Preparation of Alkanes: Building the

Simplest Hydrocarbons
For an 11th Grader
May 30, 2025

Learning how to make alkanes from other types of organic molecules!

Quick Rundown: Alkane Preparation Formulas

A summary of the general reactions used to synthesize alkanes.

• 1. Hydrogenation of Alkenes and Alkynes

– Alkene to Alkane:
Catalyst (Ni, Pt, or Pd)
Cn H2n + H2 −−−−−−−−−−−−−→ Cn H2n+2
Alkene Alkane

or (general structure):
Catalyst
R-CH=CH-R’ + H2 −−−−→ R-CH2 -CH2 -R’

– Alkyne to Alkane:
Catalyst (Ni, Pt, or Pd)
Cn H2n−2 + 2H2 −−−−−−−−−−−−−→ Cn H2n+2
Alkyne Alkane

or (general structure):
Catalyst
R-C ≡ C-R’ + 2H2 −−−−→ R-CH2 -CH2 -R’

• 2. Kolbe’s Electrolytic Synthesis (for symmetrical alkanes R-R)

Electrolysis
2RCOO− (aq) −−−−−−→ R-R + 2CO2 + 2e−
Alkane

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• 3. Decarboxylation Method (reduces carbon chain by one)
Heat (Soda Lime)
RCOONa + NaOH −−−−−−−−−−→ R-H + Na2 CO3
CaO Alkane

• 4. Reduction of Alkyl Halides (R-X → R-H)

– Using LiAlH4 :
1. LiAlH4 , Dry Ether
R-X −−−−−−−−−−−−→ −→ R-H
2. H2 O (workup)

(Simplified: 4R-X + LiAlH4 → 4R-H + LiX + AlX3 )

– Using Zn-Cu Couple in Ethanol/Acid:
Ethanol
R-X + Zn + H+ −−−−→ R-H + ZnX+ (or similar Zn salts)

or:
Zn-Cu, Ethanol
R-X + 2[H] −−−−−−−−→ R-H + HX
Dry Ether
– Via Grignard Reagent Hydrolysis: Step 1: R-X + Mg −−−−−→ R-MgX (Grig-
nard Reagent)
Step 2: R-MgX + H2 O → R-H + Mg(OH)X

• 5. Wurtz Reaction (for symmetrical alkanes R-R, doubles alkyl chain)

Dry Ether
2R-X + 2Na −−−−−→ R-R + 2NaX
Alkane

• 6. From Metal Carbides (Specific for Methane)

Hot
Al4 C3 (s) + 12H2 O(l) −−→ 3CH4 (g) + 4Al(OH)3 (s)

Al4 C3 (s) + 12HCl(aq) → 3CH4 (g) + 4AlCl3 (aq)

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Introduction
Alkanes are the simplest organic molecules, containing only carbon and hydrogen atoms
with single bonds. While they are often used as starting materials for other reactions,
it’s also important to know how alkanes themselves can be synthesized (made). Here are
some common methods:

1. Hydrogenation of Alkenes and Alkynes

This is one of the most common and effective ways to prepare alkanes. ”Hydrogenation”
literally means adding hydrogen (H2 ).

• What’s happening? We start with an unsaturated hydrocarbon – an alkene

(which has at least one C=C double bond) or an alkyne (which has at least one
C≡C triple bond) – and add hydrogen gas (H2 ) across the multiple bond(s) to form
a saturated alkane.

• Catalysts are Key: This reaction doesn’t happen easily on its own. It needs a
metal catalyst to help it along. Common catalysts include:

– Nickel (Ni): Requires an elevated temperature (around 150◦ C).

– Platinum (Pt) or Palladium (Pd): These are more reactive and can work
at ordinary (room) temperatures.

• Determining Unsaturation: By measuring how much hydrogen gas is used up

to convert an unknown unsaturated compound into an alkane, scientists can figure
out how many double or triple bonds were originally present.

