Chem Revise

1 Atoms, molecules and stoichiometry try
DEFINITION: Relative atomic mass (Ar) is the average mass of one atom
compared to one twelfth of the mass of one atom of carbon-12
DEFINITION: Relative Isotopic mass is the mass of one isotope compared to

one twelfth of the mass of one atom of carbon-12
The term molecule should only be

DEFINITION: Relative molecular mass (Mr) is the weighted average mass of a
used for covalent molecules. For
molecule compared to one twelfth of the mass of one atom of carbon-12
ionic substances use the term
relative formula mass. They are,
DEFINITION: Relative formula mass (Mr) is the weighted average masses of the however, calculated in the same
formula units compared to one twelfth of the mass of one atom of carbon-12 way.
The mole Avogadro's Number

The mole is the key concept for chemical calculations There are 6.022 x 1023 atoms in 12
grams of carbon-12. Therefore
DEFINITION: The mole is the amount of substance in grams that has the same explained in simpler terms 'One
number of particles as there are atoms in 12 grams of carbon-12. mole of any specified entity contains
6.022 x 1023 of that entity':
For pure solids, liquids and gases
Relative Formula mass (Mr) for a compound can be calculated by adding
moles = mass up the relative atomic masses(from the periodic table) of each element
in the compound
Mr eg CaCO3 = 40.1 + 12.0 +16.0 x3 = 100.1
Unit of Mass: grams
Unit of moles : mol Many questions will involve changes of units
1000 mg =1g
Example 1: What is the number of moles in 35.0g of 1000 g =1kg
CuSO4? 1000kg = 1 tonne
moles = mass/Mr
Example 2: What is the number of moles in 75.0mg of CaSO4.2H2O?
= 35.0/ (63.5 + 32.0 +16.0 x4)
moles = mass/Mr
= 0.219 mol
= 0.075/ (40 + 32.0 +16.0 x4 + 18.0x2)
= 4.36x10-4 mol
1 mole of copper atoms will contain 6.022 x 1023 atoms

Avogadro's Constant can be used
1 mole of carbon dioxide molecules will contain 6.022 x 1023 molecules
for atoms, molecules and ions
1 mole of sodium ions will contain 6.022 x 1023 ions
No of particles = moles of substance (in mol) X Avogadro's constant (L)
Example 3 : How many atoms of Tin are there Example 4 : How many chloride ions are there in a 25.0 cm3 of a
in a 6.00 g sample of Tin metal? solution of magnesium chloride of concentration 0.400 moldm-3 ?
moles = mass/Ar moles= concentration x Volume
= 6.00/ 118.7 MgCl2= 0.400 x 0.0250
= 0.05055 mol = 0.0100 mol There are two moles of
chloride ions for every one
Number atoms = moles x 6.022 x 1023 moles of chloride ions = 0.0100 x2 mole of MgCl
2
= 0.0200
= 0.05055 x 6.022 x 1023
Number ions of Cl- = moles x 6.022 x 1023
= 3.04 x1022
= 0.0200 x 6.022 x 1023
= 1.20 x1022 (to 3 sig fig)
1
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Determination of Relative Atomic Mass
The relative atomic mass quoted on the periodic table is a weighted average of all the isotopes
Fig: spectra for

100
Magnesium from mass
80 78.70% spectrometer
% abundance
60
24Mg+
If asked to give the species for a peak
40 in a mass spectrum then give charge
25Mg+ 26Mg+ and mass number e.g. 24Mg+
20 10.13%
11.17%
m/z
24 25 26
R.A.M =  (isotopic mass x % abundance) Use these equations to

work out the R.A.M
100
For above example of Mg

R.A.M = [(78.7 x 24) + (10.13 x 25) + (11.17 x 26)] /100 = 24.3
R.A.M =  (isotopic mass x relative abundance)

If relative abundance is used instead of
total relative abundance percentage abundance use this equation
Example 5: Calculate the relative atomic mass of Tellurium from the following abundance
data: 124-Te relative abundance 2; 126-Te relative abundance 4; 128-Te relative abundance
7; 130-Te relative abundance 6
R.A.M = [(124x2) + (126x4) + (128x7) + (130x6)]

19
= 127.8
Example 6: Copper has two isotopes 63-Cu and 65-Cu. The relative atomic mass of copper is 63.5.
Calculate the percentage abundances of these two isotopes.
63.55 = yx63 + (1-y)x65
63.55 = 63y +65 -65y
63.55 = 65 -2y
2y = 1.45
y = 0.725
%abundance 63-Cu =72.5% %abundance 65-Cu = 27.5%
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Empirical formulae
Definition: An empirical formula is the simplest ratio of atoms of each element in the compound.
General method
The same method can be
Step 1 : Divide each mass (or % mass) by the atomic mass of the element
used for the following types
Step 2 : For each of the answers from step 1 divide by the smallest one of those of data:
numbers.
1. masses of each element in
Step 3: sometimes the numbers calculated in step 2 will need to be multiplied up to the compound
give whole numbers.
2. percentage mass of each
These whole numbers will be the empirical formula. element in the compound
Example 7 : Calculate the empirical formula for a compound that contains 1.82g of
K, 5.93g of I and 2.24g of O
Step1: Divide each mass by the atomic mass of the element to give moles
K = 1.82 / 39.1 I = 5.93/126.9 O = 2.24/16
= 0.0465 mol = 0.0467mol = 0.14mol
Step 2 For each of the answers from step 1 divide by the smallest one of those numbers.
K = 0.0465/0.0465 I = 0.0467/0.0465 O = 0.14 / 0.0465
=1 =1 =3
Empirical formula =KIO3
Molecular formula from empirical formula
Definition: A molecular formula is the actual number of atoms of each element in the compound.
From the relative molecular mass (Mr) work out how many times the
mass of the empirical formula fits into the Mr.
Remember the Mr of a substance can be found out
from using a mass spectrometer. The molecular ion
Example 8 : work out the molecular formula for the
( the peak with highest m/z) will be equal to the Mr.
compound with an empirical formula of C3H6O and a Mr
of 116
C3H6O has a mass of 58

Spectra for C4H10
The empirical formula fits twice into Mr of 116 43
So molecular formula is C6H12O2
The Mr does not need to be exact to turn an empirical formula 29 Molecular ion
into the molecular formula because the molecular formula will 58
be a whole number multiple of the empirical formula

10 20 30 40 50 60 70 80 90 100 110
m/z
Combustion Analysis for Calculating Empirical Formula
Example 9
0.328 g of a compound containing C,H and O was burnt completely in excess oxygen,
producing 0.880 g of carbon dioxide and 0.216 g of water. Use these data to calculate
the empirical formula of the compound.
Work out moles of CO2 = Mass of CO2/Mr of CO2

= 0.88/44
=0.02mol
Moles of C in compound = moles of CO2 Mass of C in = mol of C x 12
= 0.02 mol compound =0.02 x12
=0.24g
Work out moles of H2O = Mass of H2O /Mr of H2O
= 0.216/18
=0.012mol
Moles of H in compound = 2 x moles of H2O Mass of H in = mol of H x 1

= 0.024 mol compound =0.024 x1
=0.024g
Work out mass of O = mass of compound – mass of C – mass of H

in compound = 0.328 – 0.24 -0.024
=0.064
Work out moles of O = Mass of O /Ar of O

in compound = 0.064/16
= mol 0.004
Work out molar ratio

of 3 elements (divide C = 0.02/0.004 H = 0.024/0.004 O = 0.004/0.004
by smallest moles) =5 =6 =1
empirical formula = C5H6O
Molar Gas Volume Example 10 : Calculate the volume in dm3 at room

temperature and pressure of 50.0g of Carbon dioxide gas ?
1 mole of any gas at room pressure amount = mass/Mr

(1atm) and room temperature 25oC = 50/ (12 + 16 x2)
will have the volume of 24dm3
= 1.136 mol
Gas Volume (dm3)= amount x 24
= 1.136 x 24
= or 27.3 dm3 to 3 sig fig
For most calculations at A-level use the following 3 equations to calculate amount in moles
Learn these equations carefully and what units to use in them.
1. For pure solids, liquids and gases 2. For gases 3. For solutions
moles = mass Gas Volume (dm3)= amount x 24 Concentration = moles

Mr This equation gives the volume of a volume
gas at room pressure (1atm) and
Unit of Mass: grams room temperature 25oC. Unit of concentration: mol dm-3 or M
Unit of moles : mol Unit of Volume: dm3
Note the
PV = nRT
different
Remember the Mr must be Unit of Pressure (P):Pa units for Converting volumes
calculated and quoted to Unit of Volume (V): m3 volume
1dp Unit of Temp (T): K cm3  dm3 ÷ 1000
n= moles cm3  m3 ÷ 1000 000
R = 8.31 dm3  m3 ÷ 1000
Converting temperature
oC  K add 273
Significant Figures
Give your answers to the same number of significant figures as the number of significant figures for the data you
given in a question. If you are given a mixture of different significant figures, use the smallest
Density, ρ Density calculations are usually used with pure liquids but to work out the mass from a
measured volume. It can also be used with solids and gases.
density = mass Density is usually given in g cm-3 but can be kg m–3, g dm-3
Care needs to be taken if different units are used.
Volume
Example 11 : How many molecules of ethanol are there in a Example 12 : There are 980mol of pure gold in a
0.500 dm3 of ethanol (CH3CH2OH) liquid ? The density of bar measuring 10 cm by 20 cm by 50 cm. What is
ethanol is 0.789 g cm-3 the density of gold in kg dm−3
Mass = moles x Mr
Mass = density x Volume
ethanol = 980 x 197
= 0.789 x 500
= 193060 g
= 394.5g
= 193.06kg
moles = mass/Mr
Volume = 10x20x50
= 394.5/ 46.0
= 10 000cm3
= 8.576 mol = 10dm3
Number of molecules= moles x 6.022 x 1023 density = mass/volume
= 8.576 x 6.022 x 1023 = 193/10
= 19.3 kg dm-3
= 5.16 x1024(to 3 sig fig)
Hydrated salt
A Hydrated salt contains water of crystallisation Example 13

Na2SO4 . xH2O has a molar mass of 322.1, Calculate
.
Cu(NO3)2 6H2O the value of x
hydrated copper (II) nitrate(V). Molar mass xH2O = 322.1 – (23x2 + 32.1 + 16x4)
= 180
Cu(NO3)2 X = 180/18
Anhydrous copper (II) nitrate(V). =10
This method could be used for measuring mass loss in various

Heating in a crucible
thermal decomposition reactions and also for mass gain when
reacting magnesium in oxygen.
The water of crystallisation in calcium sulphate crystals can be The lid improves the accuracy of the
removed as water vapour by heating as shown in the following experiment as it prevents loss of solid
equation. from the crucible but should be loose
CaSO4.xH2O(s) → CaSO4(s) + xH2O(g) fitting to allow gas to escape.
Method.
•Weigh an empty clean dry crucible and lid .
•Add 2g of hydrated calcium sulphate to the crucible and weigh
again
•Heat strongly with a Bunsen for a couple of minutes
•Allow to cool
•Weigh the crucible and contents again
•Heat crucible again and reweigh until you reach a constant mass (
do this to ensure reaction is complete).
Large amounts of hydrated calcium sulphate, such as 50g,

should not be used in this experiment as the decomposition is
likely to be incomplete. Small amounts of the solid , such as
0.100 g, should not be used in this
The crucible needs to be dry otherwise a wet crucible would experiment as the percentage
give an inaccurate result. It would cause mass loss to be too uncertainties in weighing will be too
large as the water would be lost when heating. high.
Example 14. 3.51 g of hydrated zinc sulphate were heated and 1.97 g of
anhydrous zinc sulphate were obtained.
Use these data to calculate the value of the integer x in ZnSO4.xH2O
Calculate the mass of H2O = 3.51 – 1.97 = 1.54g
Calculate moles = 1.97 Calculate = 1.54

of ZnSO4 161.5 moles of H2O 18
= 0.0122 = 0.085
Calculate ratio of mole of 0.0122 = 0.085

ZnSO4 to H2O =
0.0122 0.0122
=7
=1
X=7
Concentration of Solutions
A solution is a mixture formed when a solute dissolves in a solvent. In chemistry we most commonly use water as
the solvent to form aqueous solutions. The solute can be a solid, liquid or a gas.
Molar concentration can be measured for solutions. This is calculated by dividing the amount in
moles of the solute by the volume of the solution. The volume is measure is dm 3. The unit of molar
concentration is mol dm-3 ; it can also be called molar using symbol M
Concentration = moles Unit of concentration: mol dm-3 or M

volume Unit of Volume: dm3
Converting volumes
A m3 is equivalent to a cube A dm3 is equivalent to a cube A cm3 is equivalent to a cube

100cmx100cmx100cm= 1000000cm3 10cmx10cmx10cm= 1000cm3 1cmx1cmx1cm
1dm3 = 1litre 1cm3 = 1 ml
100cm
10cm
10cm 1cm
1cm
10cm 1cm
100cm
100cm 1cm3
1dm3 or 1 litre
1m3
1 m3 = 1000 dm3 or 1000L 1 dm3 = 1000 cm3 or 1000mL

To convert m3 into dm3 multiply by 1000 To convert cm3 into dm3 divide by 1000
cm3  dm3 ÷ 1000

cm3  m3 ÷ 1000 000
dm3  m3 ÷ 1000
Example 15 What is the concentration of solution Example 16 What is the concentration of solution
made by dissolving 5.00g of Na2CO3 in 250 cm3 water? made by dissolving 10kg of Na2CO3 in 0.50 m3 water?
moles = mass/Mr moles = mass/Mr
= 5 / (23.0 x2 + 12 +16 x3) = 10 000 / (23.0 x2 + 12 +16 x3)
= 0.0472 mol = 94.2 mol
conc= moles/Volume conc= moles/Volume
= 0.0472 / 0.25 = 94.2 / 500
= 0.189 mol dm-3 = 0.19 mol dm-3
Mass Concentration
The concentration of a solution can also be measured To turn concentration measured in mol dm-3 into
in terms of mass of solute per volume of solution concentration measured in g dm-3 multiply by Mr of the
substance
Mass Concentration = mass conc in g dm-3 = conc in mol dm-3 x Mr
volume The concentration in g dm-3 is the same as the mass of
solute dissolved in 1dm3
Unit of mass concentration: g dm-3
Unit of Mass g
Unit of Volume: dm3
Ions dissociating
When soluble ionic solids dissolve in water they will dissociate into separate ions. This can lead to the
concentration of ions differing from the concentration of the solute.
Example 17
If 5.86g (0.1 mol) of sodium chloride (NaCl) is dissolved in 1 dm3 of
water then the concentration of sodium chloride solution would be
0.1moldm-3 . NaCl(s) +aq  Na+(aq) + Cl- (aq)
However the 0.1mol sodium chloride would split up to form 0.1
mol of sodium ions and 0.1 mol of chloride ions. The concentration 0.1mol 0.1mol 0.1mol
of sodium ions is therefore 0.1 mol dm-3 and the concentration of
chloride ions is also 0.1 mol dm-3
Example 18
If 9.53g (0.1 mol) of magnesium chloride (MgCl2) is dissolved in 1
dm3 of water then the concentration of magnesium chloride solution
(MgCl2 aq) would be 0.1moldm-3 . MgCl2(s) +aq  Mg2+(aq) + 2Cl- (aq)
However the 0.1mol magnesium chloride would split up to form 0.1
0.1mol 0.1mol 0.2mol
mol of magnesium ions and 0.2 mol of chloride ions. The
concentration of magnesium ions is therefore 0.1 mol dm-3 and the
concentration of chloride ions is now 0.2 mol dm-3
Making a solution
• Weigh the sample bottle containing the required mass of solid Alternatively the known mass of solid
on a 2 dp balance in the weighing bottle could be
• Transfer to beaker and reweigh sample bottle transferred to beaker, washed and
• Record the difference in mass washings added to the beaker.
• Add 100cm3 of distilled water to the beaker. Use a glass rod to

stir to help dissolve the solid.
•Sometimes the substance may not dissolve well in cold water so

the beaker and its contents could be heated gently until all the
solid had dissolved.
• Pour solution into a 250cm3 graduated flask via a funnel. Remember to fill so the bottom of the
• Rinse beaker and funnel and add washings from the beaker meniscus sits on the line on the neck of the
and glass rod to the volumetric flask. flask. With dark liquids like potassium
• make up to the mark with distilled water using a dropping manganate it can be difficult to see the
pipette for last few drops. meniscus.
• Invert flask several times to ensure uniform solution.
Dilutions
Diluting a solution
Using a volumetric pipette is more accurate
than a measuring cylinder because it has a
•Pipette 25cm3 of original solution into a 250cm3 volumetric smaller uncertainty
flask
•make up to the mark with distilled water using a dropping Use a teat pipette to make up to the mark in
pipette for last few drops. volumetric flask to ensure volume of solution
• Invert flask several times to ensure uniform solution. accurately measured and one doesn’t go over
the line
Calculating Dilutions
Diluting a solution will not change the amount of moles of solute present but increase the volume of solution
and hence the concentration will lower
moles= volume x concentration
If amount of moles does not change then
Original volume x original concentration = new diluted volume x new diluted concentration
so new diluted concentration = original concentration x Original volume

new diluted volume
The new diluted volume will be equal to the original volume of solution added + the volume of water added.
Example 19
If 50 cm3 of water are added to 150 cm3 of a 0.20 mol dm-3 NaOH solution, what will the concentration of the
diluted solution be?
new diluted concentration = original concentration x Original volume
new diluted volume
new diluted concentration = 0.20 x 0.150
0.200
= 0.15 mol dm-3
Example 20
Calculate the volume of water in cm3 must be added to dilute 5.00 cm3 of 1.00 mol dm−3 hydrochloric acid so that
it has a concentration of 0.050 mol dm−3 ?
Moles original solution = conc x vol

= 1.00 x 0.005
= 0.005
New volume = moles /conc
= 0.005/0.05
= 0.1dm3 = 100cm3
Volume of water added = 100 - 5 = 95cm3
Safety and hazards

Irritant - dilute acid and alkalis- wear googles Hazardous substances in low
Corrosive- stronger acids and alkalis wear goggles concentrations or amounts will
Flammable – keep away from naked flames not pose the same risks as the
Toxic – wear gloves- avoid skin contact- wash hands after use pure substance.
Oxidising- Keep away from flammable / easily oxidised materials
Converting quantities between different substances using a balanced equation
Typically the quantity of one substance is given
N2 + 3H2  2NH3 and you are asked to calculate a quantity for
another substance in the reaction. Any of the
The balancing (stoichiometric) numbers are mole ratios
above three equations can be used.
e.g. 1 mole of N2 reacts with 3 moles of H2 to produce 2moles of NH3
1. For pure solids, liquids and gases 2. For gases 3. For solutions
PV = nRT
moles = mass Concentration = moles
Mr Or use the molar gas volume volume
1 mol gas =24dm3 at RTP
Step 3
Step 1:
Convert moles of second substance
Use one of the above 3 equations to Step 2:
into quantity question asked for
convert any given quantity into moles Use balanced equation to convert
using relevant equation
Mass moles moles of initial substance into
e.g. Moles ,Mr  mass
PVT of gas  moles moles of second substance
Mole, P, T gas  vol gas
Conc and vol of solution  moles
Moles, vol solution  conc
Example 21: What mass of Carbon dioxide would be produced Example 22: 23.6cm3 of H2SO4 neutralised 25.0cm3 of 0.150M
from heating 5.50 g of sodium hydrogencarbonate? NaOH. What is the concentration of the H2SO4?
2NaHCO3  Na2CO3 + CO2 + H2O H2SO4 + 2NaOH  Na2SO4 +2H2O
Step 1: work out moles of sodium hydrogencarbonate

Moles = mass / Mr Step 1: work out moles of sodium hydroxide
= 5.50 /84 Moles = conc x vol
= 0.0655 mol = 0.150 x 0.025
= 0. 00375 mol
Step 2: use balanced equation to give moles of CO2
2 moles NaHCO3 : 1 moles CO2
Step 2: use balanced equation to give moles of H2SO4
So 0.0655 HNO3 : 0.0328mol CO2
2 moles NaOH : 1 moles H2SO4
Step 3: work out mass of CO2 So 0.00375 NaOH : 0.001875 mol H2SO4
Mass = moles x Mr
= 0.0328 x 44.0 Step 3 work out concentration of H2SO4
=1.44g
conc= moles/Volume
= 0.001875 / 0.0236
Example 23: What is the total volume of gas produced in = 0.0794 mol dm-3
dm3 at 333K and 100kPa when 0.651 g of magnesium
nitrate decomposes when heated?
2Mg (NO3)2 (s) 2 MgO (s) + 4NO2 (g) + O2 (g) Example 24: What mass of Copper would react
completely with 150 cm3 of 1.60M nitric acid?
Step 1: work out moles of magnesium nitrate
3Cu + 8HNO3  3Cu(NO3 )2 + 2NO + 4H2O
Moles = mass / Mr
= 0.651 / 148.3 Step 1: work out moles of nitric acid
= 0.00439 mol Moles = conc x vol
= 1.6 x 0.15
Step 2: use balanced equation to give moles of gas = 0.24 mol
produced
2 moles Mg (NO3)2 : 4NO2 (g) + O2 (g) ie 5moles of gas Step 2: use balanced equation to give moles of Cu
So 0.00439 Mg (NO3)2 : 0.01098( 0.00439 x 5/2) moles gas 8 moles HNO3 : 3 moles Cu
So 0.24 HNO3 : 0.09 (0.24 x 3/8) mol Cu
Step 3: work out volume of gas
Step 3: work out mass of Cu
Volume = nRT/P
Mass = moles x Mr
= (0.01098 x 8.31 x 333 )/ 100000
= 0.09 x 63.5
= 0.000304m3
=5.71g
= 0.303dm3
Limiting and excess reactants
Example 25 Calculate the maximum mass of titanium that could be produced from reacting 100 g of TiCl4 with
80 g of sodium TiCl4 + 4 Na  4 NaCl + Ti
Step 1: work out amount, in mol, TiCl4 Step 1: work out amount, in mol, Na
amount = mass / Mr amount = mass / Mr
= 100 /189.9 = 80/23.0
= 0.527 mol = 3.48 mol
Step 2 use balanced equation to work out which reactant is in excess
Using 1TiCl4 :4 Na ratio we can see that 0.527mol of TiCl4 should react with 2.108 mol of Na. We actually have 3.48
mole of Na which is an excess of 1.372 moles. We can complete calculation using the limiting reactant of TiCl 4
Step 3: use balanced equation to work out amount in mol of Ti formed
1 mol TiCl4: 1 mole Ti
So 0.527mol TiCl4 produces 0.527 mole Ti
Step 4: work out mass of Ti formed
Mass = amount x Mr
= 0.527 x 47.9
=25.24g
% Yield
actual yield
percentage yield = x 100
theoretical yield
Example 26: 25.0g of Fe2O3 was reacted and it produced 10.0g of Fe. Calculate the percentage yield?
Fe2O3 + 3CO  2Fe + 3 CO2
First calculate maximum mass of Fe that could be produced

Step 1: work out moles of Iron oxide
Moles = mass / Mr
=25.0 / 159.6
= 0.1566 mol
Step 2: use balanced equation to give moles of Fe
1 moles Fe2O3 : 2 moles Fe
So 0.1566 Fe2O3 : 0.313moles Fe
Step 3: work out mass of Fe

Mass = moles x Ar
= 0.313 x 55.8
=17.5g
Step 4 : calculate %yield

% yield = (actual yield/theoretical yield) x 100
= (10/ 17.5) x 100
= 57.1%
Titrations
Safety precautions
The method for carrying out the titration
Acids and alkalis are corrosive
•rinse equipment (burette with acid, pipette with alkali, conical flask
(at low concentrations acids are
with distilled water)
irritants)
•pipette 25 cm3 of alkali into conical flask
Wear eye protection and gloves
•touch surface of alkali with pipette ( to ensure correct amount is
If spilled immediately wash affected
added)
parts after spillage
•adds acid solution from burette
•make sure the jet space in the burette is filled with acid
If substance is unknown treat it as
•add a few drops of indicator and refer to colour change at end point
potentially toxic and wear gloves.
•phenolphthalein [pink (alkali) to colourless (acid): end point pink
colour just disappears] [use if NaOH is used]
•methyl orange [yellow (alkali) to red (acid): end point orange] If the jet space is not filled properly prior
[use if HCl is used] to commencing the titration it will lead to
•use a white tile underneath the flask to help observe the colour errors if it then fills during the titration,
change leading to a larger than expected titre
•add acid to alkali whilst swirling the mixture and add acid dropwise at reading.
end point
•note burette reading before and after addition of acid A conical flask is used in preference to a
•repeats titration until at least 2 concordant results are obtained- two beaker because it is easier to swirl the
readings within 0.1 of each other mixture in a conical flask without spilling
the contents.
Indicators are generally weak acids so we

Working out average titre results only add a few drops of them. If too much
Only make an average of the concordant titre results is added it will affect the titration result
lf 2 or 3 values are within 0.10cm3 and therefore concordant or close
then we can say results are accurate and repeatable and the titration Distilled water can be added to the conical
technique is good/ consistent flask during a titration to wash the sides of
the flask so that all the acid on the side is
Recording results washed into the reaction mixture to react
•Results should be clearly recorded in a table with the alkali.
•Result should be recorded in full (i.e. both initial and final readings) It does not affect the titration reading as
•Record titre volumes to 2dp (0.05 cm3) water does not react with the reagents or
change the number of moles of acid
added.
Common Titration Equations Titrating mixtures

If titrating a mixture to work out the concentration of an active ingredient
CH3CO2H + NaOH  CH3CO2-Na+ + H2O it is necessary to consider if the mixture contains other substances that
H2SO4 + 2NaOH  Na2SO4 +2H2O have acid base properties.
If they don’t have acid base properties we can titrate with confidence.
HCl + NaOH  NaCl +H2O
NaHCO3 + HCl  NaCl + CO2 + H2O
Na2CO3 + 2HCl 2NaCl + CO2 + H2O Testing batches
In quality control it will be necessary to do titrations/testing on several
samples as the amount/concentration of the chemical being tested may
vary between samples.
Safely dealing with excess acid

Sodium hydrogen carbonate (NaHCO3) and calcium carbonate (CaCO3) are good for neutralising excess acid in the
stomach or acid spills because they are not corrosive and will not cause a hazard if used in excess. They also have no
toxicity if used for indigestion remedies but the CO2 produced can cause wind.
Magnesium hydroxide is also suitable for dealing with excess stomach acid as it has low solubility in water and is
only weakly alkaline so not corrosive or dangerous to drink (unlike the strong alkali sodium hydroxide). It will also
not produce any carbon dioxide gas.
12
More complicated titration calculations- taking samples
Example 27: A 25.0cm3 sample of vinegar was diluted in a Common Titration Equations
250cm3 volumetric flask. This was then put in a burette and
23.10cm3 of the diluted vinegar neutralised 25.0 cm3 of 0.100M CH3CO2H + NaOH  CH3CO2-Na+ + H2O
NaOH. What is the concentration of the vinegar in gdm-3 ?
H2SO4 + 2NaOH  Na2SO4 +2H2O
CH3CO2H + NaOH  CH3CO2-Na+ + H2O
HCl + NaOH  NaCl +H2O
Step 1: work out moles of sodium hydroxide
moles = conc x vol
NaHCO3 + HCl  NaCl + CO2 + H2O
= 0.10 x 0.025 Na2CO3 + 2HCl 2NaCl + CO2 + H2O
= 0. 00250 mol
Step 2: use balanced equation to give moles of CH3CO2H Example 29
1 moles NaOH : 1 moles CH3CO2H 950 mg of impure calcium carbonate tablet was crushed. 50.0
So 0.00250 NaOH : 0.00250 mol CH3CO2H cm3 of 1.00 mol dm–3 hydrochloric acid, an excess, was then
added. After the tablet had reacted, the mixture was
Step 3 work out concentration of diluted CH3CO2H in 23.1
transferred to a volumetric flask. The volume was made up to
(and 250 cm3) in moldm-3
exactly 100 cm3 with distilled water. 10.0 cm3 of this solution
conc= moles/Volume was titrated with 11.1cm3 of 0.300 mol dm–3 sodium
= 0.00250 / 0.0231 hydroxide solution.
What is the percentage of CaCO3 by mass in the tablet?
= 0.108 mol dm-3 1. Calculate the number of moles of sodium hydroxide used
Step 4 work out concentration of original concentrated moles= conc x vol
CH3CO2H in 25cm3 in moldm-3 = 0.30 x 0.0111
conc = 0.108 x 10 = 1.08 mol dm-3 = 0. 00333 mol
Step 5 work out concentration of CH3CO2H in original 2. Work out number of moles of hydrochloric acid left in 10.0 cm3
concentrated 25 cm3 in gdm-3 use balanced equation to give moles of HCl
conc in gdm-3 = conc in mol dm-3 x Mr 1 mol NaOH : 1 mol HCl
So 0.00333 NaOH : 0.00333 moles HCl
= 1.08 x 60 = 64.8 g dm-3
3. Calculate the number of moles of hydrochloric acid left in
100 cm3 of solution
Example 28. An unknown metal carbonate reacts with
hydrochloric acid according to the following equation. Moles in 100cm3 = 0.00333 x10
M2CO3(aq) + 2HCl(aq)  2MCl(aq) + CO2(g) + H2O(l) =0.0333
A 3.96 g sample of M2CO3 was dissolved in distilled water to
make 250 cm3 of solution. A 25.0 cm3 portion of this solution 4. Calculate the number of moles of HCl that reacted with
required 32.8 cm3 of 0.175 mol dm–3 hydrochloric acid for the indigestion tablet.
complete reaction. Calculate the Mr of M2CO3 and identify the
In original HCl 50.0 cm3 of 1.00 mol dm–3 there is 0.05moles
metal M
1. Calculate the number of moles of HCl used moles of HCl that =0.05 -0.0333
moles = conc x vol reacted with the =0.0167
= 0.175 x 0.0328 indigestion tablet.
= 0. 00574 mol
2. Work out number of moles of M2CO3 in 25.0 cm3 put in conical 5 Use balanced equation to give moles of CaCO3
flask CaCO3(s) + 2HCl(aq)  CaCl2(aq) + CO2(g) + H2O(l)
use balanced equation to give moles of M2CO3 2 mol HCl : 1 mol CaCO3
2 mol HCl : 1 mol M2CO3 So 0.0167 HCl : 0.00835 moles CaCO3
So 0. 00574 NaOH : 0.00287 moles M2CO3
6. work out the mass of CaCO3 in original tablet
3. Calculate the number of moles M2CO3 acid in original 250 cm3
of solution mass= moles x Mr
Moles in 250cm3 = 0.00287 x10 = 0.00835 x 100 = 0.835 g
=0.0287
percentage of
4. work out the Mr of M2CO3 = 0.835/0.950 x100
CaCO3 by mass in
Mr = mass / moles the tablet
= 87.9 %
= 3.96/ 0.0287= 138.0
5. Work out Ar of M = (138-12- 16x3)
2
Ar of M = 39 M= potassium
Uncertainty
Readings and Measurements
Readings Measurements The uncertainty of a reading (one judgement) is at
the values found from a single the values taken as the least ±0.5 of the smallest scale reading.
judgement when using a piece difference between the The uncertainty of a measurement (two judgements)
of equipment judgements of two values is at least ±1 of the smallest scale reading.
(e.g. using a burette in a
titration)
Calculating Apparatus Uncertainties

Each type of apparatus has a sensitivity uncertainty To decrease the apparatus uncertainties
you can either decrease the sensitivity
•balance  0.001 g uncertainty by using apparatus with a
•volumetric flask  0.1 cm3 greater resolution (finer scale divisions ) or
•25 cm3 pipette  0.1 cm3 you can increase the size of the
•burette (start & end readings and end point )  0.15 cm3 measurement made.
Calculate the percentage error for each piece of equipment used by Uncertainty of a measurement using a
burette. If the burette used in the
% uncertainty =  uncertainty x 100 titration had an uncertainty for each
Measurement made on apparatus reading of +/– 0.05 cm3 then during a
titration two readings would be taken so
e.g. for burette the uncertainty on the titre volume would
% uncertainty = 0.15/average titre result x100 be +/– 0.10 cm3 . Then often another 0.05
is added on because of uncertainty
To calculate the maximum total percentage apparatus uncertainty in the identifying the end point colour change
final result add all the individual equipment uncertainties together.
Reducing uncertainties in a titration If looking at a series of measurements in

an investigation the experiments with the
Replacing measuring cylinders with pipettes or burettes which have smallest readings will have the highest
lower apparatus uncertainty will lower the error experimental uncertainties.
To reduce the uncertainty in a burette reading it is necessary to make

the titre a larger volume. This could be done by: increasing the volume
and concentration of the substance in the conical flask or by decreasing
the concentration of the substance in the burette.
Reducing uncertainties in measuring mass

Using a more accurate balance or a larger mass will reduce the
uncertainty in weighing a solid
Weighing sample before and after addition and then
calculating difference will ensure a more accurate
measurement of the mass added.
If the %uncertainty due to the apparatus <

percentage difference between the actual value and
Calculating the percentage difference between the actual
the calculated value then there is a discrepancy in
value and the calculated value
the result due to other errors.
If we calculated an Mr of 203 and the real value is 214, then
the calculation is as follows: If the %uncertainty due to the apparatus >
Calculate difference 214-203 = 11 percentage difference between the actual value and
% = 11/214 x100 the calculated value then there is no discrepancy and
=5.41% all errors in the results can be explained by the
sensitivity of the equipment.
2 Atomic Structure
Details of the three Sub-atomic (fundamental) Particles
Particle Position Relative Mass Relative Charge
Proton Nucleus 1 +1
Neutron Nucleus 1 0
Electron Orbitals 1/1840 -1
Behaviour of beams of protons, neutrons and electrons in electric fields
+ The negatively charged electron is

attracted towards the positive plate.
e
n The neutron has no charge and is
unaffected by a charged field
p The positively charged proton is

attracted towards the negative
plate. It is deflected less than an
- electron as it has a larger mass
An atom of Lithium (Li) can be represented as follows:

Nucleon(mass) Number 7
Proton (atomic) Number 3

Li Atomic Symbol
The proton (atomic number) ,Z, is the number of protons in the nucleus.
The Nucleon (mass number) ,A, is the total number of protons and neutrons in the atom.
Number of neutrons = A - Z
Isotopes Isotopes are atoms with the same number of protons, but different numbers of neutrons.
Isotopes have similar chemical properties because they have the same electronic
structure. They may have slightly varying physical properties because they have
different masses.
Electronic Structure
Models of the atom
An early model of the atom was the Bohr model (GCSE model) (2 electrons in first shell, 8 in second etc.) with
electrons in spherical orbits. Early models of atomic structure predicted that atoms and ions with noble gas
electron arrangements should be stable.
The A-level model

Electrons are arranged on: Sub energy levels labelled s ,
p, d and f
Principle energy levels Split s holds up to 2 electrons Split
Orbitals which hold up
numbered 1,2,3,4.. to 2 electrons of
into p holds up to 6 electrons into
1 is closest to nucleus opposite spin
d holds up to 10 electrons
f holds up to 14 electrons
Shapes of orbitals
Orbitals represent the
Principle level 1 2 3 4 mathematical probabilities of
finding an electron at any point
within certain spatial
Sub-level distributions around the
1s 2s, 2p 3s, 3p, 3d 4s, 4p, 4d, 4f nucleus.
Each orbital has its own
approximate, three
An atom fills up the sub shells in order of increasing energy (note 3d is dimensional shape.
higher in energy than 4s and so gets filled after the 4s) It is not possible to draw the
1s2s2p3s3p 4s3d4p5s4d5p shape of orbitals precisely.
Writing electronic structure using letters and numbers •s sublevels are

Number of electrons spherical
in sub-level
For oxygen 1s2 2s2 2p4
Number of main Name of

energy level type of • p sublevels are shaped
sub-level like dumbbells
For Calcium 1s2 2s2 2p6 3s2 3p6 4s2
Using spin diagrams

For fluorine An arrow is one electron
2p
Box represents one
2s orbital
The arrows going in the

opposite direction represents
1s the different spins of the
electrons in the orbital
When filling up sub levels with several

orbitals, fill each orbital singly before starting
to pair up the electrons
2p
2
The periodic table is split into blocks.
A s block element is one whose outer electron is filling a s-sub shell e.g. sodium 1s2 2s2 2p6 3s1
A p block element is one whose outer electron is filling a

p-sub shell e.g. chlorine 1s2 2s2 2p6 3s2 3p5
A d block element is one whose outer electron is filling a

d-sub shell e.g. vanadium 1s22s22p63s23p6 4s23d3
Electronic structure for ions
When a positive ion is formed electrons are lost When a negative ion is formed electrons are gained
from the outermost shell O is 1s2 2s2 2p4 becomes O2- is 1s2 2s2 2p6
Mg is 1s2 2s2 2p6 3s2 becomes Mg2+ is 1s2 2s2 2p6
Electronic structure of d-block elements
The electronic structure of the d-block has some complications. As mentioned earlier, conventionally we
say that 4s fills before 3d and so we write them in that order. There is, however, disagreement in the
scientific community about whether this is true.
If you look at the electronic structures below you will see both Chromium and copper have an unusual
arrangement in having a half filled 4s sub shell.
You will also see that when d block elements form ions they lose the 4s electrons first.
You may find if you research different reasons for these observations. It may well be many of the reasons
are false and we have to accept that some things in chemistry don’t neatly follow patterns we can explain.
You do need to learn these electronic structure though!
Sc 1s22s22p63s23p6 4s23d1 Sc 3+ [Ar] 4s03d0

Ti 1s22s22p63s23p6 4s23d2 Ti 3+ [Ar] 4s03d1
V 1s22s22p63s23p6 4s23d3 V 3+ [Ar] 4s03d2
Cr 1s22s22p63s23p6 4s13d5 Cr 3+ [Ar] 4s03d3
Mn 1s22s22p63s23p6 4s23d5 Mn 2+ [Ar] 4s03d5
Fe 1s22s22p63s23p6 4s23d6 When
Fe 3+ [Ar] 4s03d5
forming
Co 1s22s22p63s23p6 4s23d7 ions lose 4s Co 2+ [Ar] 4s03d7
Ni 1s22s22p63s23p6 4s23d8 before 3d Ni 2+ [Ar] 4s03d8
Cu 1s22s22p63s23p6 4s13d10 Cu 2+ [Ar] 4s03d9
Zn 1s22s22p63s23p6 4s23d10 Zn 2+ [Ar] 4s03d10
Ionisation Energies
Definition :First ionisation energy
The first ionisation energy is the energy required when one mole of gaseous
atoms forms one mole of gaseous ions with a single positive charge
This is represented by the equation: H(g)  H+(g) + e-
Always gaseous
Be(g)  Be+(g) + e-
The equation for 1st ionisation energy always
follows the same pattern.
It does not matter if the atom does not normally
form a +1 ion or is not gaseous O(g)  O+(g) + e-
All values of ionisations are positive and therefore endothermic. This is because energy must be
supplied to overcome the electrostatic attractive force between the nucleus and the electron.
Definition :Second ionisation energy

The second ionisation energy is the energy required when one mole of gaseous ions with a
single positive charge forms one mole of gaseous ions with a double positive charge
This is represented by the equation: Ti+ (g)  Ti2+(g) + e-
Factors that affect Ionisation energy

There are three main factors
1.The attraction of the nucleus
(The more protons in the nucleus the greater the attraction) Many questions can be
2. The distance of the electrons from the nucleus answered by application
(The bigger the atom the further the outer electrons are from the nucleus and of these factors
the weaker the attraction to the nucleus)
3. Shielding of the attraction of the nucleus
(An electron in an outer shell is repelled by electrons in complete inner shells,
weakening the attraction of the nucleus)
Successive ionisation energies

An element can have as many successive ionisation energies as it has electrons
The patterns in successive ionisation energies for an element give us important

information about the electronic structure for that element.
Why are successive ionisation energies always larger?

