CHEMISTRY NOTES

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STOICHIOMITRY 1.1 Mole concept & Avogadro's constant

1.1.1 : 1 Mole of something is equivalent to 6.023 x 1023 (<-- Avogadro's constant) units of it...ie lots of atoms, molecules etc...the periodic table gives molar masses...ie the number of grams of a substance required for 1 mol of atoms. This can be extrapolated to molecules of known molecular formula. 1.1.2 : Number of mols = mass / mass per mol (Usually found on periodic table)...The coefficients in chemical equations give the molar ratios of reactants and products...ie 2A + 3B -> C. There is 2/3 as much A as B, and 3 times more B than C involved in the reaction...Assuming the reaction goes to completion, there must be 3/2times as much B as A for neither to remain...If this ratio is not followed, one will be a limiting reactant, and so the reaction will have some of the other reactant left over when it completes.

1.2 Formulae
1.2.1 : Atomic mass, Molecular Mass, Formula Mass : All the mass per mol of a particular type of species...atoms, molecules or formula units. These can be found for the periodic table, and will give the mass for 1 mol of the species (or rather the average accounting for different isotopes and their relative abundance). Mr is the ratio between the molar masses of two species. Ar is the ratio of the number of atoms between two species. These two ratios will be equal. 1.2.2 : Moles vs Mass...Moles is a number of something...every mol being 6.023x1023 individual elements. Mass is the property which results in 'weight' in the presence of Gravity. Given a molar mass, M a mass m and a number of mols N then N=m/M. 1.2.3 : An 'Empirical formula' is the formula describing the different atoms present in a molecules, and their ratios, but not the actual number present. ie AxByZc could be an empirical formula if x, y, and z are in lowest common terms. The molar mass can then be used to calculate the actual numbers of each atom present per molecule. The empirical formula can be determined by percentage composition, or anything else which gives the ratios of atoms present. 1.2.4 : A Molecular Formula is similar to an empirical formula except that it includes the the number of atoms present in each molecule, rather than the ratio. It will be an integer multiple of the empirical formula ie KAxByZc and can be calculated from the empirical formula and the molar mass of the substance.

1.3 Chemical Equations

1.3.1 : The mole ratio of two species in a chemical equation is the ratio of their coefficients...ie aX + bY -> cZ : The ratio of X/Yis a/b, Y/Z= b/cetc... 1.3.2 : Balancing equations...change only the coefficients, not the subscripts to make sure

all atoms, and charge is conserved (half equations can be balanced by addition of electrons to either side...2 half equations can be added by making the number of electrons equal in each, then vertically adding.) 1.3.3 : State symbols -- (s)-Solid , (l)-liquid, (g)-gas, (aq)-aqueous solution...ie something dissolved in water. Should be included in all chemical reactions (but won't be penalized).

1.4 Mass relationships in chemical reactions

1.4.1 : Mass is conserved throughout reactions. This fact allows masses to be calculated based on other masses in the reaction eg burning Mg in air to produce MgO and so to find the mass or Mg present in the original sample (ie purity)...can be extended to concentrations...ie titration. 1.4.2 : When a reaction contains several reactants, some may be in excess...is more is present that can be used in the reaction. The first reactant to run out is the limiting reagent (or reactant). Knowing the number of mols of the limiting reagent allows all other species to be calculated, and so the yield, and remaining quantities of other reactants.

1.5 Solutions
1.5.1 : Solvent - the stuff you're dissolving in...ie water. Solute - the stuff you're dissolving in it...an ionic compound or something...Solution - the two of them when mixed together. Concentration - the amount of solute per amount of solvent...in mols per dm3...ie mols per liter or grams per liter. 1.5.2 : Apply the equation concentration = number/volume...rather obvious from the units of concentration, but remember to covert everything into the same units. 1.5.3 : Use chemical equations to relate the amount of one species to the amounts of others.

ATOMIC THEORY (SL) 2.1 The Nuclear atom

2.1.1 : Protons -- Mass = 1 amu , charge = +1 .. Neutrons -- Mass = 1 amu , charge = 0 .. Electron -- Mass = 1/1840 amu (usually insignificant), charge = -1 2.1.2 : Protons and Neutrons form the nucleus of the atom, electrons orbit the nucleus in electron shells. 2.1.3 : Mass number (A) -- Number of protons + neutrons. Atomic number (Z) -- number of proton. Isotope -- atoms with same atomic number but different mass number (ie different numbers of neutrons) 2.1.4 : AZX... A = mass number, Z = atomic number, X = atomic symbol. 2.1.5 : Isotopes may differ in physical properties (mass/density) and radioactivity but not generally in chemical properties. 2.1.6 : Atomic masses are the average of the atomic mass of each isotope (isotopic mass) times the isotope's relative abundance. results in non integer atomic masses 2.1.7 : Atomic number = number of protons (or number of electrons - ionic charge) , mass number - atomic number = number of neutrons.

2.2 Electron Arrangement

2.2.1 : Continuous spectrum goes continuously through red, orange, yellow, green, blue, indigo, violet. A line spectrum contains only some individual lines from this spectrum. 2.2.2 : Electrons are excited (usually by running an electric current through them). This causes electrons to 'jump' into higher electron shells ( X -> X* ) this state is only temporary, however, and the electron falls back to it's ground state. This change decreases the energy of the electron, and this energy is emitted in the form of a photon. If this photon falls into the visible spectrum of light, then it produces a visible spectrum. As electrons move further away from the nucleus, the electron shells become closer together in terms of space and energy, and so lines converge towards the end of the spectrum. 2.2.3 : The main electron levels go : 2, 8, 18 etc...2n + 2 for n0, n1 and n2... 2.2.4 : Electrons are added from the left...after each shell is filled, move to the next...2, 8, 18...only up to Z = 20 is required.

ATOMIC THEORY (HL) 12.1 The mass spectrometer

12.1.1 : Stages of operation : vaporisation, ionisation, acceleration, deflection and detection...Substance to be tested is vaporised (by heat, absence of oxygen) then ionised by electric current. Ions are accelerated through an electric field, then deflected by a magnetic field. Ions are then detected...the angle of deflection reflects their mass to charge ratio. 12.1.2 : The angle of deflection of each fragment is proportional to it's mass, and so it is possible to find the relative atomic mass of each 'spike' the height of the spike represents the frequency, therefore, the abundance can be calculated. The relative atomic mass is the average of the isotope masses times their frequencies.

12.2 Electronic structure of atoms

12.2.1 : Successive electrons can be stripped from an atom until there is only the nucleus left. If the energy required to achieve this for each electron is plotted on a graph (with a log scale) against ionisation number, the 'jumps' in the required energy clearly show the main and sub energy levels. 12.2.2 : n = (1, s) (2, sp) (3, spd) (4 spdf) 12.2.3 : Energies of sub-shells : s < p < d < f 12.2.4 : Number of orbitals at each level : s=1, p=3, d=5, f=7 12.2.5 : Shapes of orbitals : s orbital is a sphere around the nucleus. p orbitals are shaped like a figure 8 (and there are 3 of them at 90 degrees around the nucleus. 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f 5s 5p 5d 5f 12.2.6 : Move diagonally down and left through each diagonal...ie 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d... Pauli's exclusion principle says that there can only be 2 electrons in each orbital (with opposite spins). Hund's rule says that each orbital should be half filled before any is completely filled (since there is less repulsion if all electrons have the same spin). Electrons will therefore fill the lowest energy levels (ie 1 then 2 and so on) with two going in each orbital, but only doubling up when all orbitals in the level are filled. 12.2.7 : Systematically fill the orbitals as shown above up to Z = 56. This can be abbreviated by writing [x] where x is a noble gas. 12.2.8 : The small double column on the left is the s shell being filled. The block on the left is the p shell being filled. The d block (in the middle) is (surprisingly) the d shell

being filled. The bits hanging off the bottom are the f shells being filled...forget them, they never matter :)

PERIODICITY (SL) 3.1 The Periodic Table

3.1.1 : Elements increase in atomic number across each period, and down each group. The history is boring and pointless (like all history)...ignore it. 3.1.2 : Group - the columns going down. Period - the rows going across. 3.1.3 : Group = number of valence electrons in the atom. Period = number of main electron shells...s, p , d and f blocks as described above.

3.2 Physical Properties

3.2.1 : Li->Cs (down the alkali metals) : Atomic radius increases due to increased electron shielding. Ionic radius increases due to increased electron shielding. Ionisation energy decreases due to increased electron shielding. Melting/boiling point decreases due to increased electron shielding->decreased forces. Electronegativity decreases due to increased shielding -> decreased attraction for outer electrons. F->I (Down the halogens) : Atomic radius increases due to increased electron shielding. Ionic radius increases due to increased electron shielding. Ionisation energy decreases due to increased electron shielding. Melting/boiling point increases due to increased number of electrons->increased london dispersion forces. Electronegativity decreases due to increased shielding -> decreased attraction for outer electrons. Na->Ar (across period 3) : Atomic radius decreases due to increased nuclear charge -> greater attraction for electrons. Ionic radius decreases Na->Al (due to increased nuclear charge) jumps Al->Si (due to reversal of ionisation direction...increased electron-electron repulsion) decreases Si->Ar (due to increased nuclear charge). Ionisation energy increases due to increased nuclear charge. Melting/boiling point increases Na->Si (due to stronger metallic bonding - more delocalized electrons then network covalent) drops Si-P (due to network->molecular covalent) increases P->S (due to increased LDF between molecules ie P4, S8). Drops to Cl, due to smaller molecules (Cl2) decreases to Ar (individual atoms->fewer electrons->smaller LDF). Electronegativity increases due to increased nuclear charge -> greater attraction for electrons.

3.3 Chemical Properties

3.3.1 : Reactions of elements in the same group are similar because they have identical outer shells (ie same number of valence electrons). Generalized reactions follow : Alkali metal (group 1) with water 2Na + 2H2O -> 2Na+ + 2OH- + H2

Alkali metal (group 1) with Halogen 2Na + Cl2 -heat-> 2NaCl (Na acts as a reducing agent...is oxidized, Cl2 is reduced) Halogen with water Cl2 + H2O <=> HCl + HClO (Exception F2 is such a strong oxidizer : 2F2 + 2H2O -> 4HF + O2 ) Halogen + Halide ion ClColorless Cl2 -> Cl2 Red Br2 -> Br2 Violet I2 -> I2 BrRed -> Br2 Red -> Br2 Violet -> I2 IViolet -> I2 Violet -> I2 Violet -> I2

Halide ion with Silver ion Ag+ + Cl- -> AgCl(s) (a white precipitate) Ag+ + Br- -> AgBr(s) (a cream precipitate) Ag+ + I- -> AgI(s) (a yellow precipitate) 3.3.2 : Elements on the left are metallic...right are non-metals...Al is a metalloid (semimetal). Oxides : Non-metals -> Acidic oxides , Metals -> Basic oxides, Metalloids -> Amphoteric (both acidic & basic) oxides. P4O10 Na2O MgO Al2O3 SiO2 SO3 Cl2O7

(or P4O6)

(or SO2)

dding H2O

Na2O + H2O - MgO + H2O > 2NaOH > Mg(OH)2 Insoluble

Insoluble

P4O10 + 6H2O SO3 + H2O -> Cl2O7 + H2O -> 4H3PO4 H2SO4 > HClO4

dding HCl

Al2O3 + 6H+ Na2O + H -> MgO + 2H -> > 2Al3+ + 2Na+ + H2O Mg2+ + H2O 3H2O No reaction
+ +

No reaction

No reaction

No reaction

dding NaOH No reaction ature Basic Oxide

No reaction Basic Oxide

Al2O3 + 2OHP4O10 + 12OHCl2O7 + OH- 3+ 3H2O -> SiO2 + 2OH - -> 4PO4 + SO3 + OH -> > 2ClO4- + 22Al(OH)4 > SiO3 + H2O 6H2O SO42- + H2O H2O Amphoteric Oxide Acidic Oxide Acidic Oxide Acidic Oxide Acidic Oxide

Halides (assuming Cl...could replace with Br, I, F etc) : Ionic Chlorides -> dissolved in H2O with little reaction, Covalent Chlorides -> dissolve + react to form HCl. NaCl : NaCl + H2O -> Na+ + Cl- + H2O MgCl2 : MgCl2 -> Mg2+ + 2ClAl2Cl6 : Al2Cl6 + 6H2O -> 2Al(OH)3 + 6HCl This isn't required....not like it's hard SiCl4 : SiCl4 + H2O -> Si(OH)4 + 4HCl PCl3 : PCl3 + 3H2O -> H3PO3 + 3HCl S2Cl2 : 2S2Cl2 + 2H2O -> 3S + SO2 + 4HCl Cl2 : Cl2 + H2O -> HCl + HClO (Exception : F2 is such a strong oxidizer : 2F2 + 2H2O -> 4HF + O2)

PERODICITY (AL) 13.1 Periodic trends Na-> Ar (the third period)

13.1.1 : (This seems very much like the last bit of SL, but now with explanations :) Elements on the left are metallic...right are non-metals...Al is a metalloid (semi-metal). Oxides : Non-metals -> Acidic oxides , Metals -> Basic oxides, Metalloids -> Amphoteric (both acidic & basic) oxides.

P4O10 Na2O MgO Al2O3 SiO2 (or P4O6)

SO3 (or SO2)

Cl2O7 Cl2O

P4O10 + 6H2O SO3 + H2O -> Cl2O7 + H2O -> 4H3PO4 H2SO4 > 2HClO4 Adding H2O Na2O + H2O - MgO + H2O > 2NaOH > Mg(OH)2 Insoluble Insoluble P4O6+ 6H2O - SO2 + H2O -> Cl2O + H2O -> > 4H3PO3 H2SO3 2HOCl

Adding HCl

Al2O3 + 6H+ Na2O + H -> MgO + 2H -> > 2Al3+ + 2Na+ + H2O Mg2+ + H2O 3H2O No reaction
+ +

No reaction

No reaction

No reaction

Adding NaOH

No reaction

No reaction

Al2O3 + 2OHH3PO4 + OH- HCl2O7 + OH+ 3H2O -> SiO2 + 2OH - > H2PO4 + SO2 + OH -> -> Cl2O72- + 22Al(OH)4 > SiO3 + H2O H2O HSO4H2O

Explaining the physical properties ... Conductivity for ionic solutions (Na2O->Al2O3) is due to ions in solution/molten state. SiO2 is network covalent...no charges therefore no significant conductivity. Others are covalent molecules therefore no conduction. Melting point...stronger bonds when atoms can be arranged in a simple structure...MgO is highest, then Al2O3, Na2O (the ratio between the two atoms should be as close to 1 as possible). SiO2 is network covalent -> high melting point (but not as high as ionic bonding). The final 3 decrease in melting point due to decreasing polarity of molecules -> smaller dipole-dipole interactions. Halides (assuming Cl...could replace with Br, I, F etc) : Ionic Chlorides -> dissolved in H2O with little reaction, Covalent Chlorides -> dissolve + react to form HCl. NaCl : NaCl + H2O -> Na+ + Cl- + H2O Good conductivity (ionic structure) MP = 801 MgCl2 : MgCl2 -> Mg2+ + 2ClGood conductivity (ionic structure) MP = 714 Al2Cl6 : Al2Cl6 + 6H2O -> 2Al(OH)3 + 6HCl Poor conductivity (Network covalent) MP = 178

SiCl4 : SiCl4 + H2O -> Si(OH)4 + 4HCl No conductivity (Covalent molecular) MP = -70 PCl3 : PCl3 + 3H2O -> H3PO3 + 3HCl PCl5 : 2PCl5 + 6H2O -> 2HPO3 + 10HCl No conductivity (Covalent molecular) MP = -112 S2Cl2 Not required Cl2 : Cl2 + H2O -> HCl + HClO (Exception : F2 is such a strong oxidizer : 2F2 + 2H2O -> 4HF + O2) No conductivity (Covalent molecular) MP = -101 MP...NaCl and MgCl2 -> decreases due to packing (as above), drops to Al2Cl6 (network covalent). Others are covalent molecules...decreases due to decreasing polarity (Cl2 higher due to more electrons...greater LDF ?)

13.2 D-block elements (first row)

13.2.1 : Typical d-block elements are generally those exhibiting multiple oxidation states (in period 4, not Sc or Zn) 13.2.2 : The multiple oxidation states of the d-block (transition metal) elements is due to the proximity between the 4s and 3d sub shells (in terms of energy). All transition metals exhibit a 2+ oxidation state (both electrons being lost form the 4s and all have other oxidation states...ie V - +4, +5 (apparently we need to know only 2 of these...weird if you ask me...but include Fe... Cr - +3, +6 Mn - +4, +7 Fe - +3 13.2.3 : Ligands are the molecules which donate an electron pair to form a dative covalent bond with the central atom (thus forming a complex ion). 13.2.4 : Complex ions are molecules which carry a charge. They are formed around a central atom, with other atoms (or molecules) donating an electron pair to form a covalent bond to this central atom. Examples...

[Fe(H2O)6]3+ - Fe is the central atom, H2O is the ligand [Fe(CN)6]3- - Fe is the central atom, CN is the ligand [CuCl4]3- - Cu is the central atom, Cl is the ligand [Cu(NH3)4]2+ - Cu is the central atom, NH3 is the ligand [Ag(NH3)2]+ - Ag is central atom, NH3 is the ligand 13.2.5 : The color in the transition metals (d-block) is predominantly due to the splitting of the d shell orbitals into slightly different energy levels. As a result, certain wavelengths of energy can be absorbed by the d-block elements (with electrons jumping between these slightly different energy levels), resulting in the complement color being visible. 13.2.6 : d-block elements make good catalysts due to their multiple oxidation states (hence their ability to react with different species and produce a path of lower activation energy, and so allow the reaction to proceed at a faster rate). Examples... MnO2 in decomposition of hydrogen peroxide V2O5in the contact process Fe in Harber process Ni in conversion of alkenes to alkanes

BONDING (SL) 4.1 Ionic Bond

4.1.1 : Ionic bond - +ve (cations) and -ve (anions) ions are attracted to each other and form a continuous ionic lattice 4.1.2 : Group 1 metals form +1 ions, group 2 metals form +2 ions, metals in group 3 for +3 ions...funny that :) Examples : Li+, Mg2+, Al3+...Greater ease of ionisation Li->Cs is due to the increased electron shielding of the nuclear attraction caused by additional inner shells of electrons. The easier atoms are to ionise, the more reactive they will be because less energy is required to ionise them, and so they react faster. 4.1.3 : Group 6 ions will form 2- ions, Group 7 ions will form - ions. Examples : O-2, Cl... 4.1.4 : The transitions metals (elements from Ti to Cu, ignore Sc and Zn) can form multiple ions (ie Fe2+, Fe3+) (due to proximity of 4s and 3d shells) 4.1.5 : The ionic or covalent nature of the bonding in a binary compound is a result in the difference between their electronegativity...NaCl(s) is ionic, HCl(g) is (polar) covalent (also, covalent molecules tend to be gases/liquids, ionic tends to be solid...except network covalent which will be solid). In general, if the difference between electronegativities is greater than 1.7, the bond will be more than 50% ionic. 4.1.6 : Take the name of the group 1,2, or 3 metal and add...fluoride, chloride, bromide, iodide etc , oxide, sulfide etc...Nitride and phosphide...how exciting :)

4.2 Covalent Bond

4.2.1 : Covalent bonds are where two atoms each donate 1 electron to form a pair held between the two atoms...Such bonds are generally formed by atoms with little difference in electronegativity...ie C, H and O in organic chemistry. 4.2.2 : All electrons must be paired...Lewis diagrams are the element symbol with the outer (valence) shell of electrons left over and spare electrons pair up...in general C forms 4 bonds, N forms 3, O forms 2, halogens form 1, H forms 1...(Li would form 1, Be 2, and B 3 but they don't usually...metallic or ionic bonding) 4.2.3 : Electronegativity values range from 0.7 to 4...from bottom left to top right respectively (hydrogen falls B and C with a electronegativity of 2.1... 4.2.4 : When covalent molecules have a difference in electronegativity (between the two bonding atoms) then the pair will be held closer to the more electronegative atom...resulting in a small -ve charge on the more electronegative atom, and a small +ve charge on the other...results in polar bonds

4.2.5 : Shape of molecule with 4 electron pairs depends on number of lone pairs. 3 lone pairs -> linear, 2 lone pairs -> bent, 1 lone pair -> trigonal pyramid, No lone pairs > tetrahedral 4.2.6 : The polarity of a molecule depends on both the shape and the polarity of the bonds...1) if there are no polar bonds, it's not polar. 2) if there are polar bonds, but the shape is symmetrical, it's not polar (think about it like 3D vector addition...if they add to zero, then it's not polar). 3) if there are polar bonds, and it's not symmetric, then the molecule is polar

4.3 Intermolecular forces

4.3.1 : van der Waal's forces -- Electrons will not be evenly spread around an atom/molecule at any given time, meaning the molecule will have a slight +ve charge on one end, and a -ve at the other. this temporary state may cause attraction between two molecules, pulling them together (also known as london dispersion forces). Dipole-dipole forces -- Polar molecules, when properly oriented, will attract each other as a result of this. Stronger than van der Waal's forces. Hydrogen bonding -- When hydrogen is bonded to nitrogen, oxygen or fluorine, a very strong dipole is formed, making the hydrogen very strongly positive. This hydrogen is then attracted to the lone pairs on other similar molecules (nitrogen, oxygen and fluorine all have lone pairs) forming a hydrogen bond, which is stronger than van der Waal's or dipole-dipole, but weaker than covalent bonding. 4.3.2 : Structural features -- Nonpolar molecules...van der Waal's forces only ...also present in all other molecules, though it's strength is insignificant compared to the others. Polar molecules...dipole-dipole forces arise from polar bonds and asymmetry in molecules. Hydrogen bonds result from hydrogen bonded as described above. This results in molecules with hydrogen bonding exhibiting stronger intermolecular forces, ie higher boiling/melting points etc. ie H2O has a higher bp then H2S due to hydrogen bonding, and so on down the strength list. (nonpolar molecules don't conduct electricity, polar +hydrogen bonding ones will...I suppose this goes here)

4.4 Metallic bond

4.4.1 : Metallic bonding...the metal atoms lose their outer electrons which then become delocalized, and free to move throughout the entire metal. These -ve delocalized electrons hold the metal cations together strongly. Since these electrons can flow, atoms with metallic bonding exhibit high electrical conductivity. Unlike ionic bonding, distorting the atoms does not cause repulsion so metallic substances are ductile (can be stretched into wires) and malleable (can be made into flat sheets). The free moving electrons also allow for high thermal conductivity, and the electrons can carry the heat energy rather than it being transferred slowly through atoms vibrating.

4.5 Physical Properties

Melting + Boiling point...High with Ionic and metallic bonding (and network covalent), Low with covalent molecular bonding.

Volatility...Covalent molecular substances are volatile, others aren't Conductivity...Metallic substances conduct. Polar molecular substances conduct, nonpolar ones don't. Ionic substances don't conduct when solid, do conduct when molten or dissolved in water. Solubility...Ionic substances -> generally dissolve in polar solvents (like water). Metallic substances...(Generally not soluble ?). Non-polar molecules are generally soluble in nonpolar solvents, and polar in polar. Organic molecules with a polar head : Short chain molecules are solubility in polar solvents, long chains can eventually outweigh the polar 'head' and will dissolve in non-polar solvents.

BONDING (HL) 14.1 Shapes of Molecules

14.1.1 : Shapes of molecules...around each atom, there are covalent bonds and lone electron pairs...all of which repel each other (the lone pairs repel a little more, so if possible, they shouldn't be together)...Therefore all the pairs will be as far away from each other as possible. How to work out the shape : 1) decide which atom is at the center...usually the on of which there is only one. 2) find (form the periodic table) the number of electrons on this atom. 3) add an electron if the molecule is negatively charged, subtract one if +ve. 4) Add one electron for each atom joined to the central one. 5) divide this by 2 to get the number of electron pairs...Match up the shape as below. 2 Pairs, bond angle = 180 : 1 bonded atom -> linear, 2 bonded atoms -> linear 3 Pairs, bond angle = 120 : 2 bonded atoms -> bent, 3 bonded atoms -> trigonal planar (4 Pairs is in SL) 14.1.2 : Continuing on with 5 and 6 pairs... 5 Pairs, bond angles = 120 and 90 : 3 bonded atoms -> T-Shaped, 4 bonded atoms -> distorted tetrahedron, 5 bonded atoms -> trigonal bipyramidal 6 Pairs, bond angle = 90 : 4 bonded atoms -> square planar, 5 bonded atoms -> square pyramid, 6 bonded atoms -> Octahedral Whenever a molecule can be drawn in multiple structures (eg ClO2- can be drawn with 2 double bonds and -ve on Cl or one double, one single, and -ve on either O) the structures differ only in the arrangement of electrons, the positions of nuclei remain constant, and so the above theory can be used to predict the shape (because the actual position is like the average of all the resonance hybrids.

14.2 Multiple bonds

14.2.1 : Sigma bonds -> these are bonds between two atoms where the bond is symmetric around the line between the two nuclei of the atoms. Pi bonds are those which are not symmetric, usually because they fall outside this line. This often occurs after a Sigma bond has formed, when the two atoms p orbitals overlap above and below the sigma bond, forming a new Pi bond. Since Pi bonds are not free to rotate, this allows for cistrans isomerisim etc...Triple bonds, such as those seen in alkynes, are the result of one sigma bond, and two pi bonds. 14.2.2 : In general, more bonds -> stronger, shorter bonds.

14.3 Hybridisation
14.3.1 : The electron structure of carbon is 1s2 2s2 2p2 ... so how come it can form 4 identical bonds ? Hybridisation!!!! :) more specifically sp3 hybridisation. Other times it forms 3 identical sigma bonds, and a pi bond (sp2 hybridisation) and yet other times, two identical bonds, and two pi bonds (like in eythene), which is sp hybridisation. sp3 hybridisation occurs when the 2s and 2p orbitals merge to become sp3 orbitals (all of equal energy, length etc.). sp2 is the same except only two of the p orbitals are hybridised, leaving one p orbital behind...and the same with sp only two p orbitals are left over. 14.3.2 : sp3 hybrids have 4 -ve charge centers -> tetrahedral shape. sp2 has 3 -ve charge centers -> trigonal planer. sp has 2 -ve charge centers -> linear. To work with lewis structures...find number of identical bonds. 4 identical -> sp3, 3 identical -> sp2, 2 identical -> sp.

14.4 Delocalisation of electrons

14.4.1 : When a particular molecule can be represented as several different ways (different lewis structures) is is generally not actually any of these, but a hybrid of all of them. this can be represented either with delocalized electrons, or through resonance (where each possible structure is drawn and the actual state 'resonates' between them. The delocalisation of these pi electrons (which is effectively what happens) makes the molecule more stable (as evidenced by lower energy) and gives the bonds a shorter length than would be expected. Classic example is benzene, but also O3 etc...

STATES OF MATTER (SL)

5.1.1 : Solids -> molecules/atoms tightly packed. force of attraction between molecules overcomes any translational motion of molecules (they do, however, vibrate in position). Liquids -> particles held close together, but not as strongly as solids in that they are free to move, but not to escape the liquid (except for fast traveling particles -> evaporation). Gas -> particles move independently and randomly, with no significant forces between particles, and a large (comparatively) amount of space between them. 5.1.2 : Ideal gas -> composed of randomly moving point masses occupying no space and with no forces between masses. The average (rms) speed of the movement of particles is proportional to temperature (in K). as a result, the kinetic energy of the particles is also proportional to temperature. 5.1.3 : Solid -> liquid , the rigid structure of the solid is overcome due to increased vibration of particles (due to energy being added in the form of heat). the particles can not escape from the liquid, but can move within it. Liquid to gas -> as energy (in the form of heat) is given to the liquid, the particles gain enough energy to escape the liquid, and become a gas, with particles widely spaced. Gas->liquid...as heat (energy) is removed, the particles slow down to the point where the forces between particles are strong enough to hold them together...a liquid ! Liquid->solid...energy is removed, particles move slower->stronger forces->more rigid structure. 5.1.4 : increase in temp -> larger volume or higher pressure...increase in volume -> decrease in temp or decrease in pressure...increase in pressure -> decrease in volume or increase in temp. 5.1.5 : Since the particles are moving at random, two separated samples of gas will eventually mix causing diffusion. This will occur at a higher rate with higher temperature since the particles are moving faster.

STATES OF MATTER (HL) 15.1 Gases

15.1.1 : PV = nRT ... P=(pressure in atm) V=(volume in cm3) n=(number of atoms in mols) R=(82.05 cm3 atm K-1 mol-1 -- in data book) T=(temperature in K) 15.1.2 : The above equation can be rearranged as P1V1=P2V2 or V1/T1=V2/T2 if temp or pressure are assumed to be constant. Avogadro's law -- equal volumes of gas contain equal numbers of particles (at 273K, 1 atm -> 22.4 dm3 mol-1 -- in data book) 15.1.3 : Dalton's law of partial pressures -> the partial pressure of a gas is the pressure the gas would exert if the gas were alone in its container. ie if there are Gases A, B and C filling a dm3, b dm3 and c dm3 respectively then the partial pressure of a = (a)/(a+b+c) x total pressure.

15.1.4 : Pp = (number of molecules in the gas)/(total number of molecules) x total pressure ... apply this relationship... Nb -- Apparently, though it's never been in the syllabus, there have been questions on Van Der Wall's equation, which is an extension of PV=nRT for non-ideal gas situations...it is (P+an2/V2)(V-nb)=nRT Where a and b are constants for a given gas...which I assume will be given if necessary.

ENERGETICS (SL) 6.1 Exothermic and endothermic reactions

6.1.1 : If the reaction produces heat (increases the temperature of the surroundings) then it's exothermic. If it decreases the temp (ie absorbs heat) then it's endothermic. Also, the yield of an equilibrium reaction which is exothermic will be increased if it occurs at low temps, and so for endothermic reactions at high temps. 6.1.2 : Exothermic -> a reaction which produces heat. Endothermic -> a reaction which absorbs heat. Enthalpy of reaction -> the change in internal energy (H) through a reaction is delta-H. 6.1.3 : delta-H will be -ve for exothermic reactions (because internal heat is being lost) and +ve for endothermic reactions (because internal energy is being gained). 6.1.4 : The most stable state is where all energy has been released...therefore when going to a more stable state, energy will be released, and when going to a less stable state, energy will be gained. On an enthalpy level diagrams, higher positions will be less stable (with more internal energy) therefore, if the product is lower, heat is released (more stable, delta-H is -ve) but if it is higher, heat is gained (less stable, delta-H is +ve). 6.1.5 : Formation of bonds -> release of energy. Breaking of bonds -> gain / absorption of energy.

6.2 Calculation of enthalpy changes

6.2.1 : change in energy = mass x specific heat capacity x change in temperature --> E = m x c x delta-T 6.2.2 : Enthalpy changes (delta-H) are related to the number of mols in the reaction...if all the coefficients are doubled, then the value of delta-H will be doubled (attention must be paid to limiting reagents though). 6.2.3 : When a reaction is carried out in water, the water will gain or lose heat from (or to) the reaction, with hopefully little escaping the water. Therefore, the change in energy, and so the delta-H value, can be calculated with E = m x c x delta-T where E is equal to delta-H, m is the mass of water present, and c = 4.18 kJ Kg-1 K-1. This delta-H value can then be calculated back to fine the enthalpy change for each mol of reactants. 6.2.4 : The solution should be placed in a container as insulated as possible, to keep as much heat as possible from escaping. The temperature should be measured continuously , and the value used in the equation is the maximum change in temp from the initial position. 6.2.5 : The results will be a change in temperature. this can be converted into a change in heat (or energy) by using the above equation and a known mass of water. this can be used

to calculate the delta-H for the amount of reactants present, and then this can be used to calculate for a given number of moles.

6.3 Hess' Law

6.3.1 : Hess' Law states that the total enthalpy change between given reactants and products is that same regardless of any intermediate steps (or the reaction pathway). To calculate...1) reverse any reactions which are going the wrong way and invert the sign of their delta-H values. 2) divide or multiply the reactions until the intermediate products will cancel out when the reactions are vertically added (always multiply/divide the deltaH value by the same number)...3) vertically add them...4) divide or multiply the resulting reaction to the correct coefficients.

6.4 Bond enthalpies

6.4.1 : Bond enthalpy (aka dissociation enthalpy) -- the enthalpy change when one mold of bonds are broken homolitically in the gas phase. ie X-Y(g) -> X(g) + Y(g) : deltaH(dissociation). Molecules such as CH4 have multiple C-H bonds to be broken, and so the bond enthalpy for C-H is actually an average value. These values can be used to calculate unknown enthalpy changes in reactions where only a few bonds are being formed/broken. 6.4.2 : If the reaction can be expressed in terms of the breaking and formation of bonds in a gaseous state, then by adding (or subtracting when bonds are formed) the delta-H values the total enthalpy of reaction can be found.

ENERGETICS (HL)
16.1 Standard enthalpy changes of reaction 16.1.1 : Standard state -- 101 kPa, 298 K (or 1 atm, 25 degrees celcuis). Standard enthalpy change of formation -- The enthalpy change when 1 mol of a substance is made from its elements in their standard states eg C(graphite) + 2H2(g) -> CH4(g). (molecules, like H2 are considered to be 'standard state. Fractions of mols->ie fractions in coefficients, may also be used if necessary as 1 mol must be produced). 16.1.2 : If a reaction can be expressed in terms of changes of formation (and bond enthalpies as in SL) then add up all the delta-H values to get the delta-H for the reaction.

16.2 Lattice enthalpy

16.2.1 : Lattice enthalpy -- the enthalpy change when 1 mol of crystals (ie an ionic lattice) is formed from its component particles at an infinite distance apart. ie M+(g) + X-(g) -> MX(s). The value of lattice enthalpy is assumed to be negative for the separation of the lattice, and positive for the formation of the lattice.

16.2.2 : As above, lattice enthalpies just add another type of reaction to those which can be shown on the Born-Harber cycle. 16.2.3 : lattice enthalpy increases with higher ionic charge and with smaller ionic radius (due to increased attraction).

16.3 Entropy
16.3.1 : Factors which increase disorder in a system : Mixing of particles, change of state to greater distance between particles (solid->liquid or liquid->gas), increased particle movement (temperature), increased number of particles (when more gas particles are produced, this generally outweighs all other factors). 16.3.2 : Predict the sign of delta-S (the change in entropy) for a reaction based on the above factors. delta-S is positive when entropy increases (more disorder) and negative when entropy decreases (less disorder). 16.3.3 : The standard entropy change can be calculated by subtracting the absolute entropy of the reactants from that of the products.

16.4 Spontaneity of a reaction

16.4.1 : Reactions which release heat (and so increase stability) tend to occur. Reactions which increase entropy (delta-S is positive) tend to occur, but neither can be used to accurately predict spontaneity alone. 16.4.2 : when delta-G is negative, the reaction is spontaneous, when it's positive, their reaction is not. 16.4.3 : delta-G = delta-H - Temperature(in kelvin) x delta-S...spontaneity depends on deltaH, deltaS and the temp at which the reaction takes place (or doesn't as the case may be). 16.4.4 : Yeah...well...stick numbers into that equation above... 16.4.5 : 4 possibilities... 1) delta-G is always negative when delta-H is negative and delta-S is positive. 2) delta-G is negative at high temperatures if delta-H is positive and delta-S is positive (ie an endothermic reaction is spontaneous when T x delta-S is greater than delta-H) 3) delta-G is negative at lower temperatures if delta-H is negative and delta-S is negative (exothermic reactions are spontaneous if delta-H is bigger than T x delta-S) 4) delta-G is never negative if delta-H is positive and delta-S negative.

KINETICS (SL) 7.1 Rates of reaction

7.1.1 : Rate of reaction is concerned with how quickly a reaction reaches a certain point (not to be confused with how far a reaction goes...ie equilibrium). 7.1.2 : Interpretation of rate graphs. Reaction rater graphs will generally be graphed with time on the x-axis and some measure of how far the reaction has gone (ie concentration, volume, mass loss etc) on the y-axis. This will generally produce a curve with, for example, the concentration of the products approaching zero.

7.2 Collision theory

7.2.1 : Collision theory -- reactions take place as a result of particles (atoms or molecules) colliding and then undergoing a reaction. Not all collisions cause reaction, however, even in a system where the reaction is spontaneous. The particles must has sufficient kinetic energy, and the correct orientation with respect to each other for the two to react.

7.2.2 : Higher temp -> greater average kE -> faster reaction. Higher concentration -> more collisions -> faster reaction. Catalysts -> lower activation energy / greater probability of proper orientation -> faster reaction. In hetrogenious reactions (where the reactants are in different states) the size of the particles of a solid may change reaction rate, since the surface is where the reaction takes place, and the surface area is increased when the particles are more finely divided...(therefore smaller solid particles in a hetrogenious reaction -> faster reaction). 7.2.3 : Most reactions involve several steps, which can be individually slow of fast, and which, all together, make up the complete reaction. The slowest of these steps is called the rate determining step, as is determines how fast the reaction will go. It is also not necessary that all the reactants are involved in ever step, and so the rate determining step may not involve all the reactants. as a result, increasing their concentration (for example) of a reactant which is not involved in the rate determining step will not change the overall

reaction rate.

KINETICS (HL) 17.1 Rate expression

17.1.1 : The rate expression will be of the form -- Rate = k[A]m[B]n...etc (for each reactant). k is a constant, and m, n etc show the order of the reaction for each reactant. 17.1.2 : Order of reaction is the total of m+n above. k is the rate constant, which will change due to any factor affecting the rate other than concentration (ie temp, catalysts...) 17.2.3 : If temperature increases, then the rate will increase and so the rate constant must increase also to account for this. If the temp decreases, the rate constant will decrease. 17.2.4 : A zero order reaction will be a straight line where the slope gives the rate constant (like y = mx + c). A first order reaction will be a curve where the half lives are constant (ie the time taken for the concentration to halve from any given point is constant). A second order reaction is a curve where the half lives are not constant. 17.1.5 : By substituting data into Rate = k[A]m[B]n, it is possible to solve the resulting simultaneous equations for m and n. for example, if the concentration of A was doubled, B was kept constant and rate doubles as a result, then the reaction would be first order with respect to A (ie m=1). If the rate increased by a factor of 4, then the reaction would be second order with respect to a (since (2a)2 = 4a2 and rate is proportional to a2). The overall order of the reaction can be calculated from graphical data as above. 7.1.6 : The rate constant can be found from a graph by taking a point, finding it's concentration, then finding a point on the graph which corresponds to half this concentration. The half life is the time between thee two points. The half life is also equal to ln2/k where k is the rate constant (equation given in data book).

17.2 Reaction mechanism

17.2.1 : Rate determining step -- the slowest step in a reaction which determines the rate for the overall reaction. Molecularity -- The number of molecules reacting in an elementary step of a reaction. Activated complex -- as two particles collide (with sufficient energy to react and in the correct orientation) they form an intermediate called the activated complex...not literally a chemical substance, but an intermediate in which the bonds are in the process of being broken and formed. 17.2.2 : The order of the reaction is defined by the particles involved in the rate determining step (which is one step in the mechanism). For example, if two of one type of particle are colliding, the order with respect to that particle will be 2 (and zero to any others). The activated complex is formed by (in this example) the two colliding molecules, weakening the bonds, which then break and form to create the new

molecule(s).

17.3 Collision theory

17.3.1 : Maxwell-Boltzman energy distribution curve...sometime I'll actually draw a picture of it, but for now...The curve is on a graph of kinetic energy (x-axis) against fraction of molecules with this kE (y-axis). The curve rises sharply to a peak, then falls off with the x-axis as an asymptote (ie is is possible, though statistically unlikely, for a molecule in any gas to be traveling at very high speed. 17.3.2 : At higher temperatures, the peak of the curve is lower, and further to the right. The graph is overall 'flatter' resulting in a greater proportion being above any given temperature...and so whatever the required activation energy, a greater proportion of the particles will have sufficient activation energy for the reaction to proceed...thus making the reaction occur faster.

17.4 Activation energy

17.4.1 : Arrhenius equation : k = Ae(-Ea/RT).(equation in data book)...The A in this equation is a constant related to the number and frequency of collisions occurring between the the reactants. 17.4.2 : Enthalpy level diagrams showing a curve demonstrating the path between the reactants and products on the graph. Energy is shown on the y-axis, and presumably the reactants and products are of different energies...the curve goes between the two levels (the reactants and products) peeking above both between them (with the distance between the highest point ant the reactants being the activation energy). A catalysed reaction graph is the same, only the curve peaks lower, representing a lower activation energy requirement. 17.4.3 : Reactions only occur when the reacting particles have energy greater than the activation energy. 17.4.4 : Homogeneous catalysts -- catalysts in the same state (phase -- ie solid, liquid or gas) as the reactants. Hetrogeneous catalysts -- catalysts in a different phase (usually a solid) from the reactants. 17.4.5 : Homogeneous catalysts operate by reacting with the reactants and eventually producing a reaction pathway of lower activation energy (and also being regenerated at the end of this process). Hetrogeneous catalysts provide a reactive site on which an activated complex forms, weakening the bonds and increasing the rate of collisions thus increasing the rate of reaction.

EQUILIBRIUM (SL) 8.1 Dynamic equilibrium

8.1.1 : In all reactions, there are in fact two reactions occurring, one where the reactants produce the products, and the other where the products react to form the reactants. In some reactions, this second reaction is insignificant, but in others there comes a point where the two reactions exactly cancel each other out...thus the reactants and products remain in equal proportions, though both are continually being used up and produced at the same time.

8.2 The position of equilibrium

8.2.1 : The equilibrium constant Kc is a constant which represents how far the reaction will proceed at a given temperature. 8.2.2 : When Kc is greater than 1, products exceed reactants (at equilibrium). When much greater than 1, the reaction goes almost to completion. When Kc is less than 1, reactants exceed products. When much less than 1 (Kc can never be negative...so when it is close to zero) the reaction hardly occurs at all. 8.2.3 : The only thing which can change the value of Kc for a given reaction is a change in temperature. The position of equilibrium, however, can change without a change in the value of Kc. Effect of Temperature : The effect of a change of temperature on a reaction will depend on whether the reaction is exothermic or endothermic. When the temperature increases, Le Chatelier's principle says the reaction will proceed in such a way as to counteract this change, ie lower the temperature. Therefore, endothermic reactions will move forward, and exothermic reactions will move backwards (thus becoming endothermic). The reverse is true for a lowering of temperature. Effect of Concentration : When the concentration of a product is increased, the reaction proceeds in reverse to decrease the concentration of the products. When the concentration of a reactant is increased, the reaction proceeds forward to decrease the concentration of reactants. Effect of Pressure : In reactions where gases are produced (or there are more mols of gas on the left), and increase in pressure will force the reaction to move to the left (in reverse). If pressure is decreased, the reaction will proceed forward to increase pressure. If there are more mols of gas on the left of the equation, this is all reversed. 8.2.4 : Yeah...well...based on the previous section, you should be able to product what's going to happen given a reaction if the temp, pressure of concentration is changed. 8.2.5 : A catalyst does not effect either Kc or the position of equilibrium, it only effects the rate of reaction.

8.2.6 : N2(g) + 3H2(g) <=> 2NH3(g) : delta-H = -92.4 kJ mol-1 ...as can be seen, there are more mols of gas on the left than the right, so a greater yield will be produced at high pressure. The reaction is exothermic, therefore it will give a greater yield at low temperatures, however this is not possible as the rate of reaction becomes too low, and the temperature must actually be increased. A catalyst of finely divided iron is also used to help speed the reaction (finely divided to maximize the surface area).

EQUILIBRIUM (HL) 18.1 Phase equilibrium

18.1.1 : A liquid in an enclosed chamber will form an equilibrium with it's own vapor. Fast moving particle in the liquid will escape from the surface and become part of the vapor, but slow moving particles in the vapor will be 'captured' by the liquid and become part of it. At a certain vapor pressure, the number of particles escaping (or evaporating) from the liquid will exactly equal the number being captured by it, and so a dynamic equilibrium is formed between the two. 18.1.2 : As the temperature increases, the average speed of particles is higher. As a result, more particles will have sufficient speed to escape the liquid, and fewer will be slow enough to be recaptured by the liquid. This means that as temperature increases, the equilibrium vapor pressure will also increase. This can be shown graphically with a graph of pressure against temperature, where, as temperature increases, so does pressure. 18.1.3 : Liquids with a high boiling point will have high intermolecular forces. Enthalpy of vaporisation is a measure of the energy change when 1 mol of liquid is converted to gas at standard pressure. As a result a lower enthalpy of vaporisation implies that less energy is required to break the intermolecular bonds, and so a lower enthalpy of vaporisation will result in a higher vapor pressure. 18.1.4 : When two liquids are in a mixture, particles from both liquids escape, forming a partial pressure for each above the mixture. The partial pressure of each liquid will be directly related to its volatility and to the mole fraction of it compared to the total number of mols in the liquid. 18.1.5 : When it is necessary to separate the components of a mixture in which there is more than one volatile component, fractional distillation must be used. (simple distillation is when there is only one volatile fraction, and it is boiled off and the condensed). Fractional distillation is achieved by continuous boiling of the two liquids while they are being condensed (like in reflux)...the more volatile liquid will escape from the top of the fractionating column (the condenser type bit with the water running through it), while the less volatile component will be condensed and returned to the boiling flask. In this way, it is possible to (in theory) completely separate the two components of the mixture.

18.2 The equilibrium law

18.2.1 : The value of Kc can be expressed for a general reaction A + 2B <=> 3C + D as Kc=([C]3[D])/([A][B]2) ie the concentrations of the products (each to the power of their

coefficient) over the concentrations of the reactants (each to the power of their coefficient). All concentrations are taken when the system has reached equilibrium, and so given all concentrations, Kc can be calculated, or given Kc and all but one of the concentrations, the final concentration can be calculated. (It should be noted, however, that concentrations are linked, and so it may not always be necessary to have all the concentrations, or in the second case all but one...but the quadratic formula is not required...so I guess they have to be simple.) The units for Kc can also be calculated by replacing each concentration with mols dm-3 (remembering to take exponents into account) and canceling out.)

ACIDS AND BASIS (SL) 9.1 Properties of acids and bases

9.1.1 : Properties of acids and bases in aqueous solutions on stuff...nb...the term alkali refers to a base dissolved in water. Indicators...they change color depending on whether they're in acidic or basic conditions...each one's different, so I suppose I'd better list some common ones...

Bromophenol Methyl orange blue Methyl red

Bromothymol blue Phenolphtalein

Acid Base

red yellow

yellow blue

red yellow

yellow blue

colorless red

Each one change color as a different pH, and so there will be cases where one is useful and others are not. (not really necessary is SL?) Reaction of acids with bases...They will often produce water, and the remaining components will combine to form a salt...ie HCl + NaOH -> H2O + NaCl. Acids with metals...will produce hydrogen ie 2HCl + Mg -> MgCl2 + H2. Acids with carbonates...will produce water and CO2 ie 2HCl + CaCO3 -> CO2 + H2O + CaCl2. 9.1.2 : Experimental properties of acids and bases...when acids and bases neutralize, the reaction is noticeably exothermic (ie heat can be felt coming from the reaction). Obviously, they will have an effect on the color of indicators as described above. The hydrogen produced in the reaction of acids with metal will produce a 'pop' sound if a match is held to it, and the CO2 from the carbonate reaction will turn limewater a milky white when bubbled trough it. Examples of some acids : HCl, CH3COOH, H2SO4,NH4+. Examples of bases : NaOH, NH3, CH3COO-.

9.2 Bronsted-Lowry acids and bases

9.2.1 : According to the bronsted-lowry theory acids are defined as proton (H+ ion) donators and bases are defined as proton acceptors. 9.2.2 : For a compound to act as a BL acid, it must have a hydrogen atom in it, which it is capable or losing while remaining fairly stable. A BL base must be capable of accepting a hydrogen ion while remaining relatively stable (or reacting to form a stable compound...ie water and a salt). Some compounds (such as water) may act as both ie (H2O-> OH- or H3O+) 9.2.3 : Acid base reactions always involve an acid-base conjugate pair...one is an acid, one is its conjugate base...ie HCl/Cl-, CH3COOH/CH3COO-, NH4+/NH3. 9.2.4 : The conjugate base will always have one less H atom that the acid (or the acid one more than the base). In compounds where there are many hydrogen atoms, the one which is held the weakest is generally the one which is lost, and this must be reflected in the writing of the compound...as in the CH3COOH example above.

9.3 Strong and weak acids and bases

9.3.1 : Strong and weak acids are defined by their ease of losing (or donating) a proton. A strong acid, when placed in water, will almost fully ionise/dissociate straight away, producing H3O+ ions from water. a weak acid will, however, only partially do this, leaving some unreacted acid remaining. This is set up as an equilibrium, and so when some of the H3O+ ions produced by a weak acid are reacted, LCP means that more of the acid will react to form H3O+ ions. This means that, given an equal number of mols of acid, they will be neutralized by the same amount of strong base, but their solutions will have different pH values. A weak base is the same as this, only it accepts protons and so produces OH- ions from water rather than H3O+. Any solution's ability to conduct electricity is defined by is charges ions in it. As a result, a strong acid will produce more charged ions than a weak one, and so it's solution will be a better electrical conductor than a weak acid. The same goes for strong/weak bases. 9.3.2 : Strong acids : HCl, HNO3, H2SO4. Weak acids : CH3COOH, H2CO3. Strong bases : group 1 hydroxides (ie NaOH etc), BaOH. Weak bases : NH3, CH3CH2NH2. 9.3.3 : The strength of an acid or base can obviously be measured with an indicator (universal) or a pH meter. also the rate of reaction...hydrogen production with metals or CO2 with CaCO3 will reveal the strength of an acid. The relative acidities (I'm assuming that means diprotic or whatever) can also be found by neutralizing two acids with a strong base in the presence of an indicator.

9.4 The pH scale

9.4.1 : pH vales range up and sown from 7 (being the neutral value of pure water at 20c and 1 atm). Lower pH value are acidic, higher values are basic. pH can be measured with a pH meter, or with pH paper (paper containing a mixture of indicators to cause a continuous color change). pH is a measure of the dissociation of an acid or base, and also of the concentration of that acid / base (actually its related to the concentration of H3O+ ions). 9.4.2 : If we have two solutions with their pH values, the lower one will be more acidic and the higher one will be more basic (though they could both still be basic/acidic with respect to water -- pH 7). 9.4.3 : a change of 1 in the pH scale represents a 10 times change in the acidity or basicity of the solution (because it's a log scale). Concentration is proportional to 10pH.

ACIDS AND BASIS (HL) 19.1 Lewis theory

19.1.1 : A lewis acid is defined as a species which accepts an electron pair to form a dative/coordinate covalent bond. A lewis base is a species which donates an electron pair to form such a bond. This is a special type of covalent bond because the bond is formed by two electrons from one species and none from the other. This often occurs in the formation of complex ions (or in BL acid/base reactions because the H+ ion has no electrons, and so must accept a pair to bond with anything...Lewis theory is more general than BL).

19.2 Calculations involving acids and bases

19.2.1 : H2O(l) <=> H+(aq) + OH-(aq). Kw=[H+][OH-] The value of Kw is 1 x 10-14 at 25c but varies with temperature. 19.2.2 : pH = -log[H+] (pH is the negative log of the concentration of H+ ions), pOH = log[OH-], pKw = -log([H+][OH-]) ( is equal to 14 at 25c) 19.2.3 : Use the above equations to calculate other values. Nb...[H+] or [OH-] are directly related to the concentration of the acid/base....therefore doubling the concentration of the acid will double [H+] and halve [OH-] (and the reverse is true for bases). 19.2.4 : in general HA(aq) <=> H+(aq) + A-(aq). -- or --> B(aq) + H2O(l) <=> BH+ + OH-(aq). therefore Ka = ( [H+][A-] / [HA] ) and Kb = ( [BH+][OH-] / [B] ) 19.2.5 : Ka is a constant which describes the ionisation of an acid (ie how strong it is) and Kb does the same for bases. pKa is the log for of Ka, defined as pKa = -log(Ka) and pKb

= -log(Kb). Like previously with the pH scale, a 1 fold change in pKa will signify a ten fold change in Ka and the same for Kb. 19.2.6 : Ka x Kb = Kw (ie they equal 1 x 10-14 at 25c) and pKa + pKb = pKw (ie 14 at 25c) 19.2.7 : Strong acids have weak conjugate bases. Strong bases have weak conjugate acids...A strong acid has a large Ka value (or a small pKa value). A strong base, likewise, has a large Kb value and a small pKb value. 19.2.8 : All the above equations need to be applied as appropriate given the required input data. The quadratic formula will not be required (but it is often easier than messing around with assumptions etc...especially when your calculator can solve it in a second :)

19.3 Buffer solutions

19.3.1 : A buffer solution is composed of a weak acid/base and it's conjugate base/acid. (assuming weak acid for what follows, reverse for base). A solution of weak acid is made, and this forms a equilibrium with the water as follows HA + H2O <=> A- + H3O+. To this solution, some of the acid's conjugate added (A-), resulting in an increase in the concentration of A-, some of which reacts with the H3O+. The result of this is, when equilibrium is reestablished, there is a considerable amount of both HA and A- present in the solution, in an dynamic equilibrium. If some other acid is added, this will react with the A-, but this causes the equilibrium to shift to the right, almost completely counteracting any pH change. The addition of a base, which reacts with the HA, cause the equilibrium to be shifted to the left, again resulting in very little pH change. This continues until one of the two components, either HA or A- are completely used up, at which time the pH then changes normally. 19.3.2 : The pH of a buffer solution can be found from the expression for Ka ( Ka = ( [H+][A-] / [HA] ). this can be rearranged to [H+] = Ka x ([HA]/[A-]). Given the concentration of both the Acid and its conjugate base, and the Ka value of the acid, the [H+] can be calculated and this can then be converted into a value for pH.

19.4 Salt solutions

19.4.1 : for cations...2A+ + H2O -> A2O + 2H+, A2+ + H2O -> AO + 2H+ etc...for anions...A- + H2O -> AH + OH-, A2- + 2H2O -> AH2 + 2OH- etc... 19.4.2 : Cations (positive ions) will be acidic, Anions (negative) will be basic in water...with the following exceptions Neutral cations ... Group 1, Be and Mg Neutral Anions ... Cl-, Br-, I-, SO42-, NO3-, ClO4-.

19.5 Acid-base titrations

19.5.1 : Titration curves... (see page 57-58 of Advanced chemistry by Michael Lewis) Strong acid, strong base...The curve starting off very low is initially very flat until at equivalence it is almost vertical then very flat again (starting and finishing very low and high respectively one the graph due to low and high pH of strong acid and base respectively. Weak acid, strong base...The curve begins comparatively high on the graph, and rises sharply initially. after a period it reaches a region where the solution acts as a buffer, still rising continually, but not as steep. the curve then then turns up sharply at equivalence and then tapers off to the strong base's pH value. Strong acid, weak base...identical to the strong acid strong base curve only the eventual point is lower since the weak base will have a lower pH. Weak acid, weak base... the graph starts sharply up, but then tapers off, reaching only a somewhat steep section in center, before flattening off to the weak base pH. There is no steep section and so it is not possible to find a suitable indicator. (One other thing...at the point halfway to equivalence pH=pKa or pOH=pKb...and pH+pOH = 14...so you can find pKa or pKb from the curve...it can be derived, but it's easier to remember it)

19.6 Indicators
19.6.1 : Indicators work by setting up a weak acid/base equilibrium where the acid and its conjugate base have different colors... HIn(aq) <=> H+(aq) + In-(aq). Where HIn is one color and In is the other. This equilibrium can be adjusted by the concentration of H+ being through the addition of acids or bases. 19.6.2 : The pH range of the indicator falls around it's pKa value, and so to be useful, the pKa must fall within the inflection of the titration curve. 19.6.3 : the value of pKa for the indicator must fall around the equivalence point of the titration to work effectively.

OXIDATION AND REDUCTION (SL) 10.1 Oxidation and reduction

10.1.1 : Oxidation is the loss of electrons, reduction is the gain of electrons...ie Oxidation half equation... Mg -> Mg2+ + 2e-. Reduction half equation... O + 2e- -> O2-. 10.1.2 : The oxidation number of an element is zero. The oxidation number of an ion is equal to the charge of the ion. In compounds, Hydrogen has an oxidation number of +1. In compounds, Oxygen (usually...except in peroxides) has an oxidation number of -2 ... that should be enough information to deduce the oxidation numbers of every element in any IB reaction. The oxidation numbers of ions will be related to the group of the element (ie group 1 elements will be +1...up to group sever elements which will be -1). The elements in the elements in the d block will have multiple oxidation states. 10.1.3 : If an element is oxidized, its oxidation number will go up. If an element is reduced, its oxidation number will go down. To find out, simply write down the oxidation numbers for each element as explained previously. 10.1.4 : An oxidizing agent is an element which causes oxidation (and is reduced as a result). A reducing agent is an element which causes reduction (and is oxidized as a result). 10.1.5 : Iron Oxide, for example, come in two forms...FeO and Fe2O3. Iron (II) oxide and Iron (III) oxide respectively. The number after the Iron is determined by the oxidation number of the iron in the compound. This convention (including the use of roman numerals) is followed for all compounds in which there is some ambiguity as to the oxidation states of elements (generally d-block elements).

10.2 Electrolysis of a molten salt

10.2.1 : a diagram of an electrolytic cell should include a positive and negative electrode, a current source and the molten salt being electrolysed. 10.2.2 : Current is carried as in a normal circuit for the circuitry, and through the reaction occurring below. At the cathode positively charges ions gain electrons...ie X+ + e- -> X (the cathode must therefore be connected to the -ve pole of the source to supply electrons. At the anode negatively charged ions lose electrons...ie Y2- -> Y + 2e-. the circuit is completed by the two oxidation and reduction half equations creating an effectively complete circuit. 10.2.3 : In the above example, X will be produced at the cathode, and Y at the anode. Since only two species are present in a molten salt, there is no possibility for any other chemicals to be produced (ie water can not be involved etc...)

10.3 Reactivity
10.3.1 : A more reactive metal will displace a less reactive one from a compound and a more reactive halogen will displace a weaker one from a compound. This can be generalized to say a stronger reducing agent will displace a weaker one from a compound, and a stronger oxidizing agent will displace a weaker one from a compound. Thus, if a metal displaces another, we know it must be more reactive and ditto for halogens (which are the given examples). 10.3.2 : Based on the information in the IB data book...Add the two half equations in question together (one will have to be reversed, invert the sign of the E-zero value also) If the total E-zero value is positive, the reaction is possible. If not, it isn't. (This can be done based on their position in the table, but it makes more sense to use E-zero values, even if SL doesn't need to know them).

OXIDATION AND REDUCTION (SL) 20.1 Redox equations

20.1.1 : Balancing...Copy down both complete half equations, reversing one so the electrons are on opposite sides and so the reactants for both are on the left, and the products on the right. Multiply the equations by the appropriate factors so the number of electrons in each equation is the same. Vertically add the equations, and cancel out any molecules which appear on both sides.

20.2 Standard electrode potentials

20.2.1 : Standard electrode potential --> The potential difference between a given half cell (at 1 mol dm-3 conc) and the standard hydrogen electrode 20.2.2 : The standard hydrogen electrode consists of a solution of H3O+ ions at 1 mol dm-3 in a beaker. Placed into this is a platinum electrode surrounded by a gas tube submerged in the solution, with hydrogen at 1 atm inside. The circuit to the other half cell is then attached to the platinum electrode, and a salt bridge saturated in potassium chloride. The entire process should take place at 298K and 1 atm pressure. 20.2.3 : The potential difference between half cells is a relative value, dependent on both half cells, and so a standard is required...the standard hydrogen electrode (why they didn't use a nice simple metal one escapes me...perhaps this is more accurate of something :) 20.2.4 : Cell potential --> the potential difference between two half cells (if one half equation is reversed and the two equations are added, the cell potential will be given...it should be positive if you reversed the right one, if it's negative the reaction occurs in the opposite direction to the one you're writing).

Super-secret-bonus stuff they just slipped in without a sub-topic number... Be able to draw a labeled diag of a half cell and how to link them together...which is basically described above. Cells should also be written in the form Cu(s)/Cu2+(aq)||Zn2+(aq)/Zn(s). which describes both half cells involved. also, the direction of current flow should also be deduced based of the standard cell potentials, as should the actual reaction occurring. The anode will lose electrons, and so the electrons must flow towards the cathode...that should allow everything else to be worked out. 20.2.5 : The cell potential will be the potential difference between two half cells (and will be positive, unless the reaction occurs backwards). The magnitude is defined by the difference between the E-zero values of each half cell. One of the half equations will have to be reversed (the one which makes the total positive) and adding these two half equations will give you the overall reaction occurring. 20.2.6 : Most reactions with positive E-zero values will occur, however it is possible that at non-standard conditions reactions may not occur, or that some reaction may have very high activation energy, and so will no occur at any reasonable rate.

20.3 Electrolysis
20.3.1 : Electrolysis is where the above cells are forced to run in reverse by attaching an electricity source to overcome the potential difference. In aqueous solutions, however, water is also present, and will sometimes be oxidized/reduced in preference to the dissolved salts (or whatever). It is possible to use the standard electrode potentials to predict this, in that species above water (when it is on the left) will not be oxidized, and species below water (on the right) will not be reduced in an aqueous solution. If necessary, this can be checked by working out the cell potential for all possible combinations (involving the, presumably, two elements and water)...the reaction with the smallest negative potential difference will be the one which occurs. Highly concentrated solutions may overcome this to some degree however...ie it is possible for Cl2 to be oxidized in a concentrated solution. 20.3.2 : The faraday constant is the charge (in magnitude because it should really be negative) of 1 mole of electrons. 20.3.3 : Faraday's law states that the mass of product produced will be proportional to the charge passed. (Nb...the equation charge = current x time , or q=It may be necessary). Farady's law may also be restated as...the number of faradays required to discharge 1 mol of an ion at an electrode equals the number of charges on that ion.

ORGANIC CHEMISTRY (SL) 11.1 Homologous series

11.1.1 : A homologous series is a set of compounds whose components differ by a single repeating functional group...in the case of (straight chain) alkanes, CH2...and their general formula is CnH2n+2. 11.1.2 : The boiling points of alkanes increase as the chains get longer (increased number of electrons -> increased van de Waal's forces), increasing rapidly initially but flattening off (since the number of additional CH2 units required to double the chain length increases rapidly...so it flattens of...or you could just believe it)

11.2 Hydrocarbons 11.2.1 : Basically, each will have a CH3 group at either end (except methane has only one CH4) and fill out the required number of CH2 groups.

11.2.2 : Names...Methane, ethane, propane, butane, pentane, hexane. 11.2.3 : Basically, move the groups around to make branches, C1 should have 1, C2 has 1, C3 has 1, C4 has 2, C5 has 3.

11.2.4 : These structures will be the same as 11.2.1, except two hydrogens on adjacent carbons are replaced by a double bond between those hydrogens.

11.2.5 : Complete combustion produces CO2 and H2O, incomplete combustion produces CO, C and H2O (usually occurs with saturated alkanes, where there is a lot of hydrogen, or where there is a limited supply of oxygen). C produces a 'dirty' flame leaving carbon deposits on everything, CO is toxic and CO2 is a greenhouse gas. Incomplete combustion is where the carbon is not completely oxidised. 11.2.6 : The combustion of hydrocarbons is an exothermic process (otherwise there wouldn't be much point in burning them would there...). This is a result of the fact that the O-H bond is stronger than the C-H bond, and the C=O bond is stronger than the C-C. This means that, the C-C and C-H bonds breaking requires energy, but this is more than made up for by the energy released by the formation of the C=O and O-H bonds.

11.3 Other functional groups 11.3.1 : Functional groups

Alkanal...RCHO (with a double bonded O coming off the C (aldehyde)...but it can be moved along the chain -> keytone). Naming...(aldehyde) end in al - ie ethanal. (keytone) end in one - ie enthanone. Alkanoic acid...R-COOH Naming...end in oic acid - ie ethanoic acid (commonly called carboxilic acid) Alkanol...R-OH. Naming...end in ol - ie ethanol. Amide...RCOONH2 Naming...end in amide - ie ethylamide.

Amine...R-NH2 The two hydrogens on the N can be replaced by R groups to give primary, secondary and tertiary structures). Naming...end in amine - ie ethylamine. Ester...R-COO-OR. Naming...Think of it like an alkanoic acid with a carbon chain rather than a H...the alkanoic acid type bit is ...oate this is preceded by the stem of the other half - ie Ethyl ethanoate. Halogenoalkane...R-X. Naming...Name of halogen (fluro, chloro, bromo, iodo) followed by R name - ie Chloroethane. 11.3.2 : Functional groups can actually be isomers (though their properties are not generally similar). For example ethanoic acid and methyl methanoate are isomers (CH3COOH vs HCOOCH3).

11.3.3 : Optical isomers result if a carbon atom has 4 different groups on each bond. If this is the case, the compound exists in 2 entantiomeric forms (ie optical isomers). In general they react very similarly except in the presence of other optical isomers (also known a chiral molecules -- the chiral center is the carbon atom with 4 different groups). The two enantiomers are mirror images of each other which cannot be superimposed on each other. Biological systems commonly have a strong preference for one enantiomer over the other ( one can be bitter, the other sweet for example ). The isomers can be identified by their effect on polarised light(by a polarimeter)...when polarised light passes through one isomer it will be rotated to the left, while the other will rotate to the right.

 11.3.4 : O-H groups create hydrogen bonding (alcohols, alkanoic acids) -> less volatile and also solubility (long chain molecules become less soluble since the non-polar chain dominates the molecule). C=O bonds in Alkanoic acids, Alkanals -> polar bond...dipole forces...higher bp (more significant in small molecules). Small molecules are soluble due to polarity (effect decreases with long chains). Esters...no Hydrogen bonding -> very volatile, low BP. Polar molecules, therefore short are soluble in water. Amides...N-H bond is polar with extensive hydrogen bonding -> highly soluble and all molecules have higher BP than alkanes. Amines...Hydrogen bonding present in Primary and secondary -> soluble (when short) and higher than alkane boiling points. Tertiary amines are very similar to alkanals (but branched -> less dense packing etc). Halogenoalkanes...short molecules will be soluble due to polar bonds, BP will be somewhat higher Acid Base properties...Alkanoic (carboxilic) acids are, obviously, acidic. Alcohols are generally not due to the donating effect of the R group. Amines are derivatives of ammonia, and so are basic (though stronger due to the donating effect of the R groups). Amides are not due to withdrawing effect of the C=O group. The others, in general, are neutral (however alkanols can, in acidic conditions act as a base and accept a proton, though the electron donating effect of the alkyl groups generally stop any acidic action). 11.3.5 : Reactions of alkenes with stuff...hydrogen, bromine, hydrogen halides and water. Before we begin : The C=C bond is not twice as strong as a C-C bond...the second is weaker making it easier to break, and thus a reactive site...this reactivity makes alkenes important starting molecules in the production of other organic molecules.

RCH=CHR + H2 -> RCH2-CH2R ... Hydrogen adds to the double bond RCH=CHR + Br2 -> RCHBr-CHBrR ... bromine adds onto the double bond RCH=CHR + HBr -> RCH2-CHBrR ... HBr adds across the double bond RCH=CHR + H2O -- With H3PO4 + water + 300c + 70 atm --> RC(OH)H-CH2R. 11.3.6 : (addition) Polymerisation of alkenes (by a free radical mechanism)... Initiation ... 2R2 -> 2R (R is a free radical with a lone electron) R + CH2=CH2 -> R-CH2-CH2 Propagation ... R~~~~ + CH2=CH2 -> R~~~~~. Termination ... R~~~~ + ~~~~~R -> R~~~~~~~~R. Polythene ... Monomer is CH2=CH2 ... General polymer is -[-CH2-CH2-]nPolyvinal chloride ... Monomer is CClH=CH2 (chloroethene) ... General polymer is -[CH2-CHCl-]n11.3.7 : Production of an ester from an alkanol and alkanoic acid...this is an addition elimination reaction (or addition-dehydration, since we're eliminating water) CH3CH2OH + HOOCCH3 -- H2SO4 and warming --> CH3CH2OOCCH3 + H2O Esters are commonly used as artificial flavoring agents ... Mmmmmm ... Ester ... 11.3.8 : Oxidation of Ethanol to ethanoic acid... This process requires a primary alcohol (which ethanol is) otherwise the reaction is stopped because the intermediate formed is a keytone rather than an aldehyde. CH3CH2OH -- oxidized by K2Cr2O7/H+ --> CH3CHO -- oxidized by K2Cr2O7/H+ --> CH3COOH Ethanal is an intermediate which is intentionally not isolated so it can be oxidized again. 11.3.9 : The reaction is between ethanoic acid and ethanamide to form N-ethyl enthanamide (the N means the ethyl group is connected to the N atom. It is also a dehydration reaction (ie water is eliminated). CH3-CO-OH + C2H5NH2 -> CH3-CO-NH-C2H5 + H2O 11.3.10 : Condensation polymers

Nylon ... hexane -1,6-diamine + hexanedioic acid H2N-(CH2)6-NH2 + HOOC(CH2)4COOH -> NH2(CH2)6-NH-CO-(CH2)4-CO-NH-(CH2)6-NH-CO-(CH2)4-CO...-NH-(CH2)6NH2. As each new group is created, a water molecule is eliminated... Polyester ... benzene-1,4-dicarboxylic acid + ethane-1,2-diol HOOC-Benzene-COOH + HOCH2CH2OH -> HOOC-Benzene-COOCH2CH2OOC-Benzene-...COOH (once again, water is eliminated each time) Notice the fact that two functional groups are required on each monomer...Otherwise the reaction would stop without producing a long chain. 11.3.11 : This reaction produces a series of stronger and stronger nucleophiles until a complex ion, (CH3CH2)4N+ is produced. NH3 + CH3CH2Br -> CH3CH2NH2 + HBr CH3CH2NH2 + CH3CH2Br -> (CH3CH2)2NH + HBr (CH3CH2)2NH + CH3CH2Br -> (CH3CH2)3N + HBr (CH3CH2)3N + CH3CH2Br -> (CH3CH2)4N+ + Br11.3.12 : Formation of peptides and proteins to form 2-amino acids Amino Acids ... H2N-CHR-CO-H ... carbon atom (asymmetric) is connected to 4 different species -> optically active (except glycene). H2N-CHX-CO-H + H2N-CHY-CO-H + H2N-CHZ-CO-H --> -NH-CHX-CO-NH-CHY-CO-NH-CHZ-CO- (poly peptide) This group can join to other peptides to form a protein.

ORGANIC CHEMISTRY (HL) 21.1 Determination of structure

21.1.1 : The structure of a chemical compound can usually not be determine accurately with information form only one source. This stems firstly form the great number of possible organic compounds possible, many of which have very similar chemical properties but different physical properties, similar physical properties but different chemical properties or very similar properties in both categories. There are a variety possible techniques which go beyond both chemical and physical properties, and by combining the information form all these sources it is generally possible to deduce the structure of a compound through the individual pieces of evidence given by each of the sources. 21.1.2 : Covalent bonds are not generally of a static length, but rather they resonate in and out rapidly. This effect allows such bonds to absorb electro-magnetic energy if it is of a certain wavelength (equivalent to a certain energy). The wavelength corresponding to many organic molecules just happens to be within the infrared spectrum. as a result, bonds can be identified in a compound by the wavelengths they absorb. This, however, is usually insufficient as it does not offer enough information about the relative placement of the bonds, or their quantity. The spectrum information is given in the data book and can be matched to any given data. 21.1.3 : We already did how it works...so skipping on...There will usually be a peak in the spectrum at the mass of the entire molecule. There may also be, if present, a peak at Mr15 representing the loss of a CH3 fragment (so there must be one in the molecule). Mr-18 represents the loss of water, Mr-31 represents CH3O and Mr-45 is COOH. Various other fragments could be lost, but the IB only seems to be worried about those listed here. 21.1.4 : H NMR spectrum are based on some complex nuclear magnetic resonance stuff, but basically it gives information about what atoms H atoms are bonded to (though other nearby functional groups have an effect, so really it identifies 'bits' of the molecule), and how many bonds of each type there are. The information is in the data book.

21.2 Hydrocarbons
21.2.1 : The C-C and C-H bonds are very unreactive due to their lack of significant polarity and the high bond energy. 21.2.2 : Homolytic (the same) fission ... A B ... each atoms remains with one lone electron -> highly reactive. Hetrolytic (different) fission ... A :B ... One atom gets a lone pair of electron, the other gets none. Reaction of alkanes with halogens (ie Cl-Cl)...(Initiation) In the presence of UV light, the Cl-Cl bond breaks homolytically resulting in two Cl free radicals ie Cl2 -- UV light --> 2Cl. (Propagation) These radicals then react with alkane (ie CH4) to form HCl and CH3

ie Cl + CH4 -> HCl + CH3. This CH3 free radical can then react with a chlorine molecule to form another chlorine free radical ie CH3 + Cl-Cl -> CH3Cl + Cl. (Termination) This reaction is continued until two free radicals react to form a single molecule ie Cl + Cl -> Cl2 or Cl + CH3 -> CH3Cl or CH3 + CH3 -> C2H6. 21.2.3 : The structure of Benzene was originally thought to be a ring of alternating double and single bonds, however this does not fit for several reasons. Firstly, there the enthalpy of combustion of Benzene as compared with this model (an unstable compound called cyclohexatriene). The enthalpy of combustion can be projected from the enthalpies of cyclohexadiene and cyclohexene, but benzene is significantly lower (and therefore more stable) than this projected value. Also significant are the reactions which benzene undergoes. Double bonds, as seen with alkenes tend to undergo addition reactions, where a double bond breaks forming a single bond between the carbons and two new bonds. Benzene, however, does not undergo such reactions, but rather has substitution where the hydrogens are replaced by other electrophiles. 21.2.4 : Octane rating is a scaled devised to measure how smoothly a fuel burns in a combustion engine. The scale is bases around two measuring points, heptane which has an octane rating of 0, and 2,2,4-trimethylpentane which has an octane rating of 100. A fuel with an octane rating of 60, for example, would be the same as a mixture of 60% 2,2,4-trimethylpentane and 40% heptane. In the past, tetraethyl lead (IV) was added to fuels to retard it's ignition and make the fuel burn more smoothly, however this has caused significant problems with lead concentrations in the atmosphere. The other way to increase octane rating is by using highly branched chains, or aromatic compounds (benzene rings) which also burn more smoothly, thus producing high octane, lead free fuels.

21.3 Halogenoalkanes
21.3.1 : Nucleophillic substitution by SN1 and SN2 mechanisms SN1 mechanism ... First, due to the electron donating effect of the alkyl groups, the carbon-halogen bond breaks hetrolytically, resulting in (using CH3Cl as an example) CH3+ and Cl- produced. This is the rater determining step (hence the 1st order reaction). The nucleophile then attacks the positive carbon atom and forms CH3N. SN2 mechanism ... Rather than completely breaking the bond, a polar bond is formed between the halogen and carbon, producing a delta+ve charge on the carbon. This is enough to attract the nuleophile to form an intermediate with carbon forming an intermediate with effectively 5 bonds...one to the nucleophile, on with the halogen and 3 others. This is the rate determining step, hence the second order reaction. The halide ion then breaks off hetrolytically forming again CH3N + Cl-, but by a different mechanism ... Some good nucleophiles are ROH, CN-, OH-, and RNH2. I think Markolnikov's rule fits in here...In this example...When HX adds across an asymmetrical double bond, the major product formed is the molecule where the less electronegative atom adds to the carbon with the most hydrogens already on it (this is since hydrogen adds on, and produces a carbocation intermediate...the intermediate where the C+ has the most electron donating groups around it will be most common...ie the most alkyl groups.)

21.3.2 : SN1 reactions tend to occur with tertiary carbon (ie with 3 alkyl groups off the carbon connected to the halogen) for two reasons. Firstly, there is not room for a nucleophile to attack due to the steric hindrance caused by the bulky alkyl groups, and secondly the inductive electron donating effect of these groups mean it is much more likely that the C-X bond will break, rather than just becoming highly polar. SN2 reactions, however, occur on primary carbons since there is plenty of space between small hydrogen atoms for the nucleophile to attack, and it is unlikely that the C-X bond will break on it's own. 21.3.3 : Different halogens will obviously have different bond strengths. the F-H bond is strongest (and shortest) while I-H is the longest (and weakest). As a result, the H-I bond is easiest to break, and does so most easily therefore has the highest rate, while H-F is the slowest.

21.4 Alkanols
21.4.1 : Dehydration to form alkenes and alkoxyalkanes Alkenes ... In the presence of H2SO4 and the proper temperature (hot for primary, warm for secondary and cool for tertiary) alcohols can lose a water molecule and form an alkene. ie - CH2H-CH2OH -- H2SO4 and heat --> CH2CH2 + H2O. Alkoxyalkanes ... In acidic conditions alcohols act as a base, and accepts a proton. This produces a positive charge on the oxygen (and inductively a delta+ve on the carbon). the spare par of electrons on the oxygen atom of another alcohol are attracted to the delta+ve carbon making it act like a nucleophile, and so it attacks the carbon atom (this assumes an SN2 reaction though SN1 is possible under other conditions...ie tertiary alcohols). Water and a proton are then split off producing an ether (alkoxyalkane) and water (and regenerating the acid as a catalyst). ie CH2OH + H+ -> CH2OHH+. then CH2OHH+ + CH2OH -> CH2OCH2 + H2O + H+. 21.4.2 : Oxidation of alkanols is different depending on whether they are primary, secondary or tertiary. For primary and secondary, a C=O bond replace the C-OH, but this bond will either be on the end (an aldehyde) or in the middle (a keytone). Aldehydes can be reoxadized to form carboxillic acid. Tertiary alcohols will not oxidize. Primary ... CH3CH2OH --Cr2O72---> CH3CHO (aldehyde/alkanal) + H2O --Cr2O72---> CH3COOH (alkanoic acid) Secondary ... CH3-CH(OH)CH3 --Cr2O72---> CH3-CO-CH3 (keytone/alkanone)

21.5 Alkanals and alkanones

21.5.1 : Carbonyl compounds are reactive because they contain a delta+ve carbon atom, and are unsaturated (both due to the C=O bond). Thus, the Pi electrons can be relatively easily shifted to form a new bond on both the carbon and oxygen atoms, and since nucleophiles are attracted to the carbon atom, the happens relatively quickly. 21.5.2 : This is the same as with the alcohols alkanals will react to for carboxillic acid as

follows. CH3CHO (aldehyde/alkanal) --Cr2O72---> CH3COOH (alkanoic acid) 21.5.3 : This is the reverse of the process shown in the alcohols above...alkanals will be reduced to primary alkanols, alkanones will be reduced to secondary alkanols by LiAlH4. Alkanals ... CH3CHO --LiAlH4--> CH3CH2OH (primary alkanol) Alkanones ... CH3-CO-CH3 --LiAlH4--> CH3-CH(OH)CH3 (secondary alkanol)

21.6 Alkanoic acids

21.6.1 : Alkanoic acids can be formed by oxidizing primary alkanols with acidified dichromate (IV) as follows. CH3CH2OH --Cr2O72---> CH3CHO (aldehyde/alkanal) + H2O --Cr2O72---> CH3COOH (alkanoic acid) 21.6.2 : The OH group in alkanols doesn't act as an acid, but that is alkanoic acids do...why ? ... This is a result of the inductive effect of the C=O group. In alkanols, the R groups are electron donating, resulting in a negative charge being inductively pushed along the chain, creating a large -ve charge on the oxygen atom. The C=O bond, however, is electron withdrawing which results in a delta+ve carbon atom. This inductively increase the polarity of the O-H bond, and also produces a more stable anion when the proton is lost (because electron density is being pulled away creating a smaller negative charge on the oxygen). 21.6.3 : Soaps are formed basically of a long hydrocarbon chain ending in a COO-Na+, or similar, head -- ie CH3-CH2-[-CH2-]n-COO-Na+. They work because the head is hydrophilic (dissolves in water) while the tail is hydrophobic (doesn't dissolve in water, but does in fats, non-polar dirt etc). this means the molecules position themselves around small 'blobs' of non-polar dirt (called micielles). these are pulled out of the fabric etc by these molecules and are then held in suspension in the water and eventually washed away.

CHEMICAL INDUSTRIES E.1 Initial overview

E.1.1 : Sources of materials Raw materials -- Natural substances which can be converted by chemical processes into useful products. By-Products -- Substances produced as a result of a chemical process, but not the major (or important) product. Waste products -- Substances produced that have no value/are dangerous and must be disposed of. Minerals -- Naturally occurring inorganic substances ... metals and their ores. Air -- O2, N2, Ar Petroleum -- Coal, Oil etc... E.1.2 : Factors influencing positions for chemical industry establishment. Must comply with regulations (ie environmental restrictions), good transport access to market and raw materials, availability and cost of labour, land, plant, equipment and energy source (electricity). Availability and cost of raw materials. E.1.3 : Specialty vs Bulk chemicals... Specialty ... Drugs, Many organic substances (w/ specific uses) Bulk ... Sulphuric acid, Nitrogen, Oxygen, Ammonia, Sodium hydroxide, Chlorine

E.2 Principles of extraction and production

E.2.1 : Metals are rarely found free in nature, and have to be extracted and processed before they can be used ... with the exception of Gold and some other stuff like that. E.2.2 : Physical separation and purification from ores... Concentration of ores ... Froth, flotation etc Separation ... Filtration, Centrifuge type stuff, magnetic properties, chromatography

Purification ... Zone refining (explained later) E.2.3 : Chemical principles in the extraction of useful substance from raw materials ... Changing into suitable form for oxidation ... ZnS + O2 -> ZnO + SO2. Reduction to metal, by electrolysis or chemical reaction (blast furnace) Also consider ... Reduction (Iron), electrolysis (Al2, Al ), equilibrium (Contact and Harber), energy requirements (electrolysis...lots of energy and heat), catalysts (rate of reaction)

E.3 Metals - iron and aluminum

E.3.1 : Main sources of iron are iron ores and scrap iron...not much else to say. E.3.2 : Reactions which occur in a blast furnace (to produce iron) C(s) + O2(g) -> CO2(g) ... Carbon is partially oxidized to CO2. CO2(g) + C(s) -> 2CO(g) ... The carbon in CO2 is reduced to CO. 3CO(s) + Fe2O3(s) -> 2Fe(s) + 3CO2(g) ... Iron (III) oxide is reduced to Fe by the CO. CaCO3(s) -> CaO(s) + CO2(g) ... This bit is about the production of slag, which is going to sit on top of the iron. CaO(s) + SiO2 -> CaSiO3(l) ... CaSiO3 is the slag. E.3.3 : Conversion of iron to steel in oxygen converter (steel is iron with a low proportion of carbon) First, the converter is charged with about 25% scrap steel. In the bottom of the converter is also calcium oxide (lime) which reacts with impurities to form slag. Molten iron is then poured into the converter. In the converter there is also a tube blowing super heated oxygen into the molten iron. This will react with the carbon in the steel to produce CO2, which then escapes. When The steel has been produced, the converter is tipped and the steel is tapped off through an outlet pipe. E.3.4 : Different forms of iron... Cast iron -- same as pig iron, high carbon content -> relatively brittle, but also harder Wrought iron -- more malleable (due to lower carbon content). Hammering/rolling removes impurities. Carbon steel -- Small ( >1% ) carbon content + Iron ... thus it's very malleable, but not

very hard. Alloy Steels -- The addition of other elements can change the physical properties of the alloy. eg Tool steels have to be strong, corrosion resistant and heat resistant. Stainless steel (18% chromium, 8% nickel) is resistant to corrosion, used in cuttlery and surgical instruments. E.3.5 : The principle uses of steel is in construction, and as reinforcement. Plus the ones given above...tools, cuttlery, surgical instruments and so on. E.3.6 : Production of Alumina from bauxite (aka Aluminum oxide, Al2O3)... Al2O3 will eventually be electrolysed, but first it must be purified... Al2O3(s) + 2NaOH + 3H2O -> 2NaAl(OH)4(aq) ... Aluminum oxide produces sodium aluminate (and dissolves out any soluble impurities) NaAl(OH)4(aq) -- dilution --> Al(OH)3(s) + NaOH(aq) ... This occurs when the solution is diluted with water, producing aluminum hydroxide...which is a solid precipitate, and can be removed (leaving impurities behind) 2Al(OH)3(s) -- heat --> Al2O3(s) + 3H2O(g) ... after heating, Pure anhydrous aluminum oxide is produced. E.3.7 : The aluminum oxide is then dissolved in molten cryolyte (Na3AlF6)..requiring the temperature to be kept above 850oc ... and then electrolysed... Cathode ... Al3+ + 3e- -> Al Anode ... 2O2- -> O2 + 4e- followed by C + O2(g) -> CO2(g) ... because the anode is made of carbon. The molten aluminum is then tapped off from the bottom of the container, since it is more dense than the cryolyte. Cryolyte is used because it greatly reduces the amount of energy to keep the aluminum oxide in a molten state. The cell is generally produced as a large 'vat' ... The cryolyte is in this, which is lined with carbon to be used as the cathode. Carbon anodes are dipped at intervals along it, and are slowly lowered as are eaten away (by the production of CO2). E.3.8 : Properties of aluminum ... Aluminum is resistant to corrosion (because it naturally forms a protective coating on Al2O3). it is also very lightweight, and inexpensive compared to some alloys (stainless steel). It can not be made hard by the addition of carbon like iron. E.3.9 : Aluminum is widely used due to its resistance to corrosion. Common uses are cans, construction (roofing, fences) and its lightweight nature also makes it useful in cars and airplanes. Aluminum can not be made hard and so it is not very useful for tools, but doesn't corrode, making it useful in areas such as roofing, where steel would corrode, and

stainless steel is too expensive. E.3.10 : Environmental impacts of Aluminum production... Mining -- Destruction of land ... may require rehabilitation Siting -- some effluent and waste gases are inevitable, and so the plant would be best situated away from population centers. Recycling -- Avoids above problems, and may be less expensive than the production from bauxite. Also, bauxite is a non renewable resource.

E.4 Air
E.4.1 : Gases (oxygen, nitrogen and argon) are obtained by cooling air to below the boiling point of the gas wanted ... O2 -> 183oc, N2 ->196oc, but I don't think these will be necessary. E.4.2 : Uses... N2... Producing NH3, HNO3, Inert gas in incandescent light bulbs (and as an inert atmosphere in general). Also, as a liquid coolant for freezing food etc. O2... Respiration (to air, eg oxygen rich air), production of steel, fuel (O2 + C2H2 or O2 + H2 -> welding) oxidizer in rocket propellant as liquid with reducer. Ar ... Inert gas -> fluorescent tubes, thermometers (above Hg), where an inert gas is needed but N2 can't be used. E.5 Equilibrium processes - The Harber and contact processes E.5.1 : Many industrial processes depend on the manipulation of equilibria. (because the expensive products are usually those which are had to make ;) ... the ones we're going to see here ar the harber and contact processes ... First the harber process (this is sort of a recap from Topic 8...) N2(g) + 3H2(g) <=> 2NH3(g) ... delta-H = -92.4 Kj/mol Considerations ... LCP predicts that the best yield will occur with low temperature and high pressure. Rate requires high temp for fast reaction. Equipment to maintain high pressure is expensive. Generally used ... 450oc, 250 atm and a catalyst (finely divided iron) => about 30% yield ... NH3 is separated by liquifying (NH3 melts at about 20oc) ... other gases are returned to the reaction. E.5.2 : Uses of ammonia ... Essential nutrient for healthy plant growth ... Problem

(nitrogen fixation) . It is difficult to use N2(g) from the atmosphere, thus nitrogen based fertilizers are used. Used to make nitric acid (HNO3), for the nitration of benzene. Also, for production of TNT (tir-nitro toluene ... methyl benzene with 3 substituted NO2 groups...at 2,4,6). and it's used to make dyes. E.5.3 : Contact process ... This is the production of H2SO4. 2SO2(g) + O2(g) <=> 2SO3(g) delta-H = -191 Kj/mol. LCP suggests low temperature and high pressure. (other considerations as above) Generally used ... 450oc, 1 atm and vanadium (v) oxide catalyst ... this produces about a 97% yield...high pressure not really necessary. SO3(g) + H2SO4 -> H2S2O7 ... when this is diluted in H2O, H2SO4 will be produced. E.5.4 : Uses of sulphuric acid ... Making fertilizers, explosives, dyes, production of other acids, detergents, catalyst for making esters, producing nitrating mixture and as a dehydrating mixture. It's the most important industrial acid...understand that ;)

E.6 The oil industry

E.6.1 : Importance of oil as a chemical feedstock. About 90% of the crude oil products from fractional distillation is used in transport, heating fuels and electricity production. The other 10% is used as a feedstock for the production of other organic chemicals, but it is still the most significant source of organic chemicals. E.6.2 : Cracking ... three types ... catalytic cracking, thermal cracking and hydrocracking. Catalytic cracking ... Superior to thermal cracking. Occurs at a lower temp (250oc) 1 atm pressure and a catalyst. Produces high quality gasoline ... less CH4, more useful C3 and C4 molecules and many alkenes rather than alkanes. Thermal cracking ... 500oc, 50 atm pressure (older and possibly out of date). Hydrocracking ... variation of thermal cracking using sodium aluminosilicate where some Na+ is replaced by Pt. Performed in the presence of H2, so products are saturated (alkanes not alkenes). E.6.3 : Reforming...a bunch of types... Catalytic reforming -- Produces branched carbon chains, which have a higher octane number. This is done at 500oc in an atmosphere of hydrogen. Aromatisation -- The production of aromatic molecules (benzene rings) (usually 500oc and H2 atmosphere like catalytic)

Cyclisation -- The production of cyclic molecules ... again at 500oc and in atmosphere of H2. Alyklation -- the reaction of alkanes and alkenes to form branched alkanes. In all of these, hydrogen will be produced, which is commonly used in the harber process. E.6.4 : Removal of sulphur from crude oil. S in crude oil, when heated or burned forms SO2 (and some SO3). which can dissolve in water and form acid rain....Removal... SO2 formed in fractional distillation can be removed by reaction with MgO or NaOH., both of which react with SO2/SO3 to form a salt and water. The SO2/SO3 can then be used in the production of H2SO4. E.6.5 : Refinery products as feedstock. Can produce from spare fractions of crude oil -- solvents, plastics, pesticides, food additives, pharmaceuticals, detergents, cosmetics, dyes. E.6.6 : Properties and uses of polymers ... Polythene -- Long branched molecules produce a soft, malleable substance, useful in packaging. Polyvinal Chloride -- Considerably more rigid, and this stronger due to polar C-Cl bonds. Useful for glue and as a sealant. Nylon -- Strong, long fibers, commonly used in tights or stockings, but also to as strength to other fibers (ie carpets are a combination of wool and nylon). Polyester -- Long chain fabrics with great strength and do not rot. Commonly used in sails, ropes and other fibers which must be strong and not rot. E.6.7 : These polymers will not break down naturally and can not be burnt without the production of toxic gases. They are also produced from oil non-renewable resource (but can sometimes come from agricultural products). E.7 Other chemical industries E.7.1 : Other chemical industries include the production of -alloys, cement, ceramics, glasses, paper, silicones and natural products. E.7.2 : Biotechnology is also an important source of some chemicals, such as ethanol, insulin and biopolymers (such as starch, rubber, proteins, wool, cotton, paper).

E.8 The chlor-alkali industry

E.8.1 : Chlorine is produced by the electrolysis of sodium chloride, because it is not easy to chemically separate them. This is, today, done in a diaphragm cell... The diaphragm cell is basically a container separated down the center with a porous (commonly asbestos) diaphragm. The container has brine (NaCl in water) pumped into the left hand side. above is a Ti anode where Chlorine is produced, and piped off. Spent brine flows through and at the steel cathode on this side, water is reduced to form H2 (and OH which forms NaOH with the sodium left over from before). This sodium hydroxide solution is then piped out from the bottom, while the H2 is piped off the top. The two gases must be separated because the would react explosively if they came into contact. E.8.2 : The fact that the above cell produces Cl2, H2 and NaOH is very convenient, since all three are useful products, and the cell uses comparatively little energy...uses Chlorine -- Dry cleaning solvents, refrigerants, PVC, disinfectant Hydrogen -- Ammonium production, fuel cells, reducing agent. NaOH -- Neutralizing acids, producing soap, aluminum production E.8.3 : The diaphragm cell above has replaced a similar one using a flowing mercury cathode due to concerns about mercury poisoning. Also, many problems with Chlorine containing solvents have been found (specifically the ozone layer) which makes this process somewhat less favorable.

E.9 Silicon
E.9.1 : Silicon is the second most abundant element in the earth's crust (28%) Extraction -- Reduction of silica (sand) by coke in an electric furnace SiO2(s) + 2C(s) -> Si(s) + 2CO(g). More pure Si can be obtained from SiCl4 by reduction in H2. SiCl4(s) + 2H2(g) -> Si(s) + 4HCl Very pure silicon can be produced by zone refining the silicon above. Long rods of impure silicon are passed through a heating element, which melts the silicon as it passes through. Impurities dissolve in this molten portion, and so as the Silicon passes through, the impurities are left behind, and eventually the end is cut off. (Silicon does have a high melting point however, so this is expensive). E.9.2 : Semiconductors ... In it's natural state, silicon is a large covalent lattice of silicon molecules. Semiconductors

are created by doping (or adding one to about every million) the silicon with either Phosphorus (P) or Boron (B). Because Phosphorus has one extra valence electron, it can be removed and effectively carry a voltage through the lattice. Boron, on the other hand, has one less, and so it is possible to excite a valence electron from an Si atom into the gap...this allows a positive charge to be carried by the hole. Phosphorus is an n-type semiconductor (n for negative) while boron is p-type (positive). E.10 Ellingham diagrams There is an ellingham diagram in the data book, it works like this...The graph shows gibbs free energies at various temperatures. If you want one reaction to force the other to occur in reverse, then it's line must be below the other for the given temperature (because the second will be reversed, and -ve will become +ve). In general, it is used to see if reaction can be used to reduce another. E.11 E.11.1 : Thermal cracking vs Catalytic ... Thermal cracking uses homolytic breaking of bonds, creating free radical carbon chains. These, therefore act with a free radical mechanism. Catalytic cracking breaks the bonds homolytically, producing complex ions, and thus an ionic mechanism. E.11.2 : LDPE vs HDPE polythene mechanisms. LDPE (Low density polythene) -- this is produced by the polymerisation of ethene of 200oc and 1200 atm, with trace amounts of O2 present. This produces highly branched chains, and so is soft, malleable etc. Mechanism ... Initiator ... Benzene(=O)-O-O-(O=)Benzene ... the central peroxide link breaks, and 2Benzene + 2CO2 is produced. These benzene radicals the react with ethene, forming a Benzene-CH2-CH2 free radical, and so on until it terminates with two free radicals meeting. HDPE (high density polythene) is produced at 60oc and 1 atm using a zieger catalyst, and an ionic mechanism. It has fewer branched chains, and so is less malleable and has a higher melting point...and obviously it's higher density. E.11.3 : Principles of condensation polymers. -- The forming of monomers with the expulsion of a small group (H2O or H2) to form a polymer. -- The monomers must have two functional groups to react and form a continual chain with other monomers.

Nylons ( 1,6-hexanedioic acid + 1,6-hexanedamide, expelling water) and Polyesters ( 1,4Benzenediol and ethanedioic acid, expelling water) Polyurethanes -- I'll come back to this (probably never)...it's hard to describe without a diagram. Silicones ... Monomer is HO-(R)Si(R)-OH and produces ---O-(R)Si(R)-O-(R)Si(R)-O(R)Si(R)-O-...Expelling water each time.