• General Equations:

– For Alkenes (Cn H2n ): One mole of H2 is needed for each double bond.
Catalyst (Ni, Pt, or Pd), Heat (if Ni)
Cn H2n + H2 −−−−−−−−−−−−−−−−−−−−−→ Cn H2n+2
Alkene Alkane

Example: But-2-ene to Butane

Ni, 150◦ C
CH3 CH=CHCH3 + H2 −−−−−→ CH3 CH2 CH2 CH3
But-2-ene Butane

– For Alkynes (Cn H2n−2 ): Two moles of H2 are needed for each triple bond to
fully saturate it to an alkane.
Catalyst (Ni, Pt, or Pd), Heat (if Ni)
Cn H2n−2 + 2H2 −−−−−−−−−−−−−−−−−−−−−→ Cn H2n+2
Alkyne Alkane

Example: But-2-yne to Butane

Ni, 150◦ C
CH3 C ≡ CCH3 + 2H2 −−−−−→ CH3 CH2 CH2 CH3
But-2-yne Butane

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• Example Problem Walkthrough: Problem: 2.24 dm3 of Hydrogen gas at s.t.p
(standard temperature and pressure) reacts completely with 8.4g of an alkene Q,
which has the structure RCH=CH2 . (1 mole of any gas occupies 22.4 dm3 at s.t.p.)

(a) Identify the functional group in hydrocarbon Q.

(b) Determine the molecular mass of Q, and then find the mass of the R group.
(c) Write the: (i) Molecular formula of Q. (ii) Possible structures and IUPAC
names for Q.

Solution:

(a) The structure RCH=CH2 contains a C=C double bond. Therefore, the func-
tional group in Q is an alkene.
(b) Step 1: Find moles of Hydrogen gas (H2 ) reacted.

Volume of H2 at s.t.p. 2.24 dm3

Moles of H2 = = = 0.1 mol
Molar volume of a gas at s.t.p. 22.4 dm3 /mol

Step 2: Find moles of alkene Q reacted. The reaction is: RCH=CH2 +

H2 → RCH2 CH3 . The stoichiometry (mole ratio) between the alkene and H2 is
1:1. So, Moles of Q = Moles of H2 = 0.1 mol. Step 3: Find the molecular
mass (Molar Mass, Mr ) of Q. We know that Moles = Mass / Molar Mass.
So, Molar Mass = Mass / Moles.

Mass of Q 8.4 g
Molar Mass of Q = = = 84 g/mol
Moles of Q 0.1 mol
So, the molecular mass of Q is 84. Step 4: Find the mass of R. The
structure of Q is RCH=CH2 . The mass of the -CH=CH2 part is: Mass of
-CH=CH2 = (1 × C) + (1 × H) + (1 × C) + (2 × H) = (1 × 12) + (1 × 1)
+ (1 × 12) + (2 × 1) = 12 + 1 + 12 + 2 = 27 g/mol. Since Molecular Mass
of Q = Mass of R + Mass of -CH=CH2 :

84 g/mol = Mass of R + 27 g/mol

Mass of R = 84 − 27 = 57 g/mol
(c) (i) Molecular formula of Q: Alkenes have the general formula Cn H2n . Molar
mass = n × (mass of C) + 2n × (mass of H) = 84

12n + 2n(1) = 84

14n = 84
84
n= =6
14
So, the molecular formula of Q is C6 H12 . (Check R group: If Q is C6 H12 and
has a -CH=CH2 (C2 H3 ) unit, then R must be C4 H9 . Mass of C4 H9 = (4×12)
+ (9×1) = 48 + 9 = 57. This matches!)
(ii) Possible isomers of Q (structure RCH=CH2 , formula C6 H12 ):
The R group is C4 H9 . We need to find isomers of C4 H9 -CH=CH2 :

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 – If R is CH3 CH2 CH2 CH2 - (n-butyl): Q is CH3 CH2 CH2 CH2 CH=CH2 , Hex-
1-ene.
– If R is CH3 CH2 CH(CH3 )- (sec-butyl, with the CH=CH2 attached to the
CH): Q is CH3 CH2 CH(CH3 )CH=CH2 . No, this is wrong. The R group
itself is C4 H9 . Let’s draw C4 H9 alkyl groups and attach -CH=CH2 to
them:
(a) R = CH3 CH2 CH2 CH2 - (n-butyl group) → Q = CH3 CH2 CH2 CH2 CH=CH2
IUPAC Name: Hex-1-ene
(b) R = CH3 CHCH2 - | CH3 (isobutyl group) → Q = (CH3 )2 CHCH2 CH=CH2
IUPAC Name: 4-Methylpent-1-ene
(c) R = CH3 CH2 CH- | CH3 (sec-butyl group) → Q = CH3 CH2 CH(CH3 )CH=CH2
IUPAC Name: 3-Methylpent-1-ene
(d) R = (CH3 )3 C- (tert-butyl group) → Q = (CH3 )3 CCH=CH2 IUPAC
Name: 3,3-Dimethylbut-1-ene

Question 1: What type of catalyst is commonly used for the hydrogenation of ethene
(C2 H4 ) to ethane (C2 H6 ) if the reaction is carried out at room temperature?

2. Kolbe’s Electrolytic Synthesis

This method involves the electrolysis of an aqueous solution of a sodium or potassium
salt of a carboxylic acid.

• What’s happening? When electricity is passed through the solution, the car-
boxylate ion (RCOO− ) loses electrons at the anode (oxidation) to form an alkyl
radical (R·) and carbon dioxide (CO2 ). Two of these alkyl radicals then combine
to form a symmetrical alkane (R-R).

• At the Anode (Oxidation):

2RCOO− → R-R + 2CO2 + 2e−

Symmetrical Alkane

• At the Cathode (Reduction): Water is reduced to hydrogen gas and hydroxide

ions.
2H2 O + 2e− → H2 + 2OH−

• Key Feature: This method is best for preparing symmetrical alkanes (where R-
R has two identical R groups). For example, using sodium ethanoate (CH3 COONa)
will produce ethane (CH3 -CH3 ). If you use a mixture of two different carboxylate
salts, you’ll get a mixture of three different alkanes, which is usually not desired.

• Example (using Sodium Ethanoate, CH3 COONa): The ethanoate ion is

CH3 COO− .
Electrolysis
2CH3 COO− −−−−−−→ CH3 -CH3 + 2CO2 + 2e−
Ethane

Question 2: If you want to prepare butane (CH3 CH2 CH2 CH3 ) using Kolbe’s electrolysis,
what sodium salt of a carboxylic acid would you start with?

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3. Decarboxylation Method
”Decarboxylation” means the removal of a carboxyl group (-COOH or -COO− ) as carbon
dioxide (CO2 ).
• What’s happening? The sodium salt of a carboxylic acid (RCOONa) is heated
strongly with soda lime. Soda lime is a mixture of sodium hydroxide (NaOH) and
calcium oxide (CaO). The CaO helps to keep the NaOH dry and prevents it from
attacking the glass apparatus at high temperatures.

• The Reaction: The overall reaction results in an alkane (RH) with one carbon
atom less than the starting carboxylic acid salt. The ”lost” carbon becomes part
of sodium carbonate (Na2 CO3 ).
Heat (Soda Lime)
RCOONa + NaOH −−−−−−−−−−→ R-H + Na2 CO3
Sodium salt of carboxylic acid CaO Alkane

• Key Feature: This method reduces the carbon chain length by one carbon atom.

• Example (using Sodium Ethanoate, CH3 COONa, to make Methane):

Here, R is CH3 .
Heat
CH3 COONa + NaOH −−→ CH4 + Na2 CO3
Sodium Ethanoate CaO Methane

Question 3: If you start with sodium propanoate (CH3 CH2 COONa) and heat it with soda
lime, what alkane will be formed?

4. From Alkyl Halides (Reduction)

Alkyl halides (R-X, where X is a halogen like Cl, Br, or I) can be converted to alkanes
by replacing the halogen atom with a hydrogen atom. This is a type of reduction.
• Method A: Using Lithium Aluminium Hydride (LiAlH4 )

– Reagent: Lithium aluminium hydride (LiAlH4 ) is a powerful reducing agent.

– Solvent: It is typically used in a dry ether solvent because LiAlH4 reacts
violently with water or other protic solvents (solvents that can donate H+ ).
– Reaction:
Dry Ether
4R-X + LiAlH4 −−−−−→ 4R-H + LiX + AlX3
(Often simplified to show just the organic product: R-X → R-H)
– Example (Bromoethane to Ethane):
1. LiAlH4 , Dry Ether
CH3 CH2 Br −−−−−−−−−−−−→ −→ CH3 CH3
Bromoethane 2. H2 O (workup) Ethane

(Note: A water workup is usually done carefully after the reaction to quench
any excess LiAlH4 and hydrolyze aluminum salts.)

• Method B: Using Zinc-Copper Couple in Ethanol

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 – Reagents: A ”Zinc-Copper couple” (Zn(Cu)) is zinc metal that has been
activated with a little copper. Ethanol (C2 H5 OH) often serves as the solvent
and a source of protons (H+ ).
– Reaction: The zinc metal effectively donates electrons to reduce the alkyl
halide.
Ethanol
R-X + Zn + H+ (from solvent/acid) −−−−→ R-H + ZnX+ or Zn2+ + X−

A more common way to write it with a specific acid like HCl or acetic acid
providing the H+ :

R-X + Zn + HCl → R-H + ZnClX (or ZnCl2 + HX)

Or simply:
Zn-Cu Couple, Ethanol
R-X + 2[H] −−−−−−−−−−−−−→ R-H + HX
(where [H] represents a reducing agent’s hydrogen)
– Example (Iodomethane to Methane):
Ethanol
CH3 I + Zn + HCl −−−−→ CH4 + ZnClI

• Method C: Hydrolysis of Grignard Reagents A Grignard reagent (RMgX) is

an organomagnesium compound. It’s very reactive.

– Step 1: Formation of Grignard Reagent Alkyl halide reacts with mag-

nesium metal in dry ether.
Dry Ether
R-X + Mg −−−−−→ R-MgX
Alkyl Halide Grignard Reagent

– Step 2: Hydrolysis of Grignard Reagent The Grignard reagent reacts

vigorously with water (or dilute acid) to produce an alkane. The R group in
RMgX acts like a strong base (R− ) and takes a proton (H+ ) from water.
Dil. HCl or H2 SO4 (workup)
R-MgX + H2 O −−−−−−−−−−−−−−−−→ R-H + Mg(OH)X

The dilute acid is used to neutralize the Mg(OH)X and make it soluble.
– Example (Methyl magnesium chloride to Methane): Step 1: CH3 Cl +
Dry Ether
Mg −−−−−→ CH3 MgCl Step 2:
H2 SO4 (dil.)
CH3 MgCl + H2 O −−−−−−−→ CH4 + Mg(OH)Cl
Methyl magnesium chloride Methane

Question 4: Why is it important to use ”dry ether” when preparing a Grignard reagent
or when using LiAlH4 ?

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5. Wurtz Reaction
This reaction is used to synthesize larger, symmetrical alkanes from alkyl halides.
• What’s happening? Two molecules of an alkyl halide (R-X) react with metallic
sodium (Na) in dry ether to form a new C-C bond, effectively joining two R groups
together.
• Reaction:
Dry Ether
2R-X + 2Na −−−−−→ R-R + 2NaX
Symmetrical Alkane

• Key Features:
– The alkane produced (R-R) has double the number of carbon atoms of the R
group in the starting alkyl halide. This means it’s good for making alkanes
with an even number of carbon atoms if you start with a single type of
alkyl halide.
– Better yields are obtained for preparing alkanes with higher molecular mass.
– If you use a mixture of two different alkyl halides (e.g., R-X and R’-X), you get
a mixture of three alkanes (R-R, R’-R’, and R-R’), which is usually undesirable
due to separation difficulties.
• Examples:
– Preparing Hexane from 1-Bromopropane:
Dry Ether
2CH3 CH2 CH2 Br + 2Na −−−−−→ CH3 CH2 CH2 CH2 CH2 CH3 + 2NaBr
1-Bromopropane Hexane

– Preparing 2,3-Dimethylbutane from 2-Bromopropane:

Dry Ether
2CH3 CH(Br)CH3 + 2Na −−−−−→ CH3 CH(CH3 )CH(CH3 )CH3 + 2NaBr
2-Bromopropane 2,3-Dimethylbutane

Question 5: If you react chloroethane (CH3 CH2 Cl) with sodium in dry ether using the
Wurtz reaction, what alkane will be the major product?

Special Preparation Method for Methane

Methane (CH4 ), the simplest alkane, can also be prepared by a specific hydrolysis reaction.
• What’s happening? Certain metal carbides, like aluminium carbide (Al4 C3 ) or
beryllium carbide (Be2 C), react with hot water or dilute mineral acids to produce
methane. These are sometimes called ”methanides.”
• Reaction (with Aluminium Carbide):
Hot
Al4 C3 (s) + 12H2 O(l) −−→ 3CH4 (g) + 4Al(OH)3 (s)
Or with dilute acid (e.g., HCl):
Al4 C3 (s) + 12HCl(aq) → 3CH4 (g) + 4AlCl3 (aq)

Question 6: What is the chemical formula of aluminium carbide?

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Physical Properties of Alkanes (A Quick Review)
• States at Room Temperature:

– C1 to C4 (e.g., Methane, Ethane, Propane, Butane) are gases.

– C5 to approximately C17 (e.g., Pentane, Hexane, Octane) are liquids.
– Alkanes with more than ∼17 carbon atoms are waxy solids.

• Boiling and Melting Points:

– Increase with molecular mass (chain length): Larger molecules have

stronger London Dispersion Forces (LDFs) between them, requiring more en-
ergy to separate them.
– Branching lowers boiling point: For isomers (same molecular formula,
different structure), branched alkanes have lower boiling points than their
straight-chain counterparts. This is because branching makes the molecule
more compact/spherical, reducing the surface area for LDFs. More branched
isomers are thus more volatile (evaporate more easily).

• Solubility:

– Immiscible with polar solvents like water: Alkanes are nonpolar molecules.
”Like dissolves like,” so nonpolar alkanes don’t mix well with polar water.
They will form separate layers.
– Soluble in nonpolar solvents: Alkanes dissolve in other nonpolar solvents
like benzene, ether, chloroform, tetrachloromethane (carbon tetrachloride).

• Density:

– Generally, density increases with molecular mass.

– Alkanes are usually less dense than water (they float on water).
– Increased branching tends to slightly decrease density compared to a straight-
chain isomer of the same mass, as branching can lead to less efficient packing
of molecules.

Question 7: Which would you expect to have a higher boiling point: n-pentane (straight
chain C5 H12 ) or neopentane (2,2-dimethylpropane, a branched C5 H12 isomer)? Why?

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Answers to Questions
1. Answer 1: • LiAlH4 reacts violently with wa-
ter, which can be dangerous and
For the hydrogenation of ethene
consumes the reagent.
(C2 H4 ) to ethane (C2 H6 ) at room
temperature, catalysts such as Plat- • Grignard reagents (RMgX) are
inum (Pt) or Palladium (Pd) are strong bases and nucleophiles.
commonly used. These catalysts are Water will protonate the R
effective at ordinary temperatures, group (which acts like R− ) to
unlike Nickel (Ni) which typically re- form an alkane (R-H), thus de-
quires elevated temperatures. stroying the Grignard reagent
and preventing it from being
2. Answer 2: used in its intended reaction.

To prepare butane (CH3 CH2 CH2 CH3 ) Dry ether, being an aprotic solvent
using Kolbe’s electrolytic synthe- (lacking acidic protons), does not re-
sis, you would start with sodium act with these reagents and provides
propanoate (CH3 CH2 COONa). a safe medium for the reactions.
In Kolbe’s electrolysis, two R-groups
5. Answer 5:
from RCOO− ions combine to form
R-R. For butane (CH3 CH2 -CH2 CH3 ), If you react chloroethane (CH3 CH2 Cl)
the R-group is an ethyl group with sodium in dry ether us-
(CH3 CH2 -). Therefore, the start- ing the Wurtz reaction, the
ing salt RCOONa must be sodium major product will be butane
propanoate. (CH3 CH2 CH2 CH3 ). The Wurtz
reaction involves coupling two alkyl
3. Answer 3: (R) groups from two molecules of an
alkyl halide (R-X) to form an alkane
If you start with sodium propanoate (R-R). For chloroethane, the R-group
(CH3 CH2 COONa) and heat it with is ethyl (CH3 CH2 -). So, R-R will be
soda lime, ethane (CH3 CH3 ) will be CH3 CH2 -CH2 CH3 .
formed. The decarboxylation method
removes the -COONa group (and the 6. Answer 6:
carbon atom within it as CO2 ) and re- The chemical formula of aluminium
places it with a hydrogen atom on the carbide is Al4 C3 .
R group. So, from CH3 CH2 COONa,
the R-group is CH3 CH2 -, and the 7. Answer 7:
product is R-H, which is CH3 CH2 -H n-pentane (straight chain C5 H12 )
or ethane. would be expected to have a higher
boiling point than neopentane (2,2-
4. Answer 4: dimethylpropane, a branched C5 H12
It is important to use ”dry ether” isomer).
when preparing a Grignard reagent or Reason: Both are isomers with
when using Lithium Aluminium Hy- the same molecular mass. How-
dride (LiAlH4 ) because both of these ever, n-pentane is a linear molecule,
reagents are highly reactive towards while neopentane is highly branched
water and other protic solvents (sol- and more compact (spherical). Lin-
vents that can donate H+ ). ear molecules have a larger surface

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area for intermolecular contact than molecules. Stronger LDFs require
branched, spherical molecules. This more energy (and thus a higher tem-
allows for stronger London Dispersion perature) to overcome for the sub-
Forces (LDFs) between n-pentane stance to boil.

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