The second ionisation energy of an element is always
bigger than the first ionisation energy. When the first Ionisation
electron is removed a positive ion is formed. The ion energy
increases the attraction on the remaining electrons and so
the energy required to remove the next electron is larger.
Each successive ionisation energy is bigger than the
previous one for the same reason.
Some of the increases are much bigger, however, and
1 2 3 4 5 6
these big jumps gives us evidence for the main principle No of electrons removed
electron shells.
How are ionisation energies linked to the main electron energy levels ?
There is a big jump between the 4th

Ionisation and 5th ionisation energies.
energy Explanation
The fifth electron is in a inner main
Notice the big shell closer to the nucleus and
jump between 4 therefore attracted much more
and 5. strongly by the nucleus than the
fourth electron.
1 2 3 4 5 6 It also does not have any shielding by
No of electrons removed inner complete shells of electron so is
easier to remove.
Example: What group must this element be in? Here there is a big jump between the 2nd and 3rd
ionisations energies which means that this
1 2 3 4 5 element must be in group 2 of the periodic table
Ionisation 590 1150 4940 6480 8120 as the 3rd electron is removed from an electron
energy kJ mol-1 shell closer to the nucleus with less shielding and
so has a larger ionisation energy
The first Ionisation energy of the elements
The pattern in the first ionisation energy of each successive element in the periodic table also gives
us useful information about electronic structure
The shape of the graph for periods two and

2500 He
three is similar. A repeating pattern across a
Ne period is called periodicity.
2000
Ionisation energy kJ mol-1
F
Ar
N
1500 Cl
O P
H
1000 Be C
Si S
Mg Ca
B
500 Al
Li Na K
0
0 5 10 15 20
Atomic number
Evidence for the main electron energy levels
The noble gases are always at the maximum peak for each period, but there is a decrease in ionisation
energy down the group. (true of all groups). This is because as one goes down the group the outer
electrons become further from the nucleus and become more shielded from the nuclear pull by complete
inner shells
There is a large drop each time between the group 0 elements and the group1 elements.
This is because the element in group 1 will have its outer electron in a new shell further from the
nucleus and is more shielded. So the group 1 element is easier to remove and has a lower ionisation
energy.
First Ionisation Energy He
Ne
H
2500 Ar
Period 1
2000 Li
Kr Period 2
1500 Na
period 3
1000 Xe
K
period 4
500 Rb
Period 5
0
1 2 3 4 5 6 7 8
Group Number
Notice the drop in ionisation energy down each group
As one goes down a group, the outer electrons are found in shells further from the nucleus and are more
shielded so the attraction of the nucleus becomes smaller
Helium has the biggest first ionisation energy because its first electron is in the first shell closest to the
nucleus and has no shielding effects from inner shells. He has a bigger first ionisation energy than H as it
has one more proton.
Evidence for the electron sub energy levels

Ar
There is in general an increase in ionisation energy across a period. This is
because as one goes across a period , the number of protons increases Cl
making the effective attraction of the nucleus greater. The electrons are being P
added to the same shell which has the same shielding effect and the
electrons are pulled in closer to the nucleus. Si S
Mg
There are two small drops in the general trend, however, that provide further
evidence for the existence of sub energy levels.
Al
Na
Notice the small drop between the group 2 elements and group 3 elements (Be +
P
B , Mg + Al). Al is starting to fill a 3p sub shell, whereas Mg has its outer electrons
in the 3s sub shell. The electrons in the 3p subshell are slightly easier to remove Si
because the 3p electron sub shell is slightly higher in energy and they are also Mg
slightly shielded by the 3s electrons.
3p 3p Al
Na
3s 3s
Magnesium Aluminium
1s22s22p63s2 1s22s22p63s23p1
Why is there a small drop from P to S?
With sulphur there are 4 electrons in the 3p sub shell and the 4th is Ar
starting to doubly fill the first 3p orbital.
When the second electron is added to a 3p orbital there is a slight
Cl
repulsion between the two negatively charged electrons which makes P
the second electron easier to remove.
Si S
Mg
3p Al
3p Na
3s
3s
Two electrons of opposite spin in
phosphorus 1s2 2s2 2p63s23p3 the same orbital
sulphur 1s2 2s2 2p63s23p4
Patterns in the second ionisation energy.
If the graph of second ionisation or each successive element is plotted then a similar pattern to the first
ionisation energy is observed but all the elements will have shifted one to the left.
5000
Na
2nd Ionisation energy
4500
4000
(kJ/mol)
3500
3000 Ar
2500 S
P
2000 Al Cl
1500
Mg Si
1000
10 12 14 16 18 20
Atomic Number
The group 1 elements are now at the peaks of the graph
Lithium would now have the second largest ionisation of all elements as its second electron
would be removed from the first 1s shell closest to the nucleus and has no shielding effects
from inner shells. Li has a bigger second ionisation energy than He as it has more protons.
First Electron affinity Second Electron affinity

The first electron affinity is the enthalpy change that
occurs when 1 mole of gaseous atoms gain 1 mole of The second electron affinity is the enthalpy change
electrons to form 1 mole of gaseous ions with a –1 charge when one mole of gaseous 1- ions gains one electron
per ion to produce gaseous 2- ions.
O (g) + e-  O- (g) [eaH] = -141.1 kJ mol-1]
O – (g) + e-  O2- (g) [eaH = +798 kJ mol-1]
The first electron affinity is exothermic for atoms that
normally form negative ions because the ion is more stable The second electron affinity for oxygen is endothermic
than the atom and there is an attraction between the because it take energy to overcome the repulsive force
nucleus and the electron between the negative ion and the electron
3 Bonding
Definition: An Ionic bond is the electrostatic force of attraction between oppositely charged
ions formed by electron transfer.
Metal atoms lose electrons to form +ve ions.

Non-metal atoms gain electrons to form -ve ions.
Mg goes from 1s2 2s2 2p63s2

to Mg2+ 1s2 2s2 2p6
O goes from 1s2 2s2 2p4 to

O2- 1s2 2s2 2p6
Ionic bonding is stronger and the melting points higher when the ions are smaller and/ or have higher
charges. E.g. MgO has a higher melting point than NaCl as the ions involved (Mg2+ & O2- are smaller and
have higher charges than those in NaCl , Na+ & Cl- )
Covalent Bonding
Definition: covalent bond is the strong electrostatic attraction between a

shared pair of electrons and the nuclei of the bonded atoms
O O Cl Cl
N B
H H x N x
x N
H xx Cl
N N
The term bond energy is used as a measurement of covalent bond strength. It is the energy
needed to break one mole of bonds of (gaseous covalent) bonds into gaseous atoms
The larger the value of the average bond enthalpy, the stronger the covalent bond
Bond length measures the distance between the two nuclei in a covalent bond.
A shorter bond will have a higher bond energy as the there will be a stronger force of attraction
between the nuclei and the shared pair of electrons as they are closer together.
Effect of multiple bonds on bond strength and length.

Nuclei joined by multiple (i.e. double and triple) bonds have a greater electron density between them.
This causes an greater force of attraction between the nuclei and the electrons between them, resulting in a shorter
bond length and greater bond strength.
Dative Covalent bonding .. +
A Dative covalent bond forms when the O
shared pair of electrons in the covalent bond
H H
come from only one of the bonding atoms. A
dative covalent bond is also called co-ordinate H
bonding.
Cl H
Common examples you should be able to
draw that contain dative covalent bond (e.g.
NH4+, H3O+, NH3BF3)
Cl B N H
The ammonium ion NH4+

Cl H
The direction of the arrow

goes from the atom that is
providing the lone pair to the
atom that is deficient
+
H Two aluminium chloride
+ Cl (AlCl3) molecules join
N
x together through two dative
bonds to form the dimer
H
Cl Al x Cl Al2Cl6
H
x Cl
H x Cl
x
Cl Al Cl Cl
Al
Al
Cl
The dative covalent bond acts like
an ordinary covalent bond when
x Cl Cl
thinking about shape so in NH4+ Cl
the shape is tetrahedral
Covalent bonding in terms of orbital overlap
When atomic orbitals overlap they form molecular orbitals. The model can be used to show how single and
double bonds form and can be used to show how why molecules have the shape they do.
sp3
The ground state electronic configuration of a A more excited arrangement can be made if a little energy is
carbon atom is 1s22s22p2 used to promote one of the 2s electrons into the empty p
orbital. The configuration is now 1s22s12p3
2p
2p
2s
2s
1s
1s
Four orbitals (a 2s and three 2p’s) hybridise to give
four new hybrid orbitals – called sp3 .
Four sp3 hybrid orbitals will lead
to a tetrahedral shape in
molecules
Sp2 as in Boron trichloride

boron atom is 1s22s22p1 used to promote one of the 2s electrons into the empty p
2p
2p
2s
2s
1s
1s
Three orbitals (a 2s and two 2p’s) can hybridise to

give thee new hybrid orbitals – called sp2 . Three sp2 hybrid orbitals will
lead to a trigonal planar shape in
molecules
Sp as in BeCl2
berylium atom is 1s22s2 used to promote one of the 2s electrons into the empty p
2p
2p
2s
2s
1s
1s
sp two orbitals (a 2s and one 2p) can hybridise to give

two new hybrid orbitals – called sp . Two sp hybrid orbitals will lead
to a linear shape in molecules
Forming multiple bonds. E.g the C=C bond
The ground state electronic configuration of a

A more excited arrangement can be made if a little energy is
carbon atom is 1s22s22p2
used to promote one of the 2s electrons into the empty p
2p orbital. The configuration is now 1s22s12p3
2s 2p
2s
1s
1s
Three orbitals (a 2s and two 2p’s) can hybridise to

give thee new hybrid orbitals – called sp2 . Leaving
one p orbital unhybridised
Formation of σ bond
C C
two sp2 orbitals (one from each carbon) overlap to sigma σ bond
form a single C-C bond called a sigma σ bond
Rotation can occur around a sigma bond
Formation of π bond p orbitals
The π bond is formed by

sideways overlap of two p
orbitals on each carbon atom
forming a π-bond above and
below the plane of molecule.
The π bond is weaker than the

C-C sigma bond σ bond.
C-C pi bond
Shape of molecules
Name No No lone Diagram Bond angle Examples

bonding pairs
pairs
linear 2 0 Cl 180 CO2, CS2, HCN,
Be Cl BeF2
Trigonal 3 0 120 BF3, AlCl3, SO3,
planar Cl Cl NO3-, CO32-
B
Cl
Tetrahedral 4 0 H 109.5 SiCl4, SO42-, ClO4-,

NH4+
H H
Trigonal 3 1 .. 107 NCl3 ,PF3 ,ClO3

pyramidal ,H3O+
N
H
H
Bent 2 2 .. .. 104.5 OCl2, H2S, OF2 ,

O SCl2
H H
Trigonal 5 0 F 120 and 90 PCl5

Bipyramidal F
P F
F
F
F
Octahedral 6 0 90 SF6
F F
F F
How to explain shape 1. State number of bonding pairs and lone pairs of electrons.
2. State that electron pairs repel and try to get as far apart as possible (or to a
position of minimum repulsion.)
3. If there are no lone pairs state that the electron pairs repel equally
4. If there are lone pairs of electrons, then state that lone pairs repel more than
bonding pairs.
5. State actual shape and bond angle.
Remember lone pairs repel more than bonding pairs and so reduce bond angles (by about 2.5o
per lone pair in above examples)
Occasionally more complex shapes are seen that are variations of octahedral and trigonal
bipyramidal where some of the bonds are replaced with lone pairs. You do not need to learn the
names of these but ought to be able to work out these shapes using the method below
: : X:
:
X X : X : : X
:
:
Square planar Bond angle ~89O Bond angle ~89O Bond angles ~119 + 89O
Bond angle 180O
Bond angle 90O (Reduced by lone pair) (Reduced by lone pairs) (Reduced by lone pair)
e.g XeF4 e.g. BrF5 e.g I3- e.g. ClF3 e.g. SF4 & IF4+
Xe has 8 electrons in its outer Cl has 7 electrons in its outer I has 7 electrons in its outer
shell. 4 F’s add 4 more shell. 3 F’s add 3 more shell. 4 F’s add 4 more
electrons. This makes a total of electrons. This makes a total of electrons. Remove one electron
12 electrons made up of 4 10 electrons made up of 3 bond as positively charged. This
bond pairs and 2 lone pairs. pairs and 2 lone pairs. The makes a total of 10 electrons
The means it is a variation of means it is a variation of the 5 made up of 4 bond pairs and 1
the 6 bond pair shape bond pair shape (trigonal lone pair. The means it is a
(octahedral) bipyramidal) variation of the 5 bond pair
shape (trigonal bipyramidal)
Electronegativity and intermediate bonding
Definition F, O, N and Cl are the most

electronegative atoms
Electronegativity is the relative tendency of an atom in a covalent bond in a
molecule to attract electrons in a covalent bond to itself.
The most electronegative
Electronegativity is measured on the Pauling scale (ranges from 0 to 4) element is fluorine and it is
given a value of 4.0
Factors affecting electronegativity
Electronegativity increases across a period as the number of protons increases and the atomic radius decreases
because the electrons in the same shell are pulled in more.
It decreases down a group because the distance between the nucleus and the outer electrons increases and the
shielding of inner shell electrons increases
Intermediate bonding
Ionic and covalent bonding are the extremes of a continuum of bonding type. Differences in
electronegativity between elements can determine where a compound lies on this scale
A compound containing elements of similar electronegativity and hence a small

electronegativity difference will be purely covalent
A compound containing elements of very different electronegativity and hence a very large
electronegativity difference (> 1.7) will be ionic
Formation of a permanent dipole – (polar covalent) bond The element with the
larger electronegativity
A polar covalent bond forms when the elements in the bond have different in a polar compound
electronegativities . (Of around 0.3 to 1.7) will be the δ- end
δ+ δ–
When a bond is a polar covalent bond it has an unequal distribution of electrons in
H – Cl
the bond and produces a charge separation, (dipole) δ+ δ- ends. This charge
separation is called bond polarity
Polar and Non Polar molecules

Symmetric molecules
A symmetric molecule (all bonds identical and no lone pairs) will not
be polar even if individual bonds within the molecular ARE polar. CO2 is a symmetrical molecule and is a
non-polar molecule
The individual dipoles on the bonds ‘cancel out’ due to the symmetrical
shape of the molecule.
H
There is no NET dipole moment: the molecule is NON POLAR
Cδ+
e.g. CCl4 will be non-polar whereas CH3Cl will be polar
H Clδ-
Intermolecular bonding H
Induced dipole–dipole interactions
Induced dipole–dipole interactions occur between all molecular substances and noble
gases. They do not occur in ionic substances.
Induced dipole–dipole interactions are also called London forces. They occur
between all simple covalent molecules and the separate atoms in noble
gases.
In any molecule the electrons are moving constantly and randomly. As this
happens the electron density can fluctuate and parts of the molecule
become more or less negative i.e. small temporary or transient dipoles form.
These temporary dipoles can cause dipoles to form in neighbouring
molecules. These are called induced dipoles. The induced dipole is always the
opposite sign to the original one.
Main factor affecting size of Induced dipole–dipole interactions

The more electrons there are in the molecule the higher the chance that temporary dipoles will form. This makes the
Induced dipole–dipole interactions stronger between the molecules and so boiling points will be greater.
The increasing boiling points of the halogens down the group 7 series can be explained by the increasing number
of electrons in the bigger molecules causing an increase in the size of the induced dipole–dipole interactions
between the molecules. This is why I2 is a solid whereas Cl2 is a gas.
The increasing boiling points of the alkane homologous series can be explained by the increasing number of
electrons in the bigger molecules causing an increase in the size of the induced dipole–dipole interactions
between molecules.
The shape of the molecule can also have an effect on the size of the induced dipole–dipole interactions forces. Long
chain alkanes have a larger surface area of contact between molecules for induced dipole–dipole interactions to form
than compared to spherical shaped branched alkanes and so have induced dipole–dipole interactions.
Permanent dipole-dipole forces
•Permanent dipole-dipole forces occurs between polar molecules
•It is stronger than van der waals and so the compounds have higher boiling points
•Polar molecules have a permanent dipole. (commonly compounds with C-Cl, C-F, C-Br H-Cl, C=O bonds)
•Polar molecules are asymmetrical and have a bond where there is a significant difference in electronegativity
between the atoms.
Permanent dipole forces

occur in addition to induced
dipole–dipole interactions
Permanent dipole–dipole and induced dipole–dipole

interactions can both be referred to as van der Waals’ forces.
Hydrogen bonding
It occurs in compounds that have a hydrogen atom attached to one of the three most electronegative atoms
of nitrogen, oxygen and fluorine, which must have an available lone pair of electrons. e.g. a –O-H -N-H F- H
bond. There is a large electronegativity difference between the H and the O,N,F
Always show the

lone pair of
electrons on the
O,F,N and the
dipoles and all
the δ- δ+ charges
Hydrogen bonding occurs in addition to van der waals forces
400
Hydrogen bonding is stronger than the other two types
H2O
of intermolecular bonding.
300 HF H2Te
Boiling point K
The anomalously high boiling points of H2O, NH3 H2Se SbH3

and HF are caused by the hydrogen bonding NH3 H2S
HI
between the molecules AsH3
200 HBr
PH3 HCl SnH4
The general increase in boiling point from H2S to GeH4
SiH4
H2Te is caused by increasing induced dipole–dipole
interactions between molecules due to an 100 CH4
increasing number of electrons.
Alcohols, carboxylic acids, proteins, amides all can
form hydrogen bonds 25 50 75 100 125
Molecular mass
Metallic bonding
Definition: A metallic bond is the electrostatic force of attraction between the positive
metal ions and the delocalised electrons
The three main factors that affect the strength of a metallic bond are:
1. Number of protons/ Strength of nuclear attraction.
The more protons the stronger the bond
2. Number of delocalised electrons per atom (the outer shell electrons are delocalised)
The more delocalised electrons the stronger the bond
3. Size of ion.
The smaller the ion, the stronger the bond.
Example
Mg has stronger metallic bonding than Na and hence a higher melting point. The Metallic bonding gets
stronger because in Mg there are more electrons in the outer shell that are released to the sea of
electrons. The Mg ion is also smaller and has one more proton. There is therefore a stronger electrostatic
attraction between the positive metal ions and the delocalised electrons and higher energy is needed
to break bonds.
Chemical reactions and bonds
Chemical reactions involve breaking and making bonds

Breaking bonds absorbs energy – is endothermic
Making bonds gives out energy – is exothermic
Whether a chemical reaction occurs can be dependent on the relative sizes of the
bonds being broken and made.
If reactants have strong bonds they will be harder to break and this leads to a high
activation energy.
In many organic reactions it is the weakest bond in the molecule that breaks.
The bond polarity of the bond can also have an effect. An attacking species might be
attracted to an atom with a dipole of opposite charge
Bonding and Structure
Bonding Structure Examples
Ionic : electrostatic force of Sodium chloride

attraction between oppositely Magnesium oxide
Giant Ionic Lattice
charged ions
Covalent : shared pair of Simple molecular: Iodine

electrons With intermolecular forces (van der Waals, Ice
permanent dipoles, hydrogen bonds) Carbon dioxide
between molecules Water
Methane
Covalent : shared pair of Macromolecular: Diamond
electrons giant molecular structures. Graphite
Silicon dioxide
Silicon
Metallic: electrostatic force of Magnesium, Sodium
attraction between the metal Giant metallic (all metals)
positive ions and the lattice
delocalised electrons
Only use the words molecules and intermolecular forces when talking about simple molecular substances
Property Ionic Molecular (simple) Macromolecular Metallic
boiling and high- because low- because of weak high- because of many high- strong electrostatic forces
melting points of giant lattice intermolecular forces strong covalent bonds between positive ions and sea of
of ions with between molecules in macromolecular delocalised electrons
strong (specify type e.g van structure. Take a lot of
electrostatic der waals/hydrogen energy to break the
forces between bond) many strong bonds
oppositely
charged ions.
Solubility in Generally good generally poor insoluble insoluble

water
conductivity poor: ions can’t poor: no ions to diamond and sand: good: delocalised electrons can
when solid move/ fixed in conduct and electrons poor, because electrons move through structure
lattice are localised (fixed in can’t move (localised)
place) graphite: good as free
delocalised electrons
between layers
conductivity good: ions can poor: no ions poor (good)

when molten move
general crystalline mostly gases and solids shiny metal

description solids liquids Malleable as the positive ions in the
lattice are all identical. So the planes
of ions can slide easily over one
another
-attractive forces in the lattice are
the same whichever ions are
adjacent
4 States of matter
Ideal Gas Equation
The ideal gas equation applies to all gases and mixtures of gases. If a PV = nRT
mixture of gases is used the value n will be the total moles of all gases
in the mixture. Unit of Pressure (P):Pa
Unit of Volume (V): m3
The biggest problems students have with this equation is choosing and Unit of Temp (T): K
converting to the correct units, so pay close attention to the units. n= moles
R = 8.31 JK–1mol–1
An ideal gas has the following properties:
1. An ideal gas is considered to be a "point mass". A point mass is a particle so small that its mass is very nearly zero.
This means an ideal gas particle has almost no volume.
2. There are no attractive or repulsive forces involved during collisions. Also, the kinetic energy of the gas
molecules remains constant since the intermolecular forces are lacking.
These assumptions do not actually hold true for There are also limitations of ideality at very high pressures
many gases. They work best for the Noble gases. and very low temperatures. Under these conditions the
Heavier gases and ones with significant particles will be closer together and the intermolecular
intermolecular forces will deviate from ideal gas forces between the closer particles will cause a deviation
behaviour from ideal behaviour
Example 1: What is the mass of Cl2 gas that has a pressure of Converting temperature
100kPa, temperature 20oC , volume 500cm3. (R = 8.31)
oC  K add 273
moles = PV/RT
100 kPa = 100 000 Pa
= 100 000 x 0.0005 / (8.31 x 293) 20oC = 20+273= 293K
= 0.0205 mol 500 cm3 = 0.0005 m3
Mass = moles x Mr
= 0.0205 x (35.5 x2)
= 1.46 g
Example 2: 0.150g of a volatile liquid was injected into a sealed gas syringe. The gas syringe was placed in an oven at
70oC at a pressure of 100kPa and a volume of 80cm3 was measured. What is the Mr of the volatile liquid ? (R = 8.31)
moles = PV/RT 100 kPa = 100 000 Pa

= 100 000 x 0.00008 / (8.31 x 343) 80 cm3 = 0.00008 m3
= 0.00281 mol
Mr = mass/moles
= 0.15 / 0.00281
= 53.4 g mol-1
Changing the Conditions of a gas
Questions may involve the same amount of gas under different conditions.
Example 3
40 cm3 of oxygen and 60 cm3 of carbon dioxide, each at 298 K and 100 kPa, were placed into an
evacuated flask of volume 0.50 dm3. What is the pressure of the gas mixture in the flask at 298 K?
There are two approaches to solving this

1. Work out moles of gas using ideal gas equation then put back into ideal gas equation
with new conditions
P1V1 = P2V2
2. Or combine the equation n= PV/RT as on right
T1 T2
Can do this as moles of gas do not change
As Temperature is the same can make the above equation P1V1 = P2V2
P2 = P1V1 /V2
= 100000 x 1x 10-4 / 5x10-4
= 20 000Pa
Reacting Volumes of Gas
Equal volumes of any gases measured under the same 1 mole of any gas at room
conditions of temperature and pressure contain equal pressure (1atm) and room
numbers of molecules (or atoms if the gas in monatomic) temperature 25oC will have the
volume of 24dm3
Volumes of gases reacting in a balanced equation
can be calculated by simple ratio
Example 4 If one burnt 500 cm3 of methane at 1atm and 300K what volume of
Oxygen would be needed and what volume of CO2 would be given off under the
same conditions?
CH4(g) + 2 O2(g)  CO2(g) + 2 H2O(l)
1 mole 2 mole 1 mole
500cm3 1dm3 500cm3
Simply multiply
gas volume x2
Example 5 An important reaction which occurs in the catalytic converter of a car is

2CO(g) + 2NO(g)  2CO2(g) + N2(g)
In this reaction, when 500 cm3 of CO reacts with 500 cm3 of NO at 650 °C and at 1 atm.
Calculate the total volume of gases produced at the same temperature and pressure ?
2CO(g) + 2NO(g)  2CO2(g) + N2(g) total volume of gases produced = 750cm3

500cm3 500cm3 500cm3 250cm3
Using a gas syringe
Gas syringes can be used for a variety of experiments where the volume of a gas is measured, possibly to work out
moles of gas or to follow reaction rates.
The volume of a gas depends on pressure and Make sure you don’t leave gaps in
temperature so when recording volume it is your diagram where gas could
important to note down the temperature and escape
pressure of the room.
Moles of gas can be calculated from gas

volume (and temperature and pressure)
using ideal gas equation PV = nRT
If drawing a gas syringe make sure

Potential errors in using a gas syringe
you draw it with some
•gas escapes before bung inserted
measurement markings on the
•syringe sticks
barrel to show measurements can
• some gases like carbon dioxide or sulphur dioxide are
be made.
soluble in water so the true amount of gas is not
measured.
The liquid state
Evaporation: In a liquid some of the particles near the

Liquid particles are randomly surface of the liquid may gain enough energy to leave
arranged the liquid as gas particles. This is vaporisation.
Liquids particles are closely spaced If the liquid is in a sealed container the gas particles
but still in constant motion, and produced through vaporisation will exert a pressure on
therefore are constantly colliding the container. This is called the vapour pressure. If the
liquid/gas is allowed to reach an equilibrium then the
pressure exerted by the vapour can be called the
Melting. If a solid is heated by supplying energy through saturated vapour pressure
heating, the energy will cause larger vibrations. Eventually
the particles will have enough energy to break away from
the solid arrangement to become a liquid.
The solid state: lattice structures
Types of crystal structure: ionic, metallic, molecular and giant covalent (macromolecular).
You should be able to draw the following diagrams or describe the structure in words to show the
four different types of crystal. You should also be able to explain the properties of these solids. The
tables in the bonding revision guide explain these properties.
Ionic: sodium chloride

The ions in an ionic solid are arranged in a regular 3D pattern called a giant
ionic lattice
The sticks in this diagram are there to help show the arrangements of
the ions. They do not represent the ionic bonds.
Ionic bonding is between ions and all their surrounding oppositely

charged ions. Each sodium ion in this structure is surrounded and
Giant Ionic lattice showing alternate
equally attracted by six chloride ions. The ionic bond is the attraction
Na+ and Cl- ions
between all these ions
Typical Physical properties of Ionic Compounds
•High melting points - There are strong electrostatic attractive forces between the oppositely charged ions
in the lattice
•Non conductor of electricity when solid- The ions are held together tightly in the lattice and can not move
so no charge is conducted
•Good conductor of electricity when in solution or molten – The ions are free to move when in solution and
molten. Charge can be carried
• They are usually soluble in aqueous solvents.
Molecular: Iodine Molecular : Carbon Fullerenes

Nanotubes and C60
Nanotubes and C60 are classed

molecular as they have fixed
formula.
Nanotubes have very high

tensile strength because of the
strong structure of many
The crystals contain a regular arrangement of strong covalent bonds
I2 molecules held together by weak induced
dipole–dipole interactions intermolecular Nanotubes can conduct electricity well along the tube because
forces one electron per carbon is free and delocalised, so electrons
can move easily along the tube.
There are covalent bonds between the
Iodine atoms in the I2 molecule
There are delocalized electrons in C60
Giant molecular Macromolecular: Graphite

Macromolecular: diamond Planar arrangement of carbon atoms
in layers. 3 covalent bonds per atom
Tetrahedral arrangement of
in each layer. 4th outer electron per
carbon atoms. 4 covalent bonds
atom is delocalised. Delocalised
per atom
electrons between layers.
Diamond cannot conduct electricity because all 4

electrons per carbon atom are involved in Graphite can conduct electricity well between layers because
covalent bonds. They are localised and cannot one electron per carbon is free and delocalised, so electrons
move can move easily along layers.
It does not conduct electricity between layers because the
energy gap between layers is too large for easy electron
transfer.
All these macromolecular structures

Macromolecular: silicon dioxide have very high melting points
Tetrahedral arrangement. Each carbon because of strong covalent forces in
atom forms 4 covalent bonds to an the giant structure. It takes a lot of
oxygen. Each oxygen forms two covalent energy to break the many strong
bonds to carbons covalent bonds
Graphene
Graphene is a new substance that is a one layer of graphite .i.e. 3 covalent bonds per atom and the 4th outer electron
per atom is delocalised.
These have very high tensile strength because of the strong structure of many strong covalent bonds
Graphene can conduct electricity well along the structure because one electron per carbon is free and delocalised, so
electrons can move easily along the structure.
4
Molecular: Ice This is a difficult diagram
to draw.
H H The main point to show is
O a central water molecule
with two ordinary covalent
bonds and two hydrogen
H bonds in a tetrahedral
H arrangement
O O
H
H H The molecules are held
HO O further apart than in liquid
H H water and this explains the
lower density of ice
Metallic: magnesium or copper

Metals can conduct electricity well because the delocalised electrons
Use this
can move through the structure
diagram
for any
metal Metals are malleable because the positive ions in the lattice are all
identical. So the planes of ions can slide easily over one another. The
Giant metallic lattice showing close attractive forces in the lattice are the same whichever ions are
packing magnesium ions adjacent
Hydrogen bonding
δ- Alcohols form hydrogen bonds. This means alcohols have higher

δ+ boiling points and relatively low volatility compared to alkanes with
O H a similar number of electrons
Hδ
+
δ+
H
δ-
O
H δ+ δ+
δ+ H H
O
δ- The strength of hydrogen bonding can also lead to higher

Water can form two hydrogen bonds per viscosity and surface tension in substances that have hydrogen
molecule, because the electronegative bonding.
oxygen atom has two lone pairs of Propane-1,2,3-triol has 3 –OH groups per molecule and
electrons on it. therefore can form multiple hydrogen bonds per molecule. It is
It can therefore form stronger hydrogen a very viscous liquid.
bonding and needs more energy to break
the bonds, leading to a higher boiling
point.
5 Chemical Energetics
Definition: Enthalpy change is the amount of heat energy taken in or given out during
any change in a system provided the pressure is constant.
If an enthalpy change occurs then energy is transferred

In an exothermic change energy is transferred from the between system and surroundings. The system is the
system (chemicals) to the surroundings. chemicals and the surroundings is everything outside the
chemicals.
The products have less energy than the reactants.
In an endothermic change, energy is transferred from
the surroundings to the system (chemicals). They
require an input of heat energy e.g. thermal
Energy
Activation decomposition of calcium carbonate

Energy: EA The products have more energy than the reactants.
reactants Activation
Energy: EA
∆H
Energy
products
Progress of Reaction reactants ∆H
In an exothermic reaction the

∆H is negative In an endothermic reaction the
∆H is positive
Common oxidation exothermic processes are the
combustion of fuels and the oxidation of carbohydrates
Progress of Reaction
such as glucose in respiration.
Definition: Enthalpy change of reaction rH is the enthalpy change when the number
of moles of reactants as specified in the balanced equation react together
Standard Enthalpy Change of Formation

The standard enthalpy change of formation of a compound is the enthalpy Mg (s) + Cl2 (g)  MgCl2 (s)
change when 1 mole of the compound is formed from its elements under 2Fe (s) + 1.5 O2 (g)  Fe2O3 (s)
standard conditions (298K and 100kpa), all reactants and products being
in their standard states. The enthalpy of formation of
Symbol fH an element = 0 kJ mol-1
Standard Enthalpy Change of Combustion

The standard enthalpy of combustion of a substance is defined as the CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (l)
enthalpy change that occurs when one mole of a substance is combusted
completely in oxygen under standard conditions. (298K and 100kPa), all Incomplete combustion will lead to
reactants and products being in their standard states. soot (carbon), carbon monoxide and
Symbol cH water. It will be less exothermic than
complete combustion.
Enthalpy changes are normally quoted at standard conditions. When an enthalpy change is
Standard conditions are: measured at standard conditions
• 100 kPa pressure the symbol is used
• 298 K (room temperature or 25oC) Eg H
• Solutions at 1mol dm-3
• all substances should have their normal state at 298K
1
Definitions of enthalpy changes
Enthalpy of atomisation The enthalpy change for a solid metal turning to

The enthalpy of atomisation of an element is the enthalpy gaseous atoms can also be called the Enthalpy of
change when 1 mole of gaseous atoms is formed from sublimation and will numerically be the same as
the element in its standard state the enthalpy of atomisation
Na (s)  Na(g) [atH = +148 kJ mol-1] Na (s)  Na(g) [subH = +148 kJ mol-1]
½ O2 (g)  O (g) [atH = +249 kJ mol-1]
Bond dissociation enthalpy (bond energy) For diatomic molecules the dissH of the
The bond dissociation enthalpy is the standard molar enthalpy molcule is the same as 2x atH of the element
change when one mole of a covalent bond is broken
Cl2 (g)  2Cl (g) Hdiss = +242 kJ mol-1
into two gaseous atoms (or free radicals)
Cl2 (g)  2Cl (g) dissH = +242 kJ mol-1 ½ Cl2 (g)  Cl (g) atH = +121 kJ mol-1
Or
CH4 (g)  CH3 (g) + H(g) dissH = +435 kJ mol-1
First Ionisation enthalpy Second Ionisation enthalpy

The first ionisation enthalpy is the enthalpy change The second ionisation enthalpy is the enthalpy change to
required to remove 1 mole of electrons from 1 mole of remove 1 mole of electrons from one mole of gaseous 1+
gaseous atoms to form 1 mole of gaseous ions with a +1 ions to produces one mole of gaseous 2+ ions.
charge Mg+ (g)  Mg 2+ (g) + e- [ IE 2H]
Mg (g)  Mg+ (g) + e- [ IE 1H]
First Electron affinity second electron affinity

The first electron affinity is the enthalpy change that
occurs when 1 mole of gaseous atoms gain 1 mole of The second electron affinity is the enthalpy change
electrons to form 1 mole of gaseous ions with a –1 charge when one mole of gaseous 1- ions gains one electron
per ion to produce gaseous 2- ions.
O (g) + e-  O- (g) [eaH] = -141.1 kJ mol-1]
O – (g) + e-  O2- (g) [eaH = +798 kJ mol-1]
The first electron affinity is exothermic for atoms that
normally form negative ions because the ion is more stable The second electron affinity for oxygen is endothermic
than the atom and there is an attraction between the because it take energy to overcome the repulsive force
nucleus and the electron between the negative ion and the electron
Enthalpy of lattice formation

The Enthalpy of lattice formation is the standard enthalpy
change when 1 mole of an ionic crystal lattice is formed
from its constituent ions in gaseous form.
Na+ (g) + Cl- (g)  NaCl (s) [H Latt = -787 kJ mol-1]
Enthalpy change of Neutralisation

The standard enthalpy change of neutralisation is the enthalpy change when solutions of an acid and
an alkali react together under standard conditions to produce 1 mole of water.
Enthalpy of Hydration Hhyd Enthalpy of solution

Enthalpy change when one mole of gaseous ions become The enthalpy of solution is the standard enthalpy
aqueous ions . change when one mole of an ionic solid dissolves in a
X+ (g) + aq  X+ (aq) For Li+ hydH = -519 kJ mol-1 large enough amount of water to ensure that the
or dissolved ions are well separated and do not interact
X- (g) + aq  X- (aq) For F- hydH= -506 kJ mol-1 with one another
This always gives out energy (exothermic, -ve) because NaCl (s) + aq  Na+ (aq) + Cl-(aq)
bonds are made between the ions and the water
molecules
Measuring the Enthalpy Change for a Reaction Experimentally
Calorimetric method This equation will only give the
energy for the actual quantities
used. Normally this value is
For a reaction in solution we use the following equation converted into the energy change
energy change = mass of solution x heat capacity x temperature change per mole of one of the reactants.
Q (J) = m (g) x cp (J g-1K-1) x T ( K) (The enthalpy change of reaction,
Hr)
Calorimetric method Practical
One type of experiment is one in which substances are This could be a solid dissolving or reacting
mixed in an insulated container and the temperature rise in a solution or it could be two solutions
measured. reacting together
General method
 washes the equipment (cup and pipettes etc) with the solutions to be used
 dry the cup after washing
 put polystyrene cup in a beaker for insulation and support
 Measure out desired volumes of solutions with volumetric pipettes and transfer to
insulated cup
 clamp thermometer into place making sure the thermometer bulb is immersed in solution
 measure the initial temperatures of the solution or both solutions if 2 are used. Do this
every minute for 2-3 minutes
 At minute 3 transfer second reagent to cup. If a solid reagent is used then add the
solution to the cup first and then add the solid weighed out on a balance.
 If using a solid reagent then use ‘before and after’ weighing method
 stirs mixture (ensures that all of the solution is at the same temperature)
 Record temperature every minute after addition for several minutes
If the reaction is slow then the exact temperature rise can be

difficult to obtain as cooling occurs simultaneously with the
reaction
To counteract this we take readings at regular time intervals

and extrapolate the temperature curve/line back to the time
the reactants were added together.
We also take the temperature of the reactants for a few

minutes before they are added together to get a better
average temperature. If the two reactants are solutions then
the temperature of both solutions need to be measured
before addition and an average temperature is used.
Errors in this method Read question

carefully. It may be
• energy transfer from surroundings (usually loss) necessary to describe:
• approximation in specific heat capacity of solution. The method assumes all • Method
solutions have the heat capacity of water. • Drawing of graph
• neglecting the specific heat capacity of the calorimeter- we ignore any with extrapolation
energy absorbed by the apparatus. • Description of the
• reaction or dissolving may be incomplete or slow. calculation
• density of solution is taken to be the same as water.
Calculating the enthalpy change of reaction, Hr from experimental data
The heat capacity of water is
General method 4.18 J g-1K-1. In any reaction
where the reactants are
1. Using q= m x cp x T calculate energy change for quantities used dissolved in water we assume
that the heat capacity is the
2. Work out the moles of the reactants used same as pure water.
3. Divide q by the number of moles of the reactant not in excess to give H Also assume that the solutions
have the density of water,
4. Add a sign and unit (divide by a thousand to convert Jmol-1 to kJmol-1
which is 1g cm-3. Eg 25cm3 will
weigh 25 g
Example 1. Calculate the enthalpy change of reaction for the reaction where 25.0cm3 of 0.200 M copper
sulfate was reacted with 0.01mol (excess of zinc). The temperature increased 7oC .
Step 1: Calculate the energy change for the amount of reactants in the calorimeter.
Q = m x cp x T Note the mass is the mass of the copper sulfate
Q = 25 x 4.18 x 7 solution only. Do not include mass of zinc powder.
Q = 731.5 J
Step 2 : calculate the number of moles of the reactant not in excess.
moles of CuSO4 = conc x vol If you are not told what is in excess, then you need to
= 0.2 x 25/1000 work out the moles of both reactants and work out
= 0.005 mol using the balanced equation which one is in excess.
Step 3 : calculate the enthalpy change per mole

H = Q/ no of moles
= 731.5/0.005
= 146300 J mol-1
Remember in these
= 146 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, 3 sig figs.
the reaction is exothermic and is given a minus sign e.g. –146 kJ mol-1
Example 2. 25.0cm3 of 2M HCl was neutralised by 25.0cm3 of 2M NaOH. The temperature increased 13.5oC
Calculate the enthalpy change per mole of HCl?
Step 1: Calculate the energy change for the amount of reactants in the calorimeter.
Q = m x cp x T Note the mass equals the mass of acid + the
Q = 50 x 4.18 x13.5 mass of alkali, as they are both solutions.
Q = 2821.5 J
Step 2 : calculate the number of moles of the HCl.
moles of HCl = conc x vol

= 2 x 25/1000
= 0. 05 mol
Step 3 : calculate H the enthalpy change per mole which can be called the enthalpy change of neutralisation
= 2821.5/0.05
= 56430 J mol-1
Remember in these
Exothermic and so is given a minus sign questions: sign,
= -56.4 kJ mol-1 to 3 sf
unit, 3 sig figs.
4
Measuring Enthalpies of Combustion using Calorimetry
Enthalpies of combustion can be calculated by using calorimetry. Generally the fuel is burnt and the flame
is used to heat up water in a metal cup.
Example 3. Calculate the enthalpy change of combustion for the reaction where 0.65g of propan-1-ol was
completely combusted and used to heat up 150g of water from 20.1 to 45.5oC
Step 1: Calculate the energy change used to heat up the water.
Q = m x cp x T
Note the mass is the mass of water in the
Q = 150 x 4.18 x 25.4 calorimeter and not the alcohol
Q = 15925.8 J
Step 2 : calculate the number of moles of alcohol combusted.
moles of propan-1-ol = mass/ Mr

= 0.65 / 60
= 0.01083 mol
Step 3 : calculate the enthalpy change per mole which is called cH (the enthalpy change of combustion)
= 15925.8/0.01083
= 1470073 J mol-1
Remember in these
= 1470 kJ mol-1 to 3 sf
questions: sign,
Finally add in the sign to represent the energy change: if temp increases unit, 3 sig figs.
the reaction is exothermic and is given a minus sign eg –1470 kJ mol-1
Errors in this method
• Energy losses from calorimeter

• Incomplete combustion of fuel
• Incomplete transfer of energy
• Evaporation of fuel after weighing
• Heat capacity of calorimeter not included
• Measurements not carried out under standard conditions as
H2O is gas, not liquid, in this experiment
Hess’s Law
Hess’s law is a version of the first
Hess’s law states that total enthalpy change for a reaction is
law of thermodynamics, which is
independent of the route by which the chemical change takes place
that energy is always conserved.
2H (g) + 2Cl(g)
On an energy level diagram the directions of the arrows can
show the different routes a reaction can proceed by.
a
In this example one route is arrow ‘a’
H2 + Cl2 b The second route is shown by arrows ΔH plus arrow ‘b’
ΔH So a = ΔH + b
2HCl (g) And rearranged
ΔH = a - b
ΔH
H+ (g) + Br - (g) H+ (aq) + Br - (aq) Interconnecting reactions can also be
shown diagrammatically.
a
d
In this example one route is arrow ‘a’ plus ΔH
The second route is shown by arrows ‘c’ plus arrow ‘d’
H (g) + Br (g) HBr (g)
c So a+ ΔH = c + d
And rearranged
ΔH = c + d - a
Often Hess’s law cycles are used to measure the enthalpy change for a reaction that cannot be measured
directly by experiments. Instead alternative reactions are carried out that can be measured experimentally.
H reaction This Hess’s law is used to work out the

CuSO4 (s) + 5H2O (l) CuSO4.5H2O (s) enthalpy change to form a hydrated salt
from an anhydrous salt.
-66.1 kJmol-1 + aq + aq +11kJmol-1

This cannot be done experimentally
because it is impossible to add the
CuSO4 (aq) exact amount of water and it is not easy
to measure the temperature change of
a solid.
H reaction + 11kJmol-1 = -66.1 kJmol-1
H reaction = -66.1 - 11
Instead both salts are dissolved in excess
water to form a solution of copper sulfate.
= -77.1 kJmol-1 The temperature changes can be measured
for these reactions.
6
Using Hess’s law to determine enthalpy changes from enthalpy changes of formation.
H reaction
Reactants Products
H reaction = Σ fH products - Σ fH reactants
Σ fH reactants Σ fH products
Elements in standard states
Example 4. Calculate the enthalpy change for this reaction

Al2O3 + 3 Mg  3 MgO + 2 Al H reaction
Remember Al2O3 (s) + 3 Mg (s) 3 MgO (s) + 2 Al (s)
H = ΣfH products – Σ fH reactants elements have
f H = 0 fH(Al2O3) 3 x fH (MgO)
H = 3 x fH (MgO) – fH (Al2O3)
H = (3 x –601.7) – –1675.7 fH(MgO)= -601.7 kJ mol-1 2Al (s) + 3 Mg (s) + 1.5O2 (g)
= -129.4 kJ mol-1 fH(Al2O3) = -1675.7 kJ mol-1
Example 5. Use the following data to calculate the enthalpy of combustion of propene
fH C3H6(g) = +20 kJ mol-1 fH CO2(g)= –394 kJ mol-1 fH H2O(g)= –242 kJ mol-1
C3H6 + 4.5 O2  3CO2 + 3H2O
 cH
C3H6 (g) + 4.5 O2 (g) 3 CO2 (g) + 3 H2O (g)
cH = Σ fH products – Σ fH reactants
cH = [3 x fH (CO2) + 3 x fH (H2O)] - fH (C3H6) 3 x fH (CO2)
fH(C3H6) 3 x fH (H2O)
cH = [(3 x –394) + (3 x –242)] – 20
= -1928 kJ mol-1 3C (s) + 3 H2 (g) + 4.5 O2 (g)
Using Hess’s law to determine enthalpy changes from enthalpy changes of combustion.
H reaction
Reactants Products
H reaction = Σ cH reactants - Σ cH products Σ cH reactants

+O2 +O2
Σ cH products
Combustion Products
Example 6. Use the following combustion data to calculate the enthalpy of reaction
CO (g) + 2H2 (g)  CH3OH (g)
cH CO(g) = -283 kJ mol-1 cH H2 (g)= –286 kJ mol-1 cH CH3OH(g)= –671 kJ mol-1
H reaction
H reaction = Σ cH reactants - Σ cH products CO (g) + 2H2(g) CH3OH(g)
H = cH (CO) + 2 x cH (H2) - cH (CH3OH) +O2 +O2
cH(CO) + cH(CH3OH)
H = -283+ 2x –286 - -671 2x cH (H2)
CO2 (g) + 2 H2O (l)
= -184 kJ mol-1
Example 7. Use the following combustion data to calculate the enthalpy of formation of propene
3C (s) + 3H2 (g)  C3H6 (g)
cH C (s) = -393kJ mol-1 cH H2 (g)= –286 kJ mol-1 cH C3H6(g)= –-2058 kJ mol-1
f H
H = Σ cH reactants - Σ cH products
3C (s) + 3H2 (g) C3H6 (g)
fH = 3 x cH (C) + 3 x cH (H2 ) - cH (C3H6)
3 x cH (C) + cH(C3H6)
fH = 3x -393+ 3x –286 - -2058 3 x cH (H2 )
= +21 kJ mol-1
3 CO2 (g) + 3 H2O (l)
Mean Bond energies

Definition: The mean bond energy is the enthalpy needed to break These values are positive because energy
the covalent bond into gaseous atoms, averaged over different is required to break a bond.
molecules
The definition only applies when the
We use values of mean bond energies because every single bond in a compound substances start and end in the gaseous
has a slightly different bond energy. E.g. In CH4 there are 4 C-H bonds. Breaking
state.
each one will require a different amount of energy. However, we use an average
value for the C-H bond for all hydrocarbons.
Gaseous atoms
Gaseous atoms
Energy
Energy
Energy
Activation In an exothermic reaction Energy
Energy
breaking
breaking Activation making
bonds Energy Energy the sum of the bonds in the Energy
bonds products bonds
reactants making
bonds
reactant molecules will be
H less than the sum of the H
products bonds in the product reactants
molecules.
Progress of reaction
Progress of reaction
Reaction profile for an Reaction profile for an
EXOTHERMIC reaction ENDOTHERMIC reaction
In general (if all substances are gases)

H =  bond energies broken -  bond energies made
H reaction
Reactants Products
Σbond energies Σbond energies made

broken in reactants in products
Gaseous atoms of
elements
H values calculated using this method will be less accuate than

using formation or combustion data because the mean bond
energies are not exact
Example 8. Use the following mean bond enthalpy data to calculate the Bond Mean enthalpy
enthalpy of combustion of propene
(kJ mol-1)
H H O C=C 612
H C C C + 4.5 O O 3 O C O + 3
H H C-C 348
H H H
H =  bond energies broken -  bond energies made O=O 496
= [E(C=C) + E(C-C) + 6 x E(C-H) + 4.5 x E(O=O)] – [ 6 xE(C=O) + 6 E(O-H)] O=C 743
= [ 612 + 348 + (6 x 412) + (4.5 x 496) ] – [ (6 x 743) + (6 X 463)] O-H 463
= - 1572 kJmol-1 C-H 412
Example 9. Use the following mean bond enthalpy data to calculate the enthalpy of formation of NH3
½ N2 + 1.5 H2  NH3 (note the balancing is to agree with the definition of heat of formation (i.e. one mole of product)
E(N≡N) = 944 kJ mol-1 E(H-H) = 436 kJ mol-1 E(N-H) = 388 kJ mol-1
H =  bond energies broken -  bond energies made
= [0.5 x E(N≡N) + 1.5 x E(H-H)] – [ 3 xE(N-H)]
= [ (0.5 x 944) + (1.5 x 436) ] – [ 3 x 388)]

= - 38 kJmol-1
A more complicated example that may occur at A - Level

This is a more complicated example
Working out ΔfH of a compound using bond energies and other data of the type in example 9
elements fH
Compound in
standard state
The H’s can be
combinations of
H to turn elements H to turn
compound into different data
into gaseous atoms
gaseous atoms
Gaseous atoms
Can be bond energies

E(Cl-Cl) Cl2  2Cl  bond energies of compound
Or atomisation energies ΔatH (if the + (H to turn to gas if
substance is not diatomic compound is not gaseous)
C(s)  C(g)
Example 10
Calculate ΔfH for propane, C3H8(g), given the following data. Bond C–C C–H H–H
C(s)  C(g) ΔatH = 715 kJ mol-1
kJ mol-1 348 412 436
3C (s) + 4H2 (g)  C3H8(g),
Σ H to turn elements into - Σ H to turn compound

 fH =
gaseous atoms into gaseous atoms
fH = (3xatH [C] + 4 x E[H-H] ) – (2 x E[C-C]+ 8 x E[C-H] )

= (3x715 + 4 x 436 ) – (2 x 348+ 8 x 412 )
=-103 kJ mol-1
Enthalpies of Combustion in a Homologous Series
When comparing the enthalpies of combustion for successive members of a homologous series such as
alkanes or alcohols there is a constant rise in the size of the enthalpies of combustion as the number of
carbon atoms increases.
H H O 1 C-C, 5C-H 1C-O 1O-H and 3 O=O

H C C O H + 3 O O 2 O C O + 3
H H
bonds are broken
H H 4 C=O and 6 O-H bonds are made
ethanol ΔHc = -1365 kJ mol-1
H H H 2C-C, 7C-H 1C-O 1O-H and 4.5 O=O

O bonds are broken
H C C C O H + 4.5 O O 3 O C O + 4
H H 6 C=O and 8 O-H bonds are made
H H H
ΔHc = -2016 kJ mol-1
Propan-1-ol
H H H H
3C-C, 9C-H 1C-O 1O-H and 6 O=O
H C C C C O H + 6 O
4 bonds are broken
O O O C O+ 5 H H
H H H H
8 C=O and 10 O-H bonds are made
Butan-1-ol
ΔHc = -2677 kJ mol-1
As one goes up the homologous series there is a constant amount and type of extra bonds being broken and
made e.g. 1C-C, 2C-H and 1.5 O=O extra bonds broken and 2 C=O and 2 O-H extra bonds made, so the
enthalpy of combustion increases by a constant amount.
calculated If the results are worked out experimentally

using a calorimeter the experimental results
mol-1
combustion kJ
Enthalpy of
will be much lower than the calculated ones

because there will be significant heat loss.
There will also be incomplete combustion
experimental which will lead to less energy being
released.
Mr of alcohol
Remember that calculated values of enthalpy of combustions will

be more accurate if calculated from enthalpy of formation data than
if calculated from average bond enthalpies. This is because
average bond enthalpy values are averaged values of the bond
enthalpies from various compounds.
Born Haber cycles
The lattice enthalpy cannot be determined directly. We calculate it indirectly by making use of changes
for which data are available and link them together in an enthalpy cycle the Born Haber cycle
Born Haber cycle: sodium Chloride

Pay attention to state
Na+ (g) + e- Cl (g) symbols and direction of
+
arrows.
EaH (Cl)
atH (Cl)
Na+ (g) + Cl- (g) Usually all pieces of data are given
Na+(g) + e- + ½ Cl2(g) except the one that needs to be
calculated
IE 1H(Na)
 LE H (NaCl)
Na (g) + ½ Cl2(g)
atH (Na)
Na (s) + ½ Cl2(g)
fH (NaCl)
NaCl (s)
By applying Hess’s law the heat of formation equals to the sum of everything else
fH =atH (Na) + IEH(Na)+ atH(Cl) + EaH(Cl) + LEH
Rearrange to give LEH = fH - (atH (Na) + IEH(Na)+ atH (Cl) EaH(Cl) )
LEH =-411 – (+107 + 496 + 122 + -349) = -787 kJmol-1
Born Haber cycle: magnesium Chloride

The data for the at H (Cl) could
Mg2+ (g) + 2e- + 2Cl (g) also be given as the bond energy
for E(Cl-Cl ) bond.
2 xEaH(Cl)
2x atH (Cl) Remember :
Mg2+ (g) + 2Cl- (g)
Mg2+ (g) + 2e- + Cl2(g) E(Cl-Cl ) = 2 x at H (Cl)
IE 2H (Mg)
Note in this example the first and
second ionisation energies of
Mg+ (g) + e- + Cl2(g)
magnesium are needed as Mg is
IE 1H(Mg) a +2 ion
LEH
Mg (g) + Cl2(g)
atH (Mg)
Mg (s) + Cl2(g)
fH (MgCl2)
MgCl2 (s)
Born Haber cycle: calcium oxide
Ca2+ (g) + O2- (g)
Ca2+ (g) + 2e- + O (g)
Ea1H(O) Notice the second electron affinity
Ea1H (O) for oxygen is endothermic
atH(O) because it take energy to
Ca2+ (g) + e- + O- (g)
Ca2+ (g) + 2e- + ½ O2(g) overcome the repulsive force
between the negative ion and
IE2H (Ca) the electron
Ca + (g) + e- + ½ O2(g))
IE1H(Ca)
Ca (g) + ½ O2(g)
LEH
atH(Ca)
Ca (s) + ½ O2(g)
fH (CaO)
CaO (s)
Trends in Lattice Enthalpies

The lattice enthalpies become
The strength of a enthalpy of lattice formation depends on the following less negative down any group.
factors e.g. LiCl, NaCl, KCl, RbCl
1. The sizes of the ions:
e.g group 1 halides (eg NaF KI) have
The larger the ions, the less negative the enthalpies of lattice formation lattice enthalpies of around –700 to -1000
(i.e. a weaker lattice). As the ions are larger the charges become further
apart and so have a weaker attractive force between them. group 2 halides (eg MgCl2) have lattice
enthalpies of around –2000 to –3500
2. The charges on the ion:
The bigger the charge of the ion, the greater the attraction between the group 2 oxides eg MgO have lattice
ions so the stronger the lattice enthalpy (more negative values). enthalpies of around –3000 to –4500
kJmol-1
Perfect Ionic Model There is a tendency towards covalent

character in ionic substances when
Theoretical lattice enthalpies assumes a perfect ionic model where the ions •the positive ion is small
are 100% ionic and spherical and the attractions are purely electrostatic. •the positive ion has multiple charges
•the negative ion is large
•the negative ion has multiple negative
Differences between theoretical and Born Haber (experimental) lattice charges.
enthalpies
When a compound has some covalent
The Born Haber lattice enthalpy is the real experimental value. character- it tends towards giant covalent
When a compound shows covalent character, the theoretical and the born so the lattice is stronger than if it was
Haber lattice enthalpies differ. The more the covalent character the bigger 100% ionic. Therefore the born haber
the difference between the values. value would be larger than the theoretical
value.
When the negative ion becomes distorted and more covalent we say it becomes polarised. The metal
cation that causes the polarisation is called more polarising if it polarises the negative ion.
100% ionic Ionic with covalent

character + -
When 100 % ionic the ions are spherical. The charge cloud is distorted .The theoretical and
The theoretical and the born Haber lattice the experimental Born Haber lattice enthalpies
enthalpies will be the same will differ 12
Why does Calcium chloride have the formula CaCl2 and not CaCl or CaCl3?
It is useful to draw out the born haber cycles for each potential case. Theoretical lattice enthalpies have
been calculated for each case
We need to calculate an enthalpy of formation for each case.
The one with the most exothermic enthalpy of formation will be the one that Theoretical lattice enthalpies
forms as it will be the most thermodynamically stable Hlatt CaCl = -719 kJ mol-1
Hlatt CaCl2 = -2218 kJ mol-1
Hlatt CaCl3 = -4650 kJ mol-1
Born Haber Cycle for CaCl
Ca+ (g) + e- + Cl (g) These get larger as the
positive charge on the
HEa(Cl)
atH (Cl) calcium ion becomes bigger.
Ca+ (g) + e- + ½ Cl2(g)
Ca+ (g) + Cl- (g)
HIE 1(Ca) The enthalpy of formation
is largely a balance of the
Ca (g) + ½ Cl2(g) LEH ionisation energy and
atH (Ca) lattice enthalpy.
Ca (s) + ½ Cl2(g)
fH (CaCl) = -163.1 kJmol-1 Hf (CaCl) is -163.1 kJ mol-1.
CaCl (s) This is exothermic.
Born Haber Cycle for CaCl2
Ca2+ (g) + 2e- + 2Cl (g)
2 xatH (Cl)
2 xHEa(Cl)
Ca2+ (g) + 2e- + Cl2(g)
HIE 2(Ca) Ca2+ (g) + 2Cl- (g)
The increased ionisation
Ca+ (g) + e- + Cl2(g) enthalpy to form Ca2+ is
more than compensated for
HIE 1(Ca) LEH by the stronger lattice
enthalpy of formation
Ca (g) + Cl2(g)
The enthalpy of formation is
atH (Ca) therefore more exothermic.
Ca (s) + Cl2(g) This is the most stable form
fH (CaCl2) = -739.2 kJmol-1
CaCl2 (s)
Born Haber Cycle for CaCl3
Ca3+ (g) + 3e- + 3Cl (g)
3 xatH (Cl)
Ca3+ (g) + 3e- + 1.5 Cl2(g) 3 xHEa(Cl)
The big increase in ionisation
Ca3+ (g) + 3Cl- (g) enthalpy to remove the 3rd
electron is not compensated
for by the stronger lattice
HIE 3(Ca) enthalpy of formation
Ca2+ (g) + 2e- + 1.5 Cl2(g)
The enthalpy of formation is
HIE 2(Ca) LEH therefore endothermic. This is
Ca+ (g) + e- + 1.5Cl2(g) the least stable form
HIE 1(Ca)
Ca (g) +1.5 Cl2(g)
CaCl3 (s)
atH (Ca)
Ca (s) + 1.5 Cl2(g) fH (CaCl3) = +1541.7 kJmol-1 13
Free-energy change (G) and entropy change (S)
A SPONTANEOUS PROCESS (e.g. diffusion) will proceed on its

own without any external influence.
Activation
Energy:
Energy
A problem with ∆H EA
reactants
A reaction that is exothermic will result in products that
are more thermodynamically stable than the reactants.
This is a driving force behind many reactions and causes ∆H
them to be spontaneous (occur without any external products
influence).
Some spontaneous reactions, however, are endothermic. Progress of Reaction

How can this be explained?
We need to consider something called entropy
Entropy is a description of the number of
Entropy, S˚
ways atoms can share quanta of energy.
If number of ways of arranging the energy
Substances with more ways of arranging their atoms and (W) is high, then system is disordered
energy (more disordered) have a higher entropy. and entropy (S) is high.
Elements Compounds
Entropy
…tend to have lower gas
Simpler compounds Complex compounds
entropies than…
Pure substances Mixtures boiling
Liquid
Solids have lower entropies than liquids which are lower than gases. solid melting
When a solid increases in temperature its entropy increases as the
particles vibrate more. Temperature
There is a bigger jump in entropy with boiling than that with melting.
Gases have large entropies as they are much more disordered At 0K substances have zero
entropy. There is no disorder
as particles are stationary
Predicting Change in entropy ‘∆S’ Qualitatively
An increase in disorder and entropy will lead to a positive entropy change ∆S˚ = +ve
In general, a significant increase in the entropy will occur if:

Balanced chemical equations can
-there is a change of state from solid or liquid to gas
often be used to predict if ∆S˚ is
- there is a significant increase in number of molecules
positive or negative.
between products and reactants.
NH4Cl (s)  HCl (g) + NH3 (g) Na (s) + ½ Cl2 (g)  NaCl (s)
∆S˚ = +ve ∆S˚ = -ve
•change from solid reactant to gaseous products •change from gaseous and solid reactant to solid
•increase in number of molecules •decrease in number of molecules
both will increase disorder both will decrease disorder
Calculating ∆S˚ quantitatively

Elements in their standard
Data books lists standard entropies (S˚) per mole for a variety of substances. states do not have zero
It is not possible for a substance to have a standard entropy of less than zero. entropy. Only perfect
crystals at absolute zero
(T = 0 K) will have zero
The unit of entropy is J K-1 mol-1 ∆S˚ = Σ S˚products - ΣS˚reactants entropy:
Example 11
Calculate ∆S˚ for the following reaction at 25˚C:
2Fe2O3 (s) + 3C (s)  4Fe (s) + 3CO2 (g) S [Fe2O3] = 87.4 J K-1 mol-1
Note: the entropy
S [C] = 5.7 J K-1 mol-1 change is very positive
∆S˚ = S˚products - S˚reactants as a large amount of
S [Fe] = 27.3 J K-1 mol-1
= (3 x 213.6 + 4 x 27.3) – (2 x 87.4 + 3 x 5.7) gas is being created
S [CO2] = 213.6 J K-1 mol-1 increasing disorder
= + 558.1 J K-1 mol-1 = + 558 J K-1 mol-1 (3 S.F.)
Gibbs Free Energy Change, ∆G

Gibbs free energy is a term that
The balance between entropy and enthalpy determines the combines the effect of enthalpy
feasibility of a reaction. and entropy into one number
This is given by the relationship :
∆G = ∆H - T∆S A reaction that has increasing entropy
(+ve ∆S) and is exothermic (-ve ∆H )
will make ∆G be negative and will
For any spontaneous change, ∆G will be negative.
always be feasible
Convert from ˚C to K (+ 273) If ∆G is negative there is still a

Unit of S= J K-1 mol-1 possibility, however, that the reaction
will not occur or will occur so slowly that
∆G = ∆H - T∆S Need to convert to effectively it doesn’t happen.
KJ K-1 mol-1 If the reaction has a high activation
Units: KJ mol-1 ( ÷1000) energy the reaction will not occur.
Units: KJ mol-1
Example 12 : Data for the following reaction, which represents the

reduction of aluminium oxide by carbon, are shown in the table. Substance ∆fH / S/
Al2O3(s) + 3C(s) → 2Al(s) + 3CO(g) kJmol–1 JK–1mol–1
Calculate the values of ∆H , ∆S and ∆G for the above reaction at 298 K
Al2O3(s) -1669 51
1. Calculate ∆S 2. Calculate ∆H˚
C(s) 0 6
∆S˚ = Σ S˚products - Σ S˚reactants ∆H˚ = Σ∆fH˚ [products] - Σ∆fH˚ [reactants]
Al(s) 0 28
= (2 x 28 + 3x198) – (51 + 3 x 6) = (3 x -111) – -1669
CO(g) -111 198
= +581J K-1 mol-1 (3 S.F.) = +1336 kJ mol-1
3. Calculate ∆G
∆G = ∆H - T∆S
∆G is positive. The reaction is not feasible
= +1336 – 298x 0.581
= +1163kJ mol-1
Calculating the temperature a reaction will become

feasible ∆G during phase changes
Example 13: Calculate the temperature range that this As physical phase changes like melting and boiling are
reaction will be feasible equilibria, the ∆G for such changes is zero.
N2(g) + O2(g)  2 NO(g)
∆ H = 180 kJ mol-1 ∆S = 25 J K-1 mol-1 Example 14 What temperature would methane melt at?
The reaction will be feasible when ∆ G ≤0 CH4(s)  CH4 (l) ∆H = 0.94 kJmol-1 ∆S = 10.3 Jmol-1K-1
Make ∆G = 0 in the following equation ∆G = ∆H - T∆S
0 = ∆H - T∆S Make ∆G = 0 in the following equation ∆G = ∆H - T∆S
0 = ∆H - T∆S
So T= ∆H / ∆S So T= ∆H / ∆S
T = 180/ (25/1000) T= 0.94 / (10.3÷1000)

= 7200K
T= 91K
The T must be >7200K which is a high Temp!
15
Effect of Temperature on feasibility If the reaction involves an increase in entropy (∆S is +ve)
then increasing temperature will make it more likely that
∆G = ∆H - T∆S
∆G is negative and more likely that the reaction
Changing temperature will change the occurs e.g. NaCl + aq  Na+(aq) + Cl-(aq)
value of - T∆S in the above equation
If the reaction has a ∆S close to zero then

If the reaction involves an decrease in entropy (∆S is -
temperature will not have a large effect on the
ve) then increasing temperature will make it more less
feasibility of the reaction as - T∆S will be
likely that ∆G is negative and less likely for the
reaction to occur. E.g. HCl(g) + NH3 (g) ➝ NH4Cl(s)
small and ∆G won’t change much
e.g. N2 (g) + O2 (g)  2NO (g)
40
This graph shows how the free-energy change for formation
of ammonia varies with temperature above 240 K.
½ N2(g) + 3/2 H2(g)  NH3(g) 30
20
Applying the equation of a straight line
ΔG kJ/ mol
y= mx+c to the ∆G = ∆H - T∆S equation. 10
c = ∆H
The gradient of this graph is equal to -∆S 0
0 200 400 600 800 1000
The positive gradient means ∆S is negative which -10 Temperature/ K
corresponds to the equation above showing
increasing order. -20
When ∆G <0 then the reaction is spontaneous. In this
case at Temperatures below around 460K -30
The slope of the line would change below 240K because ammonia would be a liquid and the
entropy change would be different
Enthalpies of solution Using Hess’s law to determine enthalpy changes of solution
When an ionic lattice dissolves in water it involves breaking up the bonds in the lattice and forming new
bonds between the metal ions and water molecules.
For MgCl2 the ionic equation for the dissolving is MgCl2 (s) + aq  Mg2+ (aq) + 2Cl- (aq)
Mg2+ (g) + 2Cl- (g) When an ionic substance dissolves the lattice must be
broken up. The enthalpy of lattice dissociation is equal
hydH Mg2+ to the energy needed to break up the lattice (to gaseous
LEH(MgCl2) ions). This step is endothermic.
Mg2+ (aq) + 2Cl- (g)
The size of the lattice enthalpy depends on the size and
2 x hydH Cl- charge on the ion. The smaller the ion and the higher its
MgCl2 (s)
charge the stronger the lattice
ΔHsolution
Mg2+ (aq) + 2Cl- (aq)
solH = - LEH + hydH
Example 15 . Calculate the enthalpy of solution of Hydration enthalpies are exothermic as energy is given
NaCl given that the lattice enthalpy of formation out as water molecules bond to the metal ions.
of NaCl is -771 kJmol-1 and the enthalpies of
hydration of sodium and chloride ions are -406 The negative ions are attracted to the δ+ hydrogens on
and -364 kJmol-1 respectively the polar water molecules and the positive ions are
attracted to the δ- oxygen on the polar water molecules.
solH = - LEH + hydH
= - (-771) + (-406-364)
= + 1 kJmol-1
ΔH solution endothermic.
Ba2+ (g) + SO42- (g)
hydH Ba2+
The higher the charge density the greater the hydration
Ba2+ (aq) + SO42- (g) enthalpy (e.g. smaller ions or ions with larger charges)
LEH(BaSO4)
hydH SO42- as the ions attract the water molecules more strongly.
Ba2+ (aq) + SO42- (aq) e.g. Fluoride ions have more negative hydration
solH enthalpies than chloride ions
BaSO4 (s) INSOLUBLE
Magnesium ions have a more negative hydration enthalpy
than barium ions
What does ΔHSolution tell us?

Generally ΔH solution is not very exo or endothermic so the hydration enthalpy is about the same as lattice
enthalpy.
In general the substance is more likely to be soluble if the ΔH solution is exothermic.
If a substance is insoluble it is often because the lattice enthalpy is much larger than the hydration enthalpy and
it is not energetically favourable to break up the lattice, making ΔH solution endothermic.
We must consider entropy, however, to give us the full picture about solubility.
When a solid dissolves into ions the entropy increases as there is more disorder as solid changes to solution
and number of particles increases.
This positive S can make G negative even if H solution is endothermic, especially at higher temperatures.
For salts where ΔH solution is exothermic For salts where ΔH solution is endothermic
the salt will always dissolve at all temperatures the salt may dissolve depending on whether the
-T∆S value is more negative than ∆H is positive
∆G = ∆H - T∆S
∆G = ∆H - T∆S
G is S is positive due to the
always H is increased disorder as more Will dissolve
S is positive due to
negative negative particles so - T∆S always if G is
H is the increased
negative negative
positive disorder as more
particles so - T∆S
always negative
Increasing the temperature will make it more

likely that G will become negative, making the
reaction feasible and the salt dissolve
6. Electrochemistry
Redox
oxidation is the process of electron loss: reduction is the process of electron gain:
Zn Zn2+ + 2e- Cl2 + 2e-  2Cl-
It involves an increase in oxidation number It involves a decrease in oxidation number
Rules for assigning oxidation numbers

1. All uncombined elements have an oxidation number of zero eg . Zn, Cl2, O2, Ar all have oxidation numbers of zero
2. The oxidation numbers of the elements in a compound add In NaCl Na= +1 Cl= -1
up to zero Sum = +1 -1 = 0
3. The oxidation number of a monoatomic ion is equal to the

e.g. Zn2+ = +2 Cl- = -1
ionic charge
4. In a polyatomic ion (CO32-) the sum of the individual e.g. in CO32- C = +4 and O = -2
oxidation numbers of the elements adds up to the charge
sum = +4 + (3 x -2) = -2
on the ion
5. Several elements have invariable oxidation numbers in their
common compounds.
Group 1 metals = +1
Group 2 metals = +2
Al = +3 We use these rules to
H = +1 (except in metal hydrides where it is –1 eg NaH) identify the oxidation
numbers of elements that
F = -1 have variable oxidation
Cl, Br, I = –1 except in compounds with oxygen and fluorine numbers.
O = -2 except in peroxides (H2O2 ) where it is –1 and in compounds with fluorine.
Note the oxidation number of Cl

What is the oxidation number of Fe in FeCl 3
in CaCl2 = -1 and not -2 because
Using rule 5, Cl has an O.N. of –1 there are two Cl’s
Using rule 2, the O.N. of the elements must add up to 0 Always work out the oxidation for
one atom of the element
Fe must have an O.N. of +3
in order to cancel out 3 x –1 = -3 of the Cl’s
Redox equations and half equations
Br2 (aq) + 2I- (aq)  I2 (aq) + 2 Br- (aq)
Br2 (aq) + 2e-  + 2 Br- (aq) 2I- (aq)  I2 (aq) + 2 e-

Br has reduced as it has gained electrons I has oxidised as it has lost electrons
A reduction half equation only shows the parts An oxidation half equation only shows the reducing agents are
of a chemical equation involved in reduction parts of a chemical equation involved in electron donors
The electrons are on the left oxidation
The electrons are on the right
oxidising agents are
electron acceptors
The oxidising agent is Bromine The reducing agent is the Iodide
water . It is an electron acceptor ion. It is an electron donor
When naming oxidising
and reducing agents
An oxidising agent (or oxidant) is the A reducing agent (or reductant) is the
species that causes another element to species that causes another element always refer to full name
oxidise. It is itself reduced in the reaction reduce. It is itself oxidised in the reaction. of substance and not
just name of element
Balancing Redox equations
Writing half equations
1. Work out oxidation numbers for element being oxidised/ reduced Zn  Zn2+ Zn changes from 0 to +2
2. Add electrons equal to the change in oxidation number

For reduction add e’s to reactants
Zn  Zn2+ + 2e-
For oxidation add e’s to products
3. check to see that the sum of the charges on the reactant side
equals the sum of the charges on the product side 0 +2 –2 =0
More complex Half equations

If the substance that is being oxidised or reduced contains a varying amount of O (eg In acidic conditions
MnO4-  Mn2+ ) then the half equations are balanced by adding H+, OH- ions and H2O. use H+ and H2O
Example: Write the half equation for the change MnO4-  Mn2+
Mn changes from +7 to +2
1. Balance the change in O.N. with electrons Add 5 electrons to reactants MnO4- + 5e-  Mn2+
2. Add H2O in products to balance O’s in MnO4- MnO4- + 5e-  Mn2+ + 4H2O
3. Add H+ in reactants to balance H’s in H2O MnO4- + 8H+ + 5e-  Mn2+ + 4H2O
equals the sum of the charges on the product side -1 + 8 -5 = +2 +2
Example: Write the half equation for the change SO42-  SO2
S changes from +6 to +4
1. Balance the change in O.N. with electrons Add 2 electrons to reactants SO42- + 2e-  SO2
2. Add H2O in products to balance O’s in SO42- SO42- + 2e-  SO2 + 2H2O
3. Add H+ in reactants to balance H’s in H2O SO42- + 4H+ + 2e-  SO2 + 2H2O
equals the sum of the charges on the product side -4 + 4 = 0 0
Combining half equations

To combine two half equations there must be
To make a full redox equation combine a reduction
equal numbers of electrons in the two half
half equation with a oxidation half equation
equations so that the electrons cancel out
Example 1
Reduction MnO4- + 8 H+ + 5 e-  Mn2+ + 4 H2O x2

Multiply the half equations to get
Oxidation C2O42-  2 CO2 + 2 e- x5 equal electrons
2MnO4- + 16 H+ + 5C2O42-  2Mn2+ + 10 CO2 + 8 H2O Add half equations together and cancel
electrons
Example 2
Reduction SO42- + 10H+ + 8e- H2S+ 4H2O Multiply the half equations to get
equal electrons
Oxidation 2I-  I2 + 2 e- x4
Add half equations together and
8I- + SO42- + 10H+  H2S+ 4I2 + 4H2O cancel electrons
Electrolysis
F = Le connects the Faraday constant, the Avogadro constant and the charge on the electron
F= Faraday constant ( a measure of the charge of 1 mole of electrons = 96320 coulombs
L = Avogadro constant = 6.022 x 1023 e = charge of on electron = 1.60 x 10-19 coulombs.
Electrolysis of molten salts

When a simple ionic compound is electrolysed in the molten state using inert electrodes, the salt splits and the
metal ion moves to the negative electrode and the negative ion moves to the positive electrode
e.g. if molten lead bromide is electrolysed, the lead will form at the negative electrode and bromine will form at
the positive electrode
At the negative electrode (cathode) At the positive electrode (anode)

At the negative electrode, positively charged ions At the positive electrode, negatively charged ions lose
gain electrons to become metal atoms. electrons.
This is classed as reduction. Reduction is gaining This is classed as oxidation. Oxidation is losing electrons
electrons 2Cl- (l)  Cl2 (g)+ 2e- (chloride ions becomes chlorine)
Na+ (l )+ e-  Na (s) (sodium ions become sodium 2Br- (l)  Br2 (l)+ 2e- (bromide ions becomes bromine)
atoms) 2I-  I2 + 2e- (Iodide ions becomes Iodine)
Cu2+ (l )+ 2e-  Cu (s) 2O2- (l)  O2 (g)+ 4e- (oxide ions becomes oxygen)
Al3+ (l )+ 3e-  Al (s)
OIL RIG can help remember that Oxidation is Loss of electrons:

Reduction is Gain of electrons
Electrolysing aqueous solutions

In aqueous solutions there is a mixture of ions: H + and
If an aqueous solution is electrolysed, using inert OH- ions are present in addition to the ions from the salt
electrodes, the ions discharged depend on the electrode e.g. in copper chloride solution there are H+ ,OH- (from
potentials of the ions involved. water) Cu2+ ,Cl- (from the salt)
The negative electrode
At the negative electrode (cathode) in aqueous mixtures the cation with the more positive electrode
potential discharges.
In aqueous solutions where the metal is more negative in the electrochemical This happens because in the
series than hydrogen, the metal will not be evolved at the cathode. (e.g. sodium aqueous solution water molecules
chloride, calcium fluoride) Hydrogen gas will be evolved at the cathode instead. break down producing hydrogen
2H+ (aq) + 2e-  H2 (g) ions and hydroxide ions that are
discharged.
In aqueous solutions where the metal has a more positive E° value than
hydrogen in the electrochemical series (e.g. copper chloride or silver fluoride,)
the metal will be evolved at the cathode.
Cu2+ (aq )+ 2e-  Cu (s)
The positive electrode

At the positive electrode (anode), oxygen is produced unless the solution
The concentration of the negative ion
contains halide ions when the halogen is produced.
can change the product evolved. A
4OH- (aq)→ O2 (g)+ 2H2O (l) + 4e- or
concentrated solution of sodium
4OH- – 4e- → O2 + 2H2O
chloride, would give mostly chlorine
gas. With increasingly dilute solutions,
If a halide ion is present then the halogen is produced
less chlorine and more oxygen will be
e.g. 2Cl- (aq) Cl2 (g)+ 2e-
evolved
Calculations with Electrolysis
Various questions can be asked using the following equations and constants (found in data book)
charge passed (in Coulombs) = current x time (in secs) F = 9.65 × 104 C mol–1
Moles of electrons = charge (in C) / F
electronic charge e = –1.60 × 10–19 C
Number of electrons passed = charge (in C) / electronic charge e
Example
A chromium salt was electrolysed. The chromium metal is
deposited on the cathode, according to the following equation.
Crn+(aq) + ne– → Cr(s)
A current of 1.2 A was passed for 50 minutes through a solution
of the chromium salt. 0.647 g of chromium was deposited.
Calculate the value of n in the above equation.
charge passed (in Coulombs) = current x time (in secs)

charge passed = 1.2 × 50 x 60 = 3600 C
Moles of electrons = charge (in C) / F

Mole of e– = 3600/ 96500 = 3.731 × 10–2 mol
Moles of Cr = mass/Mr = 0.647/ 52

= 1.244 × 10–2 mol
n = moles of electrons/moles of Cr
n = 3.731 × 10–2/ 1.244 × 10–2
= 3.00
Example: Calculating Avogadro’s constant
A current of 1.8 A was passed through dilute sulfuric acid for

30 minutes. 195 cm3 of oxygen was collected at the anode.
Conditions were 25 °C and 1 atm.
This is the reaction:
2H2O(l) → 4H+(aq) + O2(g) + 4e–
Calculate a value for the Avogadro constant, L
moles of O2 made = gas volume of O2 /molar volume

moles of O2 = 0.195 (dm3) /24
= 8.125 x 10–3 mol
Using balanced equation

moles of electrons made = 4 x 8.125 x 10–3
= 3.25x 10–2 mol
charge passed (in Coulombs) = current x time (in secs)

charge passed = 1.8 × 30 x 60 = 3240 C
Number of electrons passed = charge (in C) / electronic charge e

= 3240/ 1.6 x 10–19
= 2.025 x 1022
Avogadro constant, L = number of electrons passed/ moles of electrons

= 2.025 x 1022 / 3.25x 10–2 = 6.2 x 1023 mol–1
Redox Equilibria Electron
flow
Electrochemical cells
Salt bridge
•A cell has two half–cells. copper
•The two half cells have to be connected with a salt electrode
bridge. Zinc
•Simple half cells will consist of a metal (acts an electrode
electrode) and a solution of a compound containing
that metal (eg Cu and CuSO4). 1M
•These two half cells will produce a small voltage if 1M zinc copper
connected into a circuit. (i.e. become a Battery or cell). sulphate sulphate
solution solution
Why does a voltage form? Why use a High resistance

In the cell pictured above voltmeter?
When connected together the zinc half-cell has more of a tendency to oxidise The voltmeter needs to be of very high
to the Zn2+ ion and release electrons than the copper half-cell. (Zn Zn2+ + resistance to stop the current from
2e-) flowing in the circuit. In this state it is
More electrons will therefore build up on the zinc electrode than the copper possible to measure the maximum
electrode. possible potential difference (E).
A potential difference is created between the two electrodes. The reactions will not be occurring
The zinc strip is the negative terminal and the copper strip is the positive because the very high resistance
terminal. voltmeter stops the current from
flowing.
This potential difference is measured with a high resistance voltmeter, and is
given the symbol E. The E for the above cell is E= +1.1V.
Salt Bridge
The salt bridge is used to connect up the circuit. The free moving ions conduct the charge.
A salt bridge is usually made from a piece of filter paper (or material) soaked in a salt solution, usually Potassium Nitrate.
The salt should be unreactive with the electrodes and electrode solutions.. E.g. potassium chloride would not be suitable
for copper systems because chloride ions can form complexes with copper ions.
A wire is not used because the metal wire would set up its own electrode system with the solutions.
What happens if current is allowed to flow?

If the voltmeter is removed and replaced with a bulb or if the circuit is short circuited, a current flows. The
reactions will then occur separately at each electrode. The voltage will fall to zero as the reactants are used up.
The most positive electrode will always undergo reduction.

Cu2+ (aq) + 2e-  Cu(s) (positive as electrons are used up)
The most negative electrode will always undergo oxidation.

Zn(s)  Zn2+ (aq) + 2e- (negative as electrons are given off)
Measuring the electrode potential of a cell
• It is not possible to measure the absolute potential of a half electrode on its own. It is only
possible to measure the potential difference between two electrodes.
• To measure it, it has to be connected to another half-cell of known potential, and the
potential difference between the two half-cells measured.
• by convention we can assign a relative potential to each electrode by linking it to a reference
electrode (hydrogen electrode), which is given a potential of zero Volts
Standard Cell potential is the potential of a cell composed of two electrodes under standard conditions
The Standard Hydrogen Electrode
The potential of all electrodes are measured by comparing

their potential to that of the standard hydrogen electrode. Metal
Salt bridge
electrode
H2 gas at KNO3 (aq)
e.g. Fe
The standard hydrogen electrode (SHE) is assigned the 100kPa
potential of 0 volts.
Pt electrode
The hydrogen electrode equilibrium is:
H2 (g) 2H+ (aq) + 2e-
1M HCl
Solution containing metal

Components of a standard hydrogen electrode. ions (e.g. Fe2+) at 1 mol dm-
To make the electrode a standard reference electrode 3 concentration
some conditions apply:

1. Hydrogen gas at pressure of 100kPa Because the equilibrium does not include a
2. Solution containing the hydrogen ion at 1 M (solution is conducting metal surface a platinum wire is used
usually 1M HCl) which is coated in finely divided platinum. (The
3. Temperature at 298K platinum black is used because it is porous and can
4. Platinum Electrode absorb the hydrogen gas.)
Standard conditions are needed because the Secondary standards

position of the redox equilibrium will change The Standard Hydrogen Electrode is difficult to use, so often a different
with conditions. standard is used which is easier to use.
For example, in the equilibrium: These other standards are themselves calibrated against the SHE.
Mn+(aq) + n e- M(s) This is known as using a secondary standard - i.e. a standard electrode
that has been calibrated against the primary standard.
An increase in the concentration of Mn+ The common ones are:
would move the equilibrium to the right, so silver / silver chloride E = +0.22 V
making the potential more positive. calomel electrode E = +0.27 V
Standard Electrode Potentials E

The standard conditions are :
When an electrode system is connected to the hydrogen •All ion solutions at 1M
electrode system, and standard conditions apply the •temperature 298K
potential difference measured is called the standard •gases at 100kPa pressure
electrode potential, •No current flowing
Salt bridge
KNO3 (aq)
Standard electrode potentials are found in H2 gas at
100kPa
data books Pt electrode
They are quoted as half equations
Li+ (aq) + e- ⇌ Li (s) E= -3.03V
Pt electrode
the more oxidised form is on the left
1M HCl
1M FeSO4 and 0.5

M Fe2(SO4)3
Note: in the electrode system containing two solutions it is

necessary to use a platinum electrode and both ion solutions must
be of a 1M concentration so [Fe2+] = 1M and [Fe3+] = 1M .
6
Using Electrode Potentials
The most useful application of electrode potentials is to show the
direction of spontaneous change for redox reactions.
The easiest way to use electrode potentials is as follows:
For any two half equations The more negative half cell will
always oxidise (go backwards)
If we want to work out the Ecell
Mg2+ (aq) + 2e- ⇌ Mg(s) E= -2.37V that corresponds to this
Cu2+ (aq) + 2e- ⇌ Cu (s) E = +0.34V spontaneous change then use
The reaction would be Ecell = Ered – Eox
The more positive half cell will always reduce Mg + Cu2+  Cu + Mg 2+ A spontaneous change will always
(go forwards) have a positive Ecell.
The most negative electrode will oxidise and go from right to left
Zn2+(aq) + 2e- ⇌ Zn(s) E= - 0.76V
The half equation is therefore Zn(s)  Zn2+ (aq) +2e-
Fe2+(aq) + 2e- ⇌ Fe(s) E= -0.44V
Electrons are given off (lost) and travel to positive electrode.
To get the full equation of the reaction add the

The more positive electrode will reduce and go from left to right
two half reactions together, cancelling out the
Fe2+ (aq) +2e-  Fe(s)
electrons.
Electrons arrive at this electrode and are absorbed (gained)
Zn + Fe2+  Fe + Zn2+
Using series of standard electrode potentials

Most strong reducing
oxidation agents found here
As more +ve As more -ve

Li+ + e- ⇌ Li -3.03V
increasing increasing
Mn2+ + 2e- ⇌ Mn -1.19V
tendency for tendency for
species on left to species on right
reduce, and act as to oxidise, and act
2H+ + 2e- ⇌ H2 0V
oxidising agents as reducing agents
Ag+ + e- ⇌ Ag +0.8V
F2 + 2e- ⇌ 2F- +2.87
Most strong oxidising reduction If we want to work out the Ecell from two
agents found here standard electrode potentials then use
Ecell = Ered – Eox
The most powerful reducing agents will be found at the most negative end of the series on the
right (ie the one with the lower oxidation number).
The most powerful oxidising agents will be found at the most positive end of the series on the left
(ie the one with the higher oxidation number).
7
Example 1
Use electrode data to explain why fluorine reacts with water.
Write an equation for the reaction that occurs.
oxidise
O2(g) + 4H+(aq) + 4e– ⇌ 2H2O(I) Eo+1.23V
First apply idea that more positive Eo will reduce (go forward) and
F2(g) + 2e– ⇌ 2F–(aq) Eo +2.87V
more negative Eo will oxidise (go backwards)
reduce
Explanation to write
Can also work out Ecell and quote it as part
As Eo F2/F- > Eo O2/H2O, F2 will oxidise H2O to O2
of your answer
Equation Ecell = Ered - Eox = 2.87-1.23 =1.64V
2F2(g) + 2H2O(I) → 4F–(aq) + O2(g) + 4H+(aq) Remember to cancel out electrons in full equation
Example 2
Cl2(aq) + 2e– ⇌ 2Cl–(aq) Eo+1.36V
Use data from the table to explain why chlorine should
2HOCl(aq) + 2H+(aq) + 2e– ⇌ Cl2(aq) + 2H2O(I) Eo+1.64V
undergo a redox reaction with water. Write an
H2O2(aq) + 2H+(aq) + 2e– ⇌ 2H2O(I) Eo +1.77V
equation for this reaction.
O2(g) + 4H+(aq) + 4e– ⇌ 2H2O(I) Eo +1.23V
reduce
First select relevant half equations by considering the Eo values and
applying the idea that more positive Eo will reduce (go forward) and Cl2(aq) + 2e– ⇌ 2Cl– (aq) Eo+1.36V
more negative Eo will oxidise (go backwards). O2(g) + 4H+(aq) ⇌ 4e– → 2H2O(I) Eo +1.23V
oxidise
Explanation to write
Equation
As Eo Cl2/Cl- > Eo O2/H2O, Cl2 will oxidise H2O to O2
2Cl2(g) + 2H2O(I) → 4Cl–(aq) + O2(g) + 4H+(aq)
Example 3
Suggest what reactions occur, if any, when hydrogen gas is Fe3+ (aq) + e– ⇌ Fe2+ (aq) Eo +0.77V
bubbled into a solution containing a mixture of iron(II) and 2H+(aq) + 2e– ⇌ H2(g) Eo 0.00V
iron(III) ions. Explain your answer. Fe2+ (aq) + 2e– ⇌ Fe(s) Eo–0.44V
reduce
First select relevant half equations by considering the E o values and
applying the idea that more positive Eo will reduce (go forward) Fe3+ (aq) + e– ⇌ Fe2+ (aq) Eo +0.77V
and more negative Eo will oxidise (go backwards) 2H+(aq) + 2e– ⇌ H2(g) Eo 0.00V
Explanation to write oxidise

Fe3+ will be reduced to Fe2+ by H2 oxidising to H+
Equation
because Eo Fe3+ /Fe2+ > Eo H+/H2
2Fe3+ (aq) + H2(g) → 2Fe2+ (aq) + 2H+(aq)
Example 4
Use the half-equations to explain in terms of oxidation states what happens to
hydrogen peroxide when it is reduced.
reduce
Explanation to write H2O2(aq) + 2H+(aq) + 2e– ⇌ 2H2O(I) Eo+1.77V
As Eo H2O2/H2O > Eo O2/H2O2 , H2O2 disproportionates from - O2(g) + 2H+(aq) + 2e– ⇌ H2O2(aq) Eo +0.68V
1 oxidation state to 0 in O2 and -2 in H2O oxidise
Equation
2H2O2(aq) → 2H2O(I) + O2 (g)
Effect of conditions on Cell voltage Ecell
The effects of changing conditions on E cell can be made Ecell is a measure of how far from equilibrium the cell
by applying le Chatelier’s principle. reaction lies. The more positive the Ecell the more likely
the reaction is to occur.
If current is allowed to flow, the cell reaction will occur
and the Ecell will fall to zero as the reaction proceeds and
the reactant concentrations drop.
Zn2+(aq) + 2e- ⇌ Zn(s) E= - 0.76V
Effect of concentration on Ecell Fe2+(aq) + 2e- ⇌ Fe(s) E= -0.44V
Looking at cell reactions is a straight forward application of Zn + Fe2+  Fe + Zn2+ E= +0.32

le Chatelier. So increasing concentration of ‘reactants’
Increasing the concentration of Fe2+ and decreasing
would increase Ecell and decreasing them would cause
the concentration of Zn2+ would cause Ecell to
Ecell to decrease.
increase.
Effect of temperature on Ecell
Most cells are exothermic in the spontaneous direction so applying Le Chatelier to a temperature rise to these would
result in a decrease in Ecell because the equilibrium reactions would shift backwards.
If the Ecell positive it indicates a reaction might occur. There is still a possibility, however, that the reaction will not occur
or will occur so slowly that effectively it does not happen.
If the reaction has a high activation energy the reaction will not occur.
Nernst equation
The Nernst equation enables the electrode
potential for a system with non- standard E = E⦵ + (0.059/z) log [oxidised species]
concentrations to be calculated. [reduced species]
Z = the number of electrons transferred in the reaction equation
Example Example
Consider the half cell with the equilibrium Ag++ e- ⇌ Ag Consider the half cell with the equilibrium Fe3++ e- ⇌ Fe2+
Calculate the Ecell for the half cell when [Ag+] = 0.33 mol dm–3 Calculate the Ecell for the half cell when [Fe2+] = 0.43 mol dm–3
was used instead of the standard Ag+ solution. and [Fe3+] = 1.20 mol dm–3 were used instead of the standard
solutions.
E = E⦵ + (0.059/z) log [oxidised species]
[reduced species] E = E⦵ + (0.059/z) log [oxidised species]
z=1 as one e- in half equation [reduced species]
The reduced species is given a value of 1 as it is a
solid (silver) E = 0.77+ (0.059) log [1.20]
[0.43]
E = 0.80+ (0.059) log [0.33] =0.86 V
=0.77 V
Cells
You should be able to work out
Electrochemical cells can be used as a commercial source of electrical energy Ecell for given half reactions.
Cells can be non-rechargeable (irreversible), rechargeable and fuel cells
You do not need to learn the details of these cells. Relevant cell information will be given. You should be able to convert between
standard electrode potential half cells, full cell reactions and be able to calculate potentials from given data
Example primary non rechargeable cells Cells are non-rechargeable when the reactions that
occur with in them are non-reversible
Dry Cell Zn2+(aq) + 2e-  Zn(s) E = - 0.76 V More negative half equation will oxidise
2MnO2(s) + 2NH4+(aq) +2 e- → Mn2O3(s) + 2NH3(aq) + H2O(l) E = 0.75 V
Overall reaction 2MnO2 + 2NH4++ Zn → Mn2O3 + 2NH3 + H2O + Zn2+ Ecell =+1.51V
Example secondary Lithium ion cells are used to power cameras and mobile phones.
Li+ + CoO2 + e-  Li+[CoO2] - E=+0.6V (Co will reduce changing oxidation state from 4 to 3
Li+ + e-  Li E=-3.0V
The reagents in the cell are absorbed onto
powdered graphite that acts as a support medium.
Overall discharge Li + CoO2  LiCoO2 E=3.6V
The support medium allows the ions to react in
reaction
the absence of a solvent such as water.
The overall reaction would be reversed in
Water would not be good as a solvent as it
the recharging state
would react with the lithium metal.
Fuel cell Scientists in the car industry are developing fuel cell
vehicles, fuelled by:
A fuel cell uses the energy from the reaction of a fuel (i) hydrogen gas,
with oxygen to create a voltage (ii) hydrogen-rich fuels;
Hydrogen Fuel cell (potassium hydroxide electrolyte)
H2 O2
from from air
4e- + 4H2O  2H2 +4OH- E=-0.83V
fuel
4e- + 2H2O +O2  4OH- E=+0.4V
Overall reaction 2H2 + O2  2H2O E=1.23V
H2O
+heat
2e- + 2H+ H 2 E=0V In acidic conditions these are the
electrode potentials. The Ecell is
4e- + 4H+ +O2  2H2O E=1.23V Using standard conditions: The rate is too
the same as alkaline conditions as
slow to produce an appreciable current.
Overall 2H2 + O2  2H2O E=1.23V the overall equation is the same
Higher temperatures are therefore used to
increase rate but the reaction is exothermic
Fuel cells will maintain a constant voltage over time as they are
so by applying le chatelier would mean the
continuously fed with fresh O2 and H2 so maintaining constant
emf falls.
concentration of reactants. This differs from ordinary cells where the
A higher pressure can help counteract this
voltage drops over time as the reactant concentrations drop
Advantages of Fuel cells over conventional petrol or Limitations of hydrogen fuel cells
diesel-powered vehicles (i) storing and transporting hydrogen, in terms of safety,
(i) less pollution and less CO2. (Pure hydrogen emits feasibility of a pressurised liquid and a limited life cycle of a
only water whilst hydrogen-rich fuels produce only solid ‘adsorber’ or ‘absorber’
small amounts of air pollutants and CO2). (ii) limited lifetime (requiring regular replacement and
(ii) greater efficiency; disposal) and high production costs,
(iii) use of toxic chemicals in their production
7. Equilibria All reversible reactions reach an dynamic equilibrium state.
Many reactions are reversible

The term dynamic means both forward and backward
N2 + 3H2 2NH3 reactions are occurring simultaneously
Two features of Dynamic Equilibrium We use the expression ‘position of equilibrium’ to

1. Forward and backward reactions are describe the composition of the equilibrium mixture.
occurring at equal rates.
If the position of equilibrium favours the reactants
2. The concentrations of reactants and (also described as “towards the left”) then the
products stays constant equilibrium mixture will contain mostly reactants.
Le Chatelier’s Principle
We use Le Chatelier’s principle to work out how Le Chatelier’s principle states that if an external
changing external conditions such as temperature condition is changed the equilibrium will shift to
and pressure affect the position of equilibrium oppose the change (and try to reverse it).
Effect of Temperature on equilibrium

Typical Exam question: What effect would increasing
If temperature is increased the equilibrium will
temperature have on the yield of ammonia?
shift to oppose this and move in the
endothermic direction to try and reduce the N2 + 3H2 2NH3 H = -ve exo
temperature by absorbing heat.
Exam level answer : must include bold points
And its reverse
If temperature is increased the equilibrium will
shift to oppose this and move in the endothermic,
If temperature is decreased the equilibrium
backwards direction to try to decrease
will shift to oppose this and move in the
temperature. The position of equilibrium will shift
exothermic direction to try and increase the
towards the left, giving a lower yield of ammonia.
temperature by giving out heat.
Low temperatures may give a higher yield of product but will also result in slow
rates of reaction. Often a compromise temperature is used that gives a
reasonable yield and rate
Effect of Pressure on equilibrium
Typical Exam question: What effect would increasing
Increasing pressure will cause the equilibrium to shift
pressure have on the yield of methanol?
towards the side with fewer moles of gas to oppose
the change and thereby reduce the pressure. CO (g) + 2H2(g) CH3OH (g)
And its reverse

Exam level answer : must include bold points
If pressure is increased the equilibrium will shift
Decreasing pressure will cause the equilibrium to shift to oppose this and move towards the side with
towards the side with more moles of gas to oppose fewer moles of gas to try to reduce the
the change and thereby increase the pressure. pressure . The position of equilibrium will shift
towards the right because there are 3 moles of
If the number of moles of gas is the same on both gas on the left but only 1 mole of gas on the right,
sides of the equation then changing pressure will have giving a higher yield of methanol.
no effect on the position of equilibrium
H2 + Cl2 2HCl
Increasing pressure may give a higher yield of product and will produce a faster
rate. Industrially high pressures are expensive to produce ( high electrical
energy costs for pumping the gases to make a high pressure) and the
equipment is expensive (to contain the high pressures)
Effect of Concentration on equilibrium
I2 + 2OH- I- + IO- + H2O Increasing the concentration OH- ions causes the equilibrium to shift to oppose this
and move in the forward direction to remove and decrease the concentration of OH-
browncolourless ions. The position of equilibrium will shift towards the right, giving a higher yield of I-
and IO-. ( The colour would change from brown to colourless)
Adding H+ ions reacts with the OH- ions and reduces their concentration so the
equilibrium shifts back to the left giving brown colour.
Effect of catalysts on equilibrium

A catalyst has no effect on the position of equilibrium, but it will speed up the rate at which the
equilibrium is achieved.
It does not effect the position of equilibrium because it speeds up the rates of the forward and
backward reactions by the same amount.
Importance of equilibrium to industrial processes

You should be able to apply the above ideas to given reactions
Common examples
Contact process
Haber process
Stage 1 S (s) + O2 (g)  SO2 (g)
N2 + 3H2 2NH3 H = -ve exo
Stage 2 SO2 (g) + ½ O2 (g) SO3 (g) H = -98 kJ mol-1
T= 450oC, P= 200 – 1000 atm, catalyst = iron
T= 450oC, P= 1 or 2 atm, catalyst = V2O5
Low temp gives good yield but slow rate:
Low temp gives good yield but slow rate: compromise moderate
compromise temp used
temp used
High pressure gives good yield and high rate: too
High pressure only gives slightly better yield and high rate: too
high a pressure would lead to too high energy costs
high a pressure would lead to too high energy costs for pumps
for pumps to produce the pressure
to produce the pressure
In all cases catalysts speeds up the rate allowing lower temp to be used (and hence lower energy costs) but have
no effect on equilibrium
In all cases high pressure leads to too high energy costs for pumps to produce the pressure and too high
equipment costs to have equipment that can withstand high pressures.
Recycling unreacted reactants back into the reactor can improve the overall yields of all these processes
Both methanol and ethanol can be used as fuels
2
Equilibrium Equations
Equilibrium constant Kc Kc = equilibrium constant
Example 1
For a generalised reaction
mA + nB pC + qD [ C]p [D]q N2 (g) + 3H2 (g) 2 NH3 (g)
Kc=
m,n,p,q are the stoichiometric balancing [ A]m [B]n
numbers [NH3 (g)]2
Kc=
A,B,C,D stand for the chemical formula [N2 (g)] [H2 (g)]3
[ ] means the equilibrium concentration
The unit of Kc changes and depends on the equation.
Working out the unit of Kc

Put the unit of concentration (mol dm -3) into the Kc equation
Cancel out
[NH3 (g)]2 [mol dm-3]2 units 1
Unit = [mol dm-3]-2
Kc= Unit = Unit =
[N2 (g) ] [H2 (g)]3 [mol dm-3]2
[mol dm-3] [mol dm-3]3
Unit = mol-2 dm+6
Example 2: writing Kc expression

Working out the unit
H2 (g) +Cl2 (g) 2HCl (g) [HCl (g)]2
Kc= [mol dm-3]2
Unit Kc= = no unit
[H2 (g) ] [Cl2 (g)]
[mol dm-3] [mol dm-3]
Calculating Kc Calculating the moles at equilibrium

Most questions first involve having to work out the equilibrium moles and moles of reactant at equilibrium
then concentrations of the reactants and products. = initial moles – moles reacted
Usually the question will give the initial amounts (moles) of the reactants,
and some data that will help you work out the equilibrium amounts. moles of product at equilibrium
= initial moles + moles formed
Example 3
H2 (g) +Cl2 (g) 2HCl (g)
For the following equilibrium
In a container of volume 600cm 3 there were initially 0.5mol of H2 and 0.6 mol of Cl2.
At equilibrium there were 0.2 moles of HCl. Calculate Kc
H2 Cl2 HCl
It is often useful Using the balanced equation if 0.2 moles of
Initial moles 0.5 0.6 0
to put the mole HCl has been formed it must have used up
data in a table. 0.1 of Cl2 and 0.1 moles of H2 (as 1:2 ratio)
Equilibrium moles 0.2
Work out the moles at equilibrium for the reactants moles of reactant at equilibrium = initial moles – moles reacted
moles of hydrogen at equilibrium = 0.5 – 0.1 = 0.4 moles of chlorine at equilibrium = 0.6 – 0.1 = 0.5
H2 Cl2 HCl If the Kc has no unit then there are equal numbers of
reactants and products. In this case you do not have to
Initial moles 0.5 0.6 0 divide by volume to work out concentration and equilibrium
moles could be put straight into the kc expression
Equilibrium moles 0.4 0.5 0.2
Equilibrium 0.4/0.6 0.5/0.6 0.2/0.6

[HCl (g)]2
concentration (M) =0.67 =0.83 =0.33 Kc=
[H2 (g) ] [Cl2 (g)]
Work out the

Finally put
Kc
= 0.332 = 0.196 no unit
concentrations into 0.67x0.83
equilibrium
conc = moles/ vol (in dm3) Kc expression
concentrations
Example 4
N2 (g) + 3H2 (g ) 2 NH3 (g)
Initially there were 1.5 moles of N2 and 4 mole of H2, in a 1.5 dm3 container. At
equilibrium 30% of the Nitrogen had reacted. Calculate Kc
N2 H2 NH3
30% of the nitrogen had reacted = 0.3 x1.5 = 0.45 moles reacted.
Initial moles 1.5 4.0 0 Using the balanced equation 3 x 0.45 moles of H 2 must have
reacted and 2x 0.45 moles of NH3 must have formed
Equilibrium moles
Work out the moles at equilibrium for the reactants and products
moles of reactant at equilibrium = initial moles – moles reacted
moles of nitrogen at equilibrium = 1.5 – 0.45 = 1.05 moles of hydrogen at equilibrium =4.0 – 0.45 x3 = 2.65
moles of product at equilibrium = initial moles + moles formed
moles of ammonia at equilibrium = 0 + (0.45 x 2) = 0.9
N2 H2 NH3
Finally put concentrations into Kc expression
Equilibrium moles 1.05 2.65 0.9 [NH3 (g)]2

Kc=
Equilibrium 1.05/1.5 2.65/1.5 0.9/1.5 [N2 (g) ] [H2 (g)]3
concentration (M) =0.7 =1.77 =0.6
Kc
= 0.62 = 0.0927 mol-2 dm+6
Work out the 0.7x1.773
equilibrium
conc = moles/ vol (in dm3)
concentrations
Effect of changing conditions on value of Kc

Kc only changes with temperature.
The larger the Kc the greater the amount of products. It does not change if pressure or
If Kc is small we say the equilibrium favours the reactants concentration is altered.
A catalyst also has no effect on Kc
Effect of Temperature on position of equilibrium and Kc
In this equilibrium which is exothermic in the forward direction

Both the position of equilibrium
and the value of Kc will change it N2 (g) + 3H2 (g ) 2 NH3 (g)
temperature is altered
If temperature is increased the reaction will shift to oppose the change and
move in the backwards endothermic direction. The position of equilibrium
shifts left. The value of Kc gets smaller as there are fewer products.
Effect of Pressure on position of equilibrium and Kc
The position of equilibrium will In this equilibrium which has fewer moles of gas on the product side
change it pressure is altered but N2 (g) + 3H2 (g ) 2 NH3 (g)
the value of Kc stays constant as
Kc only varies with temperature If pressure is increased the reaction will shift to oppose the change and
move in the forward direction to the side with fewer moles of gas. The
position of equilibrium shifts right. The value of Kc stays the same though as
only temperature changes the value of Kc.
Catalysts have no effect on the value of Kc or the position of equilibrium

as they speed up both forward and backward rates by the same amount.
4
Calculating the amounts of the equilibrium mixture from Kc
Using algebra it is possible to work out the amounts of each

component in an equilibrium mixture using the value of Kc
Example 5
For the following equilibrium H2 (g) + Br2 (l) 2HBr (g)
If 0.200 mol of H2 and 0.200 mol of Br2 are mixed and allowed to reach equilibrium. If Kc = 0.210
what are the equilibrium amounts of each substance.
[HBr (g)]2 Make x = moles of H2 that have reacted

Kc=
[H2 (g) ] [Br2 (g)] at equilibrium
V = volume of container
(2x/V)2 This reaction is equimolar (same number

0.21 = (0.2-x)/V . (0.2-x)/V of moles of reactant as products) so it is
possible to cancel out the volume V
(2x)2
0.21 =
(0.2-x) . (0.2-x)
(2x)2
0.21 = Square root both sides
(0.2-x)2
2x
√0.21 = Rearrange to give x
0.2-x
0.458(0.2-x) = 2x
This example has been carefully set up to
0.0917 - 0.458x = 2x avoid the formation of a quadratic equation.
0.0917 = 2x + 0.458x It is not on the A-level syllabus to solve
quadratic equations.
x = 0.0917/2.458
x = 0.0373
So at equilibrium
Moles of H2 = 0.2000- 0.0373 Moles of Br2 = 0.2000- 0.0373 Moles of HBr = 2x 0.0373
= 0.163 mol = 0.163mol = 0.0746mol
Partial Pressures and Kp
If a reaction contains gases an alternative equilibrium expression can be
set up using the partial pressures of the gases instead of concentrations
Partial Pressure
The partial pressure of a gas in a mixture is the pressure

that the gas would have if it alone occupied the volume partial pressure = mole fraction x total pressure
occupied by the whole mixture. of gas 1 of gas 1
If a mixture of gases contains 3 different gases then the p1 = x1 P

total pressure will equal the 3 partial pressure added
together
P =p1 + p2 + p3
mole fraction
mole fraction = number of moles of a gas
total number of moles of all gases
For a 3 part mixture

x1 = y1
y1+y2 +y3
Example 6 : A mixture contains 0.2 moles N2, 0.5 moles O2 and 1.2 moles of CO2. If the total pressure is
3kPa. What are the partial pressures of the 3 gases?
Total moles of gas = 0.5 + 1.2+ 0.2

= 1.9
mole fraction = 0.2/1.9 mole fraction = 0.5/1.9 mole fraction = 1.2/1.9

of N2 =0.105 of O2 =0.263 of CO2 =0.632
Partial pressure =0.105x 3 Partial pressure = 0.263 x 3 Partial pressure = 0.632 x 3

of N2 =0.315 of O2 =0.789 of CO2 =1.896
Writing an expression for Kp
N2 (g) + 3H2 (g) 2 NH3 (g) p means the partial pressure of that gas
p 2 NH3 Kp = equilibrium constant

Kp=
p N2 p 3 H2 Only include gases in the Kp expression. Ignore
solids, liquids, and aqueous substances.
Working out the unit of Kp
Put the unit of pressure(kPa) into the Kp equation
kPa2 However, if the equation is

2 NH Unit = written the other way round, the
p 3 (g) kPa kPa3
Kp= value of Kp will be the inverse of
pN2 (g) p 3H 2 (g) above and the units will be
1
Cancel out units Unit = kPa2.
kPa2 It is important therefore to write
an equation when quoting
Unit = kPa-2 values of Kp.
Example 7
N2 (g) + 3H2 (g ) 2 NH3 (g)
1 mole of N2 and 3 moles of H2 are added together and the mixture is allowed to reach equilibrium. At
equilibrium 20% of the N2 has reacted. If the total pressure is 2kPa what is the value of Kp?
N2 H2 NH3
20% of the nitrogen had reacted = 0.2 x1.0 = 0.2 moles reacted.
Initial moles 1.0 3.0 0 Using the balanced equation 3 x 0.2 moles of H2 must have
reacted and 2x 0.2 moles of NH3 must have formed
Equilibrium moles
Work out the moles at equilibrium for the reactants and products
moles of reactant at equilibrium = initial moles – moles reacted
moles of nitrogen at equilibrium = 1.0 – 0.2 = 0.8 moles of hydrogen at equilibrium =3.0 – 0.20 x3 = 2.40
moles of product at equilibrium = initial moles + moles formed
moles of ammonia at equilibrium = 0 + (0.2 x 2) = 0.4
N2 H2 NH3
Finally put concentrations into Kp expression
Equilibrium moles 0.80 2.40 0.40 p 2 NH3 (g)

Kp=
Mole fractions 0.8/3.6 2.40/3.6 0.40/3.6 pN2 (g) p 3H2 (g)
=0.222 =0.667 =0.111
Partial pressure 0.222 0.667 x2 0.111 x2 Kp = 0.2222 = 0.0469 kPa-2

x2 = =1.33 = 0.222 0.444x1.333
0.444
Heterogeneous equilibria for Kp
Kp expressions only contain gaseous substances. Any substance with another state is left out
CaCO3 (s) CaO (s) + CO2 (g)
Kp =p CO2
Unit kPa
Effect of changing conditions on value of Kc or Kp
Kc and Kp only change with temperature.
The larger the Kc the greater the amount of products. It does not change if pressure or
If Kc is small we say the equilibrium favours the reactants concentration is altered.
A catalyst also has no effect on Kc or Kp
Effect of Temperature on position of equilibrium and Kc
In this equilibrium which is exothermic in the forward direction
Both the position of equilibrium
and the value of Kc or Kp will N2 (g) + 3H2 (g ) 2 NH3 (g)
change it temperature is altered If temperature is increased the reaction will shift to oppose the change and
move in the backwards endothermic direction. The position of equilibrium
shifts left. The value of Kc gets smaller as there are fewer products.
Effect of Pressure on position of equilibrium and Kp

In this equilibrium which has fewer moles of gas on the product side
The position of equilibrium will
change it pressure is altered but N2 (g) + 3H2 (g ) 2 NH3 (g)
the value of Kp stays constant as If pressure is increased the reaction will shift to oppose the change and
Kp only varies with temperature move in the forward direction to the side with fewer moles of gas. The
position of equilibrium shifts right. The value of Kp stays the same though
as only temperature changes the value of Kp.
Increasing pressure does not change Kp. p 2 NH3

The increased pressure increases the pressure terms on Kp=
p N2 p 3 H2
bottom of Kp expression more than the top. The system is
now no longer in equilibrium so the equilibrium shifts to the x 2 NH3 . P2
right increasing mole fractions of products and decreases Kp= Where P is total
the mole fractions of reactants. The top of Kp expression x N2.P x3 H 3 pressure and x
2.P
therefore increases and the bottom decreases until the mole fraction
original value of Kp is restored x 2 NH3 . P2
Kp=
x N2 x3 H2. P4
8
Ionic Equilibria
Bronsted-Lowry Definition of acid Base behaviour
A Bronsted-Lowry acid is defined as a substance that can donate a proton.

A Bronsted-Lowry base is defined as a substance that can accept a proton.
HCl (g) + H2O (l)  H3O+ (aq) + Cl- (aq)

Each acid is linked to a conjugate base on
acid base acid base the other side of the equation.
Calculating pH
pH = - log [H+] Where [H+] is the concentration of hydrogen ions in the solution.
Calculating pH of strong acids

The concentration of hydrogen ions in a monoprotic strong acid
Strong acids completely dissociate
will be the same as the concentration of the acid.
For HCl and HNO3 the [H+(aq)] will be the same as the
original concentration of the acid. Always give pH values to 2d.p. In the exam
For 0.1M HCl the pH will be –log[0.1] =1.00
Finding [H+] from pH

On most calculators this is Example 8
[H+] = 1 x 10-pH done by pressing What is the concentration of HCl with a pH of
Inv (or 2nd function) log 1.35?
 - number(pH) [H+] = 1 x 10-1.35 = 0.045M
Ionic Product for water

In all aqueous solutions and pure water the following equilibrium occurs: H2O (l) H+ (aq) + OH- (aq)
This equilibrium has the following Because [H2O (l)] is much bigger than the
equilibrium expression concentrations of the ions, we assume its
Rearrange to value is constant and make a new constant Kw
[H+ ][OH- (aq)]
Kc= (aq) Kc x [H2O (l)] = [H+ (aq) ][OH- (aq)]
Kw = [H+ (aq) ][OH- (aq) ]
[H2O(l)]
Learn this expression
At 25oC the value of Kw for all aqueous solutions is 1x10-14 mol2dm-6 The Kw expression can be used to
calculate [H+ (aq)] ions if we know
the [OH- (aq)] ions and vice versa.
Finding pH of pure water
Pure water/ neutral solutions are neutral because the [H+ (aq) ] = [OH-(aq)]
Using Kw = [H+ (aq) ][OH- (aq) ] then when neutral Kw = [H+ (aq) ]2
and [H+(aq) ] = √ Kw
At 25oC [H+(aq) ] = √ 1x10-14 = 1x10-7 so pH = 7
At different temperatures to 25oC the pH of

Example 9 : Calculate the pH of water at 50ºC given that Kw = pure water changes. Le Chatelier’s principle
5.476 x 10-14 mol2 dm-6 at 50ºC can predict the change. The dissociation of
[H+(aq) ] = √ Kw = √ 5.476 x 10-14 =2.34 x 10-7 mol dm-3 water is endothermic so increasing the
pH = - log 2.34 x 10-7 = 6.6 temperature would push the equilibrium to
It is still neutral though as [H+ (aq) ] = [OH- (aq)] the right giving a bigger concentration of H +
ions and a lower pH.
Calculating pH of a Strong Base
For bases we are normally given the Example 10: What is the pH of the strong base 0.1M NaOH
concentration of the hydroxide ion.
Assume complete dissociation.
To work out the pH we need to work out [H+(aq)]
Kw = [H+ (aq)][OH- (aq)] = 1x10-14
using the Kw expression.
[H+(aq)] = Kw/ [OH- (aq)] = 1x10-14 / 0.1 = 1x10-13 M
Strong bases completely dissociate into their ions. pH = - log[1x10-13 ] =13.00
NaOH  Na+ + OH-
Weak Acids
Weak acids only slightly dissociate when dissolved in water, giving an equilibrium mixture.
We can simplify this to

HA + H2O (l) H3O+ (aq) + A- (aq) HA (aq) H+ (aq) + A- (aq)
Weak acids dissociation expression Example 11 Write an equation for dissociation of propanoic acid and
its ka expression
[H+ (aq)][A- (aq)]
Ka= CH3CH2CO2H(aq) H+ (aq) + CH3CH2CO2- (aq)
[HA (aq)]
[H+ (aq)][CH3CH2CO2-(aq)]
Ka=
The Ka for ethanoic acid is 1.7 x 10-5 mol dm-3. [CH3CH2CO2H(aq)]
The larger ka the stronger the acid.
pKa
Sometimes Ka values are quoted as pKa values
pKa = -log Ka so Ka = 10-pKa
Calculating pH of a Weak Acid
To make the calculation easier two assumptions are made to [H+ (aq)][A- (aq)]
simplify the Ka expression: Ka=
[HA (aq)]
1) [H+ (aq)]eqm = [A- (aq)] eqm because they have dissociated
according to a 1:1 ratio. Simplifies to
2) As the amount of dissociation is small we assume that the initial [H+ (aq)]2
concentration of the undissociated acid has remained constant. Ka=
[HA (aq)]initial
So [HA (aq) ] eqm = [HA(aq) ] initial
Example 12 What is the pH of a solution of 0.01M ethanoic acid (ka is 1.7 x 10-5 mol dm-3)?
CH3CO2H(aq) H+ (aq) + CH3CO2- (aq)
[H+ (aq)]2 [H+ (aq)]2

[H+ (aq)][CH3CO2-(aq)]
Ka= Ka= 1.7x 10-5 =
[CH3CO2H(aq)]initial 0.01
[CH3CO2H(aq)]
[H+ (aq)]2 = 1.7 x 10-5 x 0.01 pH = - log [H+] = -log (4.12 x10-4)
pH =3.38
[H+ (aq)] = √ 1.7 x 10-7 = 4.12 x 10-4
Example13 What is the concentration of propanoic acid with a pH of 3.52 (ka is 1.35 x 10-5 mol dm-3)?
CH3CH2CO2H(aq) H+ (aq) + CH3CH2CO2- (aq)
[H+] = 1 x 10-3.52 = 0.000302M

[H+ (aq)]2 [0.000302]2
[H+ (aq)][CH3CH2CO2-(aq)]
Ka= Ka= 1.35 x 10-5 =
[CH3CH2CO2H(aq)]initial [CH3CH2CO2H(aq)]initial
[CH3CH2CO2H(aq)]
[CH3CH2CO2H(aq)] = 9.12 x 10-8 /1.35 x 10-5 [CH3CH2CO2H(aq)] = 6.75 x 10-3 M
pH Calculations involving Neutralisation Reactions
These can be quite complex calculations working out the pH of a partially neutralised acid or the pH of the solution if too
much alkali has been added and has gone past neutralisation. The method differs if the acid is strong or weak for the
partially neutralised case.
Strong Acid and Strong Base Neutralisations Work out new concentration of excess H+ ions
[H+] = moles excess H+
If excess
total volume (dm3)
acid
Total volume =
Work out moles of original acid pH = – log [H+] vol of acid + vol
Work out moles of base added of base added
Work out which one is in excess
Work out new concentration of excess OH- ions
[OH-] = moles excess OH-
If excess total volume (dm3)
alkali
[H+] = Kw /[OH– ] Total volume =
vol of acid + vol
Example 14 15cm3 of 0.5M HCl is reacted with 35cm3 of pH = – log [H+] of base added
0.55M NaOH. What will be the pH of the resulting mixture?
Example 15 45cm3 of 1M HCl is reacted with 30cm3 of
Moles HCl = conc x vol = 0.5 x 0.015 = 0.0075mol
0.65M NaOH. What will be the pH of the resulting mixture?
Moles NaOH = conc x vol = 0.55 x 0.035 = 0.01925
HCl + NaOH  NaCl + H2O
Moles of NaOH in excess = 0.01925 – 0.0075= 0.01175 (as Moles HCl = conc x vol = 1 x 0.045 = 0.045mol
1:1 ratio) Moles NaOH = conc x vol = 0.65 x 0.030 = 0.0195
[OH-] = moles excess OH- HCl + NaOH  NaCl + H2O
total volume (dm3) Moles of HCl in excess = 0.045-0.0195 = 0.0255 (as 1:1 ratio)
[H+] = moles excess H+
= 0.01175/ 0.05 = 0.235M total volume (dm3)
[H+] = Kw /[OH– ]
= 0.0255/ 0.075 = 0.34M
= 1x10-14 / 0.235 = 4.25x10-14
pH = – log [H+]
pH = – log [H+]
= -log 0.34
= -log 4.25x10-14
= 0.47
= 13.37
Weak Acid and Strong Base Neutralisations Work out new concentration of excess HA
[HA] = initial moles HA – moles OH-
If excess
total volume (dm3)
acid
Work out moles of original acid
Work out moles of base added Work out concentration of salt formed [A -]
[A-] = moles OH- added
Work out which one is in excess
total volume (dm3)
Rearrange ka = [H+] [A-] to get [H+]
If excess alkali use the same method [HA]
with excess alkali and strong acid above pH = – log [H+]
Example 16 55cm3 of 0.5M CH3CO2H is reacted with 25cm3 of 0.35M NaOH. What will be the pH of the resulting
mixture?
CH3CO2H+ NaOH  CH3CO2Na + H2O
Moles CH3CO2H = conc x vol =0.5x 0.055 = 0.0275mol
ka is 1.7 x 10-5 mol dm-3
Moles of CH3CO2H in excess = 0.0275-0.00875 = 0.01875 (as 1:1 ratio)
[CH3CO2H ] = moles excess CH3CO2H [CH3CO2- ] = moles OH- added

total volume (dm3) total volume (dm3)
= 0.01875/ 0.08 = 0.234M = 0.00875/ 0.08 = 0.109M
ka = [H+] [CH3CO2- ]
[H+] = ka x[ CH3CO2H ] / [CH3CO2- ]
[ CH3CO2H ] pH = – log [H+]
= 1.7 x 10-5x 0.234 / 0.109 = -log 3.64 x 10-5
= 3.64 x 10-5 = 4.44
11
Working out pH of a weak acid at half equivalence
Example 17
When a weak acid has been reacted with exactly half the
What is the pH of the resulting solution when
neutralisation volume of alkali, the above calculation can be simplified
25cm3 of 0.1M NaOH is added to 50cm3 of 0.1M
considerably.
CH3COOH (ka 1.7 x 10-5 )
ka = [H+] [CH3CO2- ] At half neutralisation we can make the
[ CH3CO2H ] assumption that [HA] = [A-] From the volumes and concentrations spot it is half
neutralisation (or calculate)
So [H+(aq)] = ka And pH = pka pH = pka = -log (1.7 x 10-5 ) = 4.77
Diluting an acid or alkali pH of diluted base

pH of diluted strong acid [OH–] = [OH–]old x old volume
new volume
[H+] = [H+]old x old volume
[H+] = Kw
new volume [OH– ]
pH = – log [H+] pH = – log [H+]
Example 18 Calculate the new pH when 50.0 cm 3 of 0.150 mol dm-3 HCl is mixed with 500 cm3 of water.
[H+] = [H+]old x old volume 0.05 [H+(aq)] = 0.0136
[H+(aq)] = 0.150 x
new volume 0.55 pH = – log [H+]
= -log 0.0136
= 1.87
Buffer Solutions
A Buffer solution is one where the pH does not change

significantly if small amounts of acid or alkali are added to it. A basic buffer solution is made from a weak
base and a salt of that weak base ( made
An acidic buffer solution is made from a weak acid and a salt from reacting the weak base with a strong
of that weak acid ( made from reacting the weak acid with a acid).
strong base). Example :ammonia and ammonium chloride
Example : ethanoic acid and sodium ethanoate NH3 and NH4+Cl-
CH3CO2H (aq) and CH3CO2- Na+
How Buffer solutions work

In an ethanoic acid buffer
In a buffer solution there is a much
CH3CO2H (aq) CH3CO2- (aq) + H+ (aq) higher concentration of the salt
CH3CO2- ion than in the pure acid.
Acid conjugate base
The buffer contains a reservoir of HA and A - ions
If small amounts of acid is added to the buffer: Then the above equilibrium
will shift to the left removing nearly all the H+ ions added, [CH3CO2H (aq)]
[H+(aq)] = Ka
CH3CO2- (aq) + H+ (aq)  CH3CO2H (aq) [CH3CO2-(aq) ]
As there is a large concentration of the salt ion in the buffer the ratio
[CH3CO2H]/ [CH3CO2-] stays almost constant, so the pH stays fairly
constant.
If small amounts of alkali is added to the buffer. The OH- ions will react with H+ ions to
form water.
Learn these
H+ + OH -  H2O explanations carefully
and be able to write
The Equilibrium will then shift to the right to produce more H+ ions. the equilibrium to
illustrate your
CH3CO2H (aq) CH3CO2- (aq) + H+ (aq)
answer.
Some ethanoic acid molecules are changed to ethanoate ions but as there is a large
concentration of the salt ion in the buffer the ratio [CH3CO2H]/ [CH3CO2-] stays almost
constant, so the pH stays fairly constant.
Calculating the pH of Buffer Solutions
We still use the weak acids dissociation expression

[HA(aq)]
But here we assume the [A-] Normally we [H+(aq)] = Ka
[H+ (aq)][A- (aq)] rearrange to
Ka= concentration is due to the added [A- (aq) ]
[HA (aq)] salt only
We also assume the Initial concentration of the
The salt content can be added in several ways: a salt solution could be acid has remained constant, because amount
added to the acid or some solid salt added. A buffer can also be made by that has dissociated or reacted is small.
partially neutralising a weak acid with alkali and therefore producing salt.
Example 19: making a buffer by adding a salt solution

We can enter moles of
What would be the pH of a buffer made from 45cm 3 of 0.1M ethanoic acid acid and salt straight
and 50cm3 of 0.15 M sodium ethanoate (Ka = 1.7 x 10-5) ? into the equation as
they both have the
Work out the moles of both solutions same new final volume
Moles ethanoic = conc x vol = 0.1 x 0.045 = 0.0045mol [HA(aq)]
[H+(aq)] = Ka
Moles sodium ethanoate = conc x vol = 0.15 x 0.050 = 0.0075 [A- (aq) ]
0.0045
[H+(aq)] = 1.7 x 10-5 x [H+(aq)] = 1.02x 10-5 pH = – log [H+]
0.0075 = -log 1.02x 10-5
= 4.99
Example 20 : making a buffer by adding a solid salt

A buffer solution is made by adding 1.1g of sodium ethanoate into 100 cm 3 acid and salt straight
of 0.4M ethanoic acid. What is its pH? Ka =1.7 x10 -5 into the equation as
they both have the
Work out the moles of both solutions same new final volume
Moles ethanoic = conc x vol = 0.4 x 0.1 = 0.04mol [HA(aq)]
[H+(aq)] = Ka
Moles sodium ethanoate = mass/Mr= 1.1/82 = 0.0134 [A- (aq) ]
0.04
0.0134 = -log 5.07x 10-5
= 4.29
If a buffer is made by adding sodium hydroxide to partially neutralise a weak acid then follow the method below
Example 21 55cm3 of 0.5M CH3CO2H is reacted with 25cm3 of 0.35M NaOH. What will be the pH of the resulting buffer
solution?
CH3CO2H+ NaOH  CH3CO2Na + H2O
Moles CH3CO2H = conc x vol =0.5x 0.055 = 0.0275mol
ka is 1.7 x 10-5 mol dm-3
Moles of CH3CO2H in excess = 0.0275-0.00875 = 0.01875 (as 1:1 ratio)
[CH3CO2H ] = moles excess CH3CO2H [CH3CO2- ] = moles OH- added

total volume (dm3) total volume (dm3)
= 0.01875/ 0.08 = 0.234M = 0.00875/ 0.08 = 0.109M
ka = [H+] [CH3CO2- ]
[H+] = ka x[ CH3CO2H ] / [CH3CO2- ]
[ CH3CO2H ] pH = – log [H+]
= 1.7 x 10-5 x 0.234 / 0.109 = -log 3.64 x 10-5
= 3.64 x 10-5 = 4.44
Calculating change in pH of buffer on addition of small amount of acid or alkali
If a small amount of alkali is added to a buffer then the moles of the buffer acid would reduce by the
number of moles of alkali added and the moles of salt would increase by the same amount so a new
calculation of pH can be done with the new values.
CH3CO2H (aq) +OH-  CH3CO2- (aq) + H2O (l)
If a small amount of acid is added to a buffer then the moles of the buffer salt would reduce by the
number of moles of acid added and the moles of buffer acid would increase by the same amount so a
new calculation of pH can be done with the new values.
CH3CO2- (aq) + H +  CH3CO2H (aq)
Example 22: 0.005 mol of NaOH is added to 500cm3 of a buffer where the concentration of ethanoic acid is
0.200 mol dm-3 and the concentration of sodium ethanoate is 0.250 mol dm-3 . (Ka = 1.7 x 10-5)
Calculate the pH of the buffer solution after the NaOH has been added.
Work out the moles of acid and salt in the initial buffer solution
Moles ethanoic acid= conc x vol = 0.200 x 0.500 = 0.100mol
Moles sodium ethanoate = conc x vol = 0.25 x 0.500 = 0.125mol
Work out the moles of acid and salt in buffer after the addition of 0.005mol NaOH
Moles ethanoic acid = 0.100 - 0.005 = 0.095 mol
Moles sodium ethanoate = 0.125 +0.005 = 0.130 mol
[CH3COOH (aq)] acid and salt straight
[H+(aq)] = Ka into the equation as
[CH3COO- (aq) ] they both have the
same new final
volume
0.095
0.130 = -log 1.24x 10-5
= 4.91
Titration curves
Constructing a pH curve
1. Transfer 25cm3 of acid to a conical flask with a volumetric Calibrate meter first by measuring known pH of a
pipette buffer solution. This is necessary because pH meters
2. Measure initial pH of the acid with a pH meter can lose accuracy on storage.
3. Add alkali in small amounts (2cm3) noting the volume Most pH probes are calibrated by putting probe in a
added set buffer (often pH 4) and pressing a calibration
4. Stir mixture to equalise the pH button/setting for that pH. Sometimes this is
5. Measure and record the pH to 1 d.p. repeated with a second buffer at a different pH
6. Repeat steps 3-5 but when approaching endpoint add in
Can also improve accuracy by maintaining
smaller volumes of alkali
constant temperature
7. Add until alkali in excess
Strong acid – Strong base e.g. HCl and NaOH

There are 4 main types of curve
pH
1. Strong acid and strong base
13 2. Weak acid and strong base
Long steep part from 3. Strong acid and weak base
around 3 to 9 4. Weak acid and weak base
7
pH at equivalence point = 7
25 cm3 of base
You may also have to work out the

neutralisation volume from titration data given
in the question. These are done by standard The equivalence point lies at the
titration calculations. mid point of the extrapolated
vertical portion of the curve.
The Key points to sketching a curve:
Initial and final pH
Volume at neutralisation
General Shape (pH at neutralisation)
Weak acid – Strong base e.g. CH3CO2H and NaOH

Half neutralisation volume
At the start the pH rises quickly and then For weak acids
levels off. The flattened part is called the
buffer region and is formed because a buffer [H+ (aq)][A- (aq)]
solution is made Ka=
[HA (aq)]
pH
At ½ the neutralisation
13 volume the [HA] = [A-]
Equivalence point >7 So Ka= [H+] and pKa = pH
7 If we know the Ka we can then work out

Steep part of curve >7 the pH at ½ V or vice versa.
(around 7 to 9)
If a pH curve is plotted then the pH of a
pH
1 weak acid at half neutralisation (½ V) will
starts
equal the pKa
near 3 V cm3 of base
½V
Weak acid – Weak base
Strong acid – Weak base e.g. HCl and NH3
e.g. CH3CO2H and NH3
pH
pH
13
13
No Steep part of the curve
Steep part of curve <7

7 7
(around 4 to 7)
Equivalence point < 7

1
1
25 cm3 of base
25 cm3 of base
Choosing an Indicator How indicators work
Indicators can be considered as weak acids. The acid HIn (aq) In- (aq) + H+ (aq)
must have a different colour to its conjugate base colour A colour B
We can apply Le Chatelier to give us the

An indicator changes colour from HIn to In- over a
colour.
narrow range. Different indicators change colours
over different ranges. In an acid solution the H+ ions present will
push this equilibrium towards the reactants.
Therefore colour A is the acidic colour.
The end-point of a titration is defined as the point
when the colour of the indicator changes colour In an alkaline solution the OH- ions will
react and remove H+ ions causing the
The end-point of a titration is reached when [HIn] = equilibrium to shift to the products. Colour B
[In-]. To choose a correct indicator for a titration one is the alkaline colour.
should pick an indicator whose end-point coincides
with the equivalence point for the titration.
An indicator will work if the pH range of the indicator lies on the steep part of the titration curve. In this case
the indicator will change colour rapidly and the colour change will correspond to the neutralisation point.
pH
Only use phenolphthalein in titrations with strong strong base
13
bases but not weak bases-
Colour change: colourless acid  pink alkali pH range for
weak base phenolphthalein
7
Use methyl orange with titrations with weak acid pH range for
strong acids but not weak acids methyl orange
Colour change: red acid  yellow alkali 1
strong acid
(orange end point)
25 cm3 of base
16
Diprotic acid with base Diprotic base with acid
pH
pH
13 1st protonation
13 CO32- + H+  HCO3-
7 2nd dissociation 2nd protonation

HC2O4- + OH-  C2O42- + H2O 7 HCO3- + H+  H2O + CO2
1st dissociation
1 H2C2O4 + OH-  HC2O4- + H2O
1
Vol base in cm3
Vol acid in cm3
Diprotic acids will give a two part pH curve with two
end points. Different indicators can be used to find
out the two end points.
Partition coefficients
Separating funnel organic
Solvent extraction splits a solute between two immiscible liquid solvent.
solvents. The solute will be split between the two solvents in an
equilibrium. Aqueous
solvent
Solute in aqueous solvent Solute in organic solvent
The partition coefficient Kpc [ solute in organic]

can be calculated from the Kpc =
[ solute in aqueous] The concentration term is usually mol dm-3.
equilibrium expression As the expression has the same substance in
both terms it is also possible to use g dm-3 or
gcm-3
Kpc is defined as equilibrium constant for the solution of a

solute between two immiscible solvents
Example 23 Example 24
3.56g of phenylamine was produced in an The partition coefficient of substance Y between ether
experiment. It was present in 30cm3 of an alkaline and water is 35.0
solution. The phenylamine was extracted by A solution contains 3.50 g of Y dissolved in 0.500 dm3 of
addition of 50cm3 of an organic solvent water.
dichloromethane. After the extraction, the Calculate the mass of Y that can be extracted from this
dichloromethane layer contained 3.01g of aqueous solution by mixing it with 0.050 dm3 of ether.
phenylamine.
Calculate the partition coefficient, Kpc, of mass left in water layer = 3.50 – x
phenylamine between dichloromethane and water.
Kpc = (x/0.05) = 35
((3.5-x)/0.50)
mass left in water layer = 3.56 – 3.01 = 0.55 g
10x = 35
Kpc = (3.01/50) = 3.28 (3.5-x)
(0.55/30)
x=2.72g
Solubility Product
Consider the dissolving of a solid in water as an equilibrium
BaSO4 (s) ⇌ Ba2+ (aq) + SO42- (aq)
An equilibrium expression can be written for the reaction
Ksp = [Ba2+] [SO42-] Note the BaSO4 (s) does not appear in the expression. In
a heterogeneous equilibrium, concentration terms for
solids are not included because they are constant
Note the case where multiple ions are dissociated
Na3PO4 (s) ⇌ 3Na+ (aq) + PO43- (aq)
The value of Ksp is corresponds to the case where it is a
Ksp = [Na+]3[PO43-] saturated solution (i.e. the maximum amount of solute
that can be dissolved in a solvent)
Unit of Ksp
Ksp = [Na+]3 [PO43-]
Like other equilibrium constants the unit of Ksp will
= [mol dm-3]3 [mol dm-3]
vary depending on the expression.
= mol4dm-12
Example 25 Example 26
A saturated solution of PbCl2 has the The Ksp for silver phosphate, Ag3PO4, is 1.25 × 10–20 .
concentration of [PbCl2 (aq)] of 3.5 x 10–2 mol dm–3 Calculate [Ag+(aq)] in a saturated solution of Ag3PO4.
Calulcate the Ksp for this solution.
PbCl2 (s) ⇌ Pb2+ (aq) +2 Cl- (aq) Ksp = [Ag+]3 [PO43-]

make [PO4 3–] = y and therefore [Ag+ ] = 3y
if [PbCl2] = 3.5 × 10–2 then [Pb2+ ] = 3.5 × 10–2 and
[Cl–] = 7.0 × 10–2 Ksp = [3y]3 [y] = 27y4
y = (Ksp / 27) ¼
Ksp = [Pb2+] [Cl-]2
Ksp = (3.5 × 10–2) × (7.0 × 10–2)2 y = (1.25 × 10–20 / 27) ¼ = 4.64 × 10–6 mol dm–3
= 1.715 × 10–4 mol3 dm–9 [Ag+ ] = 3y
= 1.39 × 10–5 mol dm–3
Case where concentrations are less than those of a saturated solution

If the ionic concentrations, put into the Ksp expression, give a value less
than the solubility product, then the solution is not saturated. No solid
precipitate would be seen
Common Ion Effect

If a mixture of salts present has an ion in common then they will
have an effect on each other’s solubility.
If sodium chloride solution is added to a solution of lead chloride The solubility of Ca(OH)2 in 0.1 mol dm–3 NaOH
then the increased concentration of chloride ions will shift the lead is lower than that in water.
chloride equilibrium to the left It is less soluble in NaOH due to the common
hydroxide ion effect. It causes the equilibrium
PbCl2 (s) ⇌ Pb2+ (aq) +2 Cl- (aq) Ca(OH)2 (s) ⇌ Ca2+ (aq) +2 OH- (aq)
The solubility of the lead chloride would therefore decreases to be shifted to the left by the higher hydroxide
and more solid would be produced ion concentration
8 Reaction Kinetics
Collision theory
Energy
Reactions can only occur when collisions take place Activation
between particles having sufficient energy. The energy is Energy:
usually needed to break the relevant bonds in one or EA
either of the reactant molecules. reactants
This minimum energy is called the Activation Energy
∆H
The Activation Energy is defined as the minimum
products
energy which particles need to collide to start a reaction
Maxwell Boltzmann Distribution
The Maxwell-Boltzmann energy distribution shows the spread of energies that
Learn this curve
molecules of a gas or liquid have at a particular temperature
carefully
Emp this is the most

probable energy (not the
same as mean energy) The area under the curve
represents the total number of
A few have low particles present
energies because
collisions cause some
Fraction of molecules
Most molecules have energies

particles to slow down between the two extremes but the
distribution is not symmetrical (normal)
with energy
Only a few particles

have energy greater
than the EA
Emp Collision energy 
Ea
The energy distribution

The mean energy of The energy distribution should
should go through the
the particles is not at never meet the x axis, as there is
origin because there are
the peak of the curve no maximum energy for molecules
no molecules with no
energy
Q. How can a reaction go to completion if few particles have energy greater than Ea?
A. Particles can gain energy through collisions
Measuring Reaction Rates
The rate of reaction is defined as the change in concentration of a substance in unit time
Its usual unit is mol dm-3s-1
When a graph of concentration of reactant is plotted vs Initial rate =

time, the gradient of the curve is the rate of reaction. gradient of
concentration
tangent
The initial rate is the rate at the start of the
reaction where it is fastest
Reaction rates can be calculated from graphs of

concentration of reactants or products
time
Effect of Increasing Concentration and Increasing Pressure
At higher concentrations(and pressures) there are more particles per

unit volume and so the particles collide with a greater frequency
and there will be a higher frequency of effective collisions.
Note: If a question mentions a doubling of concentration/rate

then make sure you mention double the number of particles Higher concentration
Number of molecules
per unit volume and double the frequency of effective
collisions.
lower concentration
If concentration increases, the shape of the energy distribution
with energy
curves do not change (i.e. the peak is at the same energy) so
the Emp and mean energy do not change
They curves will be higher, and the area under the curves will
be greater because there are more particles
Collision energy 
Ea
More molecules have energy > EA (although not a greater proportion)
Comparing rate curves

Need to calculate/ compare
Amount of initial moles of reactants to
product e.g. A
distinguish between different
Volume of B finishing volumes.
gas
e.g. the amount of product is
Different volumes of the C proportional to the moles of
D
same initial concentrations reactant
will have the same initial
rate (if other conditions are Time (secs)
the same) but will end at The higher the concentration/ temperature/
different amounts surface area the faster the rate (steeper the
gradient)
Rate Equations
The rate equation relates mathematically the rate of reaction to the concentration of the reactants.
For the following reaction, aA + bB  r is used as symbol for rate

products, the generalised rate equation is: r = k[A]m[B]n
The unit of r is usually mol dm-3 s-1
The square brackets [A] means

m, n are called reaction orders the concentration of A
Orders are usually integers 0,1,2 (unit mol dm-3)
0 means the reaction is zero order with respect to that reactant k is called the rate constant
1 means first order
2 means second order
The total order for a reaction is worked
NOTE: the orders have nothing to do with the stoichiometric out by adding all the individual orders
coefficients in the balanced equation. They are worked out together (m+n)
experimentally
Calculating orders from initial rate data
For zero order: the concentration of A has no effect on the

initial
rate of reaction r = k[A]0 = k
For first order: the rate of reaction is directly proportional

to the concentration of A r = k[A]1
For second order: the rate of reaction is proportional to the

concentration of A squared r = k[A]2
For a rate concentration graph to show the

Graphs of initial rate against concentration show the
order of a particular reactant the
different orders. The initial rate may have been
concentration of that reactant must be varied
calculated from taking gradients from concentration
whilst the concentrations of the other
/time graphs
reactants should be kept constant.
Continuous Monitoring
When we follow one experiment over time recording the
change in concentration we call it a continuous rate method.
concentration
The gradient represents the rate of reaction. The reaction is

fastest at the start where the gradient is steepest. The rate
drops as the reactants start to get used up and their
concentration drops. The graph will eventual become
horizontal and the gradient becomes zero which represents
the reaction having stopped.
Measurement of the change in volume of a gas
This works if there is a change in the number of moles of gas in the
reaction. Using a gas syringe is a common way of following this. It
works quite well for measuring continuous rate but a typical gas
syringe only measures 100ml of gas so you don’t want at reaction to
produce more than this volume. Quantities of reactants need to be gas syringe
calculated carefully.
Mg + HCl  MgCl2 +H2
Typical Method
The initial rate is the rate at the start of the reaction, • Measure 50 cm3 of the 1.0 mol dm–3 hydrochloric acid
where it is fastest. It is obtained by taking the gradient of and add to conical flask.
a continuous monitoring conc vs time graph at time = • Set up the gas syringe in the stand
zero. A measure of initial rate is preferable as we know
• Weigh 0.20 g of magnesium.
the concentrations at the start of the reaction
• Add the magnesium ribbon to the conical flask, place the
bung firmly into the top of the flask and start the timer.
• Record the volume of hydrogen gas collected every 15
seconds for 3 minutes.
Large Excess of reactants

In reactions where there are several reactants, if the
concentration of one of the reactant is kept in a large excess
then that reactant will appear not to affect rate and will be
pseudo-zero order . This is because its concentration stays
virtually constant and does not affect rate.
Continuous rate experiments

Continuous rate data
0.060 This is data from one experiment where the concentration of

one substance is followed throughout the experiment.
If half-lives are constant then
[A]
the order is 1st order

For this method to work the concentrations of the reactants
0.030 not being followed must be in large excess in
the experiment so their concentrations stay virtually
constant and do not affect rate.
0.015
0.0075 This data is processed by plotting the data and calculating
successive half-lives.
t½ t½ t½
Time (min) The half-life of a first-order reaction
is independent of the concentration and is constant
Second order zero order

0.060
0.060 If zero order the rate
stays constant as the
reactant is used up.
This means the
[A]
If half-lives rapidly increase

concentration has no
[A]
0.030 then the order is 2nd order

0.030 effect on rate
0.015
0.015
0.0075
0.0075
t½ t½ t½
Time (min) Time (min)
The rate constant (k)
1. The units of k depend on the overall order of For a 1st order overall reaction the unit of k is
reaction. It must be worked out from the rate s-1
equation For a 2nd order overall reaction the unit of k is
2. The value of k is independent of concentration and mol-1dm3s-1
time. It is constant at a fixed temperature. For a 3rd order overall reaction the unit of k is
3. The value of k refers to a specific temperature and mol-2dm6s-1
it increases if we increase temperature
Example (first order overall)
Rate = k[A][B]0 m = 1 and n = 0 Remember: the values of the reaction orders must
- reaction is first order in A and zero order in B be determined from experiment; they cannot be
- overall order = 1 + 0 = 1 found by looking at the balanced reaction equation
- usually written: Rate = k[A]
Calculating units of k
1. Rearrange rate equation 2. Insert units and

to give k as subject cancel
k = Rate k = mol dm-3s-1

Unit of k = s-1
[A] mol dm-3
Example: Write rate equation for reaction between A and B

where A is 1st order and B is 2nd order.
r = k[A][B]2 overall order is 3
Calculate the unit of k
1. Rearrange rate equation to 2. Insert units and 3. Simplify fraction

give k as subject cancel
k= s-1
k = Rate k = mol dm-3s-1 Unit of k = mol-2dm6s-1
mol2dm-6
[A][B]2 mol dm-3.(moldm-3)2
Comparing continuous rate curves
The higher the concentration/ If the acid is in excess of the magnesium or marble chips then the final
temperature/ surface area the faster volume of gas produced will be proportional to the amount of moles of
the rate (steeper the gradient) acid
Need to calculate/ compare

Amount of initial moles of reactants to
product e.g. distinguish between different
Volume of finishing volumes.
gas
e.g. the amount of product is
Different volumes of the proportional to the moles of
same initial concentrations reactant
will have the same initial rate
(if other conditions are the Time (secs)
same) but will end at
different amounts
Initial rate method
The initial rate can be calculated from taking the Initial rate can also be calculated from clock reactions
gradient of a continuous monitoring conc vs time where the time taken to reach a fixed concentration is
graph at time = zero measured.
A Common Clock Reaction (no need to learn details)

In clock reactions there are often two
Hydrogen peroxide reacts with iodide ions to form iodine. The
successive reactions and an end point is
thiosulfate ion then immediately reacts with iodine formed in the
achieved when one limited reactant runs
second reaction as shown below.
out, resulting in a sudden colour change
H2O2(aq) + 2H+(aq) + 2I–(aq) → I2(aq) + 2H2O(l)

By repeating the experiment several times,
2S2O32–(aq) + I2(aq) → 2I–(aq) + S4O62–(aq) varying the concentration of a reactant e.g.
I–, ( keeping the other reactants at constant
When the I2 produced has reacted with all of the limited amount of concentration )you can determine the
thiosulfate ions present, excess I2 remains in solution. Reaction with the order of reaction with respect to that
starch then suddenly forms a dark blue-black colour. reactant
A series of experiments is carried out, in which the concentration of
iodide ions is varied, while keeping the concentrations of all of the
other reagents the same. In each experiment the time taken (t) for the The initial rate of the reaction can be
reaction mixture to turn blue is measured. represented as (1/t )
Sulfuric Potassium Sodium

Experiment
acid (H+) Starch Water iodide(I-) Thiosulfate S2O32-
1 25 1 20 5 5
2 25 1 15 10 5
3 25 1 10 15 5
4 25 1 5 20 5
5 25 1 0 25 5
Working out orders from experimental initial rate data
Normally to work out the rate equation we do a series of experiments where the initial concentrations of reactants are
changed (one at a time) and measure the initial rate each time.
Working out rate order graphically

In an experiment where the concentration of one of
the reagents is changed and the reaction rate measured
it is possible to calculate the order graphically
log (rate)
gradient = n
Taking rate equation
Rate = k [Y]n = change in y
y intercept = log K
change in x
Log both sides of equation
Log rate = log k + n log [Y]
Y= c + mx
A graph of log rate vs log [Y] will yield a straight line where
the gradient is equal to the order n In this experiment high concentrations with
quick times will have the biggest percentage
errors.
This initial rate data can also be presented in a table.
Example: work out the rate equation for the following reaction, A+ B+ 2C  D + 2E, using the initial rate
data in the table
Experiment [A] [B] [C] Rate In order to calculate the order for a particular
mol dm- mol dm-3 mol dm-3 mol dm-3 s-1 reactant it is easiest to compare two
3
experiments where only that reactant is
1 0.1 0.5 0.25 0.1 being changed
2 0.2 0.5 0.25 0.2
If conc is doubled and rate stays the same: order= 0
3 0.1 1.0 0.25 0.4
If conc is doubled and rate doubles: order= 1
4 0.1 0.5 0.5 0.1
If conc is doubled and rate quadruples : order= 2
For reactant A compare between experiments 1 and 2

For reactant A as the concentration doubles (B and C staying constant) so does the
rate. Therefore the order with respect to reactant A is first order
For reactant B compare between experiments 1 and 3 :

As the concentration of B doubles (A and C staying constant) the rate quadruples.
Therefore the order with respect to B is 2nd order
For reactant C compare between experiments 1 and 4 :

As the concentration of C doubles (A and B staying constant) the rate stays the same.
Therefore the order with respect to C is zero order
The reaction is 3rd order overall and the unit of the

The overall rate equation is r = k [A] [B]2
rate constant =mol-2dm6s-1
Working out orders when two reactant concentrations are changed simultaneously
In most questions it is possible to compare between two experiments where only one reactant has its initial
concentration changed. If, however, both reactants are changed then the effect of both individual changes on
concentration are multiplied together to give the effect on rate.
In a reaction where the rate equation is r = k [A] [B]2

If the [A] is x2 that rate would x2
If the [B] is x3 that rate would x32= x9
If these changes happened at the same time then the rate would x2x9= x 18
Example work out the rate equation for the reaction, between X and Y, using the initial rate data in the table
Experiment Initial concentration of Initial concentration Initial

X/ mol dm–3 of Y/ mol dm–3 rate/ mol dm–3 s–1
1 0.05 0.1 0.15 x 10–6
2 0.10 0.1 0.30 x 10–6
3 0.20 0.2 2.40 x 10–6
For reactant X compare between experiments 1 and 2

For reactant X as the concentration doubles (Y staying constant) so does the rate.
Therefore the order with respect to reactant X is first order
Comparing between experiments 2 and 3 :
Both X and Y double and the rate goes up by 8
We know X is first order so that will have doubled rate

The overall rate equation is r = k [X] [Y]2
The effect of Y, therefore, on rate is to have quadrupled it.
The reaction is 3rd order overall and the unit of
Y must be second order
the rate constant =mol-2dm6s-1
Calculating a value for k using initial rate data
Using the above example, choose any one of the experiments and put the values into the rate equation that
has been rearranged to give k. Using experiment 3:
r = k [X] [Y]2 k= r k = 2.40 x 10–6 k = 3.0 x 10-4 mol-2dm6s-1

[X] [Y]2
0.2 x 0.22
Remember k is the same for all experiments done at the same temperature.
Increasing the temperature increases the value of the rate constant k
zero order: Calculating k from

Concentration-time graphs
For zero order reactants, the rate stays constant The gradient of this graph is
as the reactant is used up. This means the equal to the rate constant
[A]
concentration of that reactant has no effect on rate.

Rate = k [A]0 so rate = k
As the rate is the gradient of the graph on the right,
the gradient is also the value of the rate constant.
Time (min)
8
Techniques to investigate rates of reaction
There are several different methods for measuring reactions rates. Some reactions can be measured
in several ways
Measurement of the change in volume of a gas

This works if there is a change in the number of moles of
gas in the reaction. Using a gas syringe is a common
way of following this. If drawing a gas syringe make
sure you draw it with some
(CH3)2C=CH2(g) + HI(g) (CH3)3CI(g) measurement markings on the
barrel to show measurements
HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g) can be made.
Measurement of change of mass
This works if there is a gas produced which is allowed to

escape. Works better with heavy gases such as CO2
HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)
Titrating samples of reaction mixture with acid, alkali, sodium thiosulphate etc
Small samples are removed from the reaction mixture, quenched (which
stops the reaction) and the titrated with a suitable reagent.
HCOOCH3(aq) + NaOH(aq)  HCOONa(aq) + CH3OH(aq) The NaOH could be titrated with an acid
BrO3 –(aq) + 5Br –(aq) + 6H+(aq)  3Br2(aq) + 3H2O(l) The H+ could be titrated with an alkali
CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq) The I2 could be titrated with sodium
thiosulphate
Colorimetry.
If one of the reactants or products is coloured H2O2(aq) + 2I- (aq) + 2H+(aq)  2H2O(l) + I2(aq)
then colorimetry can be used to measure the
change in colour of the reacting mixtures The I2 produced is a brown solution
Measuring change in electrical conductivity

Can be used if there is a change in the number HCOOH(aq) + Br2(aq)  2H+(aq) + 2Br - (aq) + CO2(g)
of ions in the reaction mixture
Measurement of optical activity.

If there is a change in the optical activity through
the reaction this could be followed in a CH3CHBrCH3 (l) + OH−(aq)  CH3CH(OH)CH3 (l) + Br−(aq)
polarimeter
In the experiment between sodium thiosulphate and hydrochloric acid we usually measure reaction rate as
1/time where the time is the time taken for a cross placed underneath the reaction mixture to disappear due
to the cloudiness of the Sulphur . Na2S2O3 + 2HCl  2NaCl + SO2 + S + H2O
This is an approximation for rate of reaction as it does not include concentration. We can use this because
we can assume the amount of Sulphur produced is fixed and constant.
Rate Equations and Mechanisms
A mechanism is a series of steps through which the reaction Each step can have a different rate of
progresses, often forming intermediate compounds. If all the reaction. The slowest step will control the
steps are added together they will add up to the overall overall rate of reaction. The slowest step
equation for the reaction is called the rate-determining step.
The molecularity (number of moles of each substance) of the molecules in the slowest
step will be the same as the order of reaction for each substance.
e.g. 0 moles of A in slow step would mean A is zero order.
1 mole of A in the slow step would mean A is first order
Example 2 overall reaction

Example 1 A + 2B + C  D + E
overall reaction Mechanism
A + 2B + C  D + E Step 1 A + B  X + D fast
Mechanism Step 2 X+CY slow
Step 1 A + B  X + D slow Step 3 Y+BE fast
Step 2 X+CY fast
Step 3 Y+BE fast r = k [X]1[C]1
The intermediate X is not one of the reactants so
r = k [A]1[B]1[C]o must be replaced with the substances that make
C is zero order as it appears in the up the intermediate in a previous step
mechanism in a fast step after the slow step A+BX+D
r = k[A]1[B]1[C]1
Example 3
Example 4
Overall Reaction
Using the rate equation rate = k[NO]2[H2] and
NO2(g) + CO(g)  NO(g) + CO2(g)
the overall equation 2NO(g) + 2H2(g) N2(g) + 2H2O(g), the
following three-step mechanism for the reaction was
Mechanism:
suggested. X and Y are intermediate species.
Step 1 NO2 + NO2 NO + NO3 slow
Step 1 NO + NO  X
Step 2 NO3 + CO  NO2 + CO2 fast
Step 2 X + H2 Y
• NO3 is a reaction intermediate
Step 3 Y + H2  N2 + 2H2O
NO2 appears twice in the slow steps so it
is second order. CO does not appear in Which one of the three steps is the rate-determining step?
the slow step so is zero order. Step 2 – as H2 appears in rate equation and
r=k [NO2]2 combination of step 1 and 2 is the ratio that
appears in the rate equation.
Example 5: SN1 or SN2? You don’t need to remember the details here.
Remember the nucleophilic substitution reaction of

haloalkanes and hydroxide ions. The same reaction can also occur via a
different mechanism
This is a one step mechanism
Overall Reaction
H H
δ+ δ- -
(CH3)3CBr + OH–  (CH3)3COH + Br –
H3C C Br H3C C OH + :Br
-HO: Mechanism:
H H
(CH3)3CBr  (CH3)3C+ + Br – slow
CH3CH2Br + OH-  CH3CH2OH + Br- slow step
(CH3)3C+ + OH–  (CH3)3COH fast
This is called SN2.
The rate equation is Substitution, Nucleophilic, The rate equation is This is called SN1.
r = k [CH3CH2Br] [OH-] 2 molecules in rate Substitution, Nucleophilic,
determining step r = k [(CH3)3CBr] 1 molecule in rate
determining step
Increasing Temperature As the temperature increases the distribution shifts
towards having more molecules with higher energies
At higher temps both the Emp and mean energy shift to high energy
Lower temperature
values although the number of molecules with those energies decrease
T= 25OC
with energy
higher temperature
T= 1067OC
with energy
mean
Ea
The total area under the curve should remain constant
because the total number of particles is constant At higher temperatures the molecules have a wider
range of energies than at lower temperatures.
Effect of Increasing Temperature
Fraction of molecules Lower temperature

At higher temperatures the energy of the particles
increases. They collide more frequently and more
often with energy greater than the activation energy.
with energy
More collisions result in a reaction

higher temperature
As the temperature increases, the graph shows
that a significantly bigger proportion of particles
have energy greater than the activation energy,
so the frequency of successful collisions
increases Collision energy 
Ea
Effect of Increasing Surface area
Increasing surface area will cause successful collisions to occur more frequently between the
reactant particles and this increases the rate of the reaction.
11
Effect of Temperature on Rate Constant: The Arrhenius Equation
Increasing the temperature increases the value of the

rate constant k
k
Increasing temperature increases the rate constant k. The
relationship is given by the Arrhenius equation k = Ae-Ea/RT
where A is a constant R is gas constant and Ea is activation
energy. temperature
The Arrhenius equation can be rearranged 1/T
ln k = constant – Ea/(RT)
ln (Rate)
k is proportional to the rate of reaction so ln k can be
replaced by ln(rate) Gradient = - Ea/ R
From plotting a graph of ln(rate) or ln k against 1/T the
activation energy can be calculated from measuring Ea = - gradient x R
the gradient of the line
1/T
Example
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
Temperature time t -1.6
T (K) 1/T (s) 1/t Ln (1/t) x1,y1
297.3 0.003364 53 0.018868 -3.9703 -2.1
310.6 0.00322 24 0.041667 -3.1781
ln (Rate)
317.2 0.003153 16 0.0625 -2.7726 -2.6
323.9 0.003087 12 0.083333 -2.4849

-3.1
335.6 0.00298 6 0.166667 -1.7918
-3.6
x2,y2
gradient = y2-y1 The gradient should
x2-x1 always be -ve -4.1
In above example gradient =-5680 use a line of best fit

use all graph paper
Ea = - gradient x R (8.31) choose points far apart on the graph to
= - -5680 x8.31 calculate the gradient
= 47200 J mol-1
The unit of Ea using this equation will be J mol-1 .

Convert into kJ mol-1 by dividing 1000
Ea = +47.2 kJ mol-1
Effect of Catalysts
Definition: Catalysts increase reaction rates without getting used up.
Explanation: They do this by providing an alternative route or mechanism with a lower

activation energy
Activation
Comparison of the activation energies for an Energy:
uncatalysed reaction and for the same reaction with uncatalysed
a catalyst present.
reactants EA catalysed
∆H
products
If the activation energy is lower, more
With a lower activation
particles will have energy > EA, so
energy more particles have
there will be a higher frequency of

energy greater than the
effective collisions. The reaction will be
activation energy
faster
with energy
Ea un catalysed
catalysed Ea
Transition metals and their compounds can
A heterogeneous catalyst is in a different phase from the reactants
act as heterogeneous and homogeneous
catalysts. A homogeneous catalyst is in the same phase as the reactants
Heterogeneous catalysis
Adsorption of reactants at active sites on the surface may lead to
Heterogeneous catalysts are usually solids whereas the catalytic action. The active site is the place where the reactants
reactants are gaseous or in solution. The reaction adsorb on to the surface of the catalyst. This can result in the
occurs at the surface of the catalyst. bonds within the reactant molecules becoming weaker, or the
molecules being held in a more reactive configuration. There will
also be a higher concentration of reactants at the solid surface so
Strength of adsorption
leading to a higher collision frequency.
The strength of adsorption helps to determine the
effectiveness of the catalytic activity.
Some metals e.g. W have too strong adsorption and so Transition Metals can use the 3d and 4s e- of atoms on the metal
surface to form weak bonds to the reactants.
the products cannot be released.
Some metals e.g. Ag have too weak adsorption, and the
Steps in Heterogeneous Catalysis
reactants do not adsorb in high enough concentration.
Ni and Pt have about the right strength and are most 1. Reactants form bonds with atoms at active sites on the
useful as catalysts. surface of the catalyst (adsorbed onto the surface)
2. As a result bonds in the reactants are weakened and
break
Surface area:
3. New bonds form between the reactants held close
Increasing the surface area of a solid catalyst will improve
together on catalyst surface.
its effectiveness. A support medium is often used to
maximise the surface area and minimise the cost (e.g. Rh 4. This in turn weakens bonds between product and
on a ceramic support in catalytic converters). catalyst and product leaves (desorbs).
Examples of heterogeneous catalysts V2O5 is used as a catalyst in the Contact Process.
Overall equation : 2SO2 + O2  2SO3
Fe is used as a catalyst in the Haber Process
step 1 SO2 + V2O5  SO3 + V2O4
N2 + 3H2  2NH3
step 2 2V2O4 + O2  2V2O5
Catalytic converters
These remove CO, NOx and unburned hydrocarbons (e.g. octane, C8H18) from
the exhaust gases, turning them into ‘harmless’ CO 2, N2 and H2O. Converters have a ceramic
honeycomb coated with a thin
2 CO + 2 NO  2 CO2 + N2 layer of catalyst metals Platinum,
Palladium, Rhodium – to give a
C8H18 + 25 NO  8 CO2 + 12½ N2 + 9 H2O large surface area.
Poisoning has a cost implication e.g. poisoning by sulphur in

the Haber Process and by lead in catalytic converters in cars Poisoning Catalysts
means that catalysts lose their efficiency and may need to be Catalysts can become poisoned by impurities and
replaced. consequently have reduced efficiency.
Homogeneous catalysis
When catalysts and reactants are in the same phase, the The intermediate will often have a different oxidation
reaction proceeds through an intermediate species. state to the original transition metal. At the end of the
reaction the original oxidation state will reoccur. This
illustrates importance of variable oxidation states of
Examples of homogeneous catalysts transition metals in catalysis.
Reaction between iodide and persulphate ions

The uncatalysed reaction is very slow because the reaction
The reaction between I- and S2O82- catalysed by Fe2+ needs a collision between two negative ions. Repulsion
overall S2O82- + 2I-  2SO42- + I2 between the ions is going to hinder this – meaning high
activation energy.
Catalysed alternative route Both of the individual stages in the catalysed mechanism
stage 1 S2O82- + 2Fe2+  2SO42- + 2Fe3+ involve collision between positive and negative ions and will
stage2 2I- + 2Fe3+  2Fe2+ + I2 have lower activation energies.
Fe3+ ions can also act as the catalyst because the two steps in the catalysed mechanism can occur in any order.
Catalytic role of atmospheric oxides of nitrogen in the oxidation of atmospheric sulfur dioxide
Nitrogen dioxide catalyses the conversion of sulphur dioxide to sulphur trioxide.
The first step of the reaction is
NO2 (g)+ SO2 (g) SO3 (g) + NO(g)
The second step of the reaction is
The nitrogen dioxide is regenerated at the end of the
NO (g)+ ½ O2 (g)  NO2 (g) reaction so is classed as a catalyst.
Enzymes
Enzymes are proteins. They are biological catalysts
substrate
The active site is usually a hollow in the globular Hydrogen

protein structure into which a substrate molecule bonding
can bond to the amino acid side chains through a
variety of interactions including Van der waals forces
• Hydrogen bonding
ser
• Van der waals forces
• Permanent dipole forces Ionic
• Ionic interactions interactions
H 3C CO2-
The interactions need to be strong enough to phe
asp
hold the substrate for long enough for the
enzyme catalysed reaction to occur but weak
enough for the product to be released active site
When the enzyme bonds to the active site it is called and enzyme-
substrate complex
Only substrate molecules with the right shape
and correct positions of functional groups will fit The enzyme has a specific shape that is complementary to
and bind to the active site- called the lock and active site . The substrate bonds to the active site. Other
key hypothesis substrates do not fit into active site
pH and Temperature can affect the shape and bonds in an enzyme. High temperatures cause the enzymes to
change shape – called denaturing
stereospecific active site

If the substrate is chiral then its likely that only one enantiomer will fit in the enzyme and so only one isomer will be
catalysed
Drugs as Enzyme Inhibitors

Many drugs act as an enzyme inhibitor by blocking the active site.
The inhibitor will often bind to the active site strongly so stopping the substrate attaching to the
enzyme.
(Some Inhibitors can also attach elsewhere on the enzyme but in doing so can change the shape of the
active site which also stops its effectiveness)
Computers can be used to help design such drugs
Constructing a catalysed mechanism for a reaction
Example
The following reaction is catalysed by Co2+ ions in an acidic solution. SO32– + ½ O2  SO4 2–.
Write a mechanism for the catalysed reaction by writing two equations involving Co 2+ and Co3+ ions.
Split the full equation into ½ O2 + 2H+ + 2e-  H2O

its two half equations SO32– + ½ O2  SO4 2–
SO32– + H2O  SO4 2– + 2H+ + 2e-
Add in cobalt to make two

new redox equations. Co2+  Co3+ + e- ½ O2 + 2H+ + 2Co2+  H2O + 2Co3+
Making sure the oxidised
cobalt equation is
combined with the original Co3+ + e-  Co2+ 2Co3+ + SO32– + H2O  SO4 2– + 2H+ + 2Co2+
reduced half equation and
vice versa
Check your two mechanism
equations add up to the original full
non-catalysed equation.
16
9 The Periodic Table: chemical periodicity
Period 2 = Li, Be, B, C, N, O, F, Ne
Period 3 = Na, Mg, Al, Si, P, S, Cl, Ar
Atomic radius 0.2

Atomic radii decrease as you move from left to right
atomic radius (nm)

across a period, because the increased number of
protons create more positive charge attraction for 0.15
electrons which are in the same shell with similar
shielding. 0.1
Exactly the same trend in period 2 0.05
0
Na Mg Al Si P S Cl Ar
Ionic radius
Na+ Mg2+ Al3+ Si4+ all have the same electronic structure
(of the noble gas Ne) 0.3 0.271
There are increasing numbers of protons from Na to Si but 0.25 0.212
the same number of electrons. The effective nuclear ionic radius /nm
0.184 0.181
attraction per electron therefore increases and ions get 0.2
smaller
0.15
0.095
Positive ions are smaller compared to their atoms 0.1 0.065
because it has one less shell of electrons and the ratio 0.05 0.041
of protons to electrons has increased so there is 0.05
greater net force on remaining electrons holding them
0
more closely.
Na+ Mg2+ Al3+ Si4+/4- P3- S2- Cl-
Similarly Si4- P3- S2- Cl- all have the same electronic
structure (of the noble gas Ar)
There are increasing numbers of protons from Si to Cl but
the same number of electrons. The effective nuclear
attraction per electron therefore increases and ions get
smaller
Melting and boiling points 3000

For Na, Mg, Al- Metallic bonding : strong bonding – gets stronger
Melting and boiling
2500
the more electrons there are in the outer shell that are released to 2000
points (K)
the sea of electrons. A smaller positive centre also makes the 1500
bonding stronger. Higher energy is needed to break bonds.
1000
Si is Macromolecular: many strong covalent bonds between 500
atoms, high energy needed to break covalent bonds– very high mp
0
+bp Na Mg Al Si P S Cl Ar
Cl2 (g), S8 (s), P4 (S)- simple Molecular : weak van der waals between
molecules, so little energy is needed to break them – low mp+ bp Similar trend in period 2
S8 has a higher mp than P4 because it has more electrons (S8 Li,Be metallic bonding (high mp)
=128)(P4=60) so has stronger v der w between molecules B,C macromolecular (very high mp)
N2,O2 molecular (gases! Low mp as
Ar is monoatomic weak van der waals between atoms small v der w)
Ne monoatomic gas (very low mp)
Electrical conductivity
Elements with metallic bonding Macromolecular
Sodium, magnesium and aluminium are all good conductors of Silicon is a semiconductor.
electricity. The conductivity increases as you go from sodium
through to aluminium, as they have successively more Simple molecular P4 S8 Cl2 ,mono atomic Ar
delocalized electrons per atom These do not conduct electricity. There are no free
electrons to move.
1st ionisation energy

There is a general trend across is to increase. This is due to

1600
increasing number of protons as the electrons are being added to 1400
the same shell 1200
(kJ/mol)
1000
There is a small drop between Mg + Al. Mg has its outer electrons 800
600
in the 3s sub shell, whereas Al is starting to fill the 3p subshell. Al’s
400
electron is slightly easier to remove because the 3p electrons are 200
higher in energy. 0
Na Mg Al Si P S Cl Ar
There is a small drop between phosphorous and sulphur.
Sulphur’s outer electron is being paired up with an another Exactly the same trend in period 2 with
electron in the same 3p orbital. drops between Be & B and N to O for
When the second electron is added to an orbital there is a slight same reasons- make sure change 3s and
repulsion between the two negatively charged electrons which 3p to 2s and 2p in explanation!
makes the second electron easier to remove.
Ceramics
Magnesium oxide (giant ionic), aluminium oxide (giant ionic) and silicon dioxide
(giant covalent) can all be classed as ceramics. They have important properties in
common that are useful.
High melting points and strength - high
For ionic ones high because of giant lattice of ions with strong electrostatic forces
between oppositely charged ions
For giant covalent ones- high- because of many strong covalent bonds in
macromolecular structure. Take a lot of energy to break the many strong bonds
Electrical conductivity –low
For ionic ones poor: ions can’t move/ fixed in lattice
For giant covalent ones- poor, because electrons can’t move (localised)
Trends in the reactions of the elements Na, Mg, Al, Si, P and S with oxygen
The elements all react with oxygen to form

4 Na (s) + O2 (g) 2 Na2O (s) You should be able to
oxides.
2Mg (s) + O2 (g) 2MgO (s) write these equations.
Sodium burns with a yellow flame to produce
4Al (s) + 3O2 (g) 2Al2O3 (s) Learn the formulae of
a white solid
Si (s) + O2 (g) SiO2 (s) the oxides
Mg, Al, Si and P burn with a white flame to
4P (s) + 5O2 (g) P4O10 (s)
give white solid smoke
S (s) + O2 (g) SO2 (g) oxide O.N.
S burns with a blue flame to form an acidic
2S (s) + 3O2 (g) 2SO3 (g)
choking gas. Na2O +1
MgO +2
Sodium is stored under oil Note: the highest
.. O oxidation number of Al2O3 +3
and phosphorus under water
to stop these elements S the element in the
S oxide is the same as SiO2 +4
coming into contact and O O
reacting with air SO2 O O the number of P4O10 +5
SO3 valence elections in
the element SO3 +6
oxide O.N.
Reactions of the elements Na, Mg, Al, Si, P and S with chlorine
Note: the highest
NaCl +1
oxidation number of
2Na (s) + Cl2 (g) 2 NaCl (s)
the element in the MgCl2 +2
The elements of period 3 all react Mg (s) + Cl2 (g) MgCl2 (s)
chloride is the same
with chlorine to form chlorides. 2Al + 3Cl2 (g) Al2Cl6 (s) Al2Cl6 +3
as the number of
Si + 2Cl2 (g) SiCl4 (l)
valence elections in SiCl4 +4
2P + 5Cl2 (g) 2PCl5 (s)
the element
PCl5 +5
Trends in the reactions of the elements with water, limited to Na and Mg
Learn the equations
Sodium reacts with cold water. It fizzes around Magnesium reacts very slowly with cold water to form the
on surface etc. hydroxide but reacts more readily with steam to form the oxide
2 Na (s) + 2 H2O (l)  2 NaOH (aq) + H2 (g) Mg (s) + H2O (g)  MgO (s) + H2 (g)
A survey of the properties of the oxides of Period 3 elements
Ionic oxides Macromolecular oxides

The metal oxides (Na2O, MgO, Al2O3) are ionic. They have SiO2 is Macromolecular: It has many very strong
high melting points. They have Ionic giant lattice covalent bonds between atoms. High energy needed
structures: strong forces of attraction between ions : to break the many strong covalent bonds – very high
higher mp. They are ionic because of the large mp +bp
electronegativity difference between metal and O
Simple molecular oxides:
The increased charge on the cation makes the ionic forces P4O10 (s), SO2 (g) are simple molecular with
stronger (bigger lattice enthalpies of dissociation) going weak intermolecular forces between molecules (van
from Na to Al so leading to increasing melting points. der waals + permanent dipoles) so have lower mp’s.
They are covalent because of the small
Al2O3 is ionic but does show some covalent character. This electronegativity difference between the non-metal
can be explained by the electronegativity difference being and O atoms. P4O10 is a molecule containing 4P’s and
less big or alternatively by the small aluminium ion with a 10 O’s. As it is a bigger molecule and has more
high charge being able to get close to the oxide ion and electrons than SO2 it will have larger van der waals
distorting the oxide charge cloud forces and a higher melting point.
Learn the equations !

The reactions of the oxides of the elements Na  S with water
know the change in pH of the resulting
Metal ionic oxides tend to react with water to form hydroxides which solutions across the Period.
are alkaline
Na2O (s) + H2O (l)  2Na+ (aq) + 2OH- (aq) pH 13 (This is a vigorous Al2O3 and SiO2 do not dissolve in water
exothermic reaction) because of the high strength of the Al2O3
The ionic oxides are basic as the oxide ions accept protons to become ionic lattice and the SiO2 macromolecular
hydroxide ions in this reaction (acting as a bronsted lowry base) structure, so they give a neutral pH 7
MgO (s) + H2O (l)  Mg(OH)2 (s) pH 9
Mg(OH)2 is only slightly soluble in water as its lattice is stronger so MgO is better than NaOH for treating acid in
fewer free OH- ions are produced and so lower pH rivers and the stomach as it is only sparingly
soluble and weakly alkaline so using an excess
would not make the water excessively alkaline.
The non-metal, simple molecular, covalent, oxides react with water to give acids
P4O10 (s) + 6 H2O (l)  4 H3PO4(aq) pH 0 (this is a vigorous exothermic reaction) Equations showing
SO2 (g) + H2O (l)  H2SO3 (aq) pH 3 (weak acid) SO2 + H2O  H+ + HSO3- formation of ions in
SO3 (g) + H2O (l)  H2SO4 (aq) pH 0 SO3 + H2O  H+ + HSO4- solution
The trend is the ionic metal oxides show basic behaviour and the H H O
non-metal covalent oxides show acidic behaviour. O H O O
The slightly intermediate nature of the bonding in Aluminium O P
H S S O O
oxide is reflected in its amphoteric behaviour: it can act as both a O H O
O H O
base and an acid H
H2SO4 H2SO3
Displayed formulae of acids H3PO4
3
Acid base reactions between period 3 oxides and simple acids and bases.
The basic oxides react with acids to make salts
Na2O (s) + 2 HCl (aq)  2NaCl (aq) + H2O (l)
Na2O (s) + H2SO4 (aq)  Na2SO4 (aq) + H2O (l) Rather than learning the equations by rote, learn the
MgO (s) + 2 HCl (aq)  MgCl2 (aq) + H2O (l) pattern. Most follow the pattern acid + base  salt + water
Or ionically Know the charges on the ions e.g. PO4 3- , SO42-
Na2O (s) + 2H+ (aq)  2Na+ (aq) + H2O (l)
MgO (s) + 2 H+ (aq)  Mg2+ (aq) + H2O (l)
Amphoteric Oxides
Aluminium oxide can act as both an acid and an alkali and is therefore called amphoteric
Aluminum oxide acting as a base
Al2O3 (s)+ 3H2SO4 (aq) Al2(SO4)3 (aq) + 3H2O (l) Be careful for
Al2O3 + 6HCl  2AlCl3 + 3H2O whether the
Or ionically Al2O3 + 6H+  2Al3+ + 3H2O question is asking
for an ionic
Aluminum oxide acting as a acid equation or a full
Al2O3 (s)+ 2NaOH (aq) + 3H2O (l)  2NaAl(OH)4 (aq) (this equation needs learning carefully) one
Al2O3 (s)+ 2OH- (aq) + 3H2O (l)  2Al(OH)4- (aq)
The other simple molecular acidic oxides react with bases

SiO2 has a giant covalent structure with very strong
to form salts.
bonds. This stops SiO2 dissolving or reacting with water
P4O10 (s) + 12 NaOH (aq)  4Na3PO4(aq) + 6 H2O (l)
and weak solutions of alkali. It will, however, react with
P4O10 + 6 Na2O  4Na3PO4
very concentrated NaOH
SO2 (g) + 2NaOH (aq)  Na2SO3 (aq) + H2O (l)
2NaOH (l) + SiO2 (s) Na2SiO3 (aq) + H2O
SO3 (g) + 2NaOH(aq)  Na2SO4 (aq) + H2O (l)
It is still classed as an acidic oxide
Or show ionically
P4O10 (s) + 12 OH- (aq)  4PO4 3-(aq) + 6 H2O (l)
SO2 (g) + 2OH- (aq)  SO32- (aq) + H2O (l)
SO3 (g) + 2OH- (aq)  SO42- (aq) + H2O (l)
Bonding in period 3 chlorides

The metal chlorides (Na and Mg) are ionic
Ionic giant lattice structures: strong forces of attraction between ions : higher mp
Aluminium chloride is a simple covalent molecule because of the relatively small difference Cl
in electronegativity between Al and Cl. It exists as a dimer Al2Cl6
Cl
Cl Al
The non-metal chlorides are simple molecular SiCl4 Al Cl
Simple molecular: weak intermolecular forces (van der waals) so lower mp’s Cl
PCl5 has a higher than expected melting point because in solid phase it exists as a ionic
Cl
structure of PCl4+ PCl6-
The reactions of the chlorides of the elements Na  P with water
Ionic chlorides eg Na + Mg dissolve (and not hydrolyse) in NaCl (s) + aq  Na+ (aq) + Cl- (aq) pH7
water to form aqueous ions and neutral solutions MgCl2 (s) + aq  Mg2+ (aq) + 2Cl- (aq) pH7
Covalent chlorides react with water ( hydrolyse) to form

acidic solutions Al2Cl6 (s)+ 12H2O (l)  2[Al(H2O)6]3+ (aq) + 6Cl- (aq) pH3
Aluminium chloride has covalent character. It dissolves in Or simplified to
water to form an acidic solution. (Unlike Na and Mg which Al2Cl6 (s)+aq  2Al3+ (aq) + 6Cl- (aq) pH3
form neutral solutions when they dissolve in water.)
The [Al(H2O)6]3+ then reacts (hydrolyses) with water to
Note: Al acts more like the non-metals because produce H3O+ ions which make the solution acidic
its chloride is covalent [Al(H2O)6]3+(aq)+ H2O (l)  [Al(H2O)5(OH) ]2+ (aq) + H3O+ (aq)
SiCl4(l) + 4H2O(l)  Si(OH)4(s) + 4H+ (aq) + 4Cl- (aq) pH0

Observation: this is a vigorous exothermic reaction and a PCl5(s) + 4H2O(l)  H3PO4(aq) + 5H+ (aq) + 5Cl- (aq) pH0
white solid/gel forms Observation: this is a vigorous exothermic reaction
4
10. Group 2
Melting points
Down the group the melting points decrease. The
Atomic radius
metallic bonding weakens as the atomic size
Atomic radius increases down the Group.
increases. The distance between the positive ions and
As one goes down the group, the atoms have more
delocalized electrons increases. Therefore the
shells of electrons making the atom bigger.
electrostatic attractive forces between the positive
ions and the delocalized electrons weaken.

The outermost electrons are held more weakly because they are successively further from the nucleus
in additional shells.
In addition, the outer shell electrons become more shielded from the attraction of the nucleus by the
repulsive force of inner shell electrons
Group 2 reactions Reactivity of group 2 metals increases down the group

Reactions with oxygen.
Mg will also react slowly with oxygen without a flame.
The group 2 metals will burn in oxygen. Mg ribbon will often have a thin layer of magnesium oxide on it
Mg burns with a bright white flame. formed by reaction with oxygen.
2Mg + O2  2MgO 2Mg + O2  2MgO
This needs to be cleaned off by emery paper before doing
MgO is a white solid with a high melting reactions with Mg ribbon.
point due to its ionic bonding. If testing for reaction rates with Mg and acid, an un-cleaned Mg
ribbon would give a false result because both the Mg and MgO
would react but at different rates.
Mg + 2HCl  MgCl2 + H2
MgO + 2HCl  MgCl2 + H2O
Reactions with water.
Magnesium burns in steam to produce Mg will also react with warm water, giving a different
magnesium oxide and hydrogen. The Mg magnesium hydroxide product.
would burn with a bright white flame. Mg + 2 H2O  Mg(OH)2 + H2
Mg (s) + H2O (g)  MgO (s) + H2 (g) This is a much slower reaction than the reaction with
steam and there is no flame.
Make sure you learn the difference between the reaction of

Magnesium with steam and that of warm water
The hydroxides produced make the water alkaline
(if they are soluble in water)
The other group 2 metals will react with cold water with One would observe:
increasing vigour down the group to form hydroxides.
fizzing, (more vigorous down group)
Ca + 2 H2O (l) Ca(OH)2 (aq) + H2 (g)
the metal dissolving, (faster down group)
Sr + 2 H2O (l) Sr(OH)2 (aq) + H2 (g)
the solution heating up (more down group)
Ba + 2 H2O (l) Ba(OH)2 (aq) + H2 (g)
and with calcium a white precipitate
appearing (less precipitate forms down
group)
Reactions with acid
If Barium metal is reacted with sulphuric acid it will
only react slowly as the insoluble Barium sulphate
The group 2 metals will react with acids with increasing vigour produced will cover the surface of the metal and
down the group to form a salt and hydrogen act as a barrier to further attack.
Ba + H2SO4  BaSO4 + H2
Ca + 2HCl (aq) CaCl2 (aq) + H2 (g) The same effect will happen to a lesser extent with
Sr + 2 HNO3 (aq) Sr(NO3)2 (aq) + H2 (g) metals going up the group as the solubility
increases.
Mg + H2SO4 (aq) MgSO4 (aq) + H2 (g) The same effect does not happen with other acids
like hydrochloric or nitric as they form soluble
group 2 salts.
Reactions of the Oxides of Group 2 elements with water

Group 2 ionic oxides react with water to form hydroxides
The ionic oxides are basic as the oxide ions accept protons to become hydroxide ions in this
reaction (acting as a bronsted lowry base)
MgO (s) + H2O (l)  Mg(OH)2 (s) pH 9
Mg(OH)2 is only slightly soluble in water so fewer free OH- ions are produced and so lower pH
CaO (s) + H2O (l)  Ca(OH)2 (aq) pH 12
Reactions of the Oxides of Group 2 elements Reactions of the hydroxides of Group 2

with Acids elements with Acids
MgO (s) + 2 HCl (aq)  MgCl2 (aq) + H2O (l)
2HNO3 (aq) + Mg(OH)2 (aq)  Mg(NO3)2 (aq) + 2H2O (l)
SrO (s) + 2 HCl (aq)  SrCl2 (aq) + H2O (l) 2HCl (aq) + Mg(OH)2 (aq)  MgCl2 (aq) + 2H2O (l)
CaO (s) + H2SO4 (aq)  CaSO4 (aq) + H2O (l)
Reactions of the carbonates of Group 2

elements with Acids
MgCO3 (s) + 2 HCl (aq)  MgCl2 (aq) + CO2 (g) + H2O (l)
SrCO3 (s) + 2 HCl (aq)  SrCl2 (aq) + CO2 (g) + H2O (l)
CaCO3 (s) + H2SO4 (aq)  CaSO4 (aq) + CO2 (g) + H2O (l)
Thermal decomposition of Group 2 carbonates
Thermal decomposition is defined as the use of
Group 2 carbonates decompose on heating to produce group
heat to break down a reactant into more than one
2 oxides and carbon dioxide gas.
product
MgCO3(s)  MgO(s) + CO2(g)
CaCO3(s)  CaO(s) + CO2(g) The ease of thermal decomposition
decreases down the group
Group 2 carbonates are more thermally stable as you go down the
group. As the cations get bigger they have less of a polarising effect
and distort the carbonate ion less. The C-O bond is weakened less so
it less easily breaks down
Group 1 carbonates do not decompose with the exception of Lithium. As

they only have +1 charges they don’t have a big enough charge density to
polarise the carbonate ion. Lithium is the exception because its ion is small
enough to have a polarising effect
Li2CO3(s)  Li2O(s) + CO2(g)
There are a number of experiments that can be done to investigate the ease
of decomposition.
One is to heat a known mass of carbonate in a side arm boiling tube and pass lime water
the gas produced through lime water. Time for the first permanent
cloudiness to appear in the limewater. Repeat for different carbonates using
the same moles of carbonate/same volume of limewater/same Bunsen flame
and height of tube above flame.
Heat
Thermal decomposition of Group 2 Nitrates

Group 2 nitrates decompose on heating to produce group 2
oxides, oxygen and nitrogen dioxide gas.
2Mg(NO3)2 → 2MgO + 4NO2 + O2
You would observe brown gas evolving (NO2) and the White
The ease of thermal decomposition
nitrate solid is seen to melt to a colourless solution and then
decreases down the group
resolidify
The explanation for change in thermal stability is the same as for carbonates
Magnesium nitrate decomposes the easiest because the Mg 2+ ion is smallest and has the greater charge density. It
causes more polarisation of the nitrate anion and weakens the N―O bond
Group 1 nitrate do not decompose in the same way as group 2 with the
exception of Lithium nitrate. They decompose to give a Nitrate (III) salt
and oxygen.
2NaNO3 → 2NaNO2 + O2
Lithium nitrate decomposes in the same
Sodium Sodium way as group 2 nitrates
Nitrate(V) Nitrate(III)
4 LiNO3 → 2Li2O + 4NO2 + O2
Solubility of Hydroxides
Group II hydroxides become more soluble down the group.
All Group II hydroxides when not soluble appear as white precipitates.
Magnesium hydroxide is classed as insoluble in water. Calcium hydroxide is classed as partially soluble
in water and will appear as a white precipitate It
Simplest Ionic Equation for formation of Mg(OH)2 (s)
is used in agriculture to neutralise acidic soils.
Mg2+ (aq) + 2OH-(aq)  Mg(OH)2 (s).
A suspension of calcium hydroxide in water will
A suspension of magnesium hydroxide in water will appear appear more alkaline (pH 11) than magnesium
slightly alkaline (pH 9) so some hydroxide ions must therefore hydroxide as it is more soluble so there will be
have been produced by a very slight dissolving. more hydroxide ions present in solution.
Magnesium hydroxide is used in medicine (in suspension as milk An aqueous solution of calcium hydroxide is
of magnesia) to neutralise excess acid in the stomach and to called lime water and can be used a test for
treat constipation. carbon dioxide. The limewater turns cloudy as
white calcium carbonate is produced.
Mg(OH)2 + 2HCl  MgCl2 + 2H2O
Ca(OH)2 (aq) + CO2 (g)  CaCO3 (s) + H2O(l)
It is safe to use because it is so weakly alkaline. It is preferable to
using calcium carbonate as it will not produce carbon dioxide
gas. Barium hydroxide would easily dissolve in
water. The hydroxide ions present would
make the solution strongly alkaline.
Solubility of Sulphates Ba(OH)2 (S) + aq  Ba2+ (aq) + 2OH-(aq)
Group II sulphates become less soluble down the group.

BaSO4 is the least soluble.
An equation for the formation of the precipitate can be written as a full equation or simplest ionic equation
Full equation : SrCl2(aq) + Na2SO4 (aq)  2NaCl (aq) + SrSO4 (s)
Ionic equation: Sr2+ (aq) + SO42-(aq)  SrSO4 (s).
BaSO4 is used in medicine as a ‘Barium meal’ given to patients who need x-rays of their intestines. The Barium absorbs
the x-rays and so the gut shows up on the x-ray image. Even though Barium compounds are toxic it is safe to use here
because of its low solubility.
If Barium metal is reacted with sulphuric acid it will only react slowly as the insoluble Barium sulphate produced will
cover the surface of the metal and act as a barrier to further attack.
Ba + H2SO4  BaSO4 + H2
The same effect will happen to a lesser extent with metals going up the group as the solubility increases.
The same effect does not happen with other acids like hydrochloric or nitric as they form soluble group 2 salts.
Testing for Presence of a Sulphate ion

BaCl2 solution acidified with hydrochloric acid is used as a reagent to test for
Other anions should give a negative
sulphate ions.
result which is no precipitate
If acidified Barium Chloride is added to a solution that contains sulphate ions a forming.
white precipitate of Barium Sulphate forms.
Simplest ionic equation

Ba2+ (aq) + SO42-(aq)  BaSO4 (s).
The hydrochloric acid is needed to react with carbonate impurities that are often found in salts which would form
a white Barium carbonate precipitate and so give a false result. You could not used sulphuric acid because it
contains sulphate ions and so would give a false positive result.
2HCl + Na2CO3  2NaCl + H2O + CO2 Fizzing due to CO2 would be observed if a carbonate was present.
Explaining trends in solubility
Hydroxides energy
Group 2 hydroxides become more soluble down the group.
This can be explained by changes in the lattice enthalpy and hydration
enthalpy hydration
Lattice enthalpy drops down the group because the cations lattice
get bigger leading to a weaker ionic attraction
Water molecules are more strongly attracted to smaller ions with a
larger charge. Mg Ca Sr Ba Ra
Hydration enthalpy drops because the cations becomes bigger and For magnesium hydroxide the lattice enthalpy
less polarising so they attract the water molecules less. is larger than the hydration enthalpy leading
to an endothermic enthalpy of solution which
The hydroxides become more soluble because the lattice makes it less likely to dissolve
enthalpy drops more than the hydration enthalpy
For barium hydroxide the lattice enthalpy is
smaller than the hydration enthalpy leading
to an exothermic enthalpy of solution which
makes it more likely to dissolve
Sulfates energy
Group 2 sulfates become less soluble down the group.
This can be explained by same changes in the lattice enthalpy and lattice
hydration enthalpy as the above case
hydration
Lattice enthalpy drops down the group because the cations
get bigger leading to a weaker ionic attraction. The key
difference between sulfates and hydroxides is the sulfate ion is
much larger than the metal ions (and hydroxide ion). The Mg Ca Sr Ba Ra
decreasing size of the cation has less of an effect in this case
and the lattice enthalpy falls less going down the group For magnesium sulfate the lattice enthalpy is
Water molecules are more strongly attracted to smaller ions with a smaller than the hydration enthalpy leading
larger charge. to an exothermic enthalpy of solution which
makes it more likely to dissolve
Hydration enthalpy drops because the cations becomes bigger and
less polarising so they attract the water molecules less. For barium sulfate the lattice enthalpy is
larger than the hydration enthalpy leading to
The hydroxides become less soluble because the lattice an endothermic enthalpy of solution which
enthalpy drops less than the hydration enthalpy makes it less likely to dissolve
More on Insoluble salts and Precipitation reactions
Insoluble salts can be made by mixing appropriate solutions of ions so that a precipitate is formed
Barium nitrate (aq) + sodium sulphate (aq)  Barium Sulphate (s) + sodium nitrate (aq)
These are called precipitation reactions. A precipitate is a solid
There are some common rules for solubility of salts. No syllabus requires these to be learnt but a good
chemist does know them.
Soluble salts Insoluble salts
All sodium, potassium and ammonium salts
All nitrates
Most chlorides, bromides, iodides Silver, lead chlorides, bromides iodides
Most sulphates Lead sulphate strontium and barium sulphate
Sodium, potassium and ammonium Most other carbonates
carbonates
Sodium, potassium and ammonium Most other hydroxides
hydroxides
When making an insoluble salt, normally the salt would be removed by filtration, washed with distilled
water to remove soluble impurities and then dried on filter paper
Filtration
Filter
paper Buchner
residue
funnel
Filter Filter paper
funnel
Buchner flask (has Air outlet to
thicker glass walls than water pump
a normal flask to cope
filtrate with the vacuum )
This is gravitational filtration. Use This is vacuum filtration. The apparatus is

if small amounts of solid are connected to a water pump which will
formed. produce a vacuum. Use if larger amounts of
solid are formed.
Writing Ionic equations for precipitation reactions
We usually write ionic equations to show precipitation Spectator ions are ions that are
reactions. Ionic equations only show the ions that are • Not changing state
reacting and leave out spectator ions. • Not changing oxidation number
Take full equation Ba(NO3)2 (aq) + Na2SO4 (aq)  BaSO4 (s) + 2 NaNO3 (aq)
Separate (aq) solutions into Ba2+(aq) + 2NO3-(aq) + 2Na+ (aq)+ SO42-(aq)  BaSO4(s) + 2 Na+(aq)+ 2NO3- (aq)
ions
Cancel out spectator ions leaving

Ba2+ (aq) + SO42-(aq)  BaSO4 (s).
the simplest ionic equation
11 Halogens
Fluorine (F2): very pale yellow gas. It is highly reactive
All halogens exist as diatomic Chlorine : (Cl2) greenish, reactive gas, poisonous in high concentrations
molecules Bromine (Br2) : red liquid, that gives off dense brown/orange poisonous fumes
Iodine (I2) : shiny grey solid sublimes to purple gas.
Trend in melting point and boiling point

Increase down the group
As the molecules become larger they have more electrons and so have larger induced dipole-dipole forces (London
forces) between the molecules. As the intermolecular forces get larger more energy has to be put into break these
intermolecular forces. This increases the melting and boiling points
Redox reactions and reactivity of halogens and their compounds

Electronic configuration.
All group 7 elements have the outer shell s2p5 electron configuration.
The will often react by gaining of one electron in redox reactions to form 1– ions
1. The displacement reactions of halide ions by halogens.
A halogen that is a strong oxidising agent will The oxidising strength decreases down the group. Oxidising
displace a halogen that has a lower oxidising agents are electron acceptors.
power from one of its compounds
know these
Chlorine will displace both bromide and iodide ions; bromine will displace iodide ions
observations !
Chlorine (aq) Bromine (aq) Iodine (aq) The colour of the solution in the
test tube shows which free
potassium Very pale green Yellow solution, no Brown solution, halogen is present in solution.
chloride (aq) solution, no reaction no reaction Chlorine =very pale green
reaction solution (often colourless),
potassium Yellow solution, Cl Yellow solution, no Brown solution, Bromine = yellow solution
bromide (aq) has displaced Br reaction no reaction Iodine = brown solution
(sometimes black solid present)
potassium Brown solution, Cl Brown Solution, Br Brown Solution,
iodide (aq) has displaced I has displaced I no reaction
Observations if an organic solvent is added

Chlorine (aq) Bromine (aq) Iodine (aq)
The colour of the organic solvent
potassium colourless, no yellow, no purple, no layer in the test tube shows
chloride (aq) reaction reaction reaction which free halogen is present in
solution.
potassium yellow, Cl has yellow, no purple, no Chlorine = colourless
bromide (aq) displaced Br reaction reaction Bromine = yellow
Iodine = purple
potassium purple, Cl has purple, Br has purple, no
iodide (aq) displaced I displaced I reaction
Cl2(aq) + 2Br – (aq)  2Cl – (aq) + Br2(aq)

Cl2(aq) + 2I – (aq)  2Cl – (aq) + I2(aq)
Br2(aq) + 2I – (aq)  2Br – (aq) + I2(aq)
The oxidation reactions of metals and metal ion by halogens.
In all reactions where halogens are
2Na  2Na+ + 2e- reacting with metals, the metals are
Br2(l) + 2Na (s)  2NaBr (s) Br2 + 2e-  2Br - being oxidised
3Cl2(g) + 2 Fe (s)  2 FeCl3 (s) Br2(l) + Mg (s)  MgBr2 (s)
Cl2(g) + 2Fe2+ (aq)  2 Cl- (aq) + 2Fe3+ (aq) Chlorine and bromine can oxidise Fe2+ to Fe3+. Iodine is not
strong enough oxidising agent to do this reaction. The
2I- (aq) + 2Fe3+ (aq)  I2 (aq) + 2Fe2+ (aq) reaction is reversed for iodine
The reactions of the elements with hydrogen
F2(g) + H2 (g)  2 HF (g) All the halogens react with hydrogen gas to produce hydrogen halides.
The reactions decrease in speed and vigour going down the group
Br2(l) + H2 (g)  2 HBr (g)
Hydrogen Iodide easily converts back into hydrogen and iodine on
heating. The general trend is the hydrides become less stable going
I2(s) + H2 (g) ⇌ 2 HI (g)
down the group. This can be explained by the decreasing size of the
H-Hal bond energy going down the group. This is because as the halogen
atoms are get bigger their bond length is longer. The bonding pair of
electrons is gets further from the halogen nuclei.
The reactions of halide ions with silver nitrate. The role of nitric acid is to react with any
carbonates present to prevent formation of the
This reaction is used as a test to identify which halide ion is precipitate Ag2CO3. This would mask the desired
present. The test solution is made acidic with nitric acid, and observations
then silver nitrate solution is added dropwise.
2 HNO3 + Na2CO3  2 NaNO3 + H2O + CO2
Fluorides produce no precipitate
Chlorides produce a white precipitate The silver halide precipitates can be treated with ammonia
Ag+(aq) + Cl- (aq)  AgCl(s) solution to help differentiate between them if the colours look
Bromides produce a cream precipitate similar:
Ag+(aq) + Br- (aq)  AgBr(s)
Silver chloride dissolves in dilute ammonia to form a complex ion
Iodides produce a pale yellow precipitate
AgCl(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Cl- (aq)
Ag+(aq) + I- (aq)  AgI(s)
Colourless solution
Silver bromide dissolves in concentrated ammonia to form a
complex ion
AgBr(s) + 2NH3(aq) [Ag(NH3)2]+ (aq) + Br - (aq)
Colourless solution
Silver iodide does not react with ammonia – it is too insoluble.
The reaction of halide salts with concentrated sulfuric acid.
The Halides show increasing power as reducing

Explanation of differing reducing power of halides
agents as one goes down the group. This can be
A reducing agent donates electrons.
clearly demonstrated in the various reactions of
The reducing power of the halides increases down group 7
the solid halides with concentrated sulfuric acid.
They have a greater tendency to donate electrons.
This is because as the ions get bigger it is easier for the outer
Know the equations and observations of these electrons to be given away as the pull from the nucleus on them
reactions very well. becomes smaller.
Fluoride and Chloride

F- and Cl- ions are not strong enough reducing agents to reduce the S in H 2SO4. No redox
reactions occur. Only acid-base reactions occur.
NaF(s) + H2SO4(l) NaHSO4(s) + HF(g)

These are acid –base reactions and not
Observations: White steamy fumes of HF are evolved.
redox reactions. H2SO4 plays the role of
NaCl(s) + H2SO4(l)  NaHSO4(s) + HCl(g) an acid (proton donor).
Observations: White steamy fumes of HCl are evolved.
Bromide
Br- ions are stronger reducing agents than Cl- and F- and after the initial acid-base
reaction reduce the sulfur in H2SO4 from +6 to + 4 in SO2
Observations: White steamy fumes of
Acid- base step: NaBr(s) + H SO (l)  NaHSO (s) + HBr(g) HBr are evolved.
2 4 4
Redox step: 2HBr + H2SO4  Br2(g) + SO2(g) + 2H2O(l) Red fumes of bromine are also evolved
and a colourless, acidic gas SO2
Ox ½ equation 2Br -  Br2 + 2e-
Re ½ equation H2SO4 + 2 H+ + 2 e-  SO2 + 2 H2O Reduction product = sulfur dioxide
Note the H2SO4 plays the role of acid in the first step producing HBr and then
acts as an oxidising agent in the second redox step.
Iodide
I- ions are the strongest halide reducing agents. They can reduce the sulfur from +6 in
H2SO4 to + 4 in SO2, to 0 in S and -2 in H2S.
NaI(s) + H2SO4(l)  NaHSO4(s) + HI(g) Observations:

2HI + H2SO4  I2(s) + SO2(g) + 2H2O(l) White steamy fumes of HI are evolved.
6HI + H2SO4  3 I2 + S (s) + 4 H2O (l) Black solid and purple fumes of Iodine are also
8HI + H2SO4 4I2(s) + H2S(g) + 4H2O(l) evolved
A colourless, acidic gas SO2
A yellow solid of sulfur
Ox ½ equation 2I -  I2 + 2e- H2S (Hydrogen sulfide), a gas with a bad egg smell,
Re ½ equation H2SO4 + 2 H+ + 2 e-  SO2 + 2 H2O
Re ½ equation H2SO4 + 6 H+ + 6 e-  S + 4 H2O
Reduction products = sulfur dioxide, sulfur
Re ½ equation H2SO4 + 8 H+ + 8 e-  H2S + 4 H2O and hydrogen sulfide
Note the H2SO4 plays the role of acid in the first step producing HI and then
acts as an oxidising agent in the three redox steps
Often in exam questions these redox reactions are

worked out after first making the half-equations
4. The disproportionation reactions of chlorine and chlorate(I).
Disproportionation is the name for a reaction where an The greenish colour of these solutions is due to
element simultaneously oxidises and reduces. the Cl2
Chlorine with water:

If some universal indicator is added to the solution it will first
Cl2(g) + H2O(l)  HClO(aq) + HCl (aq)
turn red due to the acidity of both reaction products. It will then
turn colourless as the HClO bleaches the colour.
Chlorine is both simultaneously reducing and oxidising
Reaction of Chlorine with cold dilute NaOH solution:
Cl2,(and Br2, I2) in aqueous solutions will react with cold sodium hydroxide. The colour of the halogen
solution will fade to colourless
Cl2(aq) + 2NaOH(aq)  NaCl (aq) + NaClO (aq) + H2O(l)

The mixture of NaCl and NaClO is used as Bleach and to disinfect/ kill bacteria
If hot sodium hydroxide is used a different disproportionation reaction occurs

forming sodium chlorate(V)
3Cl2 + 6NaOH → NaClO3 + 5NaCl + 3H2O
3I2 (aq) + 6NaOH (aq)  5 NaI (aq) + NaIO3 (aq) + 3H2O (l)
3I2 (aq) + 6OH- (aq)  5 I- (aq) + IO3- (aq) + 3H2O (l)
Naming chlorates/sulfates
In IUPAC convention the various forms of sulfur

and chlorine compounds where oxygen is NaClO: sodium chlorate(I)
combined are all called sulfates and chlorates NaClO3: sodium chlorate(V)
with relevant oxidation number given in roman K2SO4 potassium sulfate(VI)
numerals. If asked to name these compounds K2SO3 potassium sulfate(IV)
remember to add the oxidation number.
Chlorine is used in water treatment to kill bacteria. It has been used to treat drinking water and the water in
swimming pools. The benefits to health of water treatment by chlorine outweigh its toxic effects.
Chlorine is used to make

• Bleaches (see above)
• PVC (see chapter 15 for description of PVC polymer)
• Halogenated hydrocarbons as solvents, refrigerants and in aerosols. (see chapter 16 for these)
12. Transition Metals
Sc 1s22s22p63s23p6 4s23d1 Sc 3+ [Ar] 4s03d0
General properties of transition metals
Ti 1s22s22p63s23p6 4s23d2 Ti 3+ [Ar] 4s03d1
transition metal characteristics of elements Sc  Cu V 1s22s22p63s23p6 4s23d3 V 3+ [Ar] 4s03d2
arise from one or more incomplete d orbitals in ions Cr 1s22s22p63s23p6 4s13d5 Cr 3+ [Ar] 4s03d3
Mn 1s22s22p63s23p6 4s23d5 Mn 2+ [Ar] 4s03d5
these characteristics include Fe 1s22s22p63s23p6 4s23d6 When Fe 3+ [Ar] 4s03d5
•complex formation, Co 1s22s22p63s23p6 4s23d7 forming Co 2+ [Ar] 4s03d7
•formation of coloured ions, ions lose
Ni 1s22s22p63s23p6 4s23d8 4s before Ni 2+ [Ar] 4s03d8
•variable oxidation state Cu 1s22s22p63s23p6 4s13d10 Cu 2+ [Ar] 4s03d9
3d
•catalytic activity. Zn 1s22s22p63s23p6 4s23d10 Zn 2+ [Ar] 4s03d10
4 of the 5 d orbitals
have this shape. Each The 5th d
one is arranged in a orbital has a
different geometry different shape
Why is Zn not a transition metal? Why is Sc not a transition metal?

Zn can only form a +2 ion. In this ion the Zn 2+ has a complete Sc can only form a +3 ion. In this ion the Sc3+
d orbital and so does not meet the criteria of having an has an empty d orbital and so does not meet
incomplete d orbital in one of its compounds. the criteria of having an incomplete d orbital
in one of its ions.
Physical properties
Melting point and Density: The transition metals have high melting points. They are higher than group 2 element calcium.
This is because they have stronger attractions between cations and electrons (as more delocalised electrons)
Transition metals also have higher densities than calcium. This is because they have greater Ar’s and smaller atomic radii.
Variable oxidation states

When transition metals form ions they
Transition elements show variable oxidation states lose the 4s electrons before the 3d
Transition metals form various oxidation

states. They are able to donate and
Sc Ti V Cr Mn Fe Co Ni Cu Zn
receive electrons and are able to oxidize
and reduce. This is because they have +3 +4 +5 +6 +7 +6 +5 +4 +3 +2
many electrons of similar energy in their
+3 +4 +5 +6 +5 +4 +3 +2
valence- shell orbital . The 4s + 3d orbitals
have similar energies. The energy +2 +3 +4 +5 +4 +3 +2 +1
differences between the oxidation states
+1 +2 +3 +4 +3 +2 +1
are small.
+1 +2 +3 +2 +1
+1 +2 +1
General trends +1
•Relative stability of +2 state with respect to +3 state increases
across the period
•Compounds with high oxidation states tend to be oxidising
agents e.g MnO4-
•Compounds with low oxidation states are often reducing
agents e.g V2+ & Fe2+
Complex formation
complex :is a central metal ion surrounded by ligands.

2+
OH2
H2O OH2
ligand.: An atom, ion or molecule which can donate a lone electron pair.
Cu
Co-ordinate bonding is involved in complex formation.
H2O OH2
Co-ordinate bonding is when the shared pair of electrons in the covalent bond come OH2
from only one of the bonding atoms.
Co-ordination number: The number of co-ordinate bonds formed to a central metal
ion.
Ligands can be monodentate (e.g. H2O, NH3 and Cl- ) which can form one coordinate bond per ligand or
bidentate (e.g. NH2CH2CH2NH2 and ethanedioate ion C2O4 2- ) which have two atoms with lone pairs and can
form two coordinate bonds per ligand or multidentate (e.g. EDTA4- which can form six coordinate bonds per
ligand).
Reaction of copper and cobalt complexes

[Cu(H2O)6]2+ is a blue solution
Metal aqua ions are formed in aqueous solution. [Co(H2O)6]2+ is a pink solution
Reaction with limited amount of OH- and limited NH3

The bases OH- and ammonia when added to aqueous complexes in limited Cu(OH)2(H2O)4 (s) blue ppt,
amounts form the hydroxide precipitates. They form in deprotonation acid base Co(OH)2(H2O)4 (s) blue ppt,
reactions
[Cu(H2O)6]2+ (aq) + 2OH- (aq)  Cu(H2O)4(OH)2 (s) + 2H2O (l) [Co(H2O)6]2+ (aq) + 2OH- (aq)  Co(H2O)4(OH)2 (s) + 2H2O (l)
[Cu(H2O)6]2+ (aq) + 2NH3 (aq)  Cu(H2O)4(OH)2 (s) + 2NH4+ (aq) [Cu(H2O)6]2+ (aq) + 2NH3 (aq)  Cu(H2O)4(OH)2 (s) + 2NH4+ (aq)
Here the NH3 and OH- ions are acting as Bronsted-Lowry bases accepting a proton
Ligand Exchange Reactions

If excess ammonia is added to cobalt and copper aqueous ions a ligand exchange reaction occurs
The ligands NH3 and H2O are similar in size and are uncharged.
Exchange of the ligands NH3 and H2O occurs without change of co-ordination number (eg Co2+ and Cu2+).
[Co(H2O)6]2+(aq) + 6NH3 (aq)  [Co(NH3)6]2+(aq) + 6H2O (l)
A pale yellow solution
This substitution may, however, be incomplete as in [Cu(H2O)6]2+(aq) + 4NH3 (aq)  [Cu(NH3)4(H2O)2]2+ (aq) + 4H2O (l)
the case with Cu. A deep blue solution
The equation can also be written from the

hydroxide precipitate Cu(OH)2(H2O)4(s) + 4NH3 (aq)  [Cu(NH3)4(H2O)2]2+ (aq) + 2H2O (l) + 2OH- (aq)
Reactions with Chloride Ions

Addition of a high concentration of chloride ions (from conc HCl or Addition of conc HCl to aqueous ions of Cu and
saturated NaCl) to an aqueous ion leads to a ligand exchange reaction. Co lead to a change in coordination number
from 6 to 4.
These are
[CuCl4]2- yellow/green solution tetrahedral in
The Cl- ligand is larger than the uncharged H2O and NH3 ligands [CoCl4]2- blue solution shape
so therefore ligand exchange can involve a change of co-
ordination number. [Cu(H2O)6]2+ + 4Cl-  [CuCl4]2- + 6H2O
[Co(H2O)6]2+ + 4Cl-  [CoCl4]2- + 6H2O
Be careful: If solid copper chloride (or any other metal) is dissolved in
water it forms the aqueous [Cu(H2O)6]2+ complex and not the chloride
[CuCl4]2- complex.
Bidentate Ligands
Ligands can be bidentate (e.g. NH2CH2CH2NH2 and ethanedioate ion C2O4 2- ) which have two
atoms with lone pairs and can form two coordinate bonds per ligand
Ethane-1-2-diamine Ethanedioate C2O4 2-

Ethane-1-2-diamine is a
CH2 3+
common bidentate
NH2 O
H2 C ligand.
NH2 NH2 CH2 C 3-
O O
A complex with Ethane-1-2-
Cr C
NH2 NH2
CH2 A complex with
diamine bidentate ligands O O O
C bidentate ethanedioate
H2 C
NH2 e.g. [Cr(NH2CH2CH2NH2)3]3+ Cr
C
ligands e.g. [Cr(C2O4)3]3-
O O O
CH2
O C O
There are 3 bidentate ligands in this complex each C

Octahedral shape with
O
bonding in twice to the metal ion. 90o bond angles
It has a coordination number of 6
Equations to show formation of bidentate complexes

Cu(H2O)62+ + 3NH2CH2CH2NH2  [Cu(NH2CH2CH2NH2)3]2+ + 6H2O
Cu(H2O)62+ + 3C2O42- [Cu(C2O4)3]4- + 6H2O
Partial substitution of ethanedioate ions may occur 2-

when a dilute aqueous solution containing OH2
ethanedioate ions is added to a solution containing O
O O O
aqueous copper(II) ions. In this reaction four water C C
molecules are replaced and a new complex is C

Cu
C
formed. O O O O
OH2
Cu(H2O)62+ + 2C2O42- [Cu(C2O4)2(H2O)2]2- + 4H2O
Multidentate Ligands
Ligands can be multidentate (e.g. EDTA4- which can form six coordinate bonds per ligand).
The EDTA4- anion has the formula

Equations to show formation of mutidentate complexes
O O
Cu(H2O)62+ + EDTA4- [Cu(EDTA)]2- + 6H2O
-O C CH2 CH2 C O-
Learn the two bidentate ligands mentioned above but it is not
N CH2 CH2 N necessary to remember the structure of EDTA.
-O C CH2 CH2 C O-
O O
with six donor sites(4O and 2N) and forms a 1:1
complex with metal(II) ions
Manganate Redox Titration The purple colour of manganate can make it
The redox titration between Fe2+ with MnO4– (purple) is a very common difficult to see the bottom of meniscus in the
exercise. This titration is self indicating because of the significant colour burette.
change from reactant to product.
If the manganate is in the burette then the
end point of the titration will be the first
MnO4-(aq) + 8H+ (aq) + 5Fe2+ (aq)  Mn2+ (aq) + 4H2O (l) + 5Fe3+ (aq)
permanent pink colour.
Purple colourless
Colourless  purple
Choosing correct acid for manganate titrations.

The acid is needed to supply the 8H+ ions. Some acids are not suitable as they set up alternative redox reactions and
hence make the titration readings inaccurate.
Only use dilute sulphuric acid for manganate titrations.
Insufficient volumes of sulphuric acid will mean the solution is not acidic enough and MnO 2 will be produced instead of
Mn2+.
MnO4-(aq) + 4H+(aq) + 3e-  MnO2 (s) + 2H2O
The brown MnO2 will mask the colour change and lead to a greater (inaccurate) volume of Manganate being used in
the titration.
Using a weak acid like ethanoic acid would have the same effect as it cannot supply the large amount of hydrogen ions
needed (8H+).
It cannot be conc HCl as the Cl- ions would be oxidised to Cl2 by MnO4- as the Eo MnO4-/Mn2+ > Eo Cl2/Cl-
MnO4-(aq) + 8H+(aq) + 5e–  Mn2+ (aq) + 4H2O(l) E+1.51V
Cl2(aq) +2e–  2Cl–(aq) E +1.36V
This would lead to a greater volume of manganate being used and poisonous Cl 2 being produced.
It cannot be nitric acid as it is an oxidising agent. It oxidises Fe 2+ to Fe3+ as Eo NO3-/HNO2> Eo Fe3+/Fe2+

NO3- (aq) + 3H+(aq) + 2e–  HNO2(aq) + H2O(l) Eo +0.94V
Fe (aq)+e  Fe (aq)
3+ – 2+ Eo +0.77 V
This would lead to a smaller volume of manganate being used.
Be able to perform calculations for these titrations and for others

when the reductant and its oxidation product are given.
Manganate titration example

Step1 : find moles of KMnO4
A 2.41g nail made from an alloy containing iron is moles = conc x vol
dissolved in 100cm3 acid. The solution formed contains
0.02 x 9.8/1000
Fe(II) ions.
10cm3 portions of this solution are titrated with = 1.96x10-4 mol
potassium manganate (VII) solution of 0.02M. 9.80cm3 Step 2 : using balanced equation find moles Fe2+ in 10cm3
of KMnO4 were needed to react with the solution = moles of KMnO4 x 5
containing the iron. = 9.8x10-4 mol
What is the percentage of Iron by mass in the nail?
Step 3 : find moles Fe2+ in 100cm3
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+(aq) + 4H2O + 5Fe3+ = 9.8x10-4 mol x 10
= 9.8x10-3 mol
Step 4 : find mass of Fe in 9.8x10-3 mol
mass= moles x RAM = 9.8x10-3 x 55.8 = 0.547g
Step 5 : find % mass
%mass = 0.547/2.41 x100
= 22.6%
4
With ethanedioate
Ox C2O42-  2CO2 + 2e-

Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O
Overall 2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l) The reaction between MnO4- and
C2O42- is slow to begin with (as the
With Iron (II) ethanedioate both the Fe2+ and the C2O42- react with the MnO4- reaction is between two negative
1MnO4- reacts with 5Fe2+ and 2 MnO4- reacts with 5C2O42- ions). To do as a titration the conical
flask can be heated to 60o C to
MnO4-(aq) + 8H+(aq) + 5Fe2+  Mn2+ (aq) + 4H2O + 5Fe3+ speed up the initial reaction.
2MnO4-(aq) + 16H+(aq) + 5C2O42-  10CO2 + 2Mn2+ (aq) + 8H2O
So overall
3MnO4-(aq) + 24H+(aq) + 5FeC2O4  10CO2 + 3Mn2+ (aq) + 5Fe3+ + 12H2O
So overall the ratio is 3 MnO4- to 5 FeC2O4
Step1 : find moles of KMnO4

A 1.412 g sample of impure FeC2O4.2H2O was
moles = conc x vol
dissolved in an excess of dilute sulphuric acid
and made up to 250 cm3 of solution. 25.0 cm3 0.0189 x 23.45/1000
of this solution decolourised 23.45 cm3 of a = 4.43x10-4 mol
0.0189 mol dm–3 solution of potassium Step 2 : using balanced equation find moles FeC2O4.2H2O in 25cm3
manganate(VII). = moles of KMnO4 x 5/3 (see above for ratio)
What is the percentage by mass of = 7.39x10-4 mol
FeC2O4.2H2O in the original sample? Step 3 : find moles FeC2O4.2H2O in 250 cm3
= 7.39x10-4 mol x 10
= 7.39x10-3 mol
Step 4 : find mass of FeC2O4.2H2O in 7.39x10-3 mol
mass= moles x Mr = 7.39x10-3 x 179.8 = 1.33g
Step 5 ; find % mass
%mass = 1.33/1.412 x100
= 94.1%
Reducing Chromium Cr2O72- + 14H+ + 3Zn  2Cr3+ + 7H2O + 3 Zn2+

Cr3+ (green) and then Cr2+ (blue) are formed by reduction of Cr2O72- Cr2O72- + 14H+ + 4Zn  2Cr2+ + 7H2O + 4 Zn2+
(orange) by the strong reducing agent zinc in (HCl) acid solution. Fe2+ is a
less strong reducing agent and will only reduce the dichromate to Cr3+ Keeping the zinc/dichromate under a hydrogen
atmosphere is needed to reduce it to Cr2+,
because O2 in air will oxidise Cr2+ up to Cr3+
The Fe2+ and Cr2O7 2- in acid solution reaction can be used as a Cr2O72- + 14H+ + 6Fe2+  2Cr3+ + 7H2O + 6 Fe3+
quantitative redox titration. This does not need an indicator Orange green
Redox Potentials
Cr2O72- + 14H+ + 6e-  2Cr3+ + 7H2O E +1.33V The electrode potential of Iron(II) is in between the
two chromium half equations, so Fe2+ will reduce
Fe3+(aq) + e–  Fe2+(aq) E +0.75V chromium down to Cr3+
Cr3+(aq) + e–  Cr2+(aq) E -0.41V

As zinc has a more negative electrode potential than
Zn2+ + 2e-  Zn E=-0.76V all the chromium half equations, zinc will reduce
chromium down to Cr2+
Shapes of complex ions
transition metal ions transition metal ions square planar

commonly form octahedral commonly form complexes are also Ag+ commonly forms
complexes with small tetrahedral complexes formed, e.g. linear complexes
ligands (e.g. H2O and NH3). with larger ligands cisplatin e.g. [Ag(NH3)2]+ used
(e.g.Cl- ). [CoCl4]2- as Tollen’s Reagent
[Co(NH3)6]2 [Cu(H2O)6]2+
2+ Cl 2-
NH3 H 3N Cl
H3 N NH3 Pt +
Ni Cu H 3N H3 N Ag NH3
H3 N Cl
NH3
NH3 Cl Cl
Cl
Isomerism in complex ions
Complexes can show two types of stereoisomerism: cis-trans isomerism and optical isomerism
Cis-trans isomerism in square planar complexes
H3N NH 3 H3N Cl cis–trans isomerism

Ni Ni is a special case of
Cl Cl Cl NH 3
E–Z isomerism
trans-Ni(NH3)2Cl2
Cis-Ni(NH3)2Cl2
Cis-trans isomerism in octahedral complexes
OH2 OH2
+ +
H2O ClH
HCl ClH 2+
2+
Cr Cr
H2O
OH2
HCl OH2
OH2 OH2
trans-[Cr(H2O )4Cl2]+
Cis-[Cr(H2O )4Cl2]+
Optical isomerism in octahedral complexes Complexes with 3 bidentate ligands can form two optical
isomers (non-superimposable mirror images).
2+
2+ CH2
CH2 H2N CH2
NH2
H2C
H2C NH2 NH2
NH2 NH2 CH2 -
Ni
Ni H2C NH2 NH2
CH2
NH2 NH2
NH2 CH
NH2 2
H2C CH2
CH2
Cisplatin
- -
The Pt(II) complex cisplatin is used as an anticancer drug. H3N Cl Cl NH3
2+ 2+
Pt Pt
The cisplatin version only works as two chloride ions are displaced H3N - H3N -
Cl Cl
and the molecule joins on to the DNA. In doing this it stops the
replication of cancerous cells. cisplatin transplatin
Cisplatin prevents DNA replication in cancer cells by a ligand

replacement reaction with DNA in which a dative covalent bond
is formed between platinum and a nitrogen atom on guanine
NH3
Pt O
NH3
N
NH
NH N NH 2
The N and O atoms marked in red can’t
bond to cis-platin as they are involved in the
bonding within the DNA
Cisplatin can also prevent the replication of healthy cells

by bonding on to healthy DNA which may lead to
unwanted side effects like hair loss. Society needs to
assess the balance between the benefits and the adverse
effects of drugs, such as the anticancer drug cisplatin.
Formation of coloured ions
Colour changes arise from changes in

1. oxidation state, O2 In this equation
2. co-ordination number [Co(NH3)6]2+ (aq)  [Co(NH3)6]3+ (aq) +e- only oxidation
3. ligand. yellow brown state is
changing.
Co(H2O)62+ + 4Cl-  [CoCl4]2- + 6H2O

pink blue
Co(H2O)62+ + 6 NH3  Co(NH3)62+ + 6H2O
In this equation both ligand and co-
Pink yellow brown
ordination number are changing.
In this equation only the ligand is changing.
How colour arises Degenerate means all

Degenerate d orbitals split into two energy orbitals have the same dz2 dx2- y 2
levels octahedral and tetrahedral complexes energy
Colour arises from electronic transitions from the E
ground state to excited states: between different d Average energy of
orbitals. degenerate d
A portion of visible light is absorbed to promote d orbitals in field of dxy dxz dyz
electrons to higher energy levels. The light that is not ligands
absorbed is transmitted to give the substance colour. Octahedral complex ion
Ligands cause the 5 d orbitals to

Equation to learn! split into two energy levels.
This equation links the colour and frequency of the
light absorbed with the energy difference between A solution will appear blue if it absorbs orange light. The energy
the split d orbitals. split in the d orbitals E will be equal to the frequency of orange
E = hv. light(5 x1014 s-1) x Planck’s constant
v = frequency of light absorbed (unit s-1 or Hz) E in a blue solution = hv
h= Planck’s constant 6.63 × 10–34 (J s)
= 6.63 × 10–34 x 5 x1014
E = energy difference between split orbitals (J)
= 3.32 × 10–19 J
Changing colour
Changing a ligand or changing the coordination number will alter the energy split between the d- orbitals, changing E
and hence change the frequency of light absorbed.
Compounds without colour
Scandium is a member of the d block. Its ion (Sc3+) In the case of Zn2+ ions and Cu+ ions the d shell is full
hasn't got any d electrons left to move around. So e.g.3d10 so there is no space for electrons to transfer.
there is not an energy transfer equal to that of visible Therefore there is not an energy transfer equal to that of
light. visible light.
Spectrophotometry
If visible light of increasing frequency is passed through a Absorption of visible light is used in spectrometry to
sample of a coloured complex ion, some of the light is determine the concentration of coloured ions.
absorbed.
method
The amount of light absorbed is proportional to the
•Add an appropriate ligand to intensify colour
concentration of the absorbing species (and to the distance
•Make up solutions of known concentration
travelled through the solution).
•Measure absorption or transmission
Some complexes have only pale colours and do not absorb
•Plot graph of absorption vs concentration
light strongly. In these cases a suitable ligand is added to
•Measure absorption of unknown and compare
intensify the colour.
Spectrometers contain a coloured filter. The colour of the filter is chosen
to allow the wavelengths of light through that would be most strongly
absorbed by the coloured solution.
Stability of complexes
The substitution of monodentate ligand with a bidentate or a multidentate ligand leads to a more stable complex. This is
called the chelate effect
This chelate effect can be explained in terms of a positive entropy change in these reactions as more molecules
of products than reactants
[Cu(H2O)6]2+ (aq) + EDTA4- (aq)  [Cu (EDTA)]2- (aq) + 6H2O (l)

The copper complex ion has changed from having unidentate ligands to a multidentate ligand.
In this reaction there is an increase in the entropy because there are more moles of products than reactants
(from 2 to 7), creating more disorder.
The enthalpy change is small as there are similar numbers of bonds in both complexes.
Free energy ΔG will be negative as ΔS is positive and ΔH is small.
The stability of the EDTA complexes has many applications. It can be added to rivers to remove poisonous heavy
metal ions as the EDTA complexes are not toxic. It is in many shampoos to remove calcium ions present in hard
water, so helping lathering.
[Co(NH3)6]2+ + 3NH2CH2CH2NH2  [Co(NH2CH2CH2NH2)3]2+ + 6NH3

This reaction has an increase in entropy because of the increase in moles from 4 to 7 in the reaction. ΔS is
positive.
Its enthalpy change ΔH is close to zero as the number of dative covalent and type (N to metal coordinate
bond) are the same so the energy required to break and make bonds will be the same.
Therefore Free energy ΔG will be negative and the complex formed is stable.
Stability constants Kstab
A ligand exchange reaction is considered as equilibria then

[Cu(H2O)6]2+ + 4Cl- ⇌ [CuCl4]2- + 6H2O
an equilibrium expression can be written
[CuCl42- aq] .
H2O is not included in the expression because it is concentration is
Kstab = assumed to be constant.
[Cu(H2O)6 aq2+] [Cl- aq]4
The value of K is called the stability constant for complex ions. The
larger the stability constant the more stable the complex ion.
Ligand Log Kstab

A complex ion with a small stability constant will not displace the
Cl- 5.62
ligand from a more stable complex ion with a larger stability constant.
eg adding ammonia to a complex ion of copper and edta will not result NH3 13.1
in a colour change
Edta4- 18.8
13 Nitrogen and Sulfur
Lack of reactivity of nitrogen
N2 has a very strong triple bond. It has a bond energy of +944 kJ mol-1. It takes
N N a lot of energy to break this bond. This explains Nitrogen’s un-reactivity
Ammonia
Basicity
Ammonia is a weak base. The lone pair of the nitrogen is able to NH3 (aq) +H2O (l)  NH4+(aq) +OH-(aq)
accept a proton relatively easily to form the ammonium ion.
The ammonium ion NH4+

+
H
+
The dative covalent bond acts like an
N ordinary covalent bond when
thinking about shape so in NH4+ the
H H shape is tetrahedral
H
Displacement of ammonia from its salts

If sodium hydroxide is added to an ammonium salt NH4+(aq) +OH-(aq)  NH3 (aq) +H2O (l)
and it is warmed, then ammonia gas will be evolved
This reaction can be used as an analytical test for the presence of an ammonium ion. The
ammonia will turn red litmus paper blue
Uses of ammonia
Making fertilisers 2NH3 + H2SO4  (NH4)2SO4
Reacting ammonia with acids can make fetilisers such as Ammonia + sulfuric acid  ammonium sulfate
ammonium sulfate, ammonium nitrate or ammonium NH3 + HNO3  NH4NO3
phosphate. Ammonia + nitric acid  ammonium nitrate
Making nitric acid
Ammonia is used to make nitric acid. Environmental consequences of nitrate fertilisers
Uses of nitric acid Nitrates are very soluble so easily wash in to rivers from
• make fertilisers such as ammonium nitrate. fields with rain. The nitrates then fertilise the algae in
• make explosives (e.g. TNT ) rivers. The algae block out sunlight, and other plants die.
• making various dyes, drugs, polymers Bacteria feeding on decaying plants use up the oxygen in
the water and all river life dies. This process is called
Eutrophication
Nitrogen Oxides NOx

Nitrogen oxides form from the reaction between N 2 and O2 inside the car engine.
The high temperature and spark in the engine provides sufficient energy to break strong N 2 bond
N2 + O2  2NO N2 + 2O2  2NO2
the exhaust gases, turning them into ‘harmless’ CO 2, N2 and H2O.
Converters have a ceramic
2 CO + 2 NO  2 CO2 + N2 honeycomb coated with a thin
layer of catalyst metals Platinum,
C8H18 + 25 NO  8 CO2 + 12½ N2 + 9 H2O Palladium, Rhodium – to give a
large surface area.
Nitrogen oxide Pollutants
NOx gases react to form smog and acid rain in the atmosphere
Nitrogen monoxide can react in the atmosphere to form nitrogen dioxide 2NO+ O2  2NO2
Nitrogen dioxide catalyses the conversion of sulphur dioxide to sulphur trioxide.

The first step of the reaction is
NO2 (g)+ SO2 (g) SO3 (g) + NO(g)
The second step of the reaction is
The nitrogen dioxide is regenerated at the end of the
NO (g)+ ½ O2 (g)  NO2 (g) reaction so is classed as a catalyst.
Sulfur: the formation of atmospheric sulfur dioxide

Sulfur containing impurities are found in petroleum fractions which
Coal is high in sulfur content, and large
produce SO2 when they are burned.
amounts of sulfur oxides are emitted
S+ O2  SO2 CH3SH+ 3O2  SO2 + CO2 + 2H2O from power stations.
The sulfur dioxide goes on to form acid rain

In the first step reactions in the atmosphere form SO3
2SO2 + O2  2 SO3
The SO3 dissolves in atmospheric water to form acid

SO3 + H2O  H2SO4 sulphuric acid
Consequences of acid rain

• Decline in fish populations in rivers
• Dissolves minerals Mg, Ca, and K from the soil
• Dissolves waxy coatings that protect leaves from bacteria
• Corrodes metals, and limestone buildings
14 Organic: Basic Concepts
Basic definitions
Hydrocarbon is a compound consisting of hydrogen and carbon only to know
Saturated: Contain single carbon-carbon bonds only Unsaturated : Contains a C=C double bond
Molecular formula: The formula which shows the actual number of each type of atom
Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound
General formula: algebraic formula for a homologous series e.g. CnH2n
Structural formula shows the minimal detail that shows the arrangement of atoms in a
molecule, eg for butane: CH3CH2CH2CH3 or CH3(CH2)2CH3,
Displayed formula: show all the covalent bonds and atoms present in a molecule
Drawing Displayed formulae Remember that the shape around the

carbon atom in saturated hydrocarbons is
H H H H tetrahedral and the bond angle is 109.5o
When drawing organic
H C C C C H compounds add the
hydrogen atoms so that H H
H H H
H C H each carbon has 4 bonds
H C C H
H
H H
Skeletal formula shows the simplified organic formula, shown by removing hydrogen atoms from alkyl chains,
leaving just a carbon skeleton and associated functional Groups.
OH
But-2-ene Butan-1-ol
2-methylbutane cyclohexane cyclohexene
Functional group is an atom or group of atoms which when present in different molecules
causes them to have similar chemical properties
Homologous series are families of organic compounds with the same functional
group and same general formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• same chemical properties.
prefix / suffix
homologous functional example
(* = usual use)
series group
Alkane
C C CH3CH2CH2CH3
-ane Butane
H H
Alkenes C C suffix -ene C C propene
H
H C
H
H
suffix* -ol H H H Propan-1-ol

Alcohols prefix hydroxy-
C OH H C C C O H
OH
H H H
H H H
Halogenoalkanes prefix chloro-
1-chloropropane
halogen H C C C Cl
C
bromo- Cl
H H H
iodo-
suffix -al H O
Aldehydes O
prefix formyl- H C C H
O ethanal
C H
H
suffix* -one H O H
O O Propanone
prefix oxo-
H C C C H
Ketones C
H H
suffix -oic acid

carboxylic acids H O O Ethanoic acid
O
H C C OH
C OH
H
OH
-yl –oate
O
methylethanoate
Esters C O H O H O
H C C O C H
H H
O
prefix / suffix
homologous functional group example
(* = usual use)
series
suffix -nitrile H H
nitriles
C N prefix cyano- H C C C N Propanenitrile
H H
suffix* -amine
amines C NH2 prefix amino-
H H H
Propylamine
H C C C NH2
Or propan-1-amine
H H H
O
O
Acyl chloride
C -oyl chloride CH 3 C ethanoylchloride
Cl
Cl
O O
Amide
C -amide CH3 C ethanamide
NH2
NH2
General rules for naming carbon chains no of

code
carbons
Count the longest carbon chain and name appropriately
meth 1
Find any branched chains and count how many carbons they contain
eth 2
 Add the appropriate prefix for each branch chain
prop 3
Eg -CH3 methyl or -C2H5 ethyl –C3H7 propyl
1 CH but 4
3
pent 5
2 CH2 hex 6
5 3,5-dimethylheptane
hept 7
H3 C CH CH2 CH CH3
3 oct 8
4
CH2 6 non 9
dec 10
CH3 7
Basic rules for naming functional groups
The functional group is named by a prefix or suffix. e.g. bromoethane, ethanol, propene
•When using a suffix, add in the following way :

If the suffix starts with a vowel- remove the –e from the stem alkane name
e.g. Propan-1-ol, butan-1-amine, ethanoic acid, ethanoylchloride, butanamide
If the suffix starts with a consonant or there are two or more of a functional group meaning di, or tri needs to be
used then do not remove the the –e from the stem alkane name
e.g. Propanenitrile, ethane-1,2-diol, propanedioic acid, propane-1,2,3-triol, Pentane-2,4-dione.
When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix, with all others taking the prefix
form. However, double and triple C-C bonds only take suffix form.
Order of priority highest first:
Carboxylic acids >carboxylic acid derivative>nitriles>aldehydes>ketones>alcohols>amines>alkenes>halogenoalkanes
The position of the functional group on the carbon H H H O H

chain is given by a number – counting from the end
H C C 3 C2 C1 H Butan-1-ol
of the molecule that gives the functional group the 4
lowest number. For aldehydes, carboxylic acids &
H H H H
nitriles, the functional group is always on carbon 1.
H H H
We only include numbers, H C C C H

methylpropane CHCl3 trichloromethane
however, if they are needed H H
to avoid ambiguity. H C H
•The functional groups take precedence over branched 3-methylbut-1-ene is correct and not 2-methylbut-3-
chains in giving the lowest number ene
H H H H H
Where there are two or more of the same groups, di-, tri- , H C C C C C H 2,3-dibromopentane.
tetra-, penta- or hexa- are used. Note the point made above
H H Br H
about the addition of ‘e’ to the stem Br
Words are separated by numbers with dashes CH2FCCl2CH2CH3 2,2-dichloro-1-fluorobutane.

 numbers are separated by commas
CH2FCH2CHBrCH2CH3 3-bromo-1-fluoropentane
If there is more than one functional group or side chain, the
groups are listed in alphabetical order (ignoring any di, tri).
Alkenes
2 4
1 3 Double bond between
The double bond will be between two carbons. Use the lower
C2 and C3 so But-2-ene
number of the two to show the position of the double bond
The name for alkenes may include E or Z at start to show Z-but-2-ene

the type of stereoisomer
If more than one double bond is present then suffix Penta-1,3-diene

ends diene or triene. The stem ends in a
The suffix -en for alkenes can go in front of other suffixes. CH2OHCHBrCH=CH2 2-bromobut-3-en-1-ol
The alcohol and carboxylic acid groups have higher priority OH
than the alkene group so take precedence with numbering
E-but-2-enoic acid
O
Halogenoalkanes H H Br H
Class the halogen as a substituent on the C chain and use 2-bromobutane
H C C C C H
the suffix -fluoro, -chloro, -bromo, or –iodo. (Give the
position number if necessary) H H H H
I
Cl
Br
Cl Br
F
2,3-dichloro-1-fluoro-3-methylpentane 5,5-dibromo-4-iodo-3-methylpent-1-ene
Multiple functional group and side chains are listed The alkene group has higher priority than the
in alphabetical order (ignoring any di, tri). halogenoalkane group so it takes the lowest number
on the carbon chain
Alcohols
These have the ending -ol and if necessary the position OH
number for the OH group is added between the name Butan-2-ol

CH3 CH CH2 CH3
stem and the –ol 1 2 3 4
If there are two or more -OH groups then di, tri are HO CH2 CH2 OH Ethane-1,2-diol
used.
Add the ‘e’ on to the stem name though. H2C CH CH2 propane-1,2,3-triol
OH OH OH
Cl
The OH group has a higher priority than the
halogenoalkane group and alkene so takes
precedence in numbering. The OH is on carbon 1 OH
Cl
E-3,6-dichlorohex-4-en-1-ol
O
If the compound has an –OH group in addition to another
H3C CH C 2-hydroxypropanoic acid
functional group with a higher priority. The priority group gets
the suffix ending and the OH can be named with the prefix OH OH
hydroxy-:
H
Aldehydes O
An aldehyde’s name ends in –al

It always has the C=O bond on the first carbon of H C C
the chain so it does not need an extra number. It is

by default number one on the chain. H
H
Ethanal
If two aldehyde groups then di is put before –al and an O O

e is added to the stem.
pentanedial
O
Aldehydes have a higher priority than alcohol so the –OH HO
group uses the hydoxy prefix. 4-hydroxybutanal
Ketones H O H
Ketones end in -one H C C C H
When ketones have 5C’s or more in a chain then H H

it needs a number to show the position of the Propanone
double bond. E.g. pentan-2-one
H O H O H
If two ketone groups then di is put before – H C C C C C H
one and an e is added to the stem.
H H H
Pentane-2,4-dione
Carboxylic acids H H
O
These have the ending -oic acid but no number is
necessary for the acid group as it must always be H C C C Propanoic acid
at the end of the chain. The numbering always
starts from the carboxylic acid end. H H
O H
O O Ethanedioic acid
If there are carboxylic acid groups on both ends of the
C C
chain then it is called a - dioic acid Note the e in this name
HO OH
O
5-hydroxy-4-methylpentanoic acid
OH OH
Amines H H H
H2N O
These end in –amine.
There is, however, rather confusingly two H C C C NH2 If there is another priority
functional group as well CH C
ways of using this suffix.
H H H as the amine group then
The exam board tend to use the common
version where the name stem ends in -yl propylamine the prefix amino is used. H 3C O H
propylamine. Or propan-1-amine 2-aminopropanoic acid.

The IUPAC version of the same chemical
is propan-1-amine. (This is used in the
same way as naming alcohols)
If there are two amine groups then name H H It could also be named
as following N (CH2)6 N 1,6-diaminohexane
H H
hexane-1,6-diamine
If amine groups are attached to a NH2

benzene ring then name as following
phenylamine
H H H OH
Nitriles
H3C
These end in –nitrile, but the C of the C
H C C C CN
CN group counts as the first carbon of C
the chain. Note the stem of the name is H3C N
H H H
different : butanenitrile and not
butannitrile. 2-hydroxy-2-methylpropanenitrile
butanenitrile
Carboxylic acid derivatives
Esters
H H O H
Esters have two parts to their names
The bit ending in –yl comes from the alcohol that has formed it H C C C O C H
and is next to the single bonded oxygen.
The bit ending in –anoate comes from the carboxylic acid. H H H
(This is the chain including the C=O bond) methylpropanoate
Acyl Chlorides
O H3C O
O O
add –oyl chloride to the stem CH3 C CH C
name
C (CH2)3 C
Cl H3C Cl
Cl Cl
ethanoyl chloride 2-methylpropanoyl chloride Pentanedioyl dichloride
Amides
O Secondary and tertiary amides are
Add –amide to the stem named differently to show the two O
name CH3 C (or three) carbon chains.
NH2 The smaller alkyl group is preceded
by an –N which plays the same role H3C CH2 C NH CH3
ethanamide as a number in positioning a side
N-methylpropanamide
alkyl chain
O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide
Naming aromatic molecules
Naming aromatic compounds can be complicated. The simplest molecules are derivatives of benzene and have benzene
at the root of the name
CH3 C2H5 Cl Br NO2 CO2H CHO
Methylbenzene ethylbenzene chlorobenzene bromobenzene nitrobenzene benzenecarboxylic acid benzaldehyde
If two or more substituents are present on the benzene ring, their positions must be indicated by the use of numbers.
This should be done to give the lowest possible numbers to the substituents. When two or more different substituents
are present, they are listed in alphabetical order and di, tri prefixes should be used.
CH3 COOH CH3

CH3 O 2N NO2
CH3
Cl OH NO2
1,3-dimethylbenzene
1-chloro- 4-methylbenzene 4-hydroxybenzenecarboxylic acid 2,4,6-trinitromethylbenzene
In other molecules the benzene ring can be regarded as a substituent side group on another molecule, like alkyl groups
are. The C6H5- group is known as the phenyl group.
O
NH2 CH CH2 CH3
H3C CH CH2 CH3 O
C
H3C C O
phenylamine phenylethene
2-phenylbutane
phenylethanone phenylethanoate
OH
OH
1-phenylpropane-1,2-diol 3-phenylpropanal
Shapes of organic molecules; σ and π bonds
Ethane C2H6
H H
Each carbon in ethane has four σ
bonds. They are arranged in a This is the shape and bond angle
C C
H H of any saturated hydrocarbon
tetrahedral way around the
carbon. The bond angle is 109.5o
H
H
Ethene C2H4
Each carbon in ethene forms two H H
σ bonds to hydrogens. The arrangement of bonds
C C
C=C double covalent bond around the >C=C< is
consists of one sigma (σ) bond H H planar and each bond has
and one pi (π) bond. the bond angle 120o
Carbonyls also have the same

planar arrangement of bonds with
a 120o bond angle
Benzene’s Structure Benzene is a planar molecule. The

The simplest arene is benzene. It has the molecular formula C6H6 evidence suggests all the C-C bonds are
Its basic structure is six C atoms in a hexagonal ring, with one H atom the same and have a length and bond
bonded to each C atom. energy between a C-C single and C=C
Each C atom is bonded to two other C atoms and one H atom by single double bond.
covalent σ-bonds. This leaves one unused electron on each C atom in a p
orbital, perpendicular to the plane of the ring. In formulae we draw a circle to show this
The Six p electrons are delocalised in a ring structure above and below delocalised system.
the plane of carbon atoms.
H H H H
H H H H Abbreviated
formula
H H H H
Displayed formula
Isomers
Structural isomers: same molecular formula different structures (or structural formulae)
Structural isomerism can arise from

•Chain isomerism
•Position isomerism
•Functional group isomerism
Chain isomers: Compounds with the same molecular formula but different
structures of the carbon skeleton
H
H H H H H H H H H
H C H
H C C C C H H H
H C C C C C H
H C C C H
H H H
H H H H H H C H H H
H C H
pentane H
H
2-methylbutane
2,2-dimethylpropane
positional isomers: Compounds with the same molecular formula but different structures due to
different positions of the same functional group on the same carbon skeleton
H H H H H H
H C C C H 1-bromopropane H C C C H 2-bromopropane
Br H H H Br H
Functional group isomers: Compounds with the same molecular formula but with
atoms arranged to give different functional groups
H H H H
Methoxymethane: an ether
H C C O H ethanol: an alcohol H C O C H
H H
H H
H H
H H
C
H C C H
Cyclohexane- cyclo alkane CH3CH2CH2CH2CH=CH2 hexene- alkene
H C C H
C Note: alkene and cyclo alkanes have the same general formula. Hexene and
H H
H H
cyclohexane have the same molecular formula but have a different functional
group
Aldehydes and ketones of the same chain length would be classed as functional
group isomers- e.g. Propanal and propanone (both C3H6O)
Questions often involve functional group isomers of carboxylic acids: including esters etc
H 3C CH2 O O O OH OH OH
CH 2 C H 3C C O CH 2 CH 3 H 3C C CH 2 CH 2 H 2C CH CH CH 2
OH
Stereoisomerism
Stereoisomers have the same structural formulae but have a different spatial arrangement of atoms.
Geometrical (cis-trans) isomerism

Alkenes can exhibit a type of isomerism called Geometrical (cis-trans) isomerism
Geometrical (cis-trans) isomers exist due Geometrical (cis-trans) arise when:

to restricted rotation about the C=C (a) There is restricted rotation around the C=C double bond.
bond due to the presence of π bonds (b) There are two different groups/atoms attached both ends of the
double bond.
Single carbon-carbon covalent
bonds can easily rotate
But-1-ene is a structural isomer of But-2-ene
H H but does not show cis-trans isomerism.
two different groups H H
H C C H attached either end of the
restricted double bond- H C C H But-1-ene
C C
leads to geometrical (cis-
H H H H trans) C C
H H
H
cis- but-2-ene H two identical groups attached to one
end of the restricted double bond –
H no cis-trans isomers
H
These are two isomers as
C H
the lack of rotation Skeletal formulae can also represent E-Z isomerism
H
C C around the double bonds
H means one cannot be cis-but-2-ene
H C switched to the other.
H
H
trans-but-2-ene
trans -but-2-ene
Optical Isomerism
The second type of stereoisomerism: is optical isomerism
Optical isomerism occurs in carbon compounds with 4 A carbon atom that has four
different groups of atoms attached to a carbon (called an H H H H
different groups attached is
asymmetric carbon). called a chiral (asymmetric)
H C C C C H
carbon atom
H H O H
These four groups are arranged
tetrahedrally around the carbon. H
OH OH This causes two different

isomers that are not
Many naturally occurring molecules
C C superimposable to be
contain chiral C atoms, but are usually
CH3 H3C C2 H5 formed. They are mirror
H5 C2 found in nature as a pure enantiomer
H H images
Two compounds that are optical isomers of Optical isomers have similar physical and chemical properties, but
each other are called enantiomers. they rotate plane polarised light in different directions.
One enantiomer rotates it in one direction and the other enantiomer

rotates it by the same amount in the opposite direction.
One optical isomer will rotate light clockwise (+)(called

dextrorotatory). The other will rotate it anticlockwise(-)(called -ve enantiomer +ve enantiomer
Anticlockwise clockwise rotation
laevorotatory).
rotation
Introduction to Mechanisms
To understand how the reaction proceeds we must first understand how bonds are broken in organic mechanisms
There are two ways to break a covalent bond:
1.HOMOLYTIC FISSION:
each atom gets one electron from the covalent bond
one headed arrow shows
movement of one electron
Y X Y
X
The bond has broken in a process called homolytic fission.
When a bond breaks by homolytic fission it forms two Free Radicals. DEFINITION
Free Radicals do not have a charge and are represented by a A Free Radical is a reactive species
which possess an unpaired electron
2. HETEROLYTIC FISSION: (one atom gets both electrons)
X Y X: - Y+
two headed arrow shows
movement of pair of
OR - electrons
X Y X+ Y:
+ -
xx xx
xx
xx
Cl Cl Cl + Cl
x
xx xx
Heterolytic fission produces IONS

Most organic reactions occur via heterolytic fission, producing ions
The Mechanism: To understand a reaction fully we must look in detail at how it proceeds step
by step. This is called its mechanism
A curly arrow will always
We use curly arrows in mechanisms to show the movement of an electron
start from a lone pair of
pair showing either breaking or formation of a covalent bond;
electrons or the centre
of a bond
The formation of a covalent The breaking of a covalent bond

bond is shown by a curly is shown by a curly arrow starting
arrow that starts from a lone from the bond.
electron pair or from HO:-
another covalent bond
H H H H
H C C δ+ X δ- H C C OH + X-
H H
H H
15 Hydrocarbons
Alkanes
Chemical Reactivity
Alkanes do not react with many reagents.
This is because the C-C bond and the C-H bond are relatively strong and so cannot form stronger bonds with other
elements that easily and there are no polar side groups .
There main reactions are combustion reactions in air although they can react with halogens in the presence of UV light
Combustion
Complete Combustion Alkanes readily burn in the

In excess oxygen alkanes will burn with complete combustion presence of oxygen. This
combustion of alkanes is highly
The products of complete combustion are CO2 and H2O. exothermic, explaining their use as
C2H6(g) + 3.5 O2(g)  2CO2(g) + 3 H2O(l) fuels.
Reaction of alkanes with bromine / chlorine in UV light

Synthesis of chloroalkanes In the presence of UV light alkanes react with chlorine to form a mixture
of products with the halogens substituting hydrogen atoms.
Overall Reaction This is the overall reaction, but a

C2H6 + Cl2  CH3CH2Cl + HCl more complex mixture of products
is actually formed
ethane chloroethane
To understand this reaction fully we must look in detail at how it
proceeds step by step. This is called its mechanism
It proceeds via a series of steps:

The MECHANISM for this reaction is called a FREE RADICAL STEP ONE: Initiation
SUBSTITUTION STEP TWO: Propagation
STEP THREE: Termination
The UV light supplies the energy to break the Cl-Cl bond. It is broken in
STEP ONE Initiation preference to the others as it is the weakest.
Essential condition: UV light
Cl2  2Cl. The bond has broken in a process called homolytic fission.
each atom gets one electron from the covalent bond
DEFINITION
When a bond breaks by homolytic fission it forms Free Radicals.
A Free Radical is a reactive species which
Free Radicals do not have a charge and are represented by a
possess an unpaired electron
STEP TWO Propagation

The chlorine free radicals are very reactive and remove an H
from the methane leaving a methyl free radical
CH4 + Cl.  HCl + .CH3
.CH + Cl  CH Cl + Cl. The methyl free radical reacts with a Cl2 molecule to
3 2 3 produce the main product and another Cl free radical
All propagation steps have a free radical in the reactants and in the products.
As the Cl free radical is regenerated, it can react with several more alkane molecules in a CHAIN REACTION
STEP THREE Termination Collision of two free radicals does not generate further free radicals: the
chain is TERMINATED.
.CH + Cl .  CH Cl
3 3
.CH + .CH  CH CH Minor step leading to impurities of ethane in product.
3 3 3 3 Write this step using structural formulae and don’t use
molecular formulae
Applying the mechanism to other alkanes The same mechanism is used: Learn the
patterns in the mechanism
Example: Write mechanism of Br2 and Propane
STEP ONE Initiation
Essential condition: UV light
Br2  2Br
. Br2 splits in the same way as Cl2
STEP TWO Propagation

.
CH3CH2CH3 + Br  HBr + CH3CH2CH2
.
Remove one H from the alkane to produce a radical
.
CH3CH2CH2 + Br2  CH3CH2CH2Br + Br
.
To the radical produced in the previous step add a Br
STEP THREE Termination
. .
CH3CH2CH2 + Br  CH3CH2CH2Br
. .
CH3CH2CH2 + CH3CH2CH2  CH3CH2CH2CH2CH2CH3
Further substitution
Excess Cl2 present will promote further substitution and could produce CH2Cl2, CHCl3 and CCl4
These reactions could occur Example propagation steps that would lead to
further substitution
CH3Cl + Cl.  HCl + .CH2Cl
CH3Cl + Cl2  CH2Cl2 + HCl
CH2Cl2 + Cl2  CHCl3 + HCl
CHCl3 + Cl2  CCl4 + HCl . CH Cl + Cl  CH Cl + Cl .
2 2 2 2
You should be able to write overall reaction equations for various reactions
Example 1. Write the overall reaction equation for the formation of CCl4 from CH4 + Cl2
CH4 + 4 Cl2  CCl4 + 4 HCl
Example 2. Write the overall reaction equation for the formation of CFCl3 from CH3F + Cl2
CH3F + 3 Cl2  CFCl3 + 3 HCl
Note HCl is always the side product – never H2
Refining crude oil fuel gas (bottled)
20° C
Fractional Distillation: Industrially petrol/gasoline
40° C
naptha (chemicals)
Petroleum is a mixture consisting mainly
Crude 110° C
of alkane hydrocarbons
oil kerosene (jet fuel)
180° C
Petroleum fraction: mixture of hydrocarbons with diesel oil
a similar chain length and boiling point range 250° C
fuel oil
300° C
Furnace
lubricating oils
340° C
• Oil is pre-heated Key points to learn
• then passed into column. bitumen
• The fractions condense at different heights
• The temperature of column decreases upwards
• The separation depends on boiling point. This is a physical process
involving the splitting of
• Boiling point depends on size of molecules.
weak van der waals forces
• The larger the molecule the larger the van der waals forces
between molecules
• Similar molecules (size, bp, mass) condense together
• Small molecules condense at the top at lower temperatures
• and big molecules condense at the bottom at higher temperatures.
Vacuum distillation unit Vacuum distillation allows

heavier fractions to be further
• Heavy residues from the fractionating column are distilled
separated without high
again under a vacuum.
temperatures which could
• Lowering the pressure over a liquid will lower its boiling break them down.
point.
Fractional Distillation: In the laboratory

Fractional distillation is used
• Heat the flask, with a Bunsen burner or electric
to separate liquids with
mantle
different boiling points
• This causes vapours of all the components in the
mixture to be produced.
• Vapours pass up the fractionating column.
• The vapour of the substance with the lower boiling
point reaches the top of the fractionating column
first.
• The thermometer should be at or below the boiling
point of the most volatile substance.
• The vapours with higher boiling points condense
back into the flask.
condenser
• Only the most volatile vapour passes into the
condenser.
fractionating column
• The condenser cools the vapours and condenses to
a liquid and is collected.
flask
Cracking
Cracking: