with the height of the flame above the liquid surface, and at
sufficient height the measured flash point temperature will coincide with the fire point. The best known example is
the Cleveland open cup (COC).
There are two types of closed cup testers: non-equilibrium, such as Pensky-Martens where the vapors above the
liquid are not in temperature equilibrium with the liquid, and equilibrium, such as Small Scale (commonly known as

106
12.3. MEASUREMENT 107

Automatic flash point tester according to Pensky-Martens closed cup method with an integrated fire extinguisher.

Setaflash) where the vapors are deemed to be in temperature equilibrium with the liquid. In both these types the cups
are sealed with a lid through which the ignition source can be introduced. Closed cup testers normally give lower
values for the flash point than open cup (typically 5–10 °C or 9–18 °F lower) and are a better approximation to the
temperature at which the vapor pressure reaches the lower flammable limit.
The flash point is an empirical measurement rather than a fundamental physical parameter. The measured value
will vary with equipment and test protocol variations, including temperature ramp rate (in automated testers), time
allowed for the sample to equilibrate, sample volume and whether the sample is stirred.
Methods for determining the flash point of a liquid are specified in many standards. For example, testing by the
108 CHAPTER 12. FLASH POINT

Pensky-Martens closed cup method is detailed in ASTM D93, IP34, ISO 2719, DIN 51758, JIS K2265 and AFNOR
M07-019. Determination of flash point by the Small Scale closed cup method is detailed in ASTM D3828 and D3278,
EN ISO 3679 and 3680, and IP 523 and 524.
CEN/TR 15138 Guide to Flash Point Testing and ISO TR 29662 Guidance for Flash Point Testing cover the key
aspects of flash point testing.

12.4 Examples
Gasoline (petrol) is a fuel for use in a spark-ignition engine. The fuel is mixed with air within its flammable limits
and heated above its flash point, then ignited by the spark plug. To ignite, the fuel must have a low flash point, but in
order to avoid preignition caused by residual heat in a hot combustion chamber, the fuel must have a high autoignition
temperature.
Diesel fuel flash points vary between 52 and 96 °C (126 and 205 °F). Diesel is suitable for use in a compression-
ignition engine. Air is compressed until it has been heated above the autoignition temperature of the fuel, which is
then injected as a high-pressure spray, keeping the fuel-air mix within flammable limits. In a diesel-fueled engine,
there is no ignition source (such as the spark plugs in a gasoline engine). Consequently, diesel fuel must have a high
flash point and a low autoignition temperature.
Jet fuel flash points also vary with the composition of the fuel. Both Jet A and Jet A-1 have flash points between
38 and 66 °C (100 and 151 °F), close to that of off-the-shelf kerosene. Yet both Jet B and JP-4 have flash points
between −23 and −1 °C (−9 and 30 °F).

12.5 Standardization
Flash points of substances are measured according to standard test methods. These test methods define the apparatus
required to carry out the measurement, key test parameters, the procedure for the operator or automated apparatus
to follow, and the precision of the test method.
Standard test methods are written and controlled by a number of national and international committees and organi-
zations. The three main bodies are the CEN / ISO Joint Working Group on Flash Point (JWG-FP), ASTM D02.8B
Flammability Section and the Energy Institute’s TMS SC-B-4 Flammability Panel.

12.6 See also

• Autoignition temperature

• Fire point
• Material Safety Data Sheet (MSDS)

• Petrotest

12.7 References
[1] NFPA 30: Flammable and Combustible Liquids Code, 2012 Edition Retrieved January 4, 2014.

[2] “Ethanol MSDS”. Retrieved January 4, 2014.

[3] “Flash Point — Fuels”. Retrieved January 4, 2014.

[4] “Fuels and Chemicals — Autoignition Temperatures”. Retrieved January 4, 2014.

12.7. REFERENCES 109

Automatic Pensky-Martens closed cup tester with an integrated fire extinguisher

Chapter 13

Autoignition temperature

The autoignition temperature or kindling point of a substance is the lowest temperature at which it will spontaneously
ignite in a normal atmosphere without an external source of ignition, such as a flame or spark. This temperature is
required to supply the activation energy needed for combustion. The temperature at which a chemical will ignite
decreases as the pressure or oxygen concentration increases. It is usually applied to a combustible fuel mixture.
Autoignition temperatures of liquid chemicals are typically measured using a 500 mL flask placed in a temperature
controlled oven in accordance with the procedure described in ASTM E659.[1]
When measured for plastics, autoignition temperature can also be measured under elevated pressure and at 100%
oxygen concentration. The resulting value is used as a predictor of viability for high-oxygen service. The main
testing standard for this is ASTM G72.[2]

13.1 Autoignition equation

The time tig it takes for a material to reach its autoignition temperature Tig when exposed to a heat flux q ′′ is given
by the following equation
( ) [ ]2
T −T
tig = π4 (kρc) igq′′ o [3]

where k = thermal conductivity (W/(m·K)), ρ = density (kg/m³), and c = specific heat capacity (J/(kg·K)) of the
material of interest. To is the temperature, in Kelvin, the material starts at (or the temperature of the bulk material),
and q ′′ is the heat flux (W/m²) incident to the material.

13.2 Autoignition point of selected substances

Temperatures vary widely in the literature and should only be used as estimates. Factors which may cause varia-
tion include partial pressure of oxygen, altitude, humidity, and amount of time required for ignition. Generally the
auto-ignition temperature for hydrocarbon/air mixtures decreases with increasing molecular weight and increasing
chain length. The auto-ignition temperature is also higher for branched-chain hydrocarbons than for straight-chain
hydrocarbons.[4]
For paper, there is considerable variation between sources, mainly because there are many physical variables over
different kinds of paper, like thickness, density and composition; in addition, it takes longer for the combustion of
paper to start at lower temperatures.[10]

13.3 See also

• Pyrolysis

• Flash point

110
13.4. REFERENCES 111

• Gas burner (For flame temperatures, combustion heat energy values and ignition temperatures)

13.4 References
[1] E659 – 78 (Reapproved 2000), “Standard Test Method for Autoignition Temperature of Liquid Chemicals”, ASTM, 100
Barr Harbor Drive, West Conshohocken, PA 19428-2959

[2] S. Grynko, “Material Properties Explained” (2012), ISBN 1-4700-7991-7, p. 46.

[3] Principles of Fire Behavior. ISBN 0-8273-7732-0. 1998.

[4] Zabetakis, M.G. (1965), Flammability characteristics of combustible gases and vapours, U.S. Department of Mines, Bul-
letin 627.

[5] “Diethyl Ether - Safety Properties”. Wolfram|Alpha.

[6] Fuels and Chemicals - Autoignition Temperatures, engineeringtoolbox.com

[7] “Butane - Safety Properties”. Wolfram|Alpha.

[8] Tony Cafe. “Physical Constants for Investigators”. Journal of Australian Fire Investigators. (Reproduced from “Firepoint”
magazine)

[9] “Hydrogen - Safety Properties”. Wolfram|Alpha.

[10] Forest Products Laboratory (1964). “Ignition and charring temperatures of wood”. Forest Service U. S. Department of
Agriculture.

13.5 External links

• Analysis of Effective Thermal Properties of Thermally Thick Materials.
• Autoignition Temperature of 100 Common Organic Chemical Compounds.
Chapter 14

Fire point

The fire point of a fuel is the temperature at which the vapour produced by that given fuel will continue to burn for at
least 5 seconds after ignition by an open flame. At the flash point, a lower temperature, a substance will ignite briefly,
but vapor might not be produced at a rate to sustain the fire. Most tables of material properties will only list material
flash points, but in general the fire points can be assumed to be about 10 °C higher than the flash points. However,
this is no substitute for testing if the fire point is safety critical. It is done by open cup apparatus [1]

14.1 See also

• Autoignition temperature
• Flash Point

14.2 Notes
[1] “FLASH POINT AND FIRE POINT”. Retrieved 2010-05-27.

112
Chapter 15

Pour point

The pour point of a liquid is the temperature at which it becomes semi solid and loses its flow characteristics. In
crude oil a high pour point is generally associated with a high paraffin content, typically found in crude deriving from
a larger proportion of plant material. That type of crude oil is mainly derived from a kerogen Type II.

15.1 Measuring the pour point of petroleum products

15.1.1 Manual Method

ASTM D5853, Standard Test Method for Pour Point of Crude Oils. The specimen is cooled inside a cooling bath to
allow the formation of paraffin wax crystals. At about 9 °C above the expected pour point, and for every subsequent
3 °C, the test jar is removed and tilted to check for surface movement. When the specimen does not flow when tilted,
the jar is held horizontally for 5 sec. If it does not flow, 3 °C is added to the corresponding temperature and the result
is the pour point temperature.
It is also useful to note that failure to flow at the pour point may also be due to the effect of viscosity or the previous
thermal history of the specimen. Therefore, the pour point may give a misleading view of the handling properties of
the oil. Additional fluidity tests may also be undertaken. An approximate range of pour point can be observed from
the specimen’s upper and lower pour point.

15.1.2 Automatic Method

ASTM D5949, Standard Test Method for Pour Point of Petroleum Products (Automatic Pressure Pulsing Method)
is an alternative to the manual test procedure. It uses automatic apparatus and yields pour point results in a format
similar to the manual method (ASTM D97) when reporting at a 3 °C.[1]
The D5949 test method determines the pour point in a shorter period of time than manual method D97. Less operator
time is required to run the test using this automatic method. Additionally, no external chiller bath or refrigeration
unit is needed. D5949 is capable of determining pour point within a temperature range of −57 °C to +51 °C. Results
can be reported at 1 °C or 3 °C testing intervals. This test method has better repeatability and reproducibility than
manual method D97.
Under ASTM D5949, the test sample is heated and then cooled by a Peltier device at a rate of 1.5 +/- 0.1 °C/min. At
either 1 °C or 3 °C intervals, a pressurized pulse of compressed gas is imparted onto the surface of the sample. Mul-
tiple optical detectors continuously monitor the sample for movement. The lowest temperature at which movement
is detected on the sample surface is determined to be the pour point.
The ASTM D5949 test method is utilized by Phase Tec

113
114 CHAPTER 15. POUR POINT

15.2 Measuring the pour point of crude oils

Two pour points can be derived which can give an approximate temperature window depending on its thermal history.
Within this temperature range, the sample may appear liquid or solid. This peculiarity happens because wax crystals
form more readily when it has been heated within the past 24 hrs and contributes to the lower pour point.
The upper pour point is measured by pouring the test sample directly into a test jar. The sample is then cooled and
then inspected for pour point as per the usual pour point method.
The lower pour point is measured by first pouring the sample into a stainless steel pressure vessel. The vessel is then
screwed tight and heated to above 100 °C in an oil bath. After a specified time, the vessel is removed and cooled for a
short while. The sample is then poured into a test jar and immediately closed with a cork carrying the thermometer.
The sample is then cooled and then inspected for pour point as per the usual pour point method.

15.3 See also

• Cloud point

• Cold filter plugging point

• Crude oil assay

• Gel point
• Petroleum

• Viscosity
• Wax

15.4 External links

• Some background knowledge about pour point and different measuring methods (manufacturer of pour point
tester)

• USFS Pour Point and Product Fluidity of Various Class A Foams

• Phase Technology Manufacturer of ASTM D5949 automatic pour point analyzers

15.5 References
[1] http://www.astm.org/Standards/D5949.htm
Chapter 16

Smoke point

In cooking, the smoke point of an oil or fat is the temperature at which, under defined conditions, enough volatile
compounds emerge from the oil that a bluish smoke becomes clearly visible. At this temperature, volatile compounds,
such as water, free fatty acids, and short-chain degradation products of oxidation come up from the oil. The smoke
point is the temperature at which the oil is decomposed and where possibly toxicological relevant compounds are
formed.
The smoke point for an oil varies widely depending on origin and refinement.[1] The smoke point of an oil does tend
to increase as free fatty acid content decreases and degree of refinement increases.[2][3] Heating the oil produces free
fatty acid and as this heating time increases, more free fatty acids are produced, thereby decreasing smoke point. It
is one reason not to use the same oil to deep fry more than twice.[1] Intermittent frying has a markedly greater effect
on oil deterioration than continuous frying.[4]
Considerably above the temperature of the smoke point is the flash point, the point at which the vapours from the oil
can first ignite when mixed with air.
The following table presents smoke points of various fats:

16.1 See also

• Boiling point

• Flash point

• Fire point

• Kindling point (Autoignition temperature)

16.2 References
[1] Wolke, Robert L. (May 16, 2007). “Where There’s Smoke, There’s a Fryer”. The Washington Post. Retrieved March 5,
2011.

[2] Morgan, D. A. (1942). “Smoke, fire, and flash points of cottonseed, peanut, and other vegetable oils”. Oil & Soap 19: 193.
doi:10.1007/BF02545481.

[3] Bockisch, Michael (1998). Fats and Oils Handbook. Champaign, IL: AOCS Press. pp. 95–6. ISBN 0-935315-82-9.

[4] Amit K. Das, et al, http://www.slideshare.net/amitkdas12/study-of-oil-deterioration-during-continuous-and-intermittent-frying

[5] Spectrum Organics, Canola Oil Manufacturer, http://www.spectrumorganics.com/shared/faq.php?fqid=34

[6] Detwiler, S. B.; Markley, K. S. (1940). “Smoke, flash, and fire points of soybean and other vegetable oils”. Oil & Soap 17
(2): 39–40. doi:10.1007/BF02543003.

[7] Nutiva, Coconut Oil Manufacturer, http://nutiva.com/introducing-nutiva-refined-coconut-oil/

115
116 CHAPTER 16. SMOKE POINT

[8] Nutiva, Coconut Oil Manufacturer, http://nutiva.com/introducing-nutiva-refined-coconut-oil/

[9] (Italian) Scheda tecnica dell'olio di palma bifrazionato PO 64.

• Cooking For Engineers: Smoke Point of Various Fats - another list of smoke points along with some discussion
on the subject
• Good Eats: Cooking Oil Smoke Points

• The Culinary Institute of America (1996). The New Professional Chef (6th ed.). John Wiley & Sons.
Chapter 17

API gravity

The American Petroleum Institute gravity, or API gravity, is a measure of how heavy or light a petroleum liquid is
compared to water: if its API gravity is greater than 10, it is lighter and floats on water; if less than 10, it is heavier
and sinks.
API gravity is thus an inverse measure of the relative density of a petroleum liquid and the density of water, but it is
used to compare the relative densities of petroleum liquids. For example, if one petroleum liquid floats on another
and is therefore less dense, it has a greater API gravity. Although mathematically API gravity is a dimensionless
quantity, see the formula below, it is nevertheless referred to as being in 'degrees’. API gravity is gradated in degrees
on a hydrometer instrument. The API scale was designed so that most values would fall between 10 and 70 API
gravity degrees.

17.1 History of development

The U.S. National Bureau of Standards in 1916 accepted the Baumé scale, developed in France in 1768, as the
U.S. standard for measuring the specific gravity of liquids less dense than water. Investigation by the U.S. National
Academy of Sciences found major errors in salinity and temperature controls that had caused serious variations in
published values. Hydrometers in the U.S. had been manufactured and distributed widely with a modulus of 141.5
instead of the Baumé scale modulus of 140. The scale was so firmly established that by 1921 the remedy implemented
by the American Petroleum Institute was to create the API Gravity scale, recognizing the scale that was actually being
used.

17.2 API gravity formulas

The formula to obtain API gravity of petroleum liquids, from Specific Gravity (SG), is:

141.5
gravity API = − 131.5
SG
Conversely, the relative density of petroleum liquids can be derived from the API gravity value as

141.5
at RD 60◦ F =
gravity API + 131.5

Thus, a heavy oil with a relative density of 1.0 (i.e., with the same density as pure water at 60 °F) would have an API
gravity of:

141.5
− 131.5 = 10.0◦ API
1.0

117
118 CHAPTER 17. API GRAVITY

17.3 Using API gravity to calculate barrels of crude oil per metric ton
In the oil industry, quantities of crude oil are often measured in metric tons. One can calculate the approximate
number of barrels per metric ton for a given crude oil based on its API gravity:

[ ]
141.5
ton metric per oil crude of barrels = 1 ÷ × 0.159
gravity API + 131.5
So, for example, a metric ton of West Texas Intermediate (39.6° API) would contain about 7.6 barrels.

17.4 Measurement of API gravity from its density

To derive the API gravity from the density, the density is first measured using either the hydrometer, detailed in
ASTM D1298 or with the oscillating U-tube method detailed in ASTM D4052.
Density adjustments at different temperatures, corrections for soda-lime glass expansion and contraction and meniscus
corrections for opaque oils are detailed in the Petroleum Measurement Tables, details of usage specified in ASTM
D1250. The relative density is then calculated from the formula below and the API gravity calculated from the first
formula above.

ρoil
RD oil =
ρH2 O
When converting between density and relative density, it is important to use the correct density of water, according
to the standard conditions used when the measurement was made. The official density of water at 60 °F according
to the 2008 edition of ASTM D1250 is 999.016 kg/m3 .[1] The 1980 value is 999.012 kg/m3 .[2] In some cases the
standard conditions may be 15 °C (59 °F) and not 60 °F (15.56 °C), in which case a different value for the water
density would be appropriate (see standard conditions for temperature and pressure).

17.5 Direct Measurement of API gravity (Hydrometer method)

There are advantages to field testing and on-board conversion of measured volumes to volume correction. This method
is detailed in ASTM D287.

17.6 Classifications or grades

Generally speaking, oil with an API gravity between 40 and 45 commands the highest prices. Above 45 degrees the
molecular chains become shorter and less valuable to refineries.[3]
Crude oil is classified as light, medium or heavy, according to its measured API gravity.

• Light crude oil is defined as having an API gravity higher than 31.1 °API (less than 870 kg/m3 )
• Medium oil is defined as having an API gravity between 22.3 °API and 31.1 °API (870 to 920 kg/m3 )
• Heavy crude oil is defined as having an API gravity below 22.3 °API (920 to 1000 kg/m3 )
• Extra heavy oil is defined with API gravity below 10.0 °API (greater than 1000 kg/m3 )

Not all parties use the same grading.[4] The United States Geological Survey uses slightly different definitions.[5]
Crude oil with API gravity less than 10 °API is referred to as extra heavy oil or bitumen. Bitumen derived from the
oil sands deposits in the Alberta, Canada area has an API gravity of around 8 °API. It can be diluted with lighter
hydrocarbons to produce diluted bitumen, having an API gravity of lower than 22.3 API, or further “upgraded” to an
API gravity of 31 °API to 33 °API as synthetic crude.[6]
17.7. SEE ALSO 119

17.7 See also

• Specific weight

17.8 References
[1] Report on the Development, Construction, Calculation and Preparation of the ASTM – IP Petroleum Measurement Tables
(ASTM D1250; IP 200), 1960, published by the Institute of Petroleum, 61 New Cavendish Street, London, W.1 and
American Society for Testing Materials, 1916 Race Street, Philadelphia 3, Pa.

[2] API Manual of Petroleum Measurement Standards, Chapter 11.1 – 1980,Volume XI/XII, Adjunct to: ASTM D1250-80
and IP 200/80

[3] “Comments on Crude Oil Gravity Adjustments”. Louisiana Department of Natural Resources. Archived from the original
on 18 January 2007. Retrieved 6 January 2014.

[4] Crude oil grades, Crudemonitor.ca, web PDF file: CMonitor-Gr-PDF

[5] USGS FS2006-3133_508, web PDF file: USGS-508-PDF

[6] Canadian Centre for Energy Information. “What is crude oil?". Retrieved on: 2012-09-10.

17.9 External links

• Link to hydrometer

• Comments on API gravity adjustment scale

• Instructions for using a glass hydrometer measured in API gravity

• API Degree history

Chapter 18

Light crude oil

Light crude oil is liquid petroleum that has a low density and flows freely at room temperature.[1] It has a low viscosity,
low specific gravity and high API gravity due to the presence of a high proportion of light hydrocarbon fractions.[2] It
generally has a low wax content. Light crude oil receives a higher price than heavy crude oil on commodity markets
because it produces a higher percentage of gasoline and diesel fuel when converted into products by an oil refinery.

18.1 Varying standards

The clear cut definition of light and heavy crude varies because the classification is based more on practical grounds
than theoretical. The New York Mercantile Exchange (NYMEX) defines light crude oil for domestic U.S. oil as
having an API gravity between 37° API (840 kg/m3 ) and 42° API (816 kg/m3 ), while it defines light crude oil for
non-U.S. oil as being between 32° API (865 kg/m3 ) and 42° API (816 kg/m3 ).[3] The National Energy Board of
Canada defines light crude oil as having a density less than 875.7 kg/m3 (API gravity greater than 30.1° API).[4] The
government of Alberta, which produces most of the oil in Canada, disagrees and defines it as oil with a density less
than 850 kg/m3 (API gravity greater than 35° API) [5] The Mexican state oil company, Pemex, defines light crude
oil as being between 27° API (893 kg/m3 ) and 38° API (835 kg/m3 ).[6] This variation in definition occurred because
countries such as Canada and Mexico tend to have heavier crude oils than are commonly found in the United States,
whose large oil fields historically produced lighter oils than are found in many other countries. Canada also uses the
SI of units to measure oil rather than American oil industry conventional units, and the base temperature for density
calculations is different in Canada at 15 °C (59 °F) than the US at 60 °F (15.56 °C), resulting in slightly different
density values.

18.2 Examples of light crude oils

A wide variety of benchmark crude oils worldwide are considered to be light. The most prominent in North America
is West Texas Intermediate which has an API gravity of 39.6° API (827 kg/m3 ). It is often referred to by publications
when quoting oil prices. The most commonly referenced benchmark oil from Europe is Brent Crude, which is 38.06°
API (835 kg/m3 ). The third most commonly quoted benchmark is Dubai Crude, which is 31° API (871 kg/m3 ).
This is considered light by Arabian standards but would not be considered light if produced in the U.S.
The largest oil field in the world, Saudi Arabia’s Ghawar field, produces light crude oils ranging from 33° API (860
kg/m3 ) to 40° API (825 kg/m3 )

18.3 U.S. price

In the United States, the price of the front month light sweet crude oil futures contract, traded on the NYMEX
commodity exchange (symbol CL), is widely reported as a proxy for the cost of imported crude oil. These contracts
have delivery dates in all 12 months of the year.[7] From below $20 a barrel in early 2002, it rose to an intraday
peak of $70.85 at the end of August 2005 in the aftermath of Hurricane Katrina. A new intraday record high of

120
18.4. SEE ALSO 121

$78.40 was set on July 14, 2006, prompted by the firing of at least six missiles by North Korea on July 4–5, 2006,
and escalating Middle East violence.
Subsequently, the price declined until on October 11, 2006, the price closed at $66.04. But, by August 2007, the price
had reached a record high of $78.71, amid production output concerns in the North Sea and Nigeria. On November
29, 2007, the price peaked at $98.70 intraday after closing at $98.03 the previous day.[8] The price of light crude set
a new intraday high on May 21, 2008, of $133.45 and closed at $133.17. A new high was reached on July 11, 2008,
as prices temporarily reached $147.27 a barrel.

18.3.1 Trading
Light crude oil is traded on the CME Globex, CME ClearPort, (CME Group) and Open Outcry (New York) futures
exchange venues and is quoted in U.S. dollars and cents per barrel. Its product symbol is “CL” and its contract size
is 1,000 barrels (160 m3 ) with a minimum fluctuation of $0.01 per barrel.[9]

18.4 See also

• Biofuel

• Benchmark (crude oil)

• Brent Crude

• West Texas Intermediate

• Sweet crude oil

• Price of petroleum

18.5 Notes
[1] “Glossary”. Canadian Association of Petroleum Producers. 2009. Retrieved 2009-08-15.

[2] “Glossary of Petroleum Industry Common Terms & Symbols”. Alken Murray Corp. 1999. Retrieved 2009-08-15.

[3] “Light Sweet Crude Oil”. New York Mercantile Exchange. 2008. Retrieved 2009-08-16.

[4] “National Energy Board Act Part VI (Oil and Gas) Regulations, SOR/96-244”. Canadian Legal Information Institute.
1996. Retrieved 2009-08-16.

[5] “Alberta Government Petroleum Marketing and Valuation Information Letter 2014-32”. Alberta Department of Energy.
August 14, 2014. Retrieved 2014-09-13.

[6] “Glossary and Nomenclature”. Pemex. 2009. Retrieved 2009-08-16.

[7] List of Commodity Delivery Dates on Wikinvest

[8] “Light Crude Oil (CL, NYMEX)". Retrieved 2007-12-11.

[9] Light Sweet Crude Oil (WTI), CME Group

Chapter 19

Heavy crude oil

Heavy crude oil or extra heavy crude oil is oil that is highly viscous, and cannot easily flow to production wells
under normal reservoir conditions.(Mai)[1] It is referred to as “heavy” because its density or specific gravity is higher
than that of light crude oil. Heavy crude oil has been defined as any liquid petroleum with an API gravity less than
20°.(Dusseault 2001)[2] Physical properties that differ between heavy crude oils and lighter grades include higher
viscosity and specific gravity, as well as heavier molecular composition. In 2010, the World Energy Council defined
extra heavy oil as crude oil having a gravity of less than 10° and a reservoir viscosity of no more than 10 000
centipoises. When reservoir viscosity measurements are not available, extra-heavy oil is considered by the WEC to
have a lower limit of 4° °API.(WEC 2007)[3] (i.e. with density greater than 1000 kg/m3 or, equivalently, a specific
gravity greater than 1 and a reservoir viscosity of no more than 10,000 centipoises.[4][5] Heavy oils and asphalt are
dense nonaqueous phase liquids (DNAPLs). They have a “low solubility and are with viscosity lower and density
higher than water.(2003 & Llamas 118)[6] “Large spills of DNAPL will quickly penetrate the full depth of the aquifer
and accumulate on its bottom."(2008 & Vrba 23)[7]
Heavy crude oil is closely related to natural bitumen from oil sands. Petroleum geologists categorize bitumen from
oil sands as ‘extra-heavy oil’ due to its density of less than 10° °API.[8] Bitumen is the heaviest, thickest form of
petroleum.[9] According to the U.S. Geological Survey, bitumen is further distinguished as extra-heavy oil with a
higher viscosity (i.e., resistance to flow): “Natural bitumen, also called tar sands or oil sands, shares the attributes
of heavy oil but is yet more dense and viscous. Natural bitumen is oil having a viscosity greater than 10,000 cP.”[8]
“Natural bitumen (often called tar sands or oil sands) and heavy oil differ from light oils by their high viscosity
(resistance to flow) at reservoir temperatures, high density (low API gravity), and significant contents of nitrogen,
oxygen, and sulfur compounds and heavy-metal contaminants. They resemble the residuum from the refining of light
oil. Most heavy oil is found at the margins of geologic basins and is thought to be the residue of formerly light oil
that has lost its light-molecular-weight components through degradation by bacteria, water-washing, and evaporation.
Conventional heavy oil and bitumens differ in the degree by which they have been degraded from the original crude
oil by bacteria and erosion.(Meyer & 2003 1) Often, bitumen is more viscous than cold molasses and does not flow
at ambient conditions.[9]
According to World Resources Institute, concentrations of remarkable quantities of heavy oil and oil sands are found
in Canada and Venezuela.[2][10] The U.S. Energy Information Administration (EIA) reported in 2001 that the largest
reserves of heavy crude oil in the world were located north of the Orinoco river 270-mile long by 40-mile wide
Orinoco Belt in eastern Venezuela. At that time Venezuela began authorizing “joint ventures to upgrade the extra-
heavy crude resources.” [11] Petroleos de Venezuela, S.A. (PDVSA) at that time estimated that there were 270 billion
barrels of recoverable reserves in the area,[11] the same amount as the conventional oil reserves of Saudi Arabia.[12]
The Orinoco Belt in Venezuela is sometimes described as oil sands, but these deposits are non-bituminous, falling
instead into the category of heavy or extra-heavy oil due to their lower viscosity.[13] Natural bitumen and extra-heavy
oil differ in the degree by which they have been degraded from the original conventional oils by bacteria. According
to the WEC, extra-heavy oil has “a gravity of less than 10° °API and a reservoir viscosity of no more than 10,000
centipoise”.[4] Thirty or more countries are known to have reserves.
Production, transportation, and refining of heavy crude oil present special challenges compared to light crude oil.
Generally, a diluent is added at regular distances in a pipeline carrying heavy crude to facilitate its flow. Dilbit
(diluted bitumen) is a means of transporting highly viscous hydrocarbon. Per the Alberta Oil Sands Bitumen Valu-
ation Methodology, “Dilbit Blends” means “Blends made from heavy crudes and/or bitumens and a diluent usually
condensate, for the purpose of meeting pipeline viscosity and density specifications, where the density of the diluent

122
19.1. ECONOMICS 123

included in the blend is less than 800 kg/m3.”[14][15]

19.1 Economics
Heavy crude oils provide an interesting situation for the economics of petroleum development. The resources of
heavy oil in the world are more than twice those of conventional light crude oil. In October 2009, the United States
Geological Survey updated the Orinoco deposits (Venezuela) recoverable value to 513 billion barrels (8.16×1010
m3 ),[16] making this area one of the world’s largest recoverable oil deposits. However, recovery rates for heavy oil
are often limited from 5-30% of oil in place. The chemical makeup is often the defining variable in recovery rates.
The technology utilized for the recovery of heavy oil has steadily increased recovery rates.[17]
On one hand, due to increased refining costs and high sulfur content for some sources, heavy crudes are often priced
at a discount to lighter ones. The increased viscosity and density also makes production more difficult (see reservoir
engineering). On the other hand, large quantities of heavy crudes have been discovered in the Americas, including
Canada, Venezuela and California. The relatively shallow depth of heavy oil fields[18] (often less than 3000 feet)
can contribute to lower production costs; however, these are offset by the difficulties of production and transport that
render conventional production methods ineffective.[18] Specialized techniques are being developed for exploration
and production of heavy oil.

19.2 Extraction
Production of heavy oil is becoming more common in many countries, with 2008 production led by Canada and
Venezuela.[18] Methods for extraction include Cold heavy oil production with sand, steam assisted gravity drainage,
steam injection, vapor extraction, Toe-to-Heel Air Injection (THAI), and open-pit mining for extremely sandy and
oil-rich deposits.

19.3 Environmental impact

With current production and transportation methods, heavy crudes have a more severe environmental impact than
light ones. With more difficult production comes the employment of a variety of enhanced oil recovery techniques,
including steam flooding and tighter well spacing, often as close as one well per acre. Heavy crude oils also carry
contaminants. For example, Orinoco extra heavy oil contains 4.5% sulfur as well as vanadium and nickel.[19] How-
ever, because crude oil is refined before use, generating specific alkanes via cracking and fractional distillation, this
comparison is not valid in a practical sense. Heavy crude refining techniques may require more energy input though,
so its environmental impact is presently more significant than that of lighter crude if the intended final products are
light hydrocarbons (gasoline motor fuels). On the other hand heavy crude is a better source for road asphalt mixes
than light crude.
With present technology, the extraction and refining of heavy oils and oil sands generates as much as three times
the total CO2 emissions compared to conventional oil,[20] primarily driven by the extra energy consumption of the
extraction process (which may include burning natural gas to heat and pressurize the reservoir to stimulate flow).
Current research into better production methods seek to reduce this environmental impact.
In a 2009 report, the National Toxics Network, citing data provided by the Carbon Dioxide Information Analysis
Center of the government of the United States and the Canadian Association of Petroleum Producers (CAPP), emis-
sions of CO2 per unit of energy produced were ~84% of those for coal (0.078/0.093), higher than CO2 emissions of
conventional oil.[21]
Environmental Research Web has reported that “because of the energy needed for extraction and processing, petroleum
from Canadian oil tar sands has higher life cycle emission” versus conventional fossil fuels; “up to 25% more.”[22]

19.4 Geological origin

Most geologists agree that crude becomes ‘heavy’ as a result of biodegradation, in which lighter ends are preferentially
consumed by bacterial activity in the reservoir, leaving heavier hydrocarbons behind. This hypothesis leans heavily
124 CHAPTER 19. HEAVY CRUDE OIL

Steam is injected into many oil fields where the oil is thicker and heavier than normal crude oil

on the techniques of petroleum geochemistry. Poor geologic reservoir sealing exposes the hydrocarbon to surface
contaminants, including organic life (such as bacteria) and contributes to this process.
Heavy oils can be found in shallow, young reservoirs, with rocks from the Pleistocene, Pliocene, and Miocene[18]
19.5. CHEMICAL PROPERTIES 125

(younger than 25 million years). In some cases, it can also be found in older Cretaceous, Mississippian, and Devonian
reservoirs. These reservoirs tend to be poorly sealed, resulting in heavy oil and oil-sands.

19.5 Chemical properties

Heavy oil is asphaltic and contains asphaltenes and resins. It is “heavy” (dense and viscous) due to the high ratio of
aromatics and naphthenes to linear alkanes and high amounts of NSO’s (nitrogen, sulfur, oxygen and heavy metals).
Heavy oil has a higher percentage of compounds with over 60 carbon atoms and hence a high boiling point and
molecular weight. For example, the viscosity of Venezuela’s Orinoco extra-heavy crude oil lies in the range 1000–
5000 cP (1–5 Pa·s), while Canadian extra-heavy crude has a viscosity in the range 5000–10,000 cP (5–10 Pa·s),
about the same as molasses, and higher (up to 100,000 cP or 100 Pa·s for the most viscous commercially exploitable
deposits).[2] A definition from the Chevron Phillips Chemical company is as follows:

The “heaviness” of heavy oil is primarily the result of a relatively high proportion of a mixed bag
of complex, high molecular weight, non-paraffinic compounds and a low proportion of volatile, low
molecular weight compounds. Heavy oils typically contain very little paraffin and may or may not
contain high levels of asphaltenes.[23]

There are two main types of heavy crude oil:

1. Those that have over 1% sulfur (high sulfur crude oils), with aromatics and asphaltenes, and these are mostly
found in North America (Canada (Alberta, Saskatchewan), United States (California), Mexico), South America
(Venezuela, Colombia and Ecuador) and the Middle East (Kuwait, Saudi Arabia).

2. Those that have less than 1% sulfur (low sulfur crude oils), with aromatics, naphthenes and resins, and these
are mostly found in Western Africa (Chad), Central Africa (Angola) and East Africa (Madagascar).

19.6 See also

• Oil shale

• Oil sands

• Mazut

• Steam injection (oil industry)

• Steam-assisted gravity drainage

19.7 References
[1] A. Mai; J. Bryan; N. Goodarzi; A. Kantas (2006). “Insights Into Non-Thermal Recovery of Heavy Oil”. World Heavy Oil
Conference (WHOC) (2006-553). Calgary, Alberta.

[2] Dusseault, M.B. (12–14 June 2001). “Comparing Venezuelan and Canadian Heavy Oil and Tar Sands” (PDF). Calgary,
Canada: Canadian International Petroleum Conference. Retrieved 5 May 2008.

[3] WEC (2007). Survey of Energy Resources 2007: Natural Bitumen - Definitions. World Energy Council.

[4] Attanasi, Emil D.; Meyer, Richard F. (2010). “Natural Bitumen and Extra-Heavy Oil”. Survey of energy resources (PDF)
(22 ed.). World Energy Council. pp. 123–140. ISBN 0-946121-26-5.

[5] Rodriguez H. A., Vaca P., Gonzalez O., and De Mirabal M. C., “Integrated study of a heavy oil reservoir in the Orinoco
Belt : A field case simulation”

[6] Manuel Ramâon Llamas; Emilio Custodio, eds. (2003). Intensive Use of Groundwater: Challenges and Opportunities. CRC
Press. p. 478.page 118
126 CHAPTER 19. HEAVY CRUDE OIL

[7] (PDF) Groundwater Early Warning Monitoring Strategy A Methodological Guide (Report). 2008. http://unesdoc.unesco.
org/images/0016/001622/162223e.pdf.

[8] Meyer, Richard; Atanasi, Emil (August 200). Heavy Oil and Natural Bitumen--Strategic Petroleum Resources - “Def-
initions.” (Report). U.S. Geological Survey Fact Sheet 70-03. http://pubs.usgs.gov/fs/fs070-03/fs070-03.html#sidebar.
Retrieved 31 July 2013.

[9] G.R. Gray; R. Luhning. Bitumen. Canadian Encyclopedia.

[10] Heavy Oil and Tar Sands (Report). Washington, DC: World Resources Institute. http://www.wri.org/publication/content/
10339.

[11] Venezuela Offers Full Market Value to Encourage Foreign Investment in Oil (Report). Washington, DC: Energy Infor-
mation Administration. 2001. http://www.eia.doe.gov/emeu/finance/usi&to/upstream/venezuela.html.

[12] Talwani, M.. The Orinoco heavy oil belt in Venezuela (Or heavy oil to the rescue? (Report). http://cohesion.rice.edu/
naturalsciences/earthscience/research.cfm?doc_id=2819.

[13] Dusseault, M. B. (12–14 June 2001). “Comparing Venezuelan and Canadian heavy oil and tar sands”. Proceedings of
Petroleum Society’s Canadian International Conference. 2001-061: 20p.

[14] Alberta Oil Sands Bitumen Valuation Methodology (PDF), 2008-9995, Calgary, Alberta: Canadian Association of Petroleum
Producers, Dec 2008

[15] Bret Schulte (4 April 2003). “Oil Spill Spotlights Keystone XL Issue: Is Canadian Crude Worse?". Fayetteville, Arkansas:
National Geographic News.

[16] Christopher J. Schenk, Troy A. Cook, Ronald R. Charpentier, Richard M. Pollastro, Timothy R. Klett, Marilyn E. Ten-
nyson, Mark A. Kirschbaum, Michael E. Brownfield, and Janet K. Pitman. (11 January 2010). “An Estimate of Recover-
able Heavy Oil Resources of the Orinoco Oil Belt, Venezuela”. USGS. Retrieved 23 January 2010.

[17] Canadian International Petroleum Comference (2001)

[18] The Leading Edge, Special Section - Heavy Oil. Vol. 27, No. 8. September, 2008. Society of Exploration Geophysicists.

[19] (Report). World Energy Council (WEC). http://www.worldenergy.org/wec-geis/publications/default/tech_papers/17th_

congress/3_1_04.asp.

[20] J.R. Century. Tar Sands: Key geologic risks and opportunities. The Leading Edge, Vol. 27, No. 9, Pg. 1202-1204.
September 2008.

[21] The Heavy Oil Power Deal. A Dark Cloud over East Timor’s Bright Future

[22] CO2 emissions from tar sands and oil infrastructure investments

[23] “What causes heavy oil if they don't have asphaltene or paraffin problems?" - Chevron Phillips Chemical

19.8 External links

• Gushor Inc. - Heavy Oil Geoscience & Reservoir Engineering
• OTS Heavy Oil Science Centre

• Schlumberger map of global heavy oil resources

• Molecular Basis of Heavy Organics in Petroleum and Heavy Oil

• Crude Oil Technical Views
Chapter 20

Furnace

For other uses, see Furnace (disambiguation).

A furnace is a device used for high temperature heating. The name derives from Greek word fornax, which means
oven.
In American English and Canadian English usage, the term furnace on its own refers to the household heating systems
based on a central furnace (known either as a boiler, or a heater in British English), and sometimes as a synonym for
kiln, a device used in the production of ceramics. In British English, a furnace is an industrial furnace used for many
things, such as the extraction of metal from ore (smelting) or in oil refineries and other chemical plants, for example
as the heat source for fractional distillation columns.
The term furnace can also refer to a direct fired heater, used in boiler applications in chemical industries or for
providing heat to chemical reactions for processes like cracking, and is part of the standard English names for many
metallurgical furnaces worldwide.
The heat energy to fuel a furnace may be supplied directly by fuel combustion, by electricity such as the electric arc
furnace, or through induction heating in induction furnaces.

20.1 Household furnaces

A household furnace is a major appliance that is permanently installed to provide heat to an interior space through
intermediary fluid movement, which may be air, steam, or hot water. (Heating appliances that use steam or hot
water as the fluid are normally referred to as a residential steam boiler or residential hot water boiler.) The most
common fuel source for modern furnaces in the United States is natural gas; other common fuel sources include LPG
(liquefied petroleum gas), fuel oil, coal or wood. In some cases electrical resistance heating is used as the source of
heat, especially where the cost of electricity is low.
Modern high-efficiency furnaces can be 98% efficient and operate without a chimney. The small amount of waste
gas and heat are mechanically ventilated through PVC pipes that can be vented through the side or roof of the house.
Fuel efficiency in a gas furnace is measured in AFUE, or Annual Fuel Utilization Efficiency.

20.1.1 Categories
Residential furnaces can be classified into four general categories, based on efficiency and design.

Gravity-fed

The first category would be “gravity fed”, atmospheric burner furnaces. These furnaces consisted of cast-iron or
riveted-steel heat exchangers built within an outer shell or brick, masonry or steel. The heat exchangers were vented
through brick or masonry chimneys. Air circulation depended on large, upwardly pitched pipes constructed of wood
or metal. The pipes would channel the warm air into floor or wall vents inside the home. This method of heating
worked because warm air rises. The system was simple, had few controls, a single automatic gas valve, and no blower.
These furnaces could be made to work with any fuel simply by adapting the burner area. They have been operated

127
128 CHAPTER 20. FURNACE

Industrial Furnace from 1907

with wood, coke, coal, trash, paper, natural gas and fuel oil. Furnaces that used solid fuels required daily maintenance
to remove ash and “clinkers” that accumulated in the bottom of the burner area. In later years, these furnaces were
adapted with electric blowers to aid air distribution and speed moving heat into the home. Gas and oil-fired gravity
systems were usually controlled by a thermostat inside the home, while most wood and coal-fired furnaces were
controlled by the amount of fuel in the burner and position of the fresh-air damper on the burner access door.

Forced air

The second category of residential furnace is the forced-air, atmospheric burner style with a cast-iron or sectional
steel heat exchanger. This style furnace was used to replace the big, gravity-fed systems, and was sometimes installed
20.1. HOUSEHOLD FURNACES 129

A condensing furnace

on the existing gravity duct work. The blowers were belt driven and designed for a wide range of speeds. These
furnaces were still big and bulky compared to modern furnaces, and had heavy-steel exteriors with bolt-on removable
panels. Energy efficiency would range anywhere from just over 50% to upward of 65% AFUE. This style furnace
still used large, masonry or brick chimneys for flues and was eventually designed to accommodate air-conditioning
systems.
130 CHAPTER 20. FURNACE

Diagram of gravity-fed gas furnace, early 20th century.

Forced draft

The third category of furnace is the forced-draft, mid-efficiency furnace with a steel heat exchanger and multi-speed
blower. These furnaces were physically much more compact than the previous styles. They were equipped with
combustion air blowers that would pull air through the heat exchanger which greatly increased fuel efficiency while
allowing the heat exchangers to become smaller. These furnace have multi-speed blowers and were designed to work
with central air-conditioning systems.
20.1. HOUSEHOLD FURNACES 131

Condensing

The fourth category of furnace is the high-efficiency, or condensing furnace. High efficiency furnaces can achieve
from 89% to 98% fuel efficiency. This style of furnace includes a sealed combustion area, combustion draft inducer
and a secondary heat exchanger. Because the heat exchanger removes most of the heat from the exhaust gas, it
actually condenses water vapor and other chemicals (which form a mild acid) as it operates. Due to the low exhaust
gas temperatur, the flue pipes are normally installed with Schedule 40 PVC pipe versus metal vent pipe. The draft
inducer allows for the exhaust piping to be routed vertically or horizontally as it exits the structure. The most efficient
arrangement for high-efficiency furnaces include PVC piping that brings fresh combustion air from the outside of
the home directly to the furnace. Normally the combustion-air (fresh air) PVC is routed alongside the exhaust PVC
during installation and the pipes exit through a sidewall of the home in the same location. High efficiency furnaces
typically deliver a 25% to 35% fuel savings over a 60% AFUE furnace.

20.1.2 Heat distribution

The furnace transfers heat to the living space of the building through an intermediary distribution system. If the
distribution is through hot water (or other fluid) or through steam, then the furnace is more commonly called a
boiler. One advantage of a boiler is that the furnace can provide hot water for bathing and washing dishes, rather
than requiring a separate water heater. One disadvantage to this type of application is when the boiler breaks down,
neither heating nor domestic hot water are available.

“Octopus” furnace with oil burner.

Air convection heating systems have been in use for over a century, but the older systems relied on a passive air
circulation system where the greater density of cooler air caused it to sink into the furnace, and the lesser density of
the warmed air caused it to rise in the ductwork, the two forces acting together to drive air circulation in a system
termed “gravity-feed; the layout of the ducts and furnace was optimized for short, large ducts. This caused the furnace
to be referred to as an “octopus” furnace.
By comparison, most modern “warm air” furnaces typically use a fan to circulate air to the rooms of house and
pull cooler air back to the furnace for reheating; this is called forced-air heat. Because the fan easily overcomes the
resistance of the ductwork, the arrangement of ducts can be far more flexible than the octopus of old. In American
132 CHAPTER 20. FURNACE

Forced-air gas furnace, design circa 1991.

practice, separate ducts collect cool air to be returned to the furnace. At the furnace, cool air passes into the furnace,
usually through an air filter, through the blower, then through the heat exchanger of the furnace, whence it is blown
throughout the building. One major advantage of this type of system is that it also enables easy installation of central
air conditioning, simply by adding a cooling coil at the outlet of the furnace.
20.2. METALLURGICAL FURNACES 133

Air is circulated through ductwork, which may be made of sheet metal or plastic “flex” duct, and is insulated or
uninsulated. Unless the ducts and plenum have been sealed using mastic or foil duct tape, the ductwork is likely to
have a high leakage of conditioned air, possibly into unconditioned spaces. Another cause of wasted energy is the
installation of ductwork in unheated areas, such as attics and crawl spaces; or ductwork of air conditioning systems
in attics in warm climates.
The following rare but difficult-to-diagnose failure can occur. If the temperature inside the furnace exceeds a maxi-
mum threshold, a safety mechanism with a thermostat will shut the furnace down. A symptom of this failure is that
the furnace repeatedly shuts down before the house reaches the desired temperature; this is commonly referred to
as the furnace “riding the high limit switch”. This condition commonly occurs if the temperature setting of the high
limit thermostat is set too close to the normal operating temperature of the furnace. Another situation may occur if a
humidifier is incorrectly installed on the furnace and the duct which directs a portion of the humidified air back into
the furnace is too large. The solution is to reduce the diameter of the cross-feed tube, or install a baffle that reduces
the volume of re-fed air.

20.1.3 Furnace types

Single-stage

A single-stage furnace has only one stage of operation, it is either on or off. This means that it is relatively noisy,
always running at the highest speed, and always pumping out the hottest air at the highest velocity.
One of the benefits to a single-stage furnace is typically the cost. Single-stage furnaces are relatively inexpensive since
the technology is rather simple. They are a good overall economical budget furnace.
The downside to single-stage furnaces is that they only have one stage of operation and therefore do not allow for as
good a comfort level as the newer, more controllable furnaces.

Two-stage

This tpye has two stages of operation, full speed and half (or reduced) speed. Depending on the demanded hear, it
can run at a lower speed most of the time, and provide a better comfort level. It is quieter, can move the air at less
velocity, and will better keep the desired temperature in the house.

Modulating

This type of furnace can modulate the heat output and air velocity nearly continuously, depending on the demanded
heat and outside temperature. This means that it only works as much as necessary and therefore saves energy.

20.2 Metallurgical furnaces

In metallurgy, several specialized furnaces are used. These include:

• Furnaces used in smelters, including:

• The blast furnace, used to reduce iron ore to pig iron

• Steelmaking furnaces, including:
• Puddling furnace
• Reverberatory furnace
• Bessemer converter
• Open hearth furnace
• Basic oxygen furnace
• Electric arc furnace
• Electric induction furnace
• Reheating furnace
134 CHAPTER 20. FURNACE

The Manufacture of Iron -- Filling the Furnace, an 1873 wood engraving

• Furnaces used to remelt metal in foundries.

• Furnaces used to reheat and heat treat metal for use in:

• Rolling mills, including tinplate works and slitting mills.

• Forges.

• Vacuum furnaces

20.3 Industrial process furnaces

An industrial furnace or direct fired heater, is an equipment used to provide heat for a process or can serve as reactor
which provides heats of reaction. Furnace designs vary as to its function, heating duty, type of fuel and method of
introducing combustion air. However, most process furnaces have some common features.
Fuel flows into the burner and is burnt with air provided from an air blower. There can be more than one burner in
a particular furnace which can be arranged in cells which heat a particular set of tubes. Burners can also be floor
mounted, wall mounted or roof mounted depending on design. The flames heat up the tubes, which in turn heat the
fluid inside in the first part of the furnace known as the radiant section or firebox. In this chamber where combustion
takes place, the heat is transferred mainly by radiation to tubes around the fire in the chamber. The heating fluid passes
through the tubes and is thus heated to the desired temperature. The gases from the combustion are known as flue gas.
After the flue gas leaves the firebox, most furnace designs include a convection section where more heat is recovered
before venting to the atmosphere through the flue gas stack. (HTF=Heat Transfer Fluid. Industries commonly use
their furnaces to heat a secondary fluid with special additives like anti-rust and high heat transfer efficiency. This
heated fluid is then circulated round the whole plant to heat exchangers to be used wherever heat is needed instead
of directly heating the product line as the product or material may be volatile or prone to cracking at the furnace
temperature.)
20.3. INDUSTRIAL PROCESS FURNACES 135

Stack

Damper

Breeching
Convection
section HTF in

Shield section HTF out

Coil
Radiant
section

Air blower
Burner

Schematic diagram of an industrial process furnace

20.3.1 Radiant section

The radiant section is where the tubes receive almost all its heat by radiation from the flame. In a vertical, cylindrical
furnace, the tubes are vertical. Tubes can be vertical or horizontal, placed along the refractory wall, in the middle,
etc., or arranged in cells. Studs are used to hold the insulation together and on the wall of the furnace. They are placed
about 1 ft (300 mm) apart in this picture of the inside of a furnace. The tubes, shown below, which are reddish brown
from corrosion, are carbon steel tubes and run the height of the radiant section. The tubes are a distance away from
the insulation so radiation can be reflected to the back of the tubes to maintain a uniform tube wall temperature. Tube
guides at the top, middle and bottom hold the tubes in place.
136 CHAPTER 20. FURNACE

Middle of radiant section

20.3.2 Convection section

The convection section is located above the radiant section where it is cooler to recover additional heat. Heat transfer
takes place by convection here, and the tubes are finned to increase heat transfer. The first two tube rows in the bottom
of the convection section and at the top of the radiant section is an area of bare tubes (without fins) and are known
as the shield section (“shock tubes”), so named because they are still exposed to plenty of radiation from the firebox
and they also act to shield the convection section tubes, which are normally of less resistant material from the high
temperatures in the firebox. The area of the radiant section just before flue gas enters the shield section and into the
convection section called the bridgezone. A crossover is the tube that connects from the convection section outlet to
the radiant section inlet. The crossover piping is normally located outside so that the temperature can be monitored
and the efficiency of the convection section can be calculated. The sightglass at the top allows personnel to see the
flame shape and pattern from above and visually inspect if flame impingement is occurring. Flame impingement
happens when the flame touches the tubes and causes small isolated spots of very high temperature.

20.3.3 Radiant Coil

This is a series of tubes horizontal/ vertical hairpin type connected at ends (with 180° bends) or helical in construction.
The radiant coil absorbs heat through radiation. They can be single pass or multi pass depending upon the process-
side pressure drop allowed. The radiant coils and bends are housed in the radiant box. Radiant coil materials vary
from carbon steel for low temperature services to high alloy steels for high temperature services. These are supported
from the radiant side walls or hanging from the radiant roof. Material of these supports is generally high alloy steel.
While designing the radiant coil, care is taken so that provision for expansion (in hot conditions) is kept.
20.3. INDUSTRIAL PROCESS FURNACES 137

Convection section

20.3.4 Burner

The burner in the vertical, cylindrical furnace as above, is located in the floor and fires upward. Some furnaces have
side fired burners, such as in train locomotives. The burner tile is made of high temperature refractory and is where
the flame is contained. Air registers located below the burner and at the outlet of the air blower are devices with
movable flaps or vanes that control the shape and pattern of the flame, whether it spreads out or even swirls around.
Flames should not spread out too much, as this will cause flame impingement. Air registers can be classified as
primary, secondary and if applicable, tertiary, depending on when their air is introduced. The primary air register
supplies primary air, which is the first to be introduced in the burner. Secondary air is added to supplement primary
air. Burners may include a pre-mixer to mix the air and fuel for better combustion before introducing into the burner.
Some burners even use steam as premix to preheat the air and create better mixing of the fuel and heated air. The
floor of the furnace is mostly made of a different material from that of the wall, typically hard castable refractory to
allow technicians to walk on its floor during maintenance.
A furnace can be lit by a small pilot flame or in some older models, by hand. Most pilot flames nowadays are lit by
an ignition transformer (much like a car’s spark plugs). The pilot flame in turn lights up the main flame. The pilot
flame uses natural gas while the main flame can use both diesel and natural gas. When using liquid fuels, an atomizer
is used, otherwise, the liquid fuel will simply pour onto the furnace floor and become a hazard. Using a pilot flame
for lighting the furnace increases safety and ease compared to using a manual ignition method (like a match).

20.3.5 Sootblower

Sootblowers are found in the convection section. As this section is above the radiant section and air movement is
slower because of the fins, soot tends to accumulate here. Sootblowing is normally done when the efficiency of the
convection section is decreased. This can be calculated by looking at the temperature change from the crossover
piping and at the convection section exit.
Sootblowers utilize flowing media such as water, air or steam to remove deposits from the tubes. This is typically
138 CHAPTER 20. FURNACE

Furnace burner

done during maintenance with the air blower turned on. There are several different types of sootblowers used. Wall
blowers of the rotary type are mounted on furnace walls protruding between the convection tubes. The lances are
connected to a steam source with holes drilled into it at intervals along its length. When it is turned on, it rotates and
blows the soot off the tubes and out through the stack.

20.3.6 Stack

The flue gas stack is a cylindrical structure at the top of all the heat transfer chambers. The breeching directly below
it collects the flue gas and brings it up high into the atmosphere where it will not endanger personnel.
The stack damper contained within works like a butterfly valve and regulates draft (pressure difference between air
intake and air exit) in the furnace, which is what pulls the flue gas through the convection section. The stack damper
also regulates the heat lost through the stack. As the damper closes, the amount of heat escaping the furnace through
the stack decreases, but the pressure or draft in the furnace increases which poses risks to those working around it if
there are air leakages in the furnace, the flames can then escape out of the firebox or even explode if the pressure is
too great.

20.3.7 Insulation

Insulation is an important part of the furnace because it improves efficiency by minimizing heat escape from the
heated chamber. Refractory materials such as firebrick, castable refractories and ceramic fibre, are used for insulation.
The floor of the furnace are normally castable type refractories while those on the walls are nailed or glued in place.
Ceramic fibre is commonly used for the roof and wall of the furnace and is graded by its density and then its maximum
temperature rating. For example, 8# 2,300 °F means 8 lb/ft3 density with a maximum temperature rating of 2,300
°F. The actual service temperature rating for ceramic fiber is a bit lower than the maximum rated temperature. (i.e.
2300 °F is only good to 2145 °F before permanent linear shrinkage).
20.4. SEE ALSO 139

Overhead view to stack:

Stack

Damper blade
Damper closed
Position indicator

Bushing

Control cables

Breeching

Damper partially open

Stack damper

20.3.8 Foundations

Concrete pillars are foundation on which the heater is mounted. They can be four nos. for smaller heaters and may be
up to 24 nos. for large size heaters. Design of pillars and entire foundation is done based on the load bearing capacity
of soil and seismic conditions prevailing in the area. Foundation bolts are grouted in foundation after installation of
the heater.

20.3.9 Access Doors

The heater body is provided with access doors at various locations. Access doors are to be used only during shutdown
of heater. The normal size of the access door is 600x400 mm, which is sufficient for movement of men/ material
into and out of the heater. During operation the access doors are properly bolted using leak proof high temperature
gaskets.

20.4 See also

• Blast furnace
140 CHAPTER 20. FURNACE

• Electric arc furnace

• Basic oxygen steelmaking

• Open hearth furnace

• Masonry heater

• Russian oven

• Shell boiler

• Jetstream furnace

• HVAC

• Solar power

• Cremation

• Fan heater

• Geothermal systems

• Fire test furnaces

• Batch oven

• Forced-air gas

20.5 Notes

20.6 References
• Gray, W.A. and Muller, R (1974). Engineering calculations in radiative heat transfer (1st ed.). Pergamon Press
Ltd. ISBN 0-08-017786-7.

• Fiveland, W.A., Crosbie, A.L., Smith A.M. and Smith, T.F. (Editors) (1991). Fundamentals of radiation heat
transfer. American Society of Mechanical Engineers. ISBN 0-7918-0729-0.

• Warring, R. H (1982). Handbook of valves, piping and pipelines (1st ed.). Gulf Publishing Company. ISBN
0-87201-885-7.

• Dukelow, Samuel G (1985). Improving boiler efficiency (2nd ed.). Instrument Society of America. ISBN
0-87664-852-9.

• Whitehouse, R.C. (Editor) (1993). The valve and actuator user’s manual. Mechanical Engineering Publica-
tions. ISBN 0-85298-805-2.

• Davies, Clive (1970). Calculations in furnace technology (1st ed.). Pergamon Press. ISBN 0-08-013366-5.

• Goldstick, R. and Thumann, A (1986). Principles of waste heat recovery. Fairmont Press. ISBN 0-88173-
015-7.

• ASHRAE (1992). ASHRAE Handbook. Heating, ventilating and air-conditioning systems and equipment.
ASHRAE. ISBN 0-910110-80-8. ISSN 1078-6066.

• Perry, R.H. and Green, D.W. (Editors) (1997). Perry’s Chemical Engineers’ Handbook (7th ed.). McGraw-Hill.
ISBN 0-07-049841-5.

• Lieberman, P. and Lieberman, Elizabeth T (2003). Working Guide to Process Equipment (2nd ed.). McGraw-
Hill. ISBN 0-07-139087-1.
20.7. EXTERNAL LINKS 141

20.7 External links

• Furnaces, Incinerators, Kilns at DMOZ

• http://www.youtube.com/ How It Works: Furnace

Chapter 21

Chemical reactor

In chemical engineering, chemical reactors are vessels designed to contain chemical reactions. One example is a
pressure reactor. The design of a chemical reactor deals with multiple aspects of chemical engineering. Chemical
engineers design reactors to maximize net present value for the given reaction. Designers ensure that the reaction
proceeds with the highest efficiency towards the desired output product, producing the highest yield of product while
requiring the least amount of money to purchase and operate. Normal operating expenses include energy input,
energy removal, raw material costs, labor, etc. Energy changes can come in the form of heating or cooling, pumping
to increase pressure, frictional pressure loss (such as pressure drop across a 90° elbow or an orifice plate) or agitation.
Chemical reaction engineering is the branch of chemical engineering which deals with chemical reactors and their
design, especially by application of chemical kinetics to industrial systems.

21.1 Overview
There are a couple of main basic vessel types:

• A tank
• A pipe or tubular reactor (laminar flow reactor(LFR))

Both types can be used as continuous reactors or batch reactors, and either may accommodate one or more solids
(reagents, catalyst, or inert materials), but the reagents and products are typically fluids. Most commonly, reactors are
run at steady-state, but can also be operated in a transient state. When a reactor is first brought into operation (after
maintenance or inoperation) it would be considered to be in a transient state, where key process variables change with
time.
There are three main basic models used to estimate the most important process variables of different chemical reac-
tors:

• batch reactor model (batch),

• continuous stirred-tank reactor model (CSTR), and
• plug flow reactor model (PFR).

Furthermore, catalytic reactors require separate treatment, whether they are batch, CST, or PF reactors, as the many
assumptions of the simpler models are not valid.
Key process variables include

• Residence time (τ, lower case Greek tau)

• Volume (V)
• Temperature (T)

142
21.2. TYPES 143

Cut-away view of a stirred-tank chemical reactor with a cooling jacket

• Pressure (P)

• Concentrations of chemical species (C1 , C2 , C3 , ... C )

• Heat transfer coefficients (h, U)

A chemical reactor, typically tubular reactor, could be a packed bed. The packing inside the bed may have catalyst
to catalyze the chemical reaction. A chemical reactor may also be a fluidized bed; see Fluidized bed reactor.
Chemical reactions occurring in a reactor may be exothermic, meaning giving off heat, or endothermic, meaning
absorbing heat. A chemical reactor vessel may have a cooling or heating jacket or cooling or heating coils (tubes)
wrapped around the outside of its vessel wall to cool down or heat up the contents.

21.2 Types

21.2.1 CSTR (Continuous Stirred-Tank Reactor)

Main article: Continuous stirred-tank reactor
In a CSTR, one or more fluid reagents are introduced into a tank reactor (typically) equipped with an impeller while
the reactor effluent is removed. The impeller stirs the reagents to ensure proper mixing. Simply dividing the volume
of the tank by the average volumetric flow rate through the tank gives the residence time, or the average amount of
time a discrete quantity of reagent spends inside the tank. Using chemical kinetics, the reaction’s expected percent
completion can be calculated. Some important aspects of the CSTR:

• At steady-state, the mass flow rate in must equal the mass flow rate out, otherwise the tank will overflow or go
empty (transient state). While the reactor is in a transient state the model equation must be derived from the
differential mass and energy balances.
144 CHAPTER 21. CHEMICAL REACTOR

Chemical reactor with half coils wrapped around it

• The reaction proceeds at the reaction rate associated with the final (output) concentration, since the concen-
tration is assumed to be homogenous throughout the reactor.

• Often, it is economically beneficial to operate several CSTRs in series. This allows, for example, the first CSTR
to operate at a higher reagent concentration and therefore a higher reaction rate. In these cases, the sizes of the
reactors may be varied in order to minimize the total capital investment required to implement the process.

• It can be demonstrated that an infinite number of infinitely small CSTRs operating in series would be equivalent
to a PFR.

The behavior of a CSTR is often approximated or modeled by that of a Continuous Ideally Stirred-Tank Reactor
(CISTR). All calculations performed with CISTRs assume perfect mixing. If the residence time is 5-10 times the
mixing time, this approximation is considered valid for engineering purposes. The CISTR model is often used to
simplify engineering calculations and can be used to describe research reactors. In practice it can only be approached,
particularly in industrial size reactors in which the mixing time may be very large.

21.2.2 PFR (Plug Flow Reactor)

Main article: Plug flow reactor model

In a PFR, one or more fluid reagents are pumped through a pipe or tube. The chemical reaction proceeds as the
reagents travel through the PFR. In this type of reactor, the changing reaction rate creates a gradient with respect to
distance traversed; at the inlet to the PFR the rate is very high, but as the concentrations of the reagents decrease and
the concentration of the product(s) increases the reaction rate slows. Some important aspects of the PFR:

• All calculations performed with PFRs assume no upstream or downstream mixing, as implied by the term "plug
flow".
21.2. TYPES 145

Checking condition inside the case of a continuous stirred tank reactor (CSTR). Note the impeller (or agitator) blades on the shaft
for mixing. Also note the baffle at the bottom of the image which also helps in mixing.

Simple diagram illustrating plug flow reactor model

146 CHAPTER 21. CHEMICAL REACTOR

• Reagents may be introduced into the PFR at locations in the reactor other than the inlet. In this way, a higher
efficiency may be obtained, or the size and cost of the PFR may be reduced.
• A PFR typically has a higher efficiency than a CSTR of the same volume. That is, given the same space-time
(or residence time), a reaction will typically proceed to a higher percentage completion in a PFR than in a
CSTR. This is not always true for reversible reactions.

For most chemical reactions of industrial interest, it is impossible for the reaction to proceed to 100% completion.
The rate of reaction decreases as the reactants are consumed until the point where the system reaches dynamic
equilibrium (no net reaction, or change in chemical species occurs). The equilibrium point for most systems is less
than 100% complete. For this reason a separation process, such as distillation, often follows a chemical reactor in
order to separate any remaining reagents or byproducts from the desired product. These reagents may sometimes be
reused at the beginning of the process, such as in the Haber process. In some cases, very large reactors would be
necessary to approach equilibrium, and chemical engineers may choose to separate the partially reacted mixture and
recycle the leftover reactants.
Continuous oscillatory baffled reactor (COBR) is a tubular plug flow reactor. The mixing in COBR is achieved by the
combination of fluid oscillation and orifice baffles, allowing plug flow to be achieved under laminar flow conditions
with the net flow Reynolds number just about 100.

21.2.3 Semi-batch reactor

Main article: Semibatch reactor

A semi-batch reactor is operated with both continuous and batch inputs and outputs. A fermenter, for example, is
loaded with a batch of medium and microbes which constantly produce carbon dioxide that must removed continu-
ously. Analogously, driving a reaction of gas with a liquid is usually difficult, since the gas bubbles off. Therefore,
a continuous feed of gas is injected into the batch of a liquid. One chemical reactant is charged to the vessel and a
second chemical is added slowly (for instance, to prevent side reactions).

21.2.4 Catalytic reactor

Although catalytic reactors are often implemented as plug flow reactors, their analysis requires more complicated
treatment. The rate of a catalytic reaction is proportional to the amount of catalyst the reagents contact, as well as
the concentration of the reactants. With a solid phase catalyst and fluid phase reagents, this is proportional to the
exposed area, efficiency of diffusion of reagents in and products out, and efficacy of mixing. Perfect mixing usually
cannot be assumed. Furthermore, a catalytic reaction pathway often occurs in multiple steps with intermediates that
are chemically bound to the catalyst; and as the chemical binding to the catalyst is also a chemical reaction, it may
affect the kinetics. Catalytic reactions often display the so-called falsified kinetics, i.e. the apparent kinetics differ
from elementary chemical kinetics due to physical transport effects.
The behavior of the catalyst is also a consideration. Particularly in high-temperature petrochemical processes, catalysts
are deactivated by sintering, coking, and similar processes.
A common example of a catalytic reactor is the catalytic converter following an engine. However, most petrochemical
reactors are catalytic, and are responsible for most of industrial chemical production in the world, with extremely high-
volume examples such as sulfuric acid, ammonia, reformate/BTEX (benzene, toluene, ethylbenzene and xylene) and
alkylate gasoline blending stock.

21.3 See also

• Chemical reaction
• Chemical engineering
• Chemical reaction engineering
• Batch reactor
21.4. EXTERNAL LINKS 147

• Continuous reactor

• Laminar flow reactor

• Trickle-bed reactor

• Fluidized bed reactor

• Membrane reactor

• Bioreactor

21.4 External links

• Simple CSTR Models in MATLAB

21.5 References
• Schmidt, Lanny D., The Engineering of Chemical Reactions. New York: Oxford University Press, 1998. ISBN
0-19-510588-5.
• Levenspiel, O.: The Chemical Reactor Omnibook, Oregon St Univ Bookstores (January 1993). ISBN 0-
88246-160-5
Chapter 22

Catalysis

“Catalyst” redirects here. For other uses, see Catalyst (disambiguation).

Catalysis is the increase in the rate of a chemical reaction due to the participation of an additional substance called

An air filter that utilizes low-temperature oxidation catalyst used to convert carbon monoxide to less toxic carbon dioxide at room
temperature. It can also remove formaldehyde from the air.

a catalyst.[1] With a catalyst, reactions occur faster and with less energy. Because catalysts are not consumed, they
are recycled. Often only tiny amounts are required.[2]

148
22.1. TECHNICAL PERSPECTIVE 149

22.1 Technical perspective

In the presence of a catalyst, less free energy is required to reach the transition state, but the total free energy from
reactants to products does not change.[1] A catalyst may participate in multiple chemical transformations. The effect
of a catalyst may vary due to the presence of other substances known as inhibitors or poisons (which reduce the
catalytic activity) or promoters (which increase the activity). The opposite of a catalyst, a substance that reduces the
rate of a reaction, is an inhibitor.[1]
Catalyzed reactions have a lower activation energy (rate-limiting free energy of activation) than the corresponding un-
catalyzed reaction, resulting in a higher reaction rate at the same temperature and for the same reactant concentrations.
However, the detailed mechanics of catalysis is complex. Catalysts may affect the reaction environment favorably,
or bind to the reagents to polarize bonds, e.g. acid catalysts for reactions of carbonyl compounds, or form specific
intermediates that are not produced naturally, such as osmate esters in osmium tetroxide-catalyzed dihydroxylation of
alkenes, or cause dissociation of reagents to reactive forms, such as chemisorbed hydrogen in catalytic hydrogenation.
Kinetically, catalytic reactions are typical chemical reactions; i.e. the reaction rate depends on the frequency of
contact of the reactants in the rate-determining step. Usually, the catalyst participates in this slowest step, and rates
are limited by amount of catalyst and its “activity”. In heterogeneous catalysis, the diffusion of reagents to the surface
and diffusion of products from the surface can be rate determining. A nanomaterial-based catalyst is an example
of a heterogeneous catalyst. Analogous events associated with substrate binding and product dissociation apply to
homogeneous catalysts.
Although catalysts are not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by sec-
ondary processes. In heterogeneous catalysis, typical secondary processes include coking where the catalyst becomes
covered by polymeric side products. Additionally, heterogeneous catalysts can dissolve into the solution in a solid–
liquid system or sublimate in a solid–gas system.

22.2 Background

The production of most industrially important chemicals involves catalysis. Similarly, most biochemically significant
processes are catalysed. Research into catalysis is a major field in applied science and involves many areas of chem-
istry, notably organometallic chemistry and materials science. Catalysis is relevant to many aspects of environmental
science, e.g. the catalytic converter in automobiles and the dynamics of the ozone hole. Catalytic reactions are pre-
ferred in environmentally friendly green chemistry due to the reduced amount of waste generated,[3] as opposed to
stoichiometric reactions in which all reactants are consumed and more side products are formed. The most common
catalyst is the hydrogen ion (H+ ). Many transition metals and transition metal complexes are used in catalysis as well.
Catalysts called enzymes are important in biology.
A catalyst works by providing an alternative reaction pathway to the reaction product. The rate of the reaction is
increased as this alternative route has a lower activation energy than the reaction route not mediated by the catalyst.
The disproportionation of hydrogen peroxide creates water and oxygen, as shown below.

2 H2 O2 → 2 H2 O + O2

This reaction is preferable in the sense that the reaction products are more stable than the starting material, though
the uncatalysed reaction is slow. In fact, the decomposition of hydrogen peroxide is so slow that hydrogen peroxide
solutions are commercially available. This reaction is strongly affected by catalysts such as manganese dioxide, or the
enzyme peroxidase in organisms. Upon the addition of a small amount of manganese dioxide, the hydrogen peroxide
reacts rapidly. This effect is readily seen by the effervescence of oxygen.[4] The manganese dioxide is not consumed
in the reaction, and thus may be recovered unchanged, and re-used indefinitely. Accordingly, manganese dioxide
catalyses this reaction.[5]

22.3 General principles

150 CHAPTER 22. CATALYSIS

22.3.1 Units

Catalytic activity is usually denoted by the symbol z [6] and measured in mol/s, a unit which was called katal and
defined the SI unit for catalytic activity since 1999. Catalytic activity is not a kind of reaction rate, but a property of
the catalyst under certain conditions, in relation to a specific chemical reaction. Catalytic activity of one katal (Symbol
1 kat = 1mol/s) of a catalyst means an amount of that catalyst (substance, in Mol) that leads to a net reaction of one Mol
per second of the reactants to the resulting reagents or other outcome which was intended for this chemical reaction.
A catalyst may and usually will have different catalytic activity for distinct reactions. See katal for an example.
There are further derived SI units related to catalytic activity, see the above reference for details.

22.3.2 Typical mechanism

Main article: catalytic cycle

Catalysts generally react with one or more reactants to form intermediates that subsequently give the final reaction
product, in the process regenerating the catalyst. The following is a typical reaction scheme, where C represents the
catalyst, X and Y are reactants, and Z is the product of the reaction of X and Y:

X + C → XC (1)
Y + XC → XYC (2)
XYC → CZ (3)
CZ → C + Z (4)

Although the catalyst is consumed by reaction 1, it is subsequently produced by reaction 4, so for the overall reaction:

X+Y→Z

As a catalyst is regenerated in a reaction, often only small amounts are needed to increase the rate of the reaction. In
practice, however, catalysts are sometimes consumed in secondary processes.
As an example of a detailed mechanism at the microscopic level, in 2008 Danish researchers first revealed the se-
quence of events when oxygen and hydrogen combine on the surface of titanium dioxide (TiO2 , or titania) to produce
water. With a time-lapse series of scanning tunneling microscopy images, they determined the molecules undergo
adsorption, dissociation and diffusion before reacting. The intermediate reaction states were: HO2 , H2 O2 , then
H3 O2 and the final reaction product (water molecule dimers), after which the water molecule desorbs from the cata-
lyst surface.[7][8]

22.3.3 Reaction energetics

Catalysts work by providing an (alternative) mechanism involving a different transition state and lower activation
energy. Consequently, more molecular collisions have the energy needed to reach the transition state. Hence, catalysts
can enable reactions that would otherwise be blocked or slowed by a kinetic barrier. The catalyst may increase reaction
rate or selectivity, or enable the reaction at lower temperatures. This effect can be illustrated with an energy profile
diagram.
In the catalyzed elementary reaction, catalysts do not change the extent of a reaction: they have no effect on the
chemical equilibrium of a reaction because the rate of both the forward and the reverse reaction are both affected
(see also thermodynamics). The second law of thermodynamics describes why a catalyst does not change the chemical
equilibrium of a reaction. Suppose there was such a catalyst that shifted an equilibrium. Introducing the catalyst to
the system would result in a reaction to move to the new equilibrium, producing energy. Production of energy is a
necessary result since reactions are spontaneous if and only if Gibbs free energy is produced, and if there is no energy
barrier, there is no need for a catalyst. Then, removing the catalyst would also result in reaction, producing energy;
i.e. the addition and its reverse process, removal, would both produce energy. Thus, a catalyst that could change the
equilibrium would be a perpetual motion machine, a contradiction to the laws of thermodynamics.[9]
22.3. GENERAL PRINCIPLES 151

Generic potential energy diagram showing the effect of a catalyst in a hypothetical exothermic chemical reaction X + Y to give Z.
The presence of the catalyst opens a different reaction pathway (shown in red) with a lower activation energy. The final result and
the overall thermodynamics are the same.

If a catalyst does change the equilibrium, then it must be consumed as the reaction proceeds, and thus it is also a
reactant. Illustrative is the base-catalysed hydrolysis of esters, where the produced carboxylic acid immediately reacts
with the base catalyst and thus the reaction equilibrium is shifted towards hydrolysis.
The SI derived unit for measuring the catalytic activity of a catalyst is the katal, which is moles per second. The
productivity of a catalyst can be described by the turn over number (or TON) and the catalytic activity by the turn
over frequency (TOF), which is the TON per time unit. The biochemical equivalent is the enzyme unit. For more
information on the efficiency of enzymatic catalysis, see the article on Enzymes.
The catalyst stabilizes the transition state more than it stabilizes the starting material. It decreases the kinetic barrier
by decreasing the difference in energy between starting material and transition state. It does not change the energy
difference between starting materials and products (thermodynamic barrier), or the available energy (this is provided
by the environment as heat or light).

22.3.4 Materials

The chemical nature of catalysts is as diverse as catalysis itself, although some generalizations can be made. Pro-
ton acids are probably the most widely used catalysts, especially for the many reactions involving water, including
hydrolysis and its reverse. Multifunctional solids often are catalytically active, e.g. zeolites, alumina, higher-order
oxides, graphitic carbon, nanoparticles, nanodots, and facets of bulk materials. Transition metals are often used to
catalyze redox reactions (oxidation, hydrogenation). Examples are nickel, such as Raney nickel for hydrogenation,
and vanadium(V) oxide for oxidation of sulfur dioxide into sulfur trioxide by the so-called contact process. Many
catalytic processes, especially those used in organic synthesis, require “late transition metals”, such as palladium,
platinum, gold, ruthenium, rhodium, or iridium.
Some so-called catalysts are really precatalysts. Precatalysts convert to catalysts in the reaction. For example,
Wilkinson’s catalyst RhCl(PPh3 )3 loses one triphenylphosphine ligand before entering the true catalytic cycle. Pre-
catalysts are easier to store but are easily activated in situ. Because of this preactivation step, many catalytic reactions
involve an induction period.
Chemical species that improve catalytic activity are called co-catalysts (cocatalysts) or promotors in cooperative
catalysis.
152 CHAPTER 22. CATALYSIS

22.4 Types
Catalysts can be heterogeneous or homogeneous, depending on whether a catalyst exists in the same phase as the
substrate. Biocatalysts (enzymes) are often seen as a separate group.

22.4.1 Heterogeneous catalysts

Main article: Heterogeneous catalysis

Heterogeneous catalysts act in a different phase than the reactants. Most heterogeneous catalysts are solids that

The microporous molecular structure of the zeolite ZSM-5 is exploited in catalysts used in refineries

act on substrates in a liquid or gaseous reaction mixture. Diverse mechanisms for reactions on surfaces are known,
depending on how the adsorption takes place (Langmuir-Hinshelwood, Eley-Rideal, and Mars-van Krevelen).[10] The
total surface area of solid has an important effect on the reaction rate. The smaller the catalyst particle size, the larger
the surface area for a given mass of particles.
22.4. TYPES 153

Zeolites are extruded as pellets for easy handling in catalytic reactors.

A heterogeneous catalyst has active sites, which are the atoms or crystal faces where the reaction actually occurs.
Depending on the mechanism, the active site may be either a planar exposed metal surface, a crystal edge with
imperfect metal valence or a complicated combination of the two. Thus, not only most of the volume, but also
most of the surface of a heterogeneous catalyst may be catalytically inactive. Finding out the nature of the active
site requires technically challenging research. Thus, empirical research for finding out new metal combinations for
catalysis continues.
For example, in the Haber process, finely divided iron serves as a catalyst for the synthesis of ammonia from nitrogen
and hydrogen. The reacting gases adsorb onto active sites on the iron particles. Once physically adsorbed, the reagents
undergo chemisorption that results in dissociation into adsorbed atomic species, and new bonds between the resulting
fragments form in part due to their close proximity. In this way the particularly strong triple bond in nitrogen is
broken, which would be extremely uncommon in the gas phase due to its high activation energy. Thus, the activation
energy of the overall reaction is lowered, and the rate of reaction increases. Another place where a heterogeneous
catalyst is applied is in the oxidation of sulfur dioxide on vanadium(V) oxide for the production of sulfuric acid.
Heterogeneous catalysts are typically "supported,” which means that the catalyst is dispersed on a second material
that enhances the effectiveness or minimizes their cost. Supports prevent or reduce agglomeration and sintering of
the small catalyst particles, exposing more surface area, thus catalysts have a higher specific activity (per gram) on a
support. Sometimes the support is merely a surface on which the catalyst is spread to increase the surface area. More
often, the support and the catalyst interact, affecting the catalytic reaction. Supports are porous materials with a high
surface area, most commonly alumina, zeolites or various kinds of activated carbon. Specialized supports include
silicon dioxide, titanium dioxide, calcium carbonate, and barium sulfate.

Electrocatalysts

Main article: Electrocatalyst

154 CHAPTER 22. CATALYSIS

In the context of electrochemistry, specifically in fuel cell engineering, various metal-containing catalysts are used to
enhance the rates of the half reactions that comprise the fuel cell. One common type of fuel cell electrocatalyst is
based upon nanoparticles of platinum that are supported on slightly larger carbon particles. When in contact with one
of the electrodes in a fuel cell, this platinum increases the rate of oxygen reduction either to water, or to hydroxide
or hydrogen peroxide.

22.4.2 Homogeneous catalysts

Main article: Homogeneous catalysis

Homogeneous catalysts function in the same phase as the reactants, but the mechanistic principles invoked in het-
erogeneous catalysis are generally applicable. Typically homogeneous catalysts are dissolved in a solvent with the
substrates. One example of homogeneous catalysis involves the influence of H+ on the esterification of carboxylic
acids, such as the formation of methyl acetate from acetic acid and methanol.[11] For inorganic chemists, homoge-
neous catalysis is often synonymous with organometallic catalysts.[12]

Organocatalysis

Main article: Organocatalysis

Whereas transition metals sometimes attract most of the attention in the study of catalysis, small organic molecules
without metals can also exhibit catalytic properties, as is apparent from the fact that many enzymes lack transition
metals. Typically, organic catalysts require a higher loading (amount of catalyst per unit amount of reactant, expressed
in mol% amount of substance) than transition metal(-ion)-based catalysts, but these catalysts are usually commercially
available in bulk, helping to reduce costs. In the early 2000s, these organocatalysts were considered “new generation”
and are competitive to traditional metal(-ion)-containing catalysts. Organocatalysts are supposed to operate akin to
metal-free enzymes utilizing, e.g., non-covalent interactions such as hydrogen bonding. The discipline organocatalysis
is divided in the application of covalent (e.g., proline, DMAP) and non-covalent (e.g., thiourea organocatalysis)
organocatalysts referring to the preferred catalyst-substrate binding and interaction, respectively.

22.4.3 Enzymes and biocatalysts

In biology, enzymes are protein-based catalysts in metabolism and catabolism. Most biocatalysts are enzymes, but
other non-protein-based classes of biomolecules also exhibit catalytic properties including ribozymes, and synthetic
deoxyribozymes.[13]
Biocatalysts can be thought of as intermediate between homogeneous and heterogeneous catalysts, although strictly
speaking soluble enzymes are homogeneous catalysts and membrane-bound enzymes are heterogeneous. Several
factors affect the activity of enzymes (and other catalysts) including temperature, pH, concentration of enzyme,
substrate, and products. A particularly important reagent in enzymatic reactions is water, which is the product of
many bond-forming reactions and a reactant in many bond-breaking processes.
In biocatalysis, enzymes are employed to prepare many commodity chemicals including high-fructose corn syrup and
acrylamide.
Some monoclonal antibodies whose binding target is a stable molecule which resembles the transition state of a
chemical reaction can function as weak catalysts for that chemical reaction by lowering its activation energy.[14] Such
catalytic antibodies are sometimes called "abzymes".

22.5 Significance
Estimates are that 90% of all commercially produced chemical products involve catalysts at some stage in the process
of their manufacture.[15] In 2005, catalytic processes generated about $900 billion in products worldwide.[16] Catalysis
is so pervasive that subareas are not readily classified. Some areas of particular concentration are surveyed below.
22.5. SIGNIFICANCE 155

Left: Partially caramelised cube sugar, Right: burning cube sugar with ash as catalyst

22.5.1 Energy processing

Petroleum refining makes intensive use of catalysis for alkylation, catalytic cracking (breaking long-chain hydrocar-
bons into smaller pieces), naphtha reforming and steam reforming (conversion of hydrocarbons into synthesis gas).
Even the exhaust from the burning of fossil fuels is treated via catalysis: Catalytic converters, typically composed of
platinum and rhodium, break down some of the more harmful byproducts of automobile exhaust.

2 CO + 2 NO → 2 CO2 + N2

With regard to synthetic fuels, an old but still important process is the Fischer-Tropsch synthesis of hydrocarbons
from synthesis gas, which itself is processed via water-gas shift reactions, catalysed by iron. Biodiesel and related
biofuels require processing via both inorganic and biocatalysts.
Fuel cells rely on catalysts for both the anodic and cathodic reactions.
Catalytic heaters generate flameless heat from a supply of combustible fuel.

22.5.2 Bulk chemicals

Some of the largest-scale chemicals are produced via catalytic oxidation, often using oxygen. Examples include nitric
acid (from ammonia), sulfuric acid (from sulfur dioxide to sulfur trioxide by the chamber process), terephthalic acid
from p-xylene, and acrylonitrile from propane and ammonia.
Many other chemical products are generated by large-scale reduction, often via hydrogenation. The largest-scale
example is ammonia, which is prepared via the Haber process from nitrogen. Methanol is prepared from carbon
monoxide.
Bulk polymers derived from ethylene and propylene are often prepared via Ziegler-Natta catalysis. Polyesters,
polyamides, and isocyanates are derived via acid-base catalysis.
Most carbonylation processes require metal catalysts, examples include the Monsanto acetic acid process and hydroformylation.

22.5.3 Fine chemicals

Many fine chemicals are prepared via catalysis; methods include those of heavy industry as well as more specialized
processes that would be prohibitively expensive on a large scale. Examples include olefin metathesis using Grubbs’
catalyst, the Heck reaction, and Friedel-Crafts reactions.
Because most bioactive compounds are chiral, many pharmaceuticals are produced by enantioselective catalysis (cat-
alytic asymmetric synthesis).
156 CHAPTER 22. CATALYSIS

22.5.4 Food processing

One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) of fats using nickel
catalyst to produce margarine.[17] Many other foodstuffs are prepared via biocatalysis (see below).

22.5.5 Environment
Catalysis impacts the environment by increasing the efficiency of industrial processes, but catalysis also plays a direct
role in the environment. A notable example is the catalytic role of chlorine free radicals in the breakdown of ozone.
These radicals are formed by the action of ultraviolet radiation on chlorofluorocarbons (CFCs).

Cl· + O3 → ClO· + O2
ClO· + O· → Cl· + O2

22.6 History
In a general sense,[18] anything that increases the rate of a process is a “catalyst”, a term derived from Greek
καταλύειν, meaning “to annul,” or “to untie,” or “to pick up.” The term catalysis was coined by Jöns Jakob Berzelius
in 1835[19] to describe reactions that are accelerated by substances that remain unchanged after the reaction. Other
early chemists involved in catalysis were Eilhard Mitscherlich[20] who referred to contact processes and Johann Wolf-
gang Döbereiner[21] who spoke of contact action and whose lighter based on hydrogen and a platinum sponge became
a huge commercial success in the 1820s. Humphry Davy discovered the use of platinum in catalysis.[22] In the
1880s, Wilhelm Ostwald at Leipzig University started a systematic investigation into reactions that were catalyzed
by the presence of acids and bases, and found that chemical reactions occur at finite rates and that these rates can
be used to determine the strengths of acids and bases. For this work, Ostwald was awarded the 1909 Nobel Prize in
Chemistry.[23]

22.7 Inhibitors, poisons and promoters

Substances that reduce the action of catalysts are called catalyst inhibitors if reversible, and catalyst poisons if irre-
versible. Promoters are substances that increase the catalytic activity, even though they are not catalysts by themselves.
Inhibitors are sometimes referred to as “negative catalysts” since they decrease the reaction rate.[24] However the term
inhibitor is preferred since they do not work by introducing a reaction path with higher activation energy; this would
not reduce the rate since the reaction would continue to occur by the non-catalyzed path. Instead they act either by
deactivating catalysts, or by removing reaction intermediates such as free radicals.[24][25]
The inhibitor may modify selectivity in addition to rate. For instance, in the reduction of acetylene to ethylene, a
palladium (Pd) catalyst partly “poisoned” with lead(II) acetate (Pb(CH3 COO)2 ) can be used. Without the deactivation
of the catalyst, the ethene produced will be further reduced to ethane.[26][27]
The inhibitor can produce this effect by, e.g., selectively poisoning only certain types of active sites. Another mech-
anism is the modification of surface geometry. For instance, in hydrogenation operations, large planes of metal
surface function as sites of hydrogenolysis catalysis while sites catalyzing hydrogenation of unsaturates are smaller.
Thus, a poison that covers surface randomly will tend to reduce the number of uncontaminated large planes but leave
proportionally more smaller sites free, thus changing the hydrogenation vs. hydrogenolysis selectivity. Many other
mechanisms are also possible.
Promoters can cover up surface to prevent production of a mat of coke, or even actively remove such material (e.g.,
rhenium on platinum in platforming). They can aid the dispersion of the catalytic material or bind to reagents.

22.8 Current market

The global demand on catalysts in 2010 was estimated at approximately 29.5 billions USD. With the rapid recovery
in automotive and chemical industry overall, the global catalyst market is expected to experience fast growth in the
22.9. SEE ALSO 157

next years.[28]

22.9 See also

• Abzyme

• Autocatalysis

• BIG-NSE (Berlin Graduate School of Natural Sciences and Engineering)

• Catalysis Science & Technology (a chemistry journal)

• Environmental triggers

• Enzyme catalysis

• Industrial catalysts

• Kelvin probe force microscope

• Pharmaceutic adjuvant

• Phase Boundary Catalysis

• Phase transfer catalyst

• Photocatalysis

• Ribozyme (RNA Biocatalysis)

• SUMO enzymes

• Temperature-programmed reduction

• Thermal desorption spectroscopy

22.10 References
• IUPAC, Compendium of Chemical Terminology, 2nd ed. (the “Gold Book”) (1997). Online corrected version:
(2006–) "catalyst".

[1] http://goldbook.iupac.org/C00876.html

[2] 7 things you may not know about catalysis Louise Lerner, Argonne National Laboratory (2011)

[3] “The 12 Principles of Green Chemistry”. United States Environmental Protection Agency. Retrieved 2012-04-30.

[4] “Genie in a Bottle”. University of Minnesota. 2005-03-02.

[5] Richard I. Masel “Chemical Kinetics and Catalysis” Wiley-Interscience, New York, 2001. ISBN 0-471-24197-0.

[6] R. Dybkaer, UNIT “KATAL” FOR CATALYTIC ACTIVITY (IUPAC Technical Report), Pure Appl. Chem., Vol. 73,
No. 6, pp. 929, 2001.

[7] Jacoby, Mitch (16 February 2009). “Making Water Step by Step”. Chemical & Engineering News. p. 10.

[8] Matthiesen J, Wendt S, Hansen JØ, Madsen GK, Lira E, Galliker P, Vestergaard EK, Schaub R, Laegsgaard E, Hammer
B, Besenbacher F; Wendt; Madsen; Lira; Galliker; Vestergaard; Schaub; Laegsgaard; Hammer; Besenbacher (2009). “Ob-
servation of All the Intermediate Steps of a Chemical Reaction on an Oxide Surface by Scanning Tunneling Microscopy”.
ACS Nano 3 (3): 517–526. doi:10.1021/nn8008245. ISSN 1520-605X. PMID 19309169. Missing |last3= in Authors list
(help)

[9] A.J.B. Robertson Catalysis of Gas Reactions by Metals. Logos Press, London, 1970.
158 CHAPTER 22. CATALYSIS

[10] Helmut Knözinger, Karl Kochloefl “Heterogeneous Catalysis and Solid Catalysts” in Ullmann’s Encyclopedia of Industrial
Chemistry 2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a05_313. Article Online Posting Date: January 15, 2003

[11] Arno Behr “Organometallic Compounds and Homogeneous Catalysis” Ullmann’s Encyclopedia of Industrial Chemistry,
2002, Wiley-VCH, Weinheim. doi:10.1002/14356007.a18_215. Article Online Posting Date: June 15, 2000

[12] C. Elschenbroich, Organometallics (2006) Wiley-VCH: Weinheim. ISBN 978-3-527-29390-2

[13] D. L. Nelson and M. M. Cox Lehninger, Principles of Biochemistry 3rd Ed. Worth Publishing: New York, 2000. ISBN
1-57259-153-6.

[14] http://www.documentroot.com/2010/03/catalytic-antibodies-simply-explained.html

[15] “Recognizing the Best in Innovation: Breakthrough Catalyst”. R&D Magazine, September 2005, p. 20.

[16] 1.4.3 INDUSTRIAL PROCESS EFFICIENCY. climatetechnology.gov

[17] “Types of catalysis”. Chemguide. Retrieved 2008-07-09.

[18] Bård Lindström and Lars J. Petterson (2003) “A brief history of catalysis,” Cattech, 7 (4) : 130-138. Available on-line at:
ScienceNet.

[19] J. J. Berzelius, Årsberättelsen om framsteg i fysik och kemi [Annual report on progress in physics and chemistry], (Stockholm,
Sweden: Royal Swedish Academy of Sciences, 1835). After reviewing Eilhard Mitscherlich’s research on the formation of
ether, Berzelius coins the word katalys (catalysis) on page 245:

Original: Jag skall derföre, för att begagna en i kemien välkänd härledning, kalla den kroppars katalytiska
kraft, sönderdelning genom denna kraft katalys, likasom vi med ordet analys beteckna åtskiljandet af kroppars
beståndsdelar medelst den vanliga kemiska frändskapen.

Translation: I shall, therefore, to employ a well-known derivation in chemistry, call [the catalytic] bodies
[i.e., substances] the catalytic force and the decomposition of [other] bodies by this force catalysis, just as we
signify by the word analysis the separation of the constituents of bodies by the usual chemical affinities.

[20] E. Mitscherlich (1834) “Ueber die Aetherbildung” (On the formation of ether), Annalen der Physik und Chemie, 31 (18) :
273-282.

[21] See:

• Döbereiner (1822) “Glühendes Verbrennen des Alkohols durch verschiedene erhitzte Metalle und Metalloxyde” (In-
candescent burning of alcohol by various heated metals and metal oxides), Journal für Chemie und Physik, 34 :
91-92.
• Döbereiner (1823) “Neu entdeckte merkwürdige Eigenschaften des Platinsuboxyds, des oxydirten Schwefel-Platins
und des metallischen Platinstaubes” (Newly discovered remarkable properties of platinum suboxide, oxidized plat-
inum sulfide and metallic platinum dust), Journal für Chemie und Physik, 38 : 321-326.

[22] Sir Humphry Davy (1817) “Some new experiments and observations on the combustion of gaseous mixtures, with an
account of a method of preserving a continued light in mixtures of inflammable gases and air without flame,” Philosophical
Transactions of the Royal Society of London, 107 : 77-85.

[23] M.W. Roberts (2000). “Birth of the catalytic concept (1800–1900)". Catalysis Letters 67 (1): 1–4. doi:10.1023/A:1016622806065.

[24] K.J. Laidler Physical Chemistry with Biological Applications, Benjamin/Cummings 1978, pp. 415–417

[25] K.J. Laidler and J.H. Meiser, Physical Chemistry, Benjamin/Cummings (1982), p. 425

[26] W.P. Jencks, Catalysis in Chemistry and Enzymology McGraw-Hill, New York, 1969. ISBN 0-07-032305-4

[27] Myron L Bender, Makoto Komiyama, Raymond J Bergeron The Bioorganic Chemistry of Enzymatic Catalysis Wiley-
Interscience, Hoboken, U.S., 1984 ISBN 0-471-05991-9

[28] “Market Report: Global Catalyst Market, 2nd Edition”. Acmite Market Intelligence.
22.11. EXTERNAL LINKS 159

22.11 External links

• Science Aid: Catalysts Page for high school level science

• W.A. Herrmann Technische Universität presentation

• Alumite Catalyst, Kameyama-Sakurai Laboratory, Japan

• Inorganic Chemistry and Catalysis Group, Utrecht University, The Netherlands

• Centre for Surface Chemistry and Catalysis

• Carbons & Catalysts Group, University of Concepcion, Chile

• Center for Enabling New Technologies Through Catalysis, An NSF Center for Chemical Innovation, USA
• “Bubbles turn on chemical catalysts”, Science News magazine online, April 6, 2009.
Chapter 23

Catalytic converter

A three-way catalytic converter on a gasoline-powered 1996 Dodge Ram Van

A catalytic converter is a vehicle emissions control device that converts toxic pollutants in exhaust gas to less toxic
pollutants by catalyzing a redox reaction (oxidation or reduction). Catalytic converters are used in internal combustion
engines fueled by either petrol (gasoline) or diesel—including lean burn engines.
The first widespread introduction of catalytic converters was in the United States automobile market. Manufacturers
of 1975 model year equipped gasoline-powered vehicles with catalytic converters to comply with the U.S. Environ-

160
23.1. HISTORY 161

mental Protection Agency's stricter regulation of exhaust emissions.[1][2][3][4] These “two-way” converters combined
carbon monoxide (CO) with unburned hydrocarbons (HC) to produce carbon dioxide (CO2 ) and water (H2 O). In
1981, two-way catalytic converters were rendered obsolete by “three-way” converters that also reduce oxides of
nitrogen (NOx);[1] however, two-way converters are still used for lean burn engines.
Although catalytic converters are most commonly applied to exhaust systems in automobiles, they are also used on
electrical generators, forklifts, mining equipment, trucks, buses, locomotives, motorcycles, and airplanes. They are
also used on some wood stoves to control emissions.[5] This is usually in response to government regulation, either
through direct environmental regulation or through health and safety regulations.

23.1 History
The catalytic converter was invented by Eugene Houdry, a French mechanical engineer and expert in catalytic oil
refining[6] who lived in the U.S. around 1950. When the results of early studies of smog in Los Angeles were published,
Houdry became concerned about the role of smoke stack exhaust and automobile exhaust in air pollution and founded
a company, Oxy-Catalyst. Houdry first developed catalytic converters for smoke stacks called cats for short. Then he
developed catalytic converters for warehouse fork lifts that used low grade non-leaded gasoline.[7] Then in the mid-
1950s he began research to develop catalytic converters for gasoline engines used on cars. He was awarded United
States Patent 2742437 for his work.[8]
Widespread adoption of catalytic converters didn't occur until more stringent emission control regulations forced the
removal of the anti-knock agent tetraethyllead, from most gasoline, because lead was a 'catalyst poison' and would
deactivate the converter by forming a coating on the catalyst’s surface, effectively disabling it.[9]
Catalytic converters were further developed by a series of engineers including John J. Mooney and Carl D. Keith at
the Engelhard Corporation,[10] creating the first production catalytic converter in 1973.[11]
Dr. William C. Pfefferle developed a catalytic combustor for gas turbines in the early 1970s, allowing combustion
without significant formation of nitrogen oxides and carbon monoxide.[12][13]

23.2 Construction

Cutaway of a metal-core converter

The catalytic converter’s construction is as follows:

1. The catalyst support or substrate. For automotive catalytic converters, the core is usually a ceramic monolith
with a honeycomb structure. Metallic foil monoliths made of Kanthal (FeCrAl)[14] are used in applications
where particularly high heat resistance is required.[15] Either material is designed to provide a large surface
162 CHAPTER 23. CATALYTIC CONVERTER

Ceramic-core converter

area. The cordierite ceramic substrate used in most catalytic converters was invented by Rodney Bagley, Irwin
Lachman and Ronald Lewis at Corning Glass, for which they were inducted into the National Inventors Hall
of Fame in 2002.[1]
2. The washcoat. A washcoat is a carrier for the catalytic materials and is used to disperse the materials over
a large surface area. Aluminum oxide, titanium dioxide, silicon dioxide, or a mixture of silica and alumina
can be used. The catalytic materials are suspended in the washcoat prior to applying to the core. Washcoat
materials are selected to form a rough, irregular surface, which greatly increases the surface area compared to
the smooth surface of the bare substrate. This in turn maximizes the catalytically active surface available to
react with the engine exhaust. The coat must retain its surface area and prevent sintering of the catalytic metal
particles even at high temperatures (1000 °C).[16]
3. The catalyst itself is most often a mix of precious metals. Platinum is the most active catalyst and is widely
used, but is not suitable for all applications because of unwanted additional reactions and high cost. Palladium
and rhodium are two other precious metals used. Rhodium is used as a reduction catalyst, palladium is used
as an oxidation catalyst, and platinum is used both for reduction and oxidation. Cerium, iron, manganese and
nickel are also used, although each has limitations. Nickel is not legal for use in the European Union because
of its reaction with carbon monoxide into toxic nickel tetracarbonyl. Copper can be used everywhere except
North America, where its use is illegal because of the formation of toxic dioxin .

23.3 Types

23.3.1 Two-way
A two-way (or “oxidation”) catalytic converter has two simultaneous tasks:

1. Oxidation of carbon monoxide to carbon dioxide: 2CO + O2 → 2CO2

2. Oxidation of hydrocarbons (unburnt and partially burnt fuel) to carbon dioxide and water: CₓH₂ₓ₊₂ + [(3x+1)/2]
O2 → xCO2 + (x+1) H2 O (a combustion reaction)

This type of catalytic converter is widely used on diesel engines to reduce hydrocarbon and carbon monoxide emis-
sions. They were also used on gasoline engines in American- and Canadian-market automobiles until 1981. Because
of their inability to control oxides of nitrogen, they were superseded by three-way converters.
23.3. TYPES 163

23.3.2 Three-way
Three-way catalytic converters (TWC) have the additional advantage of controlling the emission of nitrogen oxides
(NOₓ), in particular nitrous oxide, a greenhouse gas over three hundred times more potent than carbon dioxide,[17]
a precursor to acid rain and currently the most ozone-depleting substance.[18] Technological improvements includ-
ing three-way catalytic converters have led to motor vehicle nitrous oxide emissions in the US falling to 8.2% of
anthropogenic nitrous oxide emissions in 2008, from a high of 17.77% in 1998.
Since 1981, “three-way” (oxidation-reduction) catalytic converters have been used in vehicle emission control systems
in the United States and Canada; many other countries have also adopted stringent vehicle emission regulations that in
effect require three-way converters on gasoline-powered vehicles. The reduction and oxidation catalysts are typically
contained in a common housing, however in some instances they may be housed separately. A three-way catalytic
converter has three simultaneous tasks:

1. Reduction of nitrogen oxides to nitrogen and oxygen: 2NOₓ → xO2 + N2

2. Oxidation of carbon monoxide to carbon dioxide: 2CO + O2 → 2CO2
3. Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water: CₓH₂ₓ₊₂ + [(3x+1)/2]O2 → xCO2 +
(x+1)H2 O.

These three reactions occur most efficiently when the catalytic converter receives exhaust from an engine running
slightly above the stoichiometric point. This point is between 14.6 and 14.8 parts air to 1 part fuel, by weight,
for gasoline. The ratio for Autogas (or liquefied petroleum gas (LPG)), natural gas and ethanol fuels is each slightly
different, requiring modified fuel system settings when using those fuels. In general, engines fitted with 3-way catalytic
converters are equipped with a computerized closed-loop feedback fuel injection system using one or more oxygen
sensors, though early in the deployment of three-way converters, carburetors equipped for feedback mixture control
were used.
Three-way catalysts are effective when the engine is operated within a narrow band of air-fuel ratios near stoichiom-
etry, such that the exhaust gas oscillates between rich (excess fuel) and lean (excess oxygen) conditions. However,
conversion efficiency falls very rapidly when the engine is operated outside of that band of air-fuel ratios. Under
lean engine operation, there is excess oxygen and the reduction of NOₓ is not favored. Under rich conditions, the
excess fuel consumes all of the available oxygen prior to the catalyst, thus only stored oxygen is available for the
oxidation function. Closed-loop control systems are necessary because of the conflicting requirements for effective
NOₓ reduction and HC oxidation. The control system must prevent the NOₓ reduction catalyst from becoming fully
oxidized, yet replenish the oxygen storage material to maintain its function as an oxidation catalyst.
Three-way catalytic converters can store oxygen from the exhaust gas stream, usually when the air–fuel ratio goes
lean.[19] When sufficient oxygen is not available from the exhaust stream, the stored oxygen is released and consumed
(see cerium(IV) oxide). A lack of sufficient oxygen occurs either when oxygen derived from NOₓ reduction is un-
available or when certain maneuvers such as hard acceleration enrich the mixture beyond the ability of the converter
to supply oxygen.

Unwanted reactions

Unwanted reactions can occur in the three-way catalyst, such as the formation of odoriferous hydrogen sulfide and
ammonia. Formation of each can be limited by modifications to the washcoat and precious metals used. It is difficult
to eliminate these byproducts entirely. Sulfur-free or low-sulfur fuels eliminate or reduce hydrogen sulfide.
For example, when control of hydrogen-sulfide emissions is desired, nickel or manganese is added to the washcoat.
Both substances act to block the absorption of sulfur by the washcoat. Hydrogen sulfide is formed when the washcoat
has absorbed sulfur during a low-temperature part of the operating cycle, which is then released during the high-
temperature part of the cycle and the sulfur combines with HC.

23.3.3 Diesel engines

For compression-ignition (i.e., diesel engines), the most commonly used catalytic converter is the Diesel Oxidation
Catalyst (DOC). DOCs contain palladium / platinum with Aluminium oxide which serve as catalysts to oxidise the
hydrocarbons and carbon monoxide with oxygen to form carbon dioxide and water.
164 CHAPTER 23. CATALYTIC CONVERTER

2CO + O2 → 2CO2
CxH₂x₊₂ + [(3x+1)/2] O2 → x CO2 + (x+1) H2 O
These converters often operate at 90 percent efficiency, virtually eliminating diesel odor and helping to reduce visible
particulates (soot). These catalysts are not active for NOₓ reduction because any reductant present would react first
with the high concentration of O2 in diesel exhaust gas.
Reduction in NOₓ emissions from compression-ignition engines has previously been addressed by the addition of
exhaust gas to incoming air charge, known as exhaust gas recirculation (EGR). In 2010, most light-duty diesel manu-
facturers in the U.S. added catalytic systems to their vehicles to meet new federal emissions requirements. There are
two techniques that have been developed for the catalytic reduction of NOₓ emissions under lean exhaust conditions
- selective catalytic reduction (SCR) and the lean NOₓ trap or NOx adsorber. Instead of precious metal-containing
NOx adsorbers, most manufacturers selected base-metal SCR systems that use a reagent such as ammonia to reduce
the NOₓ into nitrogen. Ammonia is supplied to the catalyst system by the injection of urea into the exhaust, which
then undergoes thermal decomposition and hydrolysis into ammonia. One trademark product of urea solution, also
referred to as Diesel Exhaust Fluid (DEF), is AdBlue.
Diesel exhaust contains relatively high levels of particulate matter (soot), consisting in large part of elemental carbon.
Catalytic converters cannot clean up elemental carbon, though they do remove up to 90 percent of the soluble organic
fraction, so particulates are cleaned up by a soot trap or diesel particulate filter (DPF). Historically, a DPF consists
of a Cordierite or Silicon Carbide substrate with a geometry that forces the exhaust flow through the substrate walls,
leaving behind trapped soot particles. Contemporary DPFs can be manufactured from a variety of rare metals that
provide superior performance (at a greater expense).[20] As the amount of soot trapped on the DPF increases, so
does the back pressure in the exhaust system. Periodic regenerations (high temperature excursions) are required to
initiate combustion of the trapped soot and thereby reducing the exhaust back pressure. The amount of soot loaded
on the DPF prior to regeneration may also be limited to prevent extreme exotherms from damaging the trap during
regeneration. In the U.S., all on-road light, medium and heavy-duty vehicles powered by diesel and built after 1
January 2007, must meet diesel particulate emission limits that means they effectively have to be equipped with a
2-Way catalytic converter and a diesel particulate filter. Note that this applies only to the diesel engine used in the
vehicle. As long as the engine was manufactured before 1 January 2007, the vehicle is not required to have the
DPF system. This led to an inventory runup by engine manufacturers in late 2006 so they could continue selling
pre-DPF vehicles well into 2007.[21] During the re-generation cycle, most systems require the engine to consume
several gallons of fuel in a relatively short amount of time in order to generate the high temperatures necessary for
the cycle to complete. This has been shown to adversely affect the overall fuel economy of vehicles equipped with
DPF systems, especially in vehicles that are driven mostly in city conditions where frequent acceleration requires a
larger amount of fuel to be burned and therefore more soot to collect in the exhaust system.

23.3.4 Lean burn spark-ignition engines

For lean burn spark-ignition engines, an oxidation catalyst is used in the same manner as in a diesel engine. Emissions
from Lean Burn Spark Ignition Engines are very similar to emissions from a Diesel Compression Ignition engine.

23.4 Installation
Many vehicles have a close-coupled catalytic converter located near the engine’s exhaust manifold. This unit heats
up quickly due to its proximity to the engine, and reduces cold-engine emissions by burning off hydrocarbons from
the extra-rich mixture used to start a cold engine.
When catalytic converters were first introduced, most vehicles used carburetors that provided a relatively rich air-
fuel ratio. Oxygen (O2 ) levels in the exhaust stream were generally insufficient for the catalytic reaction to occur
efficiently, so most installations included secondary air injection which injected air into the exhaust stream to increase
the available oxygen and allow the catalyst to function.
Some three-way catalytic converter systems have air injection systems with the air injected between the first (NOₓ
reduction) and second (HC and CO oxidation) stages of the converter. As in the two-way converters, this injected air
provides oxygen for the oxidation reactions. An upstream air injection point, ahead of the catalytic converter, is also
sometimes present to provide oxygen during engine warm up, which causes unburned fuel to ignite in the exhaust
tract before reaching the catalytic converter. This reduces the engine runtime needed for the catalytic converter to
23.5. DAMAGE 165

reach its “light-off” or operating temperature.

Most newer vehicles are electronic fuel injection systems, and thus, do not have air injection systems. Instead,
they provide a constantly varying air-fuel mixture that quickly and continually cycles between lean and rich exhaust.
Oxygen sensors are used to monitor the exhaust oxygen content before and after the catalytic converter and this
information is used by the Electronic control unit to adjust the fuel injection so as to prevent the first (NOₓ reduc-
tion) catalyst from becoming oxygen-loaded while ensuring the second (HC and CO oxidation) catalyst is sufficiently
oxygen-saturated.

23.5 Damage

Catalyst poisoning occurs when the catalytic converter is exposed to exhaust containing substances that coat the work-
ing surfaces, encapsulating the catalyst so that it cannot contact and treat the exhaust. The most-notable contaminant
is lead, so vehicles equipped with catalytic converters can be run only on unleaded fuels. Other common catalyst
poisons include fuel sulfur, manganese (originating primarily from the gasoline additive MMT), and silicone, which
can enter the exhaust stream if the engine has a leak that allows coolant into the combustion chamber. Phosphorus
is another catalyst contaminant. Although phosphorus is no longer used in gasoline, it (and zinc, another low-level
catalyst contaminant) was until recently widely used in engine oil antiwear additives such as zinc dithiophosphate
(ZDDP). Beginning in 2004, a limit of phosphorus concentration in engine oils was adopted in the API SM and
ILSAC GF-4 specifications.
Depending on the contaminant, catalyst poisoning can sometimes be reversed by running the engine under a very
heavy load for an extended period of time. The increased exhaust temperature can sometimes liquefy or sublimate
the contaminant, removing it from the catalytic surface. However, removal of lead deposits in this manner is usually
not possible because of lead’s high boiling point.
Any condition that causes abnormally high levels of unburned hydrocarbons—raw or partially burnt fuel—to reach
the converter will tend to significantly elevate its temperature, bringing the risk of a meltdown of the substrate and
resultant catalytic deactivation and severe exhaust restriction. Vehicles equipped with OBD-II diagnostic systems are
designed to alert the driver to a misfire condition by means of flashing the “check engine” light on the dashboard.

23.6 Regulations

Emissions regulations vary considerably from jurisdiction to jurisdiction. Most automobile spark-ignition engines
in North America have been fitted with catalytic converters since 1975,[1][2][3][4] and the technology used in non-
automotive applications is generally based on automotive technology.
Regulations for diesel engines are similarly varied, with some jurisdictions focusing on NOₓ (nitric oxide and nitrogen
dioxide) emissions and others focusing on particulate (soot) emissions. This regulatory diversity is challenging for
manufacturers of engines, as it may not be economical to design an engine to meet two sets of regulations.
Regulations of fuel quality vary across jurisdictions. In North America, Europe, Japan and Hong Kong, gasoline and
diesel fuel are highly regulated, and compressed natural gas and LPG (Autogas) are being reviewed for regulation.
In most of Asia and Africa, the regulations are often lax: in some places sulfur content of the fuel can reach 20,000
parts per million (2%). Any sulfur in the fuel can be oxidized to SO2 (sulfur dioxide) or even SO3 (sulfur trioxide)
in the combustion chamber. If sulfur passes over a catalyst, it may be further oxidized in the catalyst, i.e., SO2 may
be further oxidized to SO3 . Sulfur oxides are precursors to sulfuric acid, a major component of acid rain. While it is
possible to add substances such as vanadium to the catalyst washcoat to combat sulfur-oxide formation, such addition
will reduce the effectiveness of the catalyst. The most effective solution is to further refine fuel at the refinery to
produce ultra-low sulfur diesel. Regulations in Japan, Europe and North America tightly restrict the amount of sulfur
permitted in motor fuels. However, the direct financial expense of producing such clean fuel may make it impractical
for use in developing countries. As a result, cities in these countries with high levels of vehicular traffic suffer from
acid rain, which damages stone and woodwork of buildings, poisons humans and other animals, and damages local
ecosystems, at a very high financial cost.
166 CHAPTER 23. CATALYTIC CONVERTER

23.7 Negative aspects

Some early converter designs greatly restricted the flow of exhaust, which negatively affected vehicle performance,
driveability, and fuel economy.[22] Because they were used with carburetors incapable of precise fuel-air mixture
control, they could overheat and ignite flammable materials under the car.[23] While removing a modern catalytic
converter in new condition will net only a very small increase vehicle performance, the removal of a 6-year-old
modern catalyst resulted in a 3.4% increase in horsepower[24] To many performance enthusiasts, this modest increase
in power for very little cost encourages the removal or “gutting” of the catalytic converter.[22][25] In such cases, the
converter may be replaced by a welded-in section of ordinary pipe or a flanged “test pipe” ostensibly meant to check
if the converter is clogged by comparing how the engine runs with versus without the converter, which facilitates
reinstallation of the converter in order to pass an emission test.[24] In many jurisdictions, it is illegal to remove or
disable a catalytic converter for any reason other than its direct and immediate replacement. In the United States, for
example, it is a violation of Section 203(a)(3)(A) of the 1990 Clean Air Act for a vehicle repair shop to remove a
converter from a vehicle, or cause a converter to be removed from a vehicle, except in order to replace it with another
converter.,[26] and Section 203(a)(3)(B) makes it illegal for any person to sell or to install any part that would bypass,
defeat, or render inoperative any emission control system, device, or design element. Vehicles without functioning
catalytic converters generally fail emission inspections. The automotive aftermarket supplies high-flow converters for
vehicles with upgraded engines, or whose owners prefer an exhaust system with larger-than-stock capacity.[27]

23.7.1 Warm-up period

Vehicles emit most of their pollution during the first five minutes of engine operation before the catalytic converter
has warmed up sufficiently to be effective.[28]
In 1999, BMW introduced an electrically heated catalyst, which they called “E-CAT”, in their 750iL sedan. Heating
coils inside the catalytic converter assemblies are electrified just after engine start, bringing the catalyst up to operating
temperature very quickly to qualify the vehicle for low emission vehicle (LEV) designation.[29]

23.7.2 Environmental impact

Catalytic converters have proven to be reliable and effective in reducing noxious tailpipe emissions. However, they
also have some shortcomings and adverse environmental impacts in production:

• An engine equipped with a three-way catalyst must run at the stoichiometric point, which means more fuel is
consumed than in a lean-burn engine. This means approximately 10% more CO2 emissions from the vehicle.

• Catalytic converter production requires palladium or platinum; part of the world supply of these precious metals
is produced near Norilsk, Russia, where the industry (among others) has caused Norilsk to be added to Time
magazine’s list of most-polluted places.[30]

23.8 Theft
Because of the external location and the use of valuable precious metals including platinum, palladium, rhodium,
and gold, converters are a target for thieves. The problem is especially common among late-model trucks and SUVs,
because of their high ground clearance and easily removed bolt-on catalytic converters. Welded-in converters are
also at risk of theft, as they can be easily cut off.[31][32][33] Thieves’ techniques for fast removal of a converter, for
instance using a portable reciprocating saw, can often damage other components of the car. Damage to components
like wiring, or a fuel line, can have dangerous consequences. Rises in metal costs in the U.S. during recent years have
led to a large increase in converter theft.[34] A catalytic converter can cost well over $1,000 to replace.[35]

23.9 Diagnostics
Various jurisdictions now legislate on-board diagnostics to monitor the function and condition of the emissions-control
system, including the catalytic converter. On-board diagnostic systems take several forms.
23.10. SEE ALSO 167

Temperature sensors are used for two purposes. The first is as a warning system, typically on two-way catalytic
converters such as are still sometimes used on LPG forklifts. The function of the sensor is to warn of catalytic
converter temperature above the safe limit of 750 °C (1,380 °F). More-recent catalytic-converter designs are not as
susceptible to temperature damage and can withstand sustained temperatures of 900 °C (1,650 °F). Temperature
sensors are also used to monitor catalyst functioning: usually two sensors will be fitted, with one before the catalyst
and one after to monitor the temperature rise over the catalytic-converter core.
The oxygen sensor is the basis of the closed-loop control system on a spark-ignited rich-burn engine; however, it is
also used for diagnostics. In vehicles with OBD II, a second oxygen sensor is fitted after the catalytic converter to
monitor the O2 levels. The O2 levels are monitored to see the efficiency of the burn process. The on-board computer
makes comparisons between the readings of the two sensors. The readings are taken by voltage measurements. If both
sensors show the same output or the rear O2 is “switching”, the computer recognizes that the catalytic converter either
is not functioning or has been removed, and will operate a malfunction indicator lamp and affect engine performance.
Simple “oxygen sensor simulators” have been developed to circumvent this problem by simulating the change across
the catalytic converter with plans and pre-assembled devices available on the Internet. Although these are not legal
for on-road use, they have been used with mixed results.[36] Similar devices apply an offset to the sensor signals,
allowing the engine to run a more fuel-economical lean burn that may, however, damage the engine or the catalytic
converter.[37]
NOₓ sensors are extremely expensive and are in general used only when a compression-ignition engine is fitted with
a selective catalytic-reduction (SCR) converter, or a NOₓ absorber catalyst in a feedback system. When fitted to an
SCR system, there may be one or two sensors. When one sensor is fitted it will be pre-catalyst; when two are fitted,
the second one will be post-catalyst. They are used for the same reasons and in the same manner as an oxygen sensor:
the only difference is the substance being monitored.

23.10 See also

• Catalytic heater

• Cerium(III) oxide

• NOx adsorber

• Roadway air dispersion modeling

23.11 References
[1] Palucka, Tim (Winter 2004). “Doing the Impossible”. Invention & Technology 19 (3). Archived from the original on 3
December 2008. Retrieved 14 December 2011.

[2] Petersen Publishing (1975). “The Catalytic Converter”. In Erwin M. Rosen. The Petersen Automotive Troubleshooting &
Repair Manual. New York, NY: Grosset & Dunlap. p. 493. ISBN 0-448-11946-3. For years, the exhaust system (...)
remained virtually unchanged until 1975 when a strange new component was added. It’s called a catalytic converter(...)

[3] “General Motors Believes it has an Answer to the Automotive Air Pollution Problem”. The Blade: Toledo, Ohio. 12
September 1974. Retrieved 14 December 2011.

[4] “Catalytic Converter Heads Auto Fuel Economy Efforts”. The Milwaukee Sentinel. 11 November 1974. Retrieved 14
December 2011.

[5] “Choosing the Right Wood Stove”. Burn Wise. US EPA. Retrieved 2 January 2012.

[6] Csere, Csaba (January 1988). “10 Best Engineering Breakthroughs”. Car and Driver 33 (7): 63.

[7] “Exhaust Gas Made Safe.” Popular Mechanics, September 1951, p. 134, bottom of page

[8] “His Smoke Eating Cats Now Attack Traffic Smog.” Popular Science, June 1955, pp. 83-85/244.

[9] Staff writer (undated). “Eugene Houdry”. Chemical Heritage Foundation. Retrieved 7 January 2011.

[10] (registration required) “Carl D. Keith, a Father of the Catalytic Converter, Dies at 88”. The New York Times. 15 November
2008.
168 CHAPTER 23. CATALYTIC CONVERTER

[11] Staff writer (undated). “Engelhard Corporation”. referenceforbusiness.com. Retrieved 7 January 2011.

[12] Robert N. Carter, Lance L. Smith, Hasan Karim, Marco Castaldi, Shah Etemad, George Muench, R. Samuel Boorse,
Paul Menacherry and William C. Pfefferle (1998). Catalytic Combustion Technology Development for Gas Turbine Engine
Applications. MRS Proceedings, 549, 93 doi:10.1557/PROC-549-93

[13] Worthy, Sharon. Bio-Medicine: Connecticut chemist receives award for cleaner air technology. 23 June 2003. Retrieved 11
December 2012.

[14] Pischinger, Univ.-Prof. Dr.-Ing. Stephan (2011). Verbrennungsmotoren Band 2 (24 ed.). Aachen, Germany: Lehrstuhl
Für Verbrennungskraftmachinen. p. 335.

[15] Pischinger, Univ.-Prof. Dr.-Ing. Stephan (2011). Verbrennungsmotoren Band 2 (24 ed.). Aachen, Germany: Lehrstuhl
Für Verbrennungskraftmachinen. p. 335.

[16] Martin Votsmeier, Thomas Kreuzer, Jürgen Gieshoff, Gerhard Lepperhoff. Automobile Exhaust Control, in Ullmann’s
Encyclopedia of Industrial Chemistry, Wiley-VCH 2002. DOI: 10.1002/14356007.a03_189.pub2

[17] EPA: Nitrous Oxide Emissions

[18] Ravishankara, A. R.; Daniel, J. S.; Portmann, R. W. (2009). “Nitrous Oxide (N2O): The Dominant Ozone-Depleting Sub-
stance Emitted in the 21st Century”. Science 326 (5949): 123–5. Bibcode:2009Sci...326..123R. doi:10.1126/science.1176985.
PMID 19713491.

[19] Brandt, Erich; Wang, Yanying; Grizzle, Jessy (2000). “Dynamic Modeling of a Three Way Catalyst for SI Engine Exhaust
Emission Control”. IEEE Transactions on Control Systems Technology 8 (5): 767–776. doi:10.1109/87.865850.

[20] http://www.synergycatalyst.com/catalyst-coating-technology/

[21] “Heavy-Duty Engine and Vehicle Standards and Highway Diesel Fuel Sulfur Control Requirements” PDF (123 KB)

[22] Crutsinger, Martin (29 September 1982). “Kits to Foil Auto Pollution Control Are Selling Well”. The Gainesville Sun.

[23] Ullman, Owen (14 June 1976). “Catalytic Converter Still Controversial after Two Years of Use”. The Bulletin.

[24] Beat the Law. Importtuner.com (2007-02-26). Retrieved on 2011-01-09.

[25] “Some of Us Can Only Afford a Clunker”. The Palm Beach Post. 23 February 1996.

[26] Sale and Use of Aftermarket Catalytic Converters, US Environmental Protection Agency, US Federal Register Volume 51

[27] Tanner, Keith. Mazda MX-5 Miata. Motorbooks. p. 120.

[28] Catalytic converters, nsls.bnl.gov

[29] Edgar, Julian (5 October 1999). “Goodbye 12 volts... hello 42 volts!". Autospeed. Retrieved 2 January 2012. The
current model BMW 750iL has a maximum electrical load of a staggering 428 amps (5.9 kW)! In this car, over half of
the maximum power load is from the short-term electrical heating of the catalytic converters, with the heating used so that
they come up to operating temp quickly

[30] Walsh, Bryan (12 September 2007). “Norilsk, Russia”. The World’s Most Polluted Places (Time). Retrieved 7 January
2011.

[31] Fraga, Brian (30 November 2011). “Carver police investigating catalytic converter thefts”. South Coast Today. Retrieved
21 December 2011.

[32] “Catalytic Converter Theft”.

[33] Murr, Andrew (9 January 2008). “An Exhausting New Crime — What Thieves Are Stealing from Today’s Cars”. Newsweek.
Retrieved 7 January 2011.

[34] Johnson, Alex (12 February 2008). “Stolen in 60 Seconds: The Treasure in Your Car — As Precious Metals Prices Soar,
Catalytic Converters Are Targets for Thieves”. MSNBC. Retrieved 7 January 2011.

[35] “Converters Taken by Car Lot Thieves”. PoconoNews. 2 July 2009.

[36] “Settlement Involves Illegal Emission Control 'Defeat Devices’ Sold for Autos”. 1 June 2007.

[37] “Check Engine Lights Come on for a Reason”. Concord Monitor. 12 January 2003.
23.12. FURTHER READING 169

23.12 Further reading

• Keith, C. D., et al. U.S. Patent 3,441,381: “Apparatus for purifying exhaust gases of an internal combustion
engine”. 29 April 1969
• Lachman, I. M. et al. U.S. Patent 3,885,977: “Anisotropic Cordierite Monolith” (Ceramic substrate). 5 November
1973

• Charles H. Bailey. U.S. Patent 4,094,645: “Combination muffler and catalytic converter having low backpres-
sure”. 13 June 1978

• Charles H. Bailey. U.S. Patent 4,250,146: '"Caseless monolithic catalytic converter”. 10 February 1981
• Srinivasan Gopalakrishnan. GB 2397782: “Process And Synthesizer For Molecular Engineering of Materials”.
13 March 2002

23.13 External links

• Catalytic converter at HowStuffWorks

• Automotive applications of high temperature insulation wool

Chapter 24

BTEX

BTEX is an acronym that stands for benzene, toluene, ethylbenzene, and xylenes.[1] These compounds are some of the
volatile organic compounds (VOCs) found in petroleum derivatives such as petrol (gasoline). Toluene, ethylbenzene,
and xylenes have harmful effects on the central nervous system.
BTEX compounds are notorious due to the contamination of soil and groundwater with these compounds. Con-
tamination typically occurs near petroleum and natural gas production sites, petrol stations, and other areas with
underground storage tanks (USTs) or above-ground storage tanks (ASTs), containing gasoline or other petroleum-
related products.
The amount of 'Total BTEX', the sum of the concentrations of each of the constituents of BTEX, is sometimes used
to aid in assessing the relative risk or seriousness at contaminated locations and the need of remediation of such sites.
Naphthalene may also be included in Total BTEX analysis yielding results referred to as BTEXN. In the same way,
styrene is sometimes added, making it BTEXS.

24.1 See also

• Alkylation
• BTX (chemistry)

• Friedel–Crafts reaction
• Hydrodealkylation

24.2 References
[1] “BTEX Definition Page”. USGS. December 14, 2006.

170
Chapter 25

Alkylation

Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as
an alkyl carbocation, a free radical, a carbanion or a carbene (or their equivalents).[1] Alkylating agents are widely
used in chemistry because the alkyl group is probably the most common group encountered in organic molecules.
Many biological target molecules or their synthetic precursors are composed of an alkyl chain with specific functional
groups in a specific order. Selective alkylation, or adding parts to the chain with the desired functional groups, is
used, especially if there is no commonly available biological precursor. Alkylation with only one carbon is termed
methylation.
In oil refining contexts, alkylation refers to a particular alkylation of isobutane with olefins. For upgrading of
petroleum, alkylation produces synthetic C7 –C8 alkylate, which is a premium blending stock for gasoline.[2]
In medicine, alkylation of DNA is used in chemotherapy to damage the DNA of cancer cells. Alkylation is accom-
plished with the class of drugs called alkylating antineoplastic agents.

Benzene Friedel-Crafts alkylation.

25.1 Alkylating agents

“Alkylating agent” redirects here. For the class of drugs, see alkylating antineoplastic agent.

Alkylating agents are classified according to their nucleophilic or electrophilic character.

25.1.1 Nucleophilic alkylating agents

Nucleophilic alkylating agents deliver the equivalent of an alkyl anion (carbanion). Examples include the use of
organometallic compounds such as Grignard (organomagnesium), organolithium, organocopper, and organosodium
reagents. These compounds typically can add to an electron-deficient carbon atom such as at a carbonyl group.
Nucleophilic alkylating agents can also displace halide substituents on a carbon atom. In the presence of catalysts,
they also alkylate alkyl and aryl halides, as exemplified by Suzuki couplings.

171
172 CHAPTER 25. ALKYLATION

25.1.2 Electrophilic alkylating agents

Electrophilic alkylating agents deliver the equivalent of an alkyl cation. Examples include the use of alkyl halides
with a Lewis acid catalyst to alkylate aromatic substrates in Friedel-Crafts reactions. Alkyl halides can also react
directly with amines to form C-N bonds; the same holds true for other nucleophiles such as alcohols, carboxylic
acids, thiols, etc.
Electrophilic, soluble alkylating agents are often very toxic, due to their ability to alkylate DNA. They should be
handled with proper PPE. This mechanism of toxicity is also responsible for the ability of some alkylating agents to
perform as anti-cancer drugs in the form of alkylating antineoplastic agents, and also as chemical weapons such as
mustard gas. Alkylated DNA either does not coil or uncoil properly, or cannot be processed by information-decoding
enzymes. This results in cytotoxicity with the effects of inhibition the growth of the cell, initiation of programmed cell
death or apoptosis. However, mutations are also triggered, including carcinogenic mutations, explaining the higher
incidence of cancer after exposure.
Alcohols and phenols can be alkylated to give alkyl ethers:

R-OH + R'-X → R-O-R' + H-X

The produced acid HX is removed with a base, or, alternatively, the alcohol is deprotonated first to give an alkoxide
or phenoxide. For example, dimethyl sulfate alkylates the sodium salt of phenol to give anisole, the methyl ether of
phenol. The dimethyl sulfate is dealkylated to sodium methylsulfate.[3]

Ph-O– Na+ + Me2 SO4 → Ph-O-Me + Na+ MeSO4 –

On the contrary, the alkylation of amines introduces the problem that the alkylation of an amine makes it more
nucleophilic. Thus, when an electrophilic alkylating agent is introduced to a primary amine, it will preferentially
alkylate all the way to a quaternary ammonium cation.

R-NH2 → R-NH-R' → R-N(R')2 → R-N(R')3 + (alkylating agent omitted for clarity)

If the quaternary ammonium is not the desired product, more circuitious routes such as reductive amination are
necessary.

25.1.3 Carbene alkylating agents

Carbenes are extremely reactive and are known to attack even unactivated C-H bonds. Carbenes can be generated by
elimination of a diazo group. A metal can form a carbene equivalent called a transition metal carbene complex.
Trimethyloxonium tetrafluoroborate and triethyloxonium tetrafluoroborate belong to one of these categories.

25.2 In biology
Main article: methylation

Methylation is the most common type of alkylation, being associated with the transfer of a methyl group. Methylation
is distinct from alkylation in that it is specifically the transfer of one carbon, whereas alkylation can refer to the transfer
of long chain carbon groups. Methylation in nature is typically effected by vitamin B12-derived enzymes, where the
methyl group is carried by cobalt. In methanogenesis, coenzyme M is methylated by tetrahydromethanopterin.
Electrophilic compounds may alkylate different nucleophiles in the body. The toxicity, carcinogenity, and paradox-
ically, cancer cell-killing abilities of different DNA alkylating agents are an example.

25.3 Oil refining

Main article: alkylation unit
In a standard oil refinery process, isobutane is alkylated with low-molecular-weight alkenes (primarily a mixture
25.3. OIL REFINING 173

Alkylation of alkenes (shown here is propene) by isobutane is a major process in refineries. It is catalysed by strong acids such as
HF and sulfuric acid.

of propene and butene) in the presence of a Bronsted acid catalyst, either sulfuric acid or hydrofluoric acid.[4] In
an oil refinery it is referred to as a sulfuric acid alkylation unit (SAAU) or a hydrofluoric alkylation unit, (HFAU).
Refinery workers may simply refer to it as the alky or alky unit. The catalyst protonates the alkenes (propene, butene)
to produce reactive carbocations, which alkylate isobutane. The reaction is carried out at mild temperatures (0 and
30 °C) in a two-phase reaction. Because the reaction is exothermic, cooling is needed: SAAU plants require lower
temperatures so the cooling medium needs to be chilled, for HFAU normal refinery cooling water will suffice. It is
important to keep a high ratio of isobutane to alkene at the point of reaction to prevent side reactions which produces a
lower octane product, so the plants have a high recycle of isobutane back to feed. The phases separate spontaneously,
so the acid phase is vigorously mixed with the hydrocarbon phase to create sufficient contact surface.
The product is called alkylate and is composed of a mixture of high-octane, branched-chain paraffinic hydrocarbons
(mostly isoheptane and isooctane). Alkylate is a premium gasoline blending stock because it has exceptional anti-
knock properties and is clean burning. Alkylate is also a key component of avgas. The octane number of the alkylate
depends mainly upon the kind of alkenes used and upon operating conditions. For example, isooctane results from
combining butylene with isobutane and has an octane rating of 100 by definition. There are other products in the
alkylate, so the octane rating will vary accordingly.
Since crude oil generally contains only 10 to 40 percent of hydrocarbon constituents in the gasoline range, refineries
use a fluid catalytic cracking process to convert high molecular weight hydrocarbons into smaller and more volatile
compounds, which are then converted into liquid gasoline-size hydrocarbons. Alkylation processes transform low
molecular-weight alkenes and iso-paraffin molecules into larger iso-paraffins with a high octane number.
Combining cracking, polymerization, and alkylation can result in a gasoline yield representing 70 percent of the
starting crude oil. More advanced processes, such as cyclicization of paraffins and dehydrogenation of naphthenes
forming aromatic hydrocarbons in a catalytic reformer, have also been developed to increase the octane rating of
gasoline. Modern refinery operation can be shifted to produce almost any fuel type with specified performance
criteria from a single crude feedstock.
Refineries examine whether it makes sense economically to install alkylation units. Alkylation units are complex,
with substantial economy of scale. In addition to a suitable quantity of feedstock, the price spread between the
value of alkylate product and alternate feedstock disposition value must be large enough to justify the installation.
Alternative outlets for refinery alklylation feedstocks include sales as LPG, blending of C4 streams directly into
gasoline and feedstocks for chemical plants. Local market conditions vary widely between plants. Variation in the
RVP specification for gasoline between countries and between seasons dramatically impacts the amount of butane
streams that can be blended directly into gasoline. The transportation of specific types of LPG streams can be
expensive so local disparities in economic conditions are often not fully mitigated by cross market movements of
alkylation feedstocks.
The availability of a suitable catalyst is also an important factor in deciding whether to build an alkylation plant. If
sulfuric acid is used, significant volumes are needed. Access to a suitable plant is required for the supply of fresh acid
and the disposition of spent acid. If a sulfuric acid plant must be constructed specifically to support an alkylation
unit, such construction will have a significant impact on both the initial requirements for capital and ongoing costs of
operation. Alternatively it is possible to install a WSA Process unit to regenerate the spent acid. No drying of the gas
takes place. This means that there will be no loss of acid, no acidic waste material and no heat is lost in process gas
reheating. The selective condensation in the WSA condenser ensures that the regenerated fresh acid will be 98% w/w
even with the humid process gas. It is possible to combine spent acid regeneration with disposal of hydrogen sulfide
by using the hydrogen sulfide as internal fuel in the refinery or elsewhere.[5]
The second main catalyst option is hydrofluoric acid. In typical alkylation plants, rates of consumption for acid are
much lower than for sulfuric acid. These plants also produce alkylate with better octane rating than do sulfuric plants.
However, due to its hazardous nature, HF acid is produced at very few locations and transportation must be managed
174 CHAPTER 25. ALKYLATION

rigorously.

25.4 See also

• Hydrodealkylation
• Transalkylation

• Friedel–Crafts reaction

• Category:Alkylating agents
• Category:Ethylating agents
• Category:Methylating agents

25.5 References
[1] March Jerry; (1985). Advanced Organic Chemistry reactions, mechanisms and structure (3rd ed.). New York: John Wiley
& Sons, inc. ISBN 0-471-85472-7

[2] Stefanidakis, G.; Gwyn, J.E. (1993). “Alkylation”. In John J. McKetta. Chemical Processing Handbook. CRC Press. pp.
80–138. ISBN 0-8247-8701-3.

[3] G. S. Hiers and F. D. Hager (1941), “Anisole”, Org. Synth.; Coll. Vol. 1: 58

[4] Michael Röper, Eugen Gehrer, Thomas Narbeshuber, Wolfgang Siegel “Acylation and Alkylation” in Ullmann’s Encyclo-
pedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000. doi:10.1002/14356007.a01_185

[5] Sulphur recovery; (2007). The Process Principles, details advances in sulphur recovery by the WSA process. Denmark:
Jens Kristen Laursen, Haldor Topsøe A/S. Reprinted from Hydrocarbonengineering August 2007

25.6 External links

• Macrogalleria page on polycarbonate production

• Alkylating agents at the US National Library of Medicine Medical Subject Headings (MeSH)
25.7. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 175

25.7 Text and image sources, contributors, and licenses

25.7.1 Text
• Hydrogen sulfide Source: http://en.wikipedia.org/wiki/Hydrogen%20sulfide?oldid=642341659 Contributors: AxelBoldt, Mav, Bryan
Derksen, Zundark, Tarquin, Roadrunner, Ktsquare, Tim Starling, Pit, David Martland, Wapcaplet, Ahoerstemeier, Darkwind, Julesd,
Jschwa1, Andrewman327, Timc, Haukurth, Grendelkhan, Francs2000, Denelson83, Gentgeen, Robbot, Pigsonthewing, RedWolf, Ee00224,
Antonin, Cutler, Clementi, Giftlite, Graeme Bartlett, Unconcerned, Duncharris, Mboverload, Pne, OldakQuill, Keith Edkins, Sonjaaa,
Edsanville, Sonett72, Mike Rosoft, Spiffy sperry, Noisy, Vsmith, Aardark, DcoetzeeBot, Geoking66, Odalcet, CanisRufus, Art LaPella,
Spoon!, Marco Polo, Robotje, Vortexrealm, Foobaz, Sam Korn, A Karley, Alansohn, Free Bear, Quatermass, Keenan Pepper, Moanzhu,
Benjah-bmm27, Ahruman, MarkRose, RainbowOfLight, Dirac1933, Shigernafy, Skatebiker, Versageek, Gene Nygaard, Capecodeph,
LukeSurl, Walshga, BerserkerBen, Dandv, Benbest, GregorB, SCEhardt, Palica, V8rik, BD2412, Davion, DePiep, Drbogdan, Rjwilmsi,
WCFrancis, Vuong Ngan Ha, FlaBot, Margosbot, RexNL, Parutakupiu, Physchim62, Imnotminkus, Chobot, Dj Capricorn, WriterHound,
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FF2010, Zzuuzz, Chase me ladies, I'm the Cavalry, Sbyrnes321, MacsBug, SmackBot, Snowmobile, Edgar181, Hmains, Chris the speller,
Bluebot, Ottawakismet, M m hawk, Thumperward, Salvor, Baa, Kbailey1, Laslovarga, Onorem, Addshore, RandomP, Smokefoot, Agent-
moose, Drphilharmonic, Gump Stump, Chymicus, Dgfduck, Aussie Alchemist, Gobonobo, Jaganath, Mbeychok, Stwalkerster, Beetstra,
Kyoko, Vie charlie, InedibleHulk, Gegnome, Iridescent, Shoeofdeath, IvanLanin, Twas Now, Courcelles, Thricecube, Billy Hathorn, An-
drhyo, Mellery, Nova325, Van helsing, Zureks, Cybernetic, Infodek, Stephend01, Icek, A876, Zgystardst, Mtpaley, Ufwuct, James086,
Sean2074, Amlz, Escarbot, Luna Santin, Paul from Michigan, Spencer, Mikenorton, Pi.1415926535, Fetchcomms, BeeArkKey, Probios,
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Kalothira, Broadbot, CanOfWorms, BotKung, Xhandar, Lamro, Ducky3.14, Andrewmcgibbon, SieBot, Mycomp, Da Joe, A. Carty,
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Drmies, NovaDog, Jacco Huisman, Ktr101, AssegaiAli, Eeekster, Shinkolobwe, Sun Creator, Garing, Henrylesliegrahamlong, Heffner,
Plasmic Physics, Dana boomer, Norum370, Arniepie1990, Rror, Vanished 45kd09la13, Alexius08, MystBot, Airplaneman, Arturo57,
Prowikipedians, Addbot, Danielaustinhall12, DOI bot, Element16, NjardarBot, Rickydrunk, CarsracBot, Jamie Wade, FiriBot, Baffle
gab1978, Nyc445, Rickjames112, OlEnglish, ScAvenger, Վազգեն, Peatswift, Luckas-bot, Yobot, CheMoBot, Kilom691, Plasticbot,
AnomieBOT, Casforty, Jim1138, Μυρμηγκάκι, Materialscientist, The High Fin Sperm Whale, Citation bot, Xqbot, Sionus, TechBot,
Sylwia Ufnalska, Anna Frodesiak, GrouchoBot, Amaury, FrescoBot, ShelbyBell, Riventree, Orthonto, Pigcatapult, Citation bot 1, Dig-
byDalton, Nirmos, Pinethicket, Bluescolor234, RedBot, Dinamik-bot, Clarkcj12, DARTH SIDIOUS 2, RjwilmsiBot, Bento00, ElPeste,
Mordekai wiki, WikitanvirBot, Ramones74, Lhutchinson, Scr999, NotAnonymous0, Wikipelli, Kp grewal, JSquish, Hitokui Pineapple,
Consciouslee, H3llBot, J1812, CameronTylar, Wayne Slam, Seattle, TyA, Mayur, Ego White Tray, YOSF0113, ChuispastonBot, Zaba-
cad, Laveshtyagi, Sven Manguard, DASHBotAV, Whoop whoop pull up, GrindItOut, Kabhi1995, ClueBot NG, Bjohns86, Satellizer,
Hon-3s-T, Rycecube57, Vacation9, O.Koslowski, Rezabot, Nao1958, Platonicmaria, Helpful Pixie Bot, Brad5001, JohnSRoberts99,
Bibcode Bot, Gauravjuvekar, BG19bot, Jay8g, Suicide Prevention, Dan653, Nsda, MrBill3, Chip123456, BattyBot, LegacyOfValor,
Bleistift2, Lesbolover, EuroCarGT, Amysawiki, ThunderSkunk, MilosF, Osmoregulator, Howicus, BlackDragon2712, Harlem Baker
Hughes, Simon150999, David Reay, Meteor sandwich yum, Monkbot, Bunnyluvur11, Johnsonman1234, Amandas2780, NewsOrgNet,
AwesoMan3000, Pavel989, Valeg96, Goku778777877, JBeags, Ananasanana, Cavalierhld, Sunsetcookie and Anonymous: 356
• Alkene Source: http://en.wikipedia.org/wiki/Alkene?oldid=636960861 Contributors: Tobias Hoevekamp, Magnus Manske, Bryan Derk-
sen, Tarquin, Taw, PierreAbbat, William Avery, Heron, Looxix, Jimfbleak, Andres, Ideyal, Ludwigmk, Haukurth, Johnleemk, Gentgeen,
Robbot, Securiger, Rfc1394, Wikibot, Marc Venot, Centrx, Giftlite, BenFrantzDale, Bensaccount, Kandar, Antandrus, Onco p53, Vina,
H Padleckas, Tsemii, DanMatan, ClockworkTroll, Rich Farmbrough, Guanabot, Cacycle, Dr. Strangelove, Guanabot2, ZeroOne, Andrejj,
Nickj, ~K, Janna Isabot, Arcadian, Physicistjedi, Elerium, HasharBot, Jumbuck, Keenan Pepper, Sligocki, Walkerma, Edwards, Clock-
workSoul, Richard Taytor, Max Naylor, Wimvandorst, Drbreznjev, Saxifrage, Sburke, Borb, MONGO, Flamingspinach, Crucis, V8rik,
Rjwilmsi, Salix alba, Boccobrock, FlaBot, PKM, Mhking, YurikBot, Wavelength, Joborrett, Gaius Cornelius, Giro720, Mike411, Nawl-
inWiki, Tony1, Zwobot, Tachyon01, Wknight94, Silverchemist, Chesnok, Imaninjapirate, Јованвб, JeramieHicks, Dra2k4, SmackBot,
KnowledgeOfSelf, Bomac, Eskimbot, Frymaster, Edgar181, J.Steinbock, Bluebot, Sampi, DHN-bot, Can't sleep, clown will eat me, Sun-
darBot, Zilch0000, Smokefoot, Drphilharmonic, DMacks, Chymicus, Spiritia, SashatoBot, Nishkid64, NeilUK, NongBot, Munita Prasad,
Rayleung2709, MTSbot, Iridescent, Basicdesign, Gil Gamesh, Tawkerbot2, VinceB, Iced Kola, Anakata, Jac16888, Cydebot, Kanags, Ri-
fleman 82, Palffy, Christian75, Thijs!bot, Kajisol, Devon Fyson, AntiVandalBot, Vishal raina90, Textilestudent1, Malcolm, Omegakent,
MikeLynch, Deflective, Plantsurfer, Savant13, Magioladitis, Saamb, DerHexer, JaGa, Tom Herbert, MartinBot, Glrx, J.delanoy, MrBell,
Markbri16, LordAnubisBOT, FJPB, CardinalDan, VolkovBot, TXiKiBoT, Imjewish, KyleRGiggs, Don4of4, Themcman1, Dmo8706,
Shanata, EmxBot, SieBot, Emmmmmms, YAYsocialism, BotMultichill, Andrewjlockley, Momo san, Colbuckshot, ClueBot, Jakede-
haas, Puchiko, Latigid on, DragonBot, Excirial, Alexbot, Jstewart1991, Bishoys, Plasmic Physics, Addbot, Some jerk on the Internet,
DOI bot, Dawynn, Atethnekos, LinkFA-Bot, Jarble, Luckas-bot, Yobot, Naudefjbot, AnakngAraw, AnomieBOT, Shootbamboo, Ru-
binbot, EryZ, Materialscientist, Citation bot, Xqbot, TinucherianBot II, DSisyphBot, ‫حسن علي البط‬, Bellerophon, JulianDelphiki,
Sandcherry, FrescoBot, Liridon, Citation bot 1, Secalinum, Xhmikos, Trappist the monk, 777sms, RjwilmsiBot, Wilson2e, EmausBot,
Challisrussia, ZéroBot, Lateg, Spookyrunner13, Llightex, Mephisto spa, Whoop whoop pull up, ClueBot NG, A09150748, Movses-
bot, Raymon5639, JohnSRoberts99, Bibcode Bot, Vagobot, Hallows AG, Srodrig, Afavr007, DarafshBot, ChrisGualtieri, Physomania,
Dexbot, Webclient101, ThunderSkunk, Wamiq, Jurniesmith, Rkoohpaee, Raytuzio, 1999sportsfan, Y-S.Ko and Anonymous: 210
• Alkane Source: http://en.wikipedia.org/wiki/Alkane?oldid=640082542 Contributors: Magnus Manske, Carey Evans, Bryan Derksen,
Tarquin, AstroNomer, Taw, Andre Engels, Ktsquare, Heron, Fruge, Dcljr, SebastianHelm, Ahoerstemeier, Jimfbleak, Александър,
Whkoh, Andres, Schneelocke, Ideyal, Mulad, Ludwigmk, Stone, Wik, Haukurth, LMB, SEWilco, Samsara, Rschmertz, Donarreiskof-
fer, Gentgeen, Robbot, Fredrik, Tomchiukc, Wikibot, Ungvichian, Rsduhamel, Vacuum, Giftlite, Jacoplane, Mikez, Herbee, Leonard
G., Unconcerned, Darrien, Kandar, Wmahan, Keith Edkins, Lqs, Antandrus, Onco p53, The MoUsY spell-checker, SudhirP, Sam Ho-
cevar, Tsemii, Klemen Kocjancic, Grunt, Mike Rosoft, Grand Edgemaster, Rich Farmbrough, Guanabot, Silence, ZeroOne, Zaslav,
Brian0918, Joanjoc, Gilgamesh he, Chuayw2000, Spoon!, Rcsheets, Guettarda, Cmdrjameson, Arcadian, Avitek, Tomgally, Ardric47,
HasharBot, Jumbuck, Alansohn, Anthony Appleyard, Arthena, Benjah-bmm27, Riana, Walkerma, MarkRose, Cburnett, Max Naylor,
Metju, Gmaxwell, Etacar11, PoccilScript, Guy M, Borb, Firien, Graham87, V8rik, Malangthon, Josh Parris, Rjwilmsi, Vuong Ngan
Ha, FlaBot, Nihiltres, Nivix, RexNL, Gurch, Jrtayloriv, Mattman00000, Srleffler, Physchim62, Chobot, Frappyjohn, YurikBot, Wave-
176 CHAPTER 25. ALKYLATION

length, Huw Powell, Jimp, RussBot, Postglock, Chris Capoccia, Bergsten, Hellbus, Gaius Cornelius, Yyy, Pseudomonas, Tavilis, ENeville,
EWS23, Moppet65535, Yahya Abdal-Aziz, Zwobot, BOT-Superzerocool, Silverchemist, U.S.Vevek, Јованвб, KGasso, Lapin rossig-
nol, Itub, MacsBug, SmackBot, Bomac, Scifiintel, Delldot, Eskimbot, TheKillerAngel, Edgar181, Gilliam, ERcheck, J.Steinbock, Chris
the speller, Kurykh, TimBentley, MrDrBob, Jon513, Hichris, DHN-bot, Colonies Chris, Oatmeal batman, Drphilharmonic, DMacks,
Kukini, Ohconfucius, Chatvany, Euchiasmus, Zaphraud, Caim, Jaganath, Pthag, Mbeychok, Olin, 16@r, JHunterJ, Munita Prasad, Beet-
stra, Kyoko, Mets501, Ace Frahm, Ryulong, MTSbot, Asyndeton, Txtayloc, JoeBot, J Di, Igoldste, Exander, Tawkerbot2, Fvasconcellos,
Mmdoogie, JForget, Mikiemike, CmdrObot, Tarchon, Gyopi, Joelholdsworth, INVERTED, Cydebot, Pais, Kanags, LotusBG, Rifleman
82, Meno25, Hebrides, Christian75, Chrislk02, Abtvctkto61, Calvero JP, Thijs!bot, Epbr123, Pstanton, Roland1952, WillMak050389,
JustAGal, AntiVandalBot, Seaphoto, Opelio, Jayron32, Zadernet, Myanw, JAnDbot, SimonJones, Deflective, Plantsurfer, Hydro, An-
donic, RebelRobot, LittleOldMe, .anacondabot, Magioladitis, VoABot II, [email protected], GODhack, Nikevich, Quantockgob-
lin, Jjasi, MetsBot, Spellmaster, Charlie MacKenzie, Mathnerd314, ChemNerd, R'n'B, Tsing 306, Largehairy, J.delanoy, Adavidb, Bo-
gey97, Dhruv17singhal, LordAnubisBOT, Ncmvocalist, Spinach Dip, Thehodder, Joeinwap, TeamZissou, Hellno2, VolkovBot, Ryan032,
Philip Trueman, TXiKiBoT, Java7837, SueHay, Rei-bot, Qxz, JhsBot, From-cary, Shanata, Dralexander, Staka, Brianga, K. Aain-
sqatsi, Sanjetti, Ponyo, SieBot, BotMultichill, Andrewjlockley, Kaypoh, Wizzard2k, Momo san, Candycarrasco, Fornaeffe, Anchor Link
Bot, PerryTachett, Efe, Denisarona, ClueBot, Mel 100percent, 3meandEr, Arakunem, Hystrix, DragonBot, Alexbot, GoldenGoose100,
Lattanzisc, Umair uamrCH, EdRaper2, Versus22, AC+79 3888, SoxBot III, Albambot, AVand, DOI bot, FUMMY2008, Wickey-nl,
AkhtaBot, Leszek Jańczuk, Crankelwitz, LinkFA-Bot, 84user, Frasmacon, Tide rolls, Wikkidd, Gail, Legobot, Luckas-bot, Yobot,
Tohd8BohaithuGh1, Sarrus, AnomieBOT, Rubinbot, 1exec1, Daniele Pugliesi, Galoubet, Ulric1313, EryZ, Wiki007wiki, Materialsci-
entist, Citation bot, Elm-39, Xqbot, Zad68, Slimcallum94, DSisyphBot, Jü, Br77rino, BritishWatcher, ‫حسن علي البط‬, GrouchoBot,
JerryBot, Doulos Christos, CumulousSpears, Esmu Igors, Thehelpfulbot, FrescoBot, Beaber, LucienBOT, Lol0147, Yungmoney11, Sa-
credchicken, Citation bot 1, Machn, The does, Allthingstoallpeople, What do i want to..., Double sharp, Achandrasekaran99, PPerviz,
Vrenator, Ge0nk, Reaper Eternal, Jordan Duarte, Suffusion of Yellow, Jamiespinks, Jynto, Dickmuncher456, Marie Poise, PetRock-
sRule, Ripchip Bot, Regancy42, Techguy78, RA0808, DancingHorses, Quasihuman, Saddaf72, Spookyrunner13, SophiePoijes, SatMi9,
Carmichael, Joonyoungsun, 28bot, ClueBot NG, Ds2207, Cracked acorns, Snotbot, 123Hedgehog456, Widr, VH2, Helpful Pixie Bot,
Johnny C. Morse, Doorknob747, Nikos 1993, Reformation32, Gorthian, VTJenkins, NotWith, Mejoribus, MrJohnnyMorales, Techstepp,
Uberkill160, Glacialfox, Razzat99, Torchwood999, ChrisGualtieri, Necronomicron8, Pwdent, Dollarmorph, Dexbot, Burzuchius, TwoT-
woHello, Earthhands2, Reatlas, Басилей, Wamiq, Jem100, Evano101, Wikifan2744, Die Antwoorde, Gh gdrycvhygjnm ,l bhjubtvfctu75,
Monkbot, Muelleum, Banoodle, Forbidden User, Shahzaibzaibshah, TD712, Ridhwanullah and Anonymous: 366

• Methane Source: http://en.wikipedia.org/wiki/Methane?oldid=642335801 Contributors: AxelBoldt, Kpjas, Marj Tiefert, Mav, Bryan
Derksen, Tarquin, Taw, Josh Grosse, Fredbauder, Enchanter, Anthere, Merphant, DrBob, Zoe, Daniel C. Boyer, Icarus, Xlation, Booy-
abazooka, Pit, Tompagenet, Ixfd64, Mcarling, Minesweeper, Shimmin, Looxix, Mkweise, Ahoerstemeier, Mac, William M. Connolley,
Lupinoid, Habj, Mxn, Smack, Vargenau, Dino, Haukurth, Nv8200p, SEWilco, Rei, Wetman, Denelson83, Donarreiskoffer, Robbot, Jo-
tomicron, Kristof vt, Altenmann, Nurg, Securiger, Bobbyanalog, Sverdrup, Rebrane, Hadal, Mushroom, Antonin, Superm401, Pengo,
Terjepetersen, Alan Liefting, Giftlite, TimGrin, Marnanel, Jyril, Tom harrison, Everyking, Niteowlneils, Duncharris, Jorge Stolfi, Siroxo,
Chameleon, SWAdair, Gyrofrog, Neilc, Andycjp, Keith Edkins, Antandrus, Beland, DragonflySixtyseven, Richardb43, Urhixidur, Tsemii,
Edsanville, JohnArmagh, M1ss1ontomars2k4, Mike Rosoft, Ta bu shi da yu, O'Dea, Discospinster, Rich Farmbrough, Guanabot, Super-
coop, ArnoldReinhold, Xezbeth, Exabyte, Paul August, Rubicon, Kelvinc, MaxPower, CanisRufus, Kwamikagami, Shanes, RoyBoy,
Femto, Leftmostcat, Thuresson, Janna Isabot, Vortexrealm, Kappa, Larry V, Egonw, Jumbuck, Alansohn, Ocean57, Eric Kvaalen, Atlant,
Keenan Pepper, Paleorthid, Benjah-bmm27, Yamla, SHIMONSHA, Malo, Snowolf, Rebroad, Cburnett, Jheald, Tony Sidaway, Shoefly,
Zxcvbnm, Gene Nygaard, HenryLi, João Carlos de Campos Pimentel, Velho, Boothy443, Firsfron, Rechlin, Yansa, StradivariusTV, Jere-
myA, MONGO, Tabletop, SDC, Fi9, Palica, V8rik, BD2412, DePiep, Drbogdan, Rjwilmsi, JHMM13, Tangotango, Oblivious, DirkvdM,
Titoxd, FlaBot, Nihiltres, RexNL, Fresheneesz, Abdominator, Physchim62, King of Hearts, CJLL Wright, Chobot, DVdm, YurikBot,
Wavelength, Jimp, WAvegetarian, Eupator, Hellbus, Hydrargyrum, Stephenb, Gaius Cornelius, Ihope127, Pseudomonas, Wimt, Nawl-
inWiki, Wiki alf, Obarskyr, Howcheng, Dureo, Irishguy, Dank235, El Pollo Diablo, JHCaufield, Lockesdonkey, DeadEyeArrow, Ryan-
Jones, Hamstersanonymous, Wknight94, FF2010, Csyria, Deville, Zzuuzz, A-Hrafn, Јованвб, Arthur Rubin, Fang Aili, NHSavage, Reyk,
Allens, JDspeeder1, GrinBot, DVD R W, Luk, Itub, Deuar, SmackBot, Hkhenson, Robotbeat, Nsayer, Bomac, Kilo-Lima, Davewild,
Matthuxtable, Jrockley, Atomota, Frymaster, ProveIt, Edgar181, Wittylama, PeterSymonds, Gilliam, Russ4555, Angelbo, Alias777,
Bluebot, Ottawakismet, Persian Poet Gal, NCurse, Raymond arritt, GregRM, MalafayaBot, SchfiftyThree, Robocoder, RayAYang, Oat-
meal batman, Zsinj, Decibel, Lchiarav, Jorvik, Realberserker, Hospitallier, Wonderstruck, Golfman, Dreadstar, Pwjb, Richard001,
Smokefoot, BinaryTed, Maximumlobster, DMacks, ILike2BeAnonymous, Mion, Pilotguy, SashatoBot, Nishkid64, Anlace, Bluerhinos,
JosiShewellBrockway, Kuru, Scientizzle, Heimstern, Jaganath, Breno, AstroChemist, Minna Sora no Shita, Olin, Interestingstuffadder,
Tlesher, Aleenf1, IronGargoyle, Keber, LightYear, RandomCritic, 16@r, Stupid Corn, Werdan7, Ccubedd, Beetstra, Stizz, Meco, Wag-
gers, Ryulong, Buttle, MTSbot, Jose77, RMHED, DabMachine, Masoninman, Paul venter, Basicdesign, S0me l0ser, Thricecube, Tawker-
bot2, JForget, Vaughan Pratt, CWY2190, N2e, Evil00, Pewwer42, Nbound, Kanags, Rifleman 82, Doomed Rasher, Go229, MattButts,
Rracecarr, Naudefj, Christian75, Chrislk02, Jaerik, Hithisishal, Omicronpersei8, Tunheim, Rspeed, Satori Son, DJBullfish, Thijs!bot,
Bezking, KimDabelsteinPetersen, RolfSander, HappyInGeneral, Mojo Hand, Marek69, Mr pand, Alkane-man, Nick Number, Pap3rw8,
TangentCube, MichaelMaggs, Natalie Erin, Sbandrews, Mentifisto, Porqin, David D., AntiVandalBot, Luna Santin, MsDivagin, Prolog,
Leftynm, Pro crast in a tor, Itistoday, Gdo01, Spencer, Zidane tribal, Samuel Erau, JAnDbot, D99figge, Deflective, MER-C, Fetchcomms,
QuantumEngineer, IanOsgood, Hello32020, Andrew Swallow, Jacksatan, OhanaUnited, Xeno, Pkoppenb, Jahoe, Rothorpe, Acroterion,
Steevo714, Achero, Magioladitis, Bongwarrior, VoABot II, Happycool, AtticusX, EOBeav, Arnavwik, Harel, Kaiserkarl13, WODUP,
Prestonmcconkie, Avicennasis, Gabriel Kielland, BatteryIncluded, Dirac66, Geoffrussell, 28421u2232nfenfcenc, Sustainableyes, Just
James, DerHexer, JaGa, Arthuralbano, Partymetroid, Rover999, Hdt83, MartinBot, Rettetast, Juansidious, R'n'B, Dirt palace, Shut-
ing0424, Smokizzy, Tgeairn, J.delanoy, Rgoodermote, Afforess, Bogey97, Hans Dunkelberg, Maurice Carbonaro, Dbiel, Jerry, Of-
ficeGirl, Katalaveno, McSly, Baconbitsrox, Skier Dude, Blah123451234, JWarburg, SJP, 83d40m, Biglovinb, Pish9ijek, KylieTastic,
Cometstyles, Usp, Kevin1222, KudzuVine, MartinBotIII, Squids and Chips, Sar200, VolkovBot, Soupo, Paranoid600, Jeff G., TheMind-
sEye, AlnoktaBOT, LeilaniLad, Barneca, Philip Trueman, Jvdunn25, Cubbyfan1, TXiKiBoT, BlueCanary9999, Rei-bot, Aaronmiles2,
OlavN, Anna Lincoln, Thejasomeister, Seb26, Geremieken, Slysplace, Ryanmoffet, Jackfork, Tombarker, Raymondwinn, Tombarker2,
Psyche825, BotKung, Mills192, Porktober1, Lamro, Tomaxer, Jlaskey, Agentq314, Temporaluser, Mare Griz, Sssprkrao, Jim.amen,
Euryalus, Sophos II, Luboogers25, OlliffeObscurity, Dawn Bard, Voigts99, Corruptionis, Jason Patton, Andrewjlockley, AfroSoldier,
Hilosoph, Bentogoa, Flyer22, Cuvette, Elcobbola, Momo san, Godfinger, Oxymoron83, PhilMacD, Gmac101, Lightmouse, Radzewicz,
BenoniBot, Anchor Link Bot, AllHailZeppelin, Dabomb87, Kalidasa 777, Tomcloyd, Escape Orbit, Chem-awb, Mrfebruary, PuercoPop,
Martarius, Arugia, ClueBot, Jackollie, The Thing That Should Not Be, Insaneingus, Catonz, Drmies, CounterVandalismBot, Niceguyedc,
Nualran, LizardJr8, Getalifedotorg, 718 Bot, Lchappell, Awickert, Excirial, Gnome de plume, Alexbot, Momo135, Paskino, Davidar-
25.7. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 177

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Sudharsan, Aminaq, Plasmic Physics, Cbake, SoxBot III, DumZiBoT, Janstr, D0nj03, XLinkBot, JWhitt433, Nathan Johnson, Wikin-
aut11, Megtec, PL290, Zodon, Lemchesvej, Addbot, Proofreader77, Pyfan, Mr0t1633, DOI bot, Yoenit, Jojhutton, Landon1980, Wda,
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Ehrenkater, Tide rolls, Malwinder25, Qemist, Zorrobot, Jarble, LuK3, आशीष भटनागर, TUNES111, Luckas-bot, Yobot, Ptbotgourou,
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sharp, Mercy11, Wikibleedia, Javierito92, Poitrine, Raidon Kane, 4, Drjohntoconnorpe, Suffusion of Yellow, Jynto, Andrea105, Whisky
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Ghostinwow, Shayne10, Sam147258369, Filiosus’s Saga, Mossy2100, BattyBot, Tutelary, Cprez10, Khazar2, EuroCarGT, Uraniumduck,
JYBot, Qocheedy daiin, EagerToddler39, BrightStarSky, Dexbot, Chenwkz, Farder22, G.Kiruthikan, JZNIOSH, Hectorlinda, TwoT-
woHello, Lugia2453, Sfgiants1995, Forestwerk, Reatlas, Nononononononono, PC-XT, Spider48, Epicgenius, Jared429, Davidlester-
morris, TrueOne99, Babitaarora, Jerryarkansas, Prokaryotes, Eagle3399, Ramendoctor, Cosineofthetimes, Daniel Smith97, Monkbot,
Trackteur, Hmsalmon, Vikbox123, Paullitely, Scott247, 2Mars4$2Billion, Poiuytrewqvtaatv123321, TheMagikCow, Vamsikrishna.1999,
JBeags, RitikjainRJ, Ridhwanullah, Du dum fanden, Cavalierhld and Anonymous: 925
• Ethane Source: http://en.wikipedia.org/wiki/Ethane?oldid=632900709 Contributors: Bryan Derksen, Tarquin, Ixfd64, Shimmin, Looxix,
Ellywa, Wmmorrow, Andres, Popsracer, Peregrine981, Nv8200p, Denelson83, Robbot, YahoKa, Securiger, Sverdrup, Bkell, Anthony,
Mikez, Monedula, Peruvianllama, Dratman, Niteowlneils, OldakQuill, Keith Edkins, LiDaobing, Edsanville, Dr. Strangelove, Michall,
LemRobotry, Joanjoc, Kwamikagami, Evand, Jerryseinfeld, HasharBot, Jumbuck, Anthony Appleyard, Benjah-bmm27, Walkerma, Sid-
neySM, Wimvandorst, Boothy443, Kupos, Spamguy, Tabletop, Palica, Marudubshinki, V8rik, DePiep, Rjwilmsi, Hiberniantears, Vuong
Ngan Ha, FlaBot, Carrionluggage, Physchim62, Chobot, Gwernol, YurikBot, RobotE, Yyy, Anetode, DeadEyeArrow, Emijrp, Јованвб,
Tomj, Mpjohans, Owain.davies, Tim R, Luk, ChemGardener, ZorkFox, Canthusus, Nil Einne, Edgar181, Gilliam, Sbharris, Darth Panda,
V1adis1av, Kindall, SundarBot, Will Beback, SashatoBot, Bluerhinos, Kuru, Rigadoun, Scientizzle, JoshuaZ, Keber, LightYear, Munita
Prasad, Beetstra, Novangelis, MTSbot, Eastfrisian, Mthsmith, IvanLanin, Courcelles, Luminaux, Dlohcierekim, Cacahueten, CmdrObot,
Sulfis, WeggeBot, Rzepa, Nbound, Rracecarr, Richhoncho, Epbr123, LeeG, Alkane-man, Northumbrian, Mentifisto, Catgut, Docpel-
letier, Enaidmawr, ChemNerd, R'n'B, CommonsDelinker, Nono64, J.delanoy, EscapingLife, Psygnet, MartinBotIII, VolkovBot, Af648,
A4bot, Tacofan, Insanity Incarnate, EmxBot, SieBot, Da Joe, Flyer22, Pyros89, Chem-awb, ClueBot, Alexbot, Jotterbot, Thingg, Plas-
mic Physics, Lahosken, Jamesscottbrown, Hseo, Noctibus, Getsnoopy, Addbot, C6541, Vchorozopoulos, Qjim, Luckas-bot, Yobot, 2D,
CheMoBot, Tonyrex, AnomieBOT, Materialscientist, Citation bot, SciberDoc, RibotBOT, Fotaun, Shortygetlow, Thehelpfulbot, Liridon,
Yungmoney11, William915, Citation bot 1, Hoo man, Plasticspork, Jynto, Jslipscomb, WikitanvirBot, JSquish, Donner60, ClueBot NG,
Bibcode Bot, BG19bot, Northamerica1000, Swaggmasta, IA-chemist, Mevagiss, Monkbot, Banjomatt and Anonymous: 133
• Propane Source: http://en.wikipedia.org/wiki/Propane?oldid=641862226 Contributors: Marj Tiefert, Gorm, Rmhermen, Enchanter,
William Avery, DrBob, D, Mike dill, Tim Starling, Ixfd64, Looxix, Gabriel, Netsnipe, Schneelocke, Rrostie, Greenrd, WhisperToMe,
Wik, SEWilco, AnthonyQBachler, Denelson83, Twang, Riddley, Dale Arnett, Securiger, Academic Challenger, Hadal, Anthony, Giftlite,
TimGrin, DocWatson42, Mikez, BenFrantzDale, Niteowlneils, Leonard G., Brockert, Darrien, Keith Edkins, Antandrus, Sebbe, Scott
Burley, Iantresman, Urhixidur, Edsanville, Sonett72, Trevor MacInnis, Alsocal, Shagie, Mike Rosoft, Swedophile, Discospinster, Gua-
nabot, Sladen, Zombiejesus, Dr. Strangelove, Xezbeth, Quistnix, Pavel Vozenilek, Jordanmills, Kbh3rd, Neko-chan, Kaszeta, MBisanz,
Kwamikagami, Mwanner, Dennis Brown, Bobo192, Janna Isabot, Chtito, Phidauex, Merope, Alansohn, Anthony Appleyard, Benjah-
bmm27, Walkerma, InShaneee, Plange, DreamGuy, Snowolf, Velella, Wimvandorst, Skatebiker, Gene Nygaard, EasyTarget, Nuno
Tavares, Woohookitty, Ataru, LOL, Mazca, Scjessey, Pol098, Rickjpelleg, Emops, Wayward, The Lightning Stalker, Graham87, Qw-
ertyus, DePiep, Jclemens, Rjwilmsi, T.John.E, Wikirao, Kazrak, Geoduck, DoubleBlue, Matt Deres, Yamamoto Ichiro, Titoxd, FlaBot,
SchuminWeb, Fahrenme, RexNL, Fresheneesz, Physchim62, Chobot, Jaraalbe, DVdm, Shardsofmetal, Gwernol, YurikBot, Wavelength,
RobotE, Sceptre, Metalloid, Jtkiefer, Hede2000, Lexi Marie, GarageBay9, SpuriousQ, Hellbus, Hydrargyrum, Stephenb, Shaddack,
Skubasteve834, Astral, Aeusoes1, Janke, RazorICE, B5baxter, Misza13, Nescio, Trcunning, Scheinwerfermann, Jkhoury, Emijrp, Ph-
gao, Nikkimaria, Closedmouth, Јованвб, Pb30, Frederik.Questier, Wsiegmund, DGaw, Fram, Staxringold, Katieh5584, Mdwyer, Jr9999,
Thomas Blomberg, Carlosguitar, Mejor Los Indios, DonutLover, Cidvicious, Cedricblais, Luk, SmackBot, Sagie, Incnis Mrsi, Olorin28,
Shoy, C.Fred, Chairman S., Eskimbot, Arny, Canthusus, Boris Barowski, Flameeyes, Timotheus Canens, Edgar181, Apple2, Gilliam,
Fogster, Bluebot, Kurykh, Liamdaly620, SchfiftyThree, Deli nk, Bob the ducq, PetrolMan, Rolypolyman, Whispering, Bubbaprog,
Colonies Chris, Can't sleep, clown will eat me, Lchiarav, UNHchabo, VMS Mosaic, Kcordina, Dharmabum420, Ambix, Downwards,
Jmesserly, ShaunES, Smokefoot, Cryoruggie, DMacks, Mion, J.smith, Vina-iwbot, Kukini, The Pelican, SashatoBot, Schnazola, Bluerhi-
nos, Ocee, Ktinga, LightYear, Munita Prasad, Beetstra, Martian.knight, Ace Frahm, Peter Horn, MTSbot, MBob, Skapur, Hydra Rider,
Pimlottc, MottyGlix, Courcelles, Tawkerbot2, JForget, Cacahueten, Mikiemike, CmdrObot, Quantumstate, Makeemlighter, Funion987,
RedRollerskate, Rockn-Roll, Ethancfbz, Joelholdsworth, Cydebot, Kanags, DrunkenSmurf, Rifleman 82, Gogo Dodo, Bookgrrl, Em-
jay-es, Billtubbs, Johnny the kung fu lama, Jhu, Epbr123, Biggishben, GMERCADO, Hola hola hola, John254, Pulseczar, Electron9,
Alkane-man, CharlotteWebb, Greg L, Natalie Erin, Navdar, Dzubint, Mentifisto, Sabeen557, Danabc2, Living Ghost, Gadlen, JAnDbot,
Husond, MER-C, Hskibbe, Hoagiej, Andonic, Garda40, Bookinvestor, Kirrages, LittleOldMe, Magioladitis, Bongwarrior, VoABot II,
Ferritecore, Philg88, MartinBot, FlieGerFaUstMe262, James Saladin, ChemNerd, NReitzel, Anaxial, Miltnoda, Leyo, Tgeairn, J.delanoy,
Captain panda, Princemackenzie, Trusilver, Rgoodermote, Javelin42, Rhinestone K, Eliz81, Nothingofwater, AtholM, DrDisco, Mc-
Sly, Skier Dude, Youngjim, Belovedfreak, Student7, Shoessss, TottyBot, Vanguard anon, King Toadsworth, Kaiserbailey, MartinBotIII,
Cartiod, Deor, TheMindsEye, Philip Trueman, A4bot, Skylar44, Knowsetfree, CanOfWorms, Madhero88, Rich5411, Billgordon1099,
Lamro, Falcon8765, Kehrbykid, Laganeze, Eloc Jcg, GUSTAVOMERCADO, Theoneintraining, EJF, 172mach1, SieBot, Etbnc, Tid-
dly Tom, Scarian, Augiecrazy8, Da Joe, Rob.bastholm, Caltas, Triwbe, Connorhalsell, Blackjays1, Toddst1, Oda Mari, Monkey 135,
Granf, Candycarrasco, Mizpoon, Fishnet37222, Chem-awb, WikipedianMarlith, ClueBot, Mariordo, Hustvedt, Juanricos, Hoser795,
Mtt124, Qwertylex, Mild Bill Hiccup, Solidfacts, Super propane, Mspraveen, XofWiki, Alexbot, Jusdafax, CrazyChemGuy, Draeath,
KyuubiSeal, Lunchscale, Jotterbot, HBHGasSystems, Dibbynet, Texnik, Aitias, Ixkeys, Plasmic Physics, Burner0718, Nicolas.dasnois,
178 CHAPTER 25. ALKYLATION

Berean Hunter, SoxBot III, Glacier Wolf, DumZiBoT, Life of Riley, Darkicebot, InternetMeme, Wikinaut11, Greek2, Wikiuser100,
Dthomsen8, Little Mountain 5, NellieBly, Milo and Otis, Addbot, Twaz, Tcncv, Wickey-nl, Thomas888b, Friginator, Leped, Fieldday-
sunday, Vchorozopoulos, CanadianLinuxUser, Twinkie eater91, Chempedia, Qjim, 84user, Numbo3-bot, DavidLGCrawford, Good
Grill Freak, Tide rolls, Lightbot, Teles, Legobot, Luckas-bot, Yobot, Fraggle81, CheMoBot, THEN WHO WAS PHONE?, IW.HG,
Andrewinalaska, AnomieBOT, KDS4444, Casforty, Killiondude, Jim1138, Neptune5000, Piano non troppo, Mahmudmasri, Materi-
alscientist, Jstnhughes93, The High Fin Sperm Whale, Danno uk, Maxis ftw, GB fan, LilHelpa, TinucherianBot II, Sionus, Capri-
corn42, Thekingofthe25, NODAKPLUMBER, GrouchoBot, Abce2, Crunkteezy1, SteveOak25, GorgeCustersSabre, Brutaldeluxe, Jedi-
Master362, N419BH, Spinach Monster, PiFanatic, WaysToEscape, Darkspartan2011, Surv1v4l1st, Ringerfan23, TheFSaviator, William915,
‫امیرشاهین‬, Economictrouble, Rydog12, Todddd, Pinethicket, Dgdeckard, Jonesey95, Seriousbusiness12345678987654321, Chelubai,
Black Squirrel 2, ReportingfromNY, SteveWGriffin, Swindlefun, Reaper Eternal, Weedwhacker128, Jynto, Nevin.williams, DARTH
SIDIOUS 2, Hwy43, Alph Bot, Andyhodapp, WildBot, EmausBot, Eekerz, Tommy2010, Wikipelli, Ornithikos, Flushing258, Lilyelk,
ZéroBot, Colbias14, Redhanker, Dffgd, Kiwi128, Aflafla1, Tolly4bolly, Demirmahmutkysr, Derpistan, Deutschgirl, TYelliot, DASHBo-
tAV, Mikhail Ryazanov, ClueBot NG, Gahazy, Frietjes, Braincricket, 123Hedgehog456, Rezabot, Morgan Riley, JackieParlay, Nao1958,
Cja110, Oddbodz, AOCJedi, JohnSRoberts99, Tabbywrangler, Lowercase sigmabot, Ericagolehr, MusikAnimal, PropaneIsSafe, Amp71,
Smontreuil, Pocketthis, ProudIrishAspie, Glacialfox, Mr. sekwaF, Nitrobutane, BetterThanTheNews, Pratyya Ghosh, ChrisGualtieri,
LHcheM, TheJJJunk, Mogism, Graphium, Oakleytr, 069952497a, Jonas0077, Bir.johannessen, CsDix, Nonsenseferret, Qwh, Tentina-
tor, ClubbyClubman, Syldexia, Cbuccella, Jordanberner, HankOfTheHill, Juangarcia69, Plupien79, Quekd, Clamatoboy, Switchy621,
GreatChicken, Medgirl131, Crylol, Athomasan64 and Anonymous: 670
• Butane Source: http://en.wikipedia.org/wiki/Butane?oldid=640932147 Contributors: Marj Tiefert, The Anome, Tarquin, Andre En-
gels, Enchanter, SimonP, Tim Starling, Ixfd64, Eric119, Egil, Looxix, Ahoerstemeier, Mac, TUF-KAT, Ping, Julesd, Andres, Schnee-
locke, Wolfgang Kufner, Thomasgl, Christin, JorgeGG, Denelson83, Gentgeen, Robbot, Noldoaran, Romanm, Hadal, Raeky, Dina, Alan
Liefting, Dbenbenn, DavidCary, Mikez, Monedula, Jorge Stolfi, Darrien, OldakQuill, Bumm13, Iantresman, Edsanville, Deglr6328,
M1ss1ontomars2k4, Adashiel, Cacycle, YUL89YYZ, Kwamikagami, Evand, Shanes, Femto, Kaganer, Towel401, Sergio Macías, An-
thony Appleyard, Fornadan, Benjah-bmm27, Walkerma, Mrholybrain, Cburnett, Dirac1933, Wimvandorst, Shoefly, Tchaika, Nuno
Tavares, Bushytails, LOL, 25or6to4, Rickjpelleg, Justin Custer, MC MasterChef, DePiep, T.John.E, Wikibofh, Yamamoto Ichiro,
Titoxd, FlaBot, RexNL, Physchim62, Chobot, Roeeyaron, Jaraalbe, DVdm, YurikBot, Metalloid, Pacaro, Serinde, Conscious, Hellbus,
Yyy, NawlinWiki, Astral, Zirland, Smaines, Tetracube, Јованвб, Fang Aili, Mastercampbell, Tomj, Tim R, Allens, Thomas Blomberg,
Kf4bdy, Itub, Slashme, Bomac, Edgar181, Apple2, Pzavon, Betacommand, Bluebot, Kurykh, Thumperward, DroEsperanto, Sonicblue4,
Xmastree, VMS Mosaic, Peter Corbett, Zirconscot, Emre D., Smokefoot, Mion, D3j4vu, Bluerhinos, LightYear, Ckatz, Munita Prasad,
Beetstra, Roregan, Caiaffa, IvanLanin, Ethoen, Courcelles, Tawkerbot2, Alex-thong, Cacahueten, Joelholdsworth, Dss971, Johner, Van-
ishedUser30023402384023, Cydebot, Reywas92, Sxeraverx, Vanished user vjhsduheuiui4t5hjri, Hebrides, Peppage, Thijs!bot, Charlot-
teWebb, Escarbot, AntiVandalBot, Widefox, Seaphoto, QuiteUnusual, Ian Donaldson, Andonic, PhilKnight, Hurmata, Karlhahn, VoABot
II, MartinBot, Dbc334, CommonsDelinker, RatedAAA, Yonidebot, Derlay, Benny McBen, AtholM, Ajcfreak, Teol, Bobber0001, Mar-
tinBotIII, Kezbigfrank, Franky77, VolkovBot, Philip Trueman, Zamphuor, A4bot, Skylar44, Zoolatry, Qxz, Corvus cornix, Finngall,
Belamp, Altermike, Temporaluser, SieBot, LeadSongDog, Joaosampaio, Flyer22, Reinderien, Oxymoron83, Skiview, Tombomp, Jclov-
ing, Eli Rabett, Maralia, Chem-awb, Martarius, ClueBot, LAX, The Thing That Should Not Be, Cptmurdok, Alexbot, Rubén Mar,
Pmacc, Jotterbot, Peachypoh, Razorflame, Happy1n n, Plasmic Physics, Johnuniq, Wikinaut11, Addbot, Mr0t1633, Wickey-nl, Ateth-
nekos, Jncraton, Qjim, Sun Ladder, Naidevinci, Hunting dog, Crunk cat 4 l1fe, Tide rolls, Epop fr, Peko, Swarm, Luckas-bot, Ptbot-
gourou, Superdirt21, CheMoBot, AnomieBOT, KDS4444, Rubinbot, Götz, Jim1138, Materialscientist, Citation bot, GB fan, ArthurBot,
Xqbot, 4twenty42o, Unveiled, Maduncle16, GrouchoBot, Rice.brendan, FrescoBot, Surv1v4l1st, LucienBOT, William915, Citation bot
1, ‫امیرشاهین‬, Kopiersperre, Biker Biker, Cnwilliams, Swindlefun, CDXX420, Specs112, Mttcmbs, Paal.foyn, LettFujiwara, EmausBot,
Wikipelli, Cobaltcigs, ChuispastonBot, Xakepp35, Louisajb, ClueBot NG, Firehouse123, Frietjes, Widr, HMSSolent, BG19bot, Wiki13,
BrightStarSky, LUKERAVI, Pappyo, Beckhamkilburn, TCMemoire, TOON82, Doctor88s, Aaronzull, SantiLak, Medgirl131, Alrich44,
Thesquidthomas and Anonymous: 272
• Pentane Source: http://en.wikipedia.org/wiki/Pentane?oldid=637376956 Contributors: Schneelocke, Maximus Rex, Nv8200p, Denel-
son83, Robbot, Noldoaran, Securiger, Isopropyl, Pretzelpaws, Podom, Jorge Stolfi, Bobblewik, Architeuthis, H Padleckas, Edsanville,
M1ss1ontomars2k4, Xmlizer, Pak21, Dennis Brown, Rrh02, Jag123, Alansohn, Pinar, Keenan Pepper, Complex01, Benjah-bmm27,
Saga City, Wimvandorst, V8rik, DePiep, Rjwilmsi, FlaBot, Physchim62, YurikBot, RobotE, Shaddack, Јованвб, Itub, SmackBot,
Edgar181, Apple2, Bluebot, Jjalexand, Thumperward, Xcomradex, Smokefoot, SashatoBot, Bluerhinos, Jaganath, LightYear, Munita
Prasad, Beetstra, CapitalR, Tawkerbot2, Joelholdsworth, Rifleman 82, Pöllö, Luka Krstulović, Thijs!bot, Navdar, JAnDbot, Karlhahn,
Leyo, J.delanoy, Atropos235, Bennelliott, MartinBotIII, Philip Trueman, Piperh, Broadbot, Falcon8765, Bobo The Ninja, AlleborgoBot,
Meathammers91, SieBot, Da Joe, Le Pied-bot, Chem-awb, BartYgor, ClueBot, DragonBot, Alexbot, Balabinrm, Plasmic Physics, Duttler,
Addbot, Wickey-nl, EjsBot, 84user, OlEnglish, Luckas-bot, CheMoBot, Materialscientist, Xqbot, ‫قلی زادگان‬, Rice.brendan, Jaeljojo,
FrescoBot, William915, Citation bot 1, AmphBot, RedBot, Lotje, Xonoro, LcawteHuggle, EmausBot, Slartibartfast505, RaymondSu-
tanto, ClueBot NG, O.Koslowski, Rezabot, Per1234, Glacialfox, KhoousesWiki, Iamsomud, Mrt3366, ChrisGualtieri, Bluepablo3, En-
zaiBot, Numbermaniac, Motkralc and Anonymous: 65
• Engine knocking Source: http://en.wikipedia.org/wiki/Engine%20knocking?oldid=640616269 Contributors: Rjstott, William Avery,
Stevertigo, Liftarn, Samw, GRAHAMUK, Rjones, Arteitle, Bemoeial, Myshkin, Earthsound, Lumos3, Altenmann, PlatinumX, Neilc,
Alexf, Gzuckier, Togo, Sonett72, Canterbury Tail, JeDi, Bobo192, O18, Longhair, Hooperbloob, Linmhall, Distantbody, Woohookitty,
AlbertCahalan, Hard Raspy Sci, Graham87, Rjwilmsi, Quale, Vegaswikian, ScottJ, Brighterorange, Motorhead, Arnero, YurikBot, Shad-
dack, Jaxl, Elkman, Novasource, Scheinwerfermann, Closedmouth, Vaudeville, RG2, Bernd in Japan, MacsBug, SmackBot, Edgar181,
Gilliam, Ohnoitsjamie, MalafayaBot, Radagast83, MrDolomite, Rudjek, Rifleman 82, Go229, Brianpie, Thijs!bot, Whistopathe, CZ-
marlin, Alphachimpbot, Myanw, Connormah, VoABot II, Soulbot, VegKilla, DerHexer, Ravagewing, Dav115, SU Linguist, AE86 GTR,
Sno2, M109fan, TXiKiBoT, Caster23, Melsaran, Mtflight, Andy Dingley, Capper13, Typ932, Gprince007, E8, Dolphin51, Dp67, Clue-
Bot, Justin W Smith, Turbojet, Black190, Anon lynx, MahmudAlam, XLinkBot, Subversive.sound, Freestyle-69, Addbot, Fraggle81,
KamikazeBot, AnomieBOT, Dwayne, Godofthemachines, Materialscientist, Danno uk, Capricorn42, Captain deathbeard, TarenGarond,
Rkr1991, Lukeclimber, CaptainPinko, Pinethicket, 10metreh, RedBot, Ohtavala, Jamiebates1987, A.digaeta, Humble bin khalid, Bound-
arylayer, GoingBatty, Francisco Quiumento, Fæ, GrindtXX, Zap Rowsdower, Staszek Lem, Andy S2010, ClueBot NG, Icecon, Helpful
Pixie Bot, Gauravjuvekar, Csracing87, Registreernu, Dipankan001, Gihanper, CsDix, Abchaudhary, Monkbot, Tomschou, Saq.saq.saq
and Anonymous: 169
• Octane rating Source: http://en.wikipedia.org/wiki/Octane%20rating?oldid=641086327 Contributors: AxelBoldt, Ed Poor, Leandrod,
Twilsonb, Shoaler, Gbleem, SebastianHelm, 5ko, Jdforrester, Julesd, Hpa, Mulad, Charles Matthews, Qwertyu, Omegatron, Jooler, To-
25.7. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 179

bias Bergemann, Dinomite, Ivanl, Leonard G., Mboverload, Rchandra, Mrtrey99, Tsemii, Quota, Sonett72, Eladts, Danh, Corti, Philip
lamb, Michall, Paul August, Night Gyr, Brian0918, Terrell Larson, Zr40, Vuo, Gene Nygaard, Mattbrundage, Popefelix, Mullet, Firs-
fron, Rintojiang, Tabletop, Zilog Jones, JohnC, GraemeLeggett, Palica, Mandarax, BD2412, Rjwilmsi, Tixity, Kchoboter, Yamamoto
Ichiro, FlaBot, Physchim62, Bgwhite, The Rambling Man, YurikBot, Borgx, Angus Lepper, Jimp, AKADriver, Shawn81, Hydrar-
gyrum, Bovineone, Salsb, Wiki alf, Janke, Trovatore, Felix01, Lexicon, Brandon, RFBailey, CecilWard, Bobak, Mikeblas, Biopresto,
Lcmortensen, A Doon, Oscarcwk, Wkienzle, MojaveNC, Ankurdave, SmackBot, Slashme, InverseHypercube, Unyoyega, Arny, Jpvinall,
Ohnoitsjamie, Chris the speller, Mnbf9rca, Sebhaque, Erzahler, Wikipedia brown, Smokefoot, Henning Makholm, Fabexplosive, John,
Agent11345a, Jpogi, Soumyasch, Mbeychok, Mgiganteus1, Imzjustplayin, Kondspi, Mattjm, Optakeover, Robb0995, Juneau10, Amitch,
Astrobradley, Xajel, Iridescent, Muhaidib, JoeBot, Drek ocp, Davidbspalding, RSido, Stockdiver, CmdrObot, SJFriedl, Rifleman 82,
Zginder, Odie5533, Q43, Christian75, Darkwraith, Satori Son, Aldis90, Max Randor, PaulRonney, Thijs!bot, Epbr123, Headbomb,
Gerry Ashton, Eljamoquio, Xasxas256, Uruiamme, Visik, ColourBurst, AntiVandalBot, Orionus, Salgueiro, Bigjimr, JAnDbot, Can-
cerward, Albany NY, Hamsterlopithecus, BenB4, PhilKnight, 28421u2232nfenfcenc, LorenzoB, Beagel, Berlo84, Dennisthe2, R'n'B,
Robert, Natebakken, Jeepday, Skippiikai, Warut, Sculptorjones, Eternalnoob, Requiem mn, Pdcook, TheNewPhobia, Hugo999, Door-
sAjar, TXiKiBoT, Tr-the-maniac, Shreditor, Fxhomie, Rei-bot, Gruntguru, Bodybagger, Rep movsd, Eminem.prashanth, Minimac93,
Jonknight73, Phmoreno, Bobo The Ninja, Vandepavert, SieBot, Macdonaldinho, Sailstar, GlassCobra, IRSpeshul, Radon210, ScAvenger
lv, Nyelvmark, Hatster301, Anchor Link Bot, Dale-DCX, Nerdygeek101, FlamingSilmaril, ClueBot, Identification01, Gayasri, Siipikarja,
Mild Bill Hiccup, Npyrhone, John Nevard, Teutonic Tamer, Dave seer, Jellyfish dave, DumZiBoT, Nnewton, Rabbitbunny, Bodhisattv-
aBot, Dthomsen8, Subversive.sound, Addbot, C3r4, Paraphrased, Leszek Jańczuk, Qjim, Dusty.crockett, AtheWeatherman, Di99, Алиса
Селезньова, Matt.T, Luckas-bot, Yobot, Legobot II, Axpde, RoB, AnomieBOT, Materialscientist, Alawadhi3000, Ianamiryokuteki,
Wrelwser43, LilHelpa, GrouchoBot, SassoBot, PAULOGARCIA2005, Scottra 2000, FrescoBot, Inwood5000, Hexafluoride, Louperi-
bot, Pinethicket, GuidoRN, Adamswc, Oscar Alho II, TobeBot, Katkort, Rotbloodi, Racerr, Brandenkgynizio, AShadowed, Ekkoria,
EmausBot, MrFawwaz, Dewritech, Haleming, Satchmo Sings, Wikipelli, Jogruni, Michaeloqu, William Leadford, Mezzfit, GrindtXX,
Sastrawijaya, Donner60, Grug17, Mark Martinec, Ultra food, Mäkirömpe, Nikolas Ojala, Whoop whoop pull up, ClueBot NG, John-
SRoberts99, Aland38, Shaderlie, BG19bot, Krontach, MasashiInoue, Metricopolus, Kendall-K1, GerH, Akihito tan, BattyBot, WikiJe-
fredo, DJFission, Mogism, Steve244, Princenackamakie, Huxly Alex, Frankmabo, Notdansnyder, Anthony thompson2109, Evankouros,
Monkbot, Hendersz, A.Minkowiski, KarimKoueider, Rafabe and Anonymous: 431
• Cetane number Source: http://en.wikipedia.org/wiki/Cetane%20number?oldid=641892297 Contributors: GCarty, Mulad, Robbot, Dale
Arnett, Smjg, Graeme Bartlett, Leonard G., Tsemii, Andros 1337, GPoss, Meggar, Avitek, Kjkolb, Hooperbloob, Zachlipton, Jeltz, Pal-
ica, SixWingedSeraph, Rjwilmsi, Physchim62, P0per, YurikBot, RussBot, Shaddack, Salsb, Yrithinnd, Zwobot, Biopresto, SmackBot,
Alexander Noé, C.Fred, Knuto, Edgar181, Firekite, Chris the speller, DaddyT, Smokefoot, Zaphraud, Hallvor, LouisBB, Zginder, Heyne-
jos, JLD, Thijs!bot, Epbr123, Orthabok, Hamsterlopithecus, FuzzyMO, Beagel, ChemNerd, Theultimatejoeshmo, Arjmandqayyum,
Shocklord, WilfriedC, VolkovBot, Drdstny, Shreditor, Biscuittin, Moletrouser, Hatster301, ClueBot, Cookiehead, Delicious carbun-
cle, Addbot, C3r4, BepBot, OlEnglish, Zorrobot, Ben Ben, AnomieBOT, Materialscientist, Br77rino, GrouchoBot, Kyng, Esmu Igors,
Carel.jonkhout, ‫علی ویکی‬, DARTH SIDIOUS 2, Grondemar, EmausBot, Wikipelli, Manubot, Widr, Xawonder, Wonderchem, Pisi-
pala, Ilya Zhitomirsky, Morning Sunshine, Nitrobutane, DarafshBot, Epicgenius, Rowan Storey, Ericnary and Anonymous: 74
• Flash point Source: http://en.wikipedia.org/wiki/Flash%20point?oldid=642036689 Contributors: Tarquin, Heron, Shimmin, TUF-KAT,
Julesd, Kaihsu, Fuzheado, Gutza, Omegatron, Morven, Eugene van der Pijll, Robbot, Hankwang, Litefantastic, Wereon, Carnildo,
Buster2058, Matt Gies, Alexwcovington, Alistair1978, Andrejj, Konstantin, Avitek, Giraffedata, Toh, Nk, Hooperbloob, Jhertel, In-
teriot, Cctoide, Deboerjo, Water Bottle, Soelmese, Harej, Dirac1933, Shoefly, Japanese Searobin, Scriberius, LOL, Chochopk, Alexis
Domjan, Astronaut, Quuxplusone, Fresheneesz, YurikBot, Charles Gaudette, RussBot, DarkPhoenix, Grafen, Tough Little Ship, Schein-
werfermann, David Biddulph, KnightRider, SmackBot, Slashme, RobotJcb, Srnec, Pzavon, DinosaursLoveExistence, Nibuod, Bige1977,
BIS Ondrej, Jaganath, Mbeychok, JHunterJ, Caiaffa, Iridescent, CmdrObot, Bensnowden, Rjm656s, Epbr123, .anacondabot, Catgut,
Darrenbeards, Motley Crue Rocks, Rettetast, R'n'B, AntiSpamBot, Dgturnerr, KudzuVine, Idioma-bot, VolkovBot, Bry9000, TXiK-
iBoT, TheMperor, Venny85, Kilmer-san, Tomaxer, Coffee, Jab416171, WereSpielChequers, Correogsk, Wahrmund, GameEducator,
Bradman006, ClueBot, PipepBot, Yellier, Turbojet, Excirial, Mikaey, Johnuniq, Erodium, Mifter, Addbot, AkhtaBot, AtheWeatherman,
Zorrobot, Luckas-bot, Yobot, Doogleface, KDS4444, Wikipedroo, Helvetica13, Götz, Jim1138, LlywelynII, Brane.Blokar, Xqbot, Anna
Frodesiak, BritishWatcher, GrouchoBot, Vertikal Design, PauAmma, Shadowjams, Sirflashpoint, Pinethicket, Drthomasj, Amkilpatrick,
Phlegat, EmausBot, WikitanvirBot, Dcirovic, Olhp, ChuispastonBot, ClueBot NG, KDS444, Widr, Titodutta, YodaWhat, Blamb16,
Testem, Ryanlam003, Saehry, Frosty, Tentinator, Anton-paar-wiki, Filedelinkerbot, Neatsfoot, Himanil34 and Anonymous: 163
• Autoignition temperature Source: http://en.wikipedia.org/wiki/Autoignition%20temperature?oldid=635271467 Contributors: Chris-
tian List, Shimmin, Timwi, Omegatron, DavidCary, Bfinn, Eequor, Bobblewik, Wesha, Vsmith, Avitek, Interiot, Spangineer, Harej, Egg,
Shoefly, Gene Nygaard, Theloniouszen, Urod, Bennetto, Trevor Andersen, DePiep, Seandop, Bladeofgrass, Ian Pitchford, Fresheneesz,
Compotatoj, Physchim62, Stephantom, Gwernol, The Rambling Man, Gaius Cornelius, Bug42, Ghent, Bota47, Silverchemist, StuRat,
Tim R, SmackBot, StefanoC, Valley2city, Chris the speller, Bluebot, CharonM72, Dillona, DinosaursLoveExistence, -Ozone-, Solon.KR,
Johnsen953, JorisvS, Aboutblank, Mgiganteus1, Beetstra, Pezant, Naaman Brown, Chadnibal, Tjoneslo, Thijs!bot, Gioto, Mvv1827,
JAnDbot, Coolhandscot, Steveprutz, Marcinj, Trusilver, STBotD, Senecalja, KudzuVine, VolkovBot, Jehan60188, Àlex, Prussianpanther,
Q Science, SieBot, Arkwatem, Texnic, WikiBotas, Ideal gas equation, Johnuniq, Tealwisp, Vivo, Addbot, AkhtaBot, ScAvenger, Luckas-
bot, Götz, Roger 80Knots, Flickr.d5e, Brane.Blokar, Xqbot, Anna Frodesiak, BritishWatcher, Mikhael 666 mikhailovich, EmausBot,
ChuispastonBot, EdoBot, Rmashhadi, ClueBot NG, JohnSRoberts99, Magicka81, Enervation, CitationCleanerBot, RIceCracker5963,
RazWiki, Sai Kalyan98, Proshanto5002 and Anonymous: 81
• Fire point Source: http://en.wikipedia.org/wiki/Fire%20point?oldid=635667244 Contributors: Heron, GTBacchus, Denelson83, Tim
Ivorson, Litefantastic, Seth Ilys, D6, Remuel, Avitek, Microtony, Bennetto, Physchim62, Ihope127, Pegship, Gilliam, Bluebot, Preslav,
Aktron, Gothmog.es, Butko, Cotinis, Peripitus, Thijs!bot, AntiVandalBot, JAnDbot, Reubent, MrBell, Idioma-bot, TXiKiBoT, Qxz,
Denisarona, Jmk, Alexbot, Addbot, Luckas-bot, Daniele Pugliesi, Materialscientist, Brane.Blokar, Erik9bot, Moloch09, WikitanvirBot,
Firepoint999 and Anonymous: 31
• Pour point Source: http://en.wikipedia.org/wiki/Pour%20point?oldid=634510715 Contributors: TotoBaggins, Sbrools, DVdm, Some
guy, SmackBot, Knuto, DinosaursLoveExistence, Smokefoot, John, Linnormlord, Jac16888, Kmadhu53, Kosm, Cooluv2k3, Ivarley,
MrBell, Venny85, Correogsk, Capitalismojo, ClueBot, PipepBot, ChrisHodgesUK, Roxy the dog, Addbot, SpBot, Yobot, Amirobot,
KamikazeBot, Xqbot, Shadowjams, Pinethicket, WikitanvirBot, ZéroBot, Jack Greenmaven, Turner chris1, Cody Hammersmith, Reb5012,
Proshanto5002 and Anonymous: 29
• Smoke point Source: http://en.wikipedia.org/wiki/Smoke%20point?oldid=636070593 Contributors: Pagingmrherman, Charles Matthews,
Ruakh, Bfinn, Remuel, Interiot, MrDarcy, Pfalstad, Gringer, Unixan, Waitak, Rowan Moore, Lockesdonkey, Zephalis, Elkman, KnightRider,
180 CHAPTER 25. ALKYLATION

Nbarth, Zymatik, Kanji, Gobonobo, ChazYork, Platte Daddy, Nemo bis, Rekiwi, Idioma-bot, JrBr, Temporaluser, SieBot, BotMulti-
chill, Alexbot, WikHead, Addbot, CactusWriter, Luckas-bot, Hohenloh, AnomieBOT, Citation bot, CXCV, Doughnut4020, Helium4,
Chicago2020, Jprokos, Orange Suede Sofa, ClueBot NG, Raghith, Kenorb, Helpful Pixie Bot, BG19bot, Yowanvista, YFdyh-bot, Trzn-
jane, Electricmuffin11, Asisman, Ndtodd84, MasterTriangle12 and Anonymous: 54
• API gravity Source: http://en.wikipedia.org/wiki/API%20gravity?oldid=637003777 Contributors: SimonP, Heron, Cherkash, Random832,
Sunray, Pengo, DocWatson42, BozMo, Icairns, Rctay, Eric Shalov, Cmdrjameson, Jonathan888, Gene Nygaard, Camw, Bluemoose,
Rjwilmsi, Fred Bradstadt, YurikBot, Jimp, Richardbondi, Knuto, Bluebot, Berland, Caomhin, Yourdeadin, Cydebot, Thijs!bot, Wikid77,
Beagel, Duckysmokton, Novickas, Bramfab, McSly, TXiKiBoT, Venny85, LeadSongDog, ClueBot, BenXM8, Richardlw, Crowsnest,
Avoided, Addbot, LaaknorBot, Luckas-bot, AnomieBOT, ‫قلی زادگان‬, Johnnie Rico, FrescoBot, LucienBOT, RedBot, MastiBot, Oviguan,
Kturini, Jamison Lofthouse, Astalavista b, Strike Eagle, BG19bot, Tmc.2013, CyberXRef and Anonymous: 36
• Light crude oil Source: http://en.wikipedia.org/wiki/Light%20crude%20oil?oldid=625430646 Contributors: Mac, Thue, DocWatson42,
FT2, Kappa, BRW, Rjwilmsi, TexasDawg, Caerwine, Wsiegmund, DocendoDiscimus, SmackBot, Monni95, Hu12, Gnome (Bot), Rock-
yMtnGuy, Cydebot, Bouchecl, Fx6893, Fireice, Huseyx2, Maghnus, Nergaal, Vikramparsani, DumZiBoT, Addbot, Lightbot, Kwinkunks,
D'ohBot, Full-date unlinking bot, EmausBot, Virtuscience, JYBot and Anonymous: 29
• Heavy crude oil Source: http://en.wikipedia.org/wiki/Heavy%20crude%20oil?oldid=629552678 Contributors: Cherkash, Sunray, Aetheling,
Antandrus, BozMo, Expatkiwi, Vsmith, Ejrrjs, Kjkolb, Stephen Bain, Siim, Gene Nygaard, RM, Rjwilmsi, Smithfarm, Nimur, Yurik-
Bot, Wavelength, Witan, TastyCakes, Silverchemist, SV Resolution, Peyna, Jonathan.s.kt, SmackBot, Twerges, Edgar181, Gilliam,
Ghosts&empties, Worthawholebean, Vina-iwbot, Kuru, CaptainVindaloo, BioTube, Monni95, Joseph Solis in Australia, Yourdeadin,
Iokseng, Christian75, Marek69, James086, Pap3rw8, Tillman, Yunipo, Harel, KConWiki, Beagel, Wuzuwu, Waqar-Khan, GeorgeCB,
Oceanflynn, NewEnglandYankee, Philip Trueman, Zamphuor, Beater566, Jamelan, Dirkbb, Vector Potential, Pepiss, LeadSongDog,
23funnel23, ClueBot, Secretseeker, Faheem121, Environnement2100, Green immortal, Atethnekos, Willplatts, Cuaxdon, Tide rolls,
QuadrivialMind, Yobot, AnomieBOT, Materialscientist, Capricorn42, Earlypsychosis, Sophus Bie, D'ohBot, DARTH SIDIOUS 2, John
of Reading, Jargoness, Jenks24, Rangoon11, 9Questions, ClueBot NG, Razghandi, Helpful Pixie Bot, Alex Kurdar, BattyBot, Yamaha5,
HaugenErik, Monkbot and Anonymous: 72
• Furnace Source: http://en.wikipedia.org/wiki/Furnace?oldid=642032206 Contributors: Magnus Manske, DavidLevinson, Maury Markowitz,
Jaknouse, Hfastedge, Danhicks, Josie, Darkwind, Andrewa, Glenn, Tristanb, Samw, Pizza Puzzle, Dcoetzee, Katana0182, Finlay McWal-
ter, Seglea, Lupo, Rjkaes, Fabiform, Rchandra, Khalid hassani, Bobblewik, Zeimusu, Quadell, Ouro, Noisy, Rich Farmbrough, Adam850,
GPoss, Mwanner, Harris000, NetBot, Takis, Billymac00, Reinyday, Dolce850, Kjkolb, Haham hanuka, Anthony Appleyard, MrB, At-
lant, Romary, Sourcer66, Riana, Velella, Wtshymanski, RJFJR, Zntrip, Mindmatrix, Commander Keane, Tabletop, Saperaud, Rjwilmsi,
Eptalon, Dbrook, Sprezzatura, Enon, Wongm, DVdm, YurikBot, Peterkingiron, Stephenb, Shaddack, T.E. Goodwin, Aeusoes1, Nick-
Bush24, Hugh Manatee, Avalon, Sandstein, Yonidebest, Closedmouth, Aranymalinko, GrinBot, Tom Morris, Anthony717, SmackBot,
Commander Keane bot, BirdValiant, Chris the speller, Bluebot, Saint Midge, Droll, Deli nk, Smoken Flames, Jwillbur, COMPFUNK2,
Radagast83, Suttonpubcrawl, DMacks, Mbeychok, JHunterJ, Makyen, Beetstra, [email protected], P199, Hu12, Wizard191, Ollie,
Gogo Dodo, Teratornis, Barticus88, WhaleyTim, Dawnseeker2000, Mentifisto, Gioto, Fayenatic london, Saxophobia, Afaz, Barek, MER-
C, Amvakar, Connormah, Endeneon, Ekotkie, Enaidmawr, Gun Powder Ma, Marktj, R'n'B, J.delanoy, FactsAndFigures, Jorourke92,
Pthareja, TreasuryTag, Philip Trueman, Nw-srjones, Una Smith, Dudenarmo, Venny85, Andy Dingley, Mikez302, Bottlecapninja, Fleela,
DimiKosta, MCTales, Michael Frind, PericlesofAthens, WereSpielChequers, Jack Merridew, Northlanddistrib, Alexfusco5, Lightmouse,
Roland Goossens, Xnatedawgx, ClueBot, Elegie, Blanchardb, Immrnicegy, Thingg, Scalziand, Helixweb, Badgernet, Sharafy, Addbot,
Anchorage48, Captain-tucker, Mr. Wheely Guy, Cst17, Morning277, Smokingunholdingape, Tide rolls, JSR, TaBOT-zerem, Pdery,
Mmclean9150, Foolo, Aboalbiss, Kostan1, Kellimuzzy, Ceramres, AnomieBOT, Jim1138, Materialscientist, SecretAgentCat, Citation
bot, BritishWatcher, JayJay, Vijay1403, Furnace123, FrescoBot, Riventree, Expansionvalve, , SoftwareSimian, Citation bot 1,
Pinethicket, Metricmike, Pikiwyn, Lorenzson, Susan Hoffmann, Jenday, சதீஷ், JeepdaySock, Salvio giuliano, K6ka, Gertdam, OnePt618,
Hudson Stern, Noggo, Gillian Aird, GrayFullbuster, CraigERama, ClueBot NG, Bped1985, Kayostar, Cntras, Lrkleine, Widr, Briandda,
Dougmcdonell, MerlIwBot, Nareto, Helpful Pixie Bot, Choqa zanbil, RudolfRed, Mogism, Snipekiller1000, Vgeek15, Aladdin Ali Baba,
AnandGirish, GuruvayurappanG, Eks9, Tentinator, Robert.Buye, Gus Scorchio, Monugeni, Nick heckford, Vieque, Bonner62, John-
chapin1, Smartypants717, Utkarsh53 and Anonymous: 158
• Chemical reactor Source: http://en.wikipedia.org/wiki/Chemical%20reactor?oldid=623871855 Contributors: Bearcat, COGDEN, Whit-
eDragon, H Padleckas, Cmdrjameson, Keenan Pepper, Shoefly, Vuo, Gene Nygaard, Amaxson, Amire80, YurikBot, Prometheus235,
BeastRHIT, Bota47, Saittam, Eno-ja, Slashme, Chris the speller, Lovecz, Bluebot, Sadi Carnot, CredoFromStart, 16@r, Woodshed,
RSido, CmdrObot, Hispalois, Escarbot, MER-C, Lulurascal, Email4mobile, User A1, Leftfoot69, Bfesser, R'n'B, Echis, WilfriedC,
Deor, Hughesy127, AlleborgoBot, SieBot, Aruton, Niceguyedc, Tha Stunna, Encyclopedia77, Nitech2008, XLinkBot, Addbot, W Derob,
Zorrobot, Luckas-bot, Ptbotgourou, Daniele Pugliesi, ArthurBot, LilHelpa, Elvim, ‫قلی زادگان‬, LucienBOT, Nojan, Gire 3pich2005,
Lobito09, MastiBot, Andresmb, RA0808, Francisco Quiumento, ZéroBot, Bamyers99, Scientific29, Helpful Pixie Bot, RscprinterBot,
Tadpoleleesie, Dexbot, Akassam441 and Anonymous: 42
• Catalysis Source: http://en.wikipedia.org/wiki/Catalysis?oldid=642202680 Contributors: AxelBoldt, Tobias Hoevekamp, Bryan Derk-
sen, Andre Engels, Heron, Edward, D, Lexor, Pnm, Kku, Wapcaplet, Ixfd64, Egil, Ugen64, Glenn, Raven in Orbit, Reddi, Stone, Bjh21,
Haukurth, Jakenelson, Saltine, Taxman, Paul-L, Jose Ramos, Betterworld, Robbot, Giftlite, Dratman, Utcursch, Alexf, Onco p53, Fab-
rício Kury, Fanghong, Shanes, Triona, Bobo192, Smalljim, HasharBot, Orzetto, Anthony Appleyard, Minority Report, Kdkirsch, Harej,
Amorymeltzer, Dirac1933, Vuo, Metju, Bsadowski1, Alex.g, Cimex, Pol098, WadeSimMiser, JRHorse, JohnJohn, V8rik, Nanite, Nneon-
neo, DoubleBlue, Bfigura, FlaBot, StephanCom, Rune.welsh, Czar, TheDJ, Physchim62, Whosasking, Wavelength, Michael4444, Yyy,
Shaddack, Coderzombie, Iancarter, Tony1, Wknight94, Closedmouth, Pb30, Peter, Itub, SmackBot, Bomac, AndreasJS, K shaurya, Gaff,
Anwar saadat, Bluebot, Bduke, Jprg1966, Fadeev, O keyes, Deli nk, Shalom Yechiel, Theonlyedge, RandomP, Smokefoot, N Shar, Jóna
Þórunn, Mion, Klandagi, Spiritia, Harryboyles, Mbeychok, IronGargoyle, 16@r, Knights who say ni, Beetstra, Shinryuu, Wizard191,
Dockingman, JackaFord, Eastlaw, Jakabcin, JohnCD, ShelfSkewed, FlyingToaster, Myasuda, Butakun, LouisBB, Rifleman 82, Chasing-
sol, Tkynerd, Christian75, DumbBOT, MagnusGallant, Tunheim, Thijs!bot, Epbr123, Dtgriscom, Doyley, Dawnseeker2000, Escarbot,
Seaphoto, Birdman149, TimVickers, LibLord, Omegakent, Gökhan, JAnDbot, Correctist, Aevangelica, PhilKnight, Acroterion, Wasell,
Charlesreid1, Ling.Nut, Quantockgoblin, JJ Harrison, Dirac66, 28421u2232nfenfcenc, Cpl Syx, Ldewitte, Sinharaja2002, MartinBot,
STBot, BetBot, R'n'B, CommonsDelinker, Nono64, Dhruv17singhal, Xris0, Mintz l, EZisthebest, Bob, Juliancolton, Actarux, Hadinur,
Idioma-bot, VolkovBot, Lear’s Fool, TXiKiBoT, Z.E.R.O., Dhi2cr, Raymondwinn, BotKung, Sorenmarklund, Scorpiotra, Falcon8765,
Compi456, Kosigrim, Psychokid100, Biscuittin, Newbyguesses, SieBot, OMCV, Open state, Cwkmail, Yintan, Mike Kotke, Lightmouse,
Techman224, Hobartimus, Matthewcib, Nandobike, LonelyMarble, Jons63, ClueBot, Vladkornea, Blackangel25, Petermlambert, Imper-
fectlyInformed, Alexbot, Jusdafax, Emieldesmit, Eeekster, Razorflame, ChrisHodgesUK, JBernardi, Thingg, Darkking3, Davemody,
25.7. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 181

SoxBot III, Ano-User, Buggia, XLinkBot, Little Mountain 5, Amitahanda, Addbot, Hbudge, Maria-Elisabeth, DOI bot, Element16,
Frazerschool, Professor malcolm willis, Tanhabot, Cognatus, Dr James Watson, Tide rolls, Avono, Yobot, Granpuff, Bdog9121, Nguyen-
baophuong, Body1 Inc, AnomieBOT, Kristen Eriksen, Rubinbot, Daniele Pugliesi, Jim1138, Neut Nuttinbutter, Dwayne, Kingpin13,
Ulric1313, Crystal whacker, Materialscientist, Citation bot, GB fan, Brackenheim, Xqbot, Elvim, Jmundo, Burlap, Jordi picart, Der-
ryTaylor, Tarselli, Mnmngb, Shadowjams, AlimanRuna, , FrescoBot, LucienBOT, Originalwana, Pepper, Recognizance, Jbsfsax,
Pinethicket, Tinton5, Dr-b-m, Markzebitz, Vrenator, DARTH SIDIOUS 2, Ram3500, Regancy42, Thephantomphantom, Improving-
Wiki, Orphan Wiki, Logical Cowboy, Immunize, Alex117234, Slightsmile, Tommy2010, Dcirovic, K6ka, JSquish, Michel Awkal,
Yhy21, ChuispastonBot, Jamestong4321, Haianqutang, ClueBot NG, TehGrauniad, Jaguessar, Ceng258midttveit, Widr, Helpful Pixie
Bot, Curb Chain, Polyethylen, Alexbonline1, Neøn, Dickyralph, Glacialfox, Aisteco, Shadow intelligence, Mrt3366, Jumballe, Soni,
Kcoopersmith, Cmrufo, Organometallics, Dexbot, Leesh-peetamellark, ChemistryMatters, Pranav Shankar, Charleswang2601, Soham,
Gmichaelow, Wtmwarrick24, Ginsuloft, SwagDeamon5000, Jackeys12, Patel1234321, Filedelinkerbot, Goblinshark17, Trackteur, Aban-
dad, Kennedyr11, Stephanie Payne and Anonymous: 387
• Catalytic converter Source: http://en.wikipedia.org/wiki/Catalytic%20converter?oldid=642087534 Contributors: The Epopt, Roadrun-
ner, Lexor, Suisui, Timc, Snicker, Morven, Pakaran, Ukuk, Wjhonson, Giftlite, Smjg, Cobaltbluetony, Leonard G., Gzornenplatz, Bob-
blewik, Pgan002, Antandrus, Saucepan, Neffk, Rogerzilla, Zfr, Sfoskett, Sonett72, Adashiel, DmitryKo, DanielCD, Discospinster, Rich
Farmbrough, Sladen, Alistair1978, Arthur Holland, Verbalcontract, El C, Aude, C1k3, Triona, Bobo192, Shenme, Brim, Jhamby, Gi-
raffedata, Hooperbloob, Nsaa, ReconTanto, Alansohn, Anthony Appleyard, Shawn K. Quinn, Babajobu, Andrewpmk, Riana, Sobolewski,
Wtmitchell, Vuo, Ringbang, Capecodeph, Ceyockey, Forteblast, Unixxx, Stemonitis, Mindmatrix, Justguy, Sirimiri, Pol098, Tabletop,
Mechanicalamit, Dysepsion, Mandarax, ThomasOwens, Hydrodrive, Jshadias, Pmj, Bubuka, George Burgess, Aronomy, Brighterorange,
Eyas, Ground Zero, Arnero, Ysangkok, Gary Cziko, Gurch, Intgr, Tedder, Imnotminkus, Bgwhite, Wolfmankurd, RussBot, DanMS,
Drt1245, RadioFan, Gaius Cornelius, Shaddack, Lavenderbunny, Rsrikanth05, Wimt, Afinemetsfan, NawlinWiki, Wiki alf, Exir Kamal-
abadi, Malcolma, Ahanix1989, Syrthiss, DeadEyeArrow, John Sheu, Htmlguru4242, Nlu, Nick123, Scheinwerfermann, Jwissick, E Wing,
NHSavage, Jake Spooky, Cojoco, Johnpseudo, Kajerm, Jonathan.s.kt, Jaycarlson, Groyolo, DVD R W, SmackBot, KnowledgeOfSelf,
Verne Equinox, Anastrophe, Canthusus, UrbanTerrorist, HalfShadow, Gilliam, Brianski, Chris the speller, Thumperward, Martin Blank,
Trekphiler, Writtenright, KevM, E. Taylor, Decltype, WWJD, Smokefoot, Lifetime, Drphilharmonic, Dan Parnell, Jóna Þórunn, Mion,
FlyHigh, TiCPU, Ohconfucius, Harryboyles, Dr. Sunglasses, Kuru, Zaphraud, Rigadoun, Titaniumcranium, IronGargoyle, Joeylawn,
Beetstra, Jimmy Pitt, Hu12, HisSpaceResearch, Joebrown0791, Polymerbringer, Skalman, JoeBot, StephenBuxton, GDallimore, Igoldste,
KazKylheku, KimChee, Tawkerbot2, Zahn, Covalent, CmdrObot, NaBUru38, Pseudo-Richard, Ballista, Clappingsimon, Reywas92, Ri-
fleman 82, Zomic13, Scott14, Studerby, Christian75, DumbBOT, Cancun771, ACamposPinho, Thijs!bot, IJB TA, Nslsmith, Uruiamme,
AntiVandalBot, BigNate37, Tuor, The Vindictive, Erredmek, JAnDbot, Freepsbane, Pipedreamergrey, Barek, MER-C, Bewenched,
SiobhanHansa, Pedro, VoABot II, Karkaputto, J.P.Lon, Avicennasis, Green Idea Factory, Mkdw, Allstarecho, LorenzoB, DerHexer, Ex-
oSynth, Pax:Vobiscum, Robman123, MartinBot, Joecctai, Rettetast, Rplyons, J.delanoy, Msmi121, Rgoodermote, Brien Clark, AtholM,
BrokenSphere, LordAnubisBOT, Hermann Luyken, Gurchzilla, Chiswick Chap, Molly-in-md, Searles a, WJBscribe, Natl1, Doctorox-
enbriery, Use the force, Inwind, Icarus4586, Philip Trueman, Caster23, GcSwRhIc, BomberJoe, Cataclasite, Raymondwinn, PDFbot,
Zhenqinli, Girona7, Tgm1024, Laroach, Jwilson14, Nstott, Unregistered.coward, Caltas, Quarryshark, Yintan, Monkeymox, Snideol-
ogy, Antonio Lopez, Acahopkins, Lightmouse, MASQUERAID, Xeltran, Escape Orbit, Sfan00 IMG, ClueBot, PipepBot, Pakaraki,
EoGuy, P38fln, Turbojet, SuperHamster, Auntof6, Kansoku, LeoFrank, Alexbot, Three-quarter-ten, Eeekster, John Nevard, Fredthe-
builder, Rowena-ballerina, Zahnrad, Hunkcheese, Sarilox, VerSx, DumZiBoT, Steveozone, RMFan1, Vanished user 01, Andrenel366,
Rror, Ost316, Avoided, Skarebo, NellieBly, Kavehrazm, Hydrazillawik, Addbot, Yoenit, Tcncv, Atethnekos, Binary TSO, Fluffernutter,
Chamal N, Sean1535, West.andrew.g, Rent A Troop, Tide rolls, Lightbot, Legobot, Luckas-bot, Fraggle81, Cflm001, II MusLiM HyBRiD
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Bot, Frank.manus, Mattmorr, BG19bot, Ralison, Robosorne, MyNameWasTaken, Enginemisfire, Hist406-11Hdoukmaj, Repentsinner,
Marcela Preininger, Bredfiel1, Rannusmash, Khazar2, EuroCarGT, SlobMike, Borisjlvin, VX1NG, Hodder69, CsDix, Ubewu, Tentinator,
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Adrian 1001, Luckas-bot, Yobot, Amirobot, AnomieBOT, Daniele Pugliesi, Citation bot, LilHelpa, Xqbot, Bharel, Elvim, Prari, Amse12,
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25.7.2 Images
• File:150_gallon_Propane_Tank.jpg Source: http://upload.wikimedia.org/wikipedia/commons/0/09/150_gallon_Propane_Tank.jpg Li-
cense: CC BY-SA 3.0 Contributors: Own work Original artist: Jessie Eastland aka Robert DeMeo
• File:3,3copeexpansion.svg Source: http://upload.wikimedia.org/wikipedia/commons/8/8d/3%2C3copeexpansion.svg License: Public
domain Contributors: Originally from en.wikipedia; description page is/was here. Original artist: Original uploader was Marco Polo at
en.wikipedia Later versions were uploaded by Bkell at en.wikipedia.
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cyclopentadiene_O2.svg License: CC BY 3.0 Contributors: Own work Original artist: Livewire61
182 CHAPTER 25. ALKYLATION

• File:AIRS_Methane.png Source: http://upload.wikimedia.org/wikipedia/commons/8/8f/AIRS_Methane.png License: CC BY-SA 3.0

Contributors: Own work Original artist: Giorgiogp2
• File:APM-932hd-1.png Source: http://upload.wikimedia.org/wikipedia/commons/e/ef/APM-932hd-1.png License: CC BY-SA 3.0
Contributors: Own work Original artist: Sirflashpoint
• File:AlkaneBoilingMeltingPoint.png Source: http://upload.wikimedia.org/wikipedia/commons/8/82/AlkaneBoilingMeltingPoint.png
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• File:AlkeneGroups.png Source: http://upload.wikimedia.org/wikipedia/commons/7/72/AlkeneGroups.png License: Public domain Con-
tributors: Own work Original artist: Walkerma
• File:Alkene_nomenclature.png Source: http://upload.wikimedia.org/wikipedia/commons/b/bb/Alkene_nomenclature.png License: Pub-
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• File:AlkyneToAlkene.png Source: http://upload.wikimedia.org/wikipedia/commons/0/02/AlkyneToAlkene.png License: Public do-
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• File:Aufgeschnittener_Metall_Katalysator_für_ein_Auto.jpg Source: http://upload.wikimedia.org/wikipedia/commons/7/7a/Aufgeschnittener_
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tributors: ? Original artist: Echis at English Wikipedia
• File:Benzene_Friedel-Crafts_alkylation-diagram.svg Source: http://upload.wikimedia.org/wikipedia/commons/f/f4/Benzene_Friedel-Crafts_
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• File:Buckminsterfullerene-perspective-3D-balls.png Source: http://upload.wikimedia.org/wikipedia/commons/0/0f/Buckminsterfullerene-perspective-3D-
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• File:Burner1.jpg Source: http://upload.wikimedia.org/wikipedia/en/2/27/Burner1.jpg License: PD Contributors:
self-made
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• File:Butane-3D-balls.png Source: http://upload.wikimedia.org/wikipedia/commons/7/76/Butane-3D-balls.png License: Public domain
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25.7. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 183

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184 CHAPTER 25. ALKYLATION

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25.7. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES 185

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186 CHAPTER 25. ALKYLATION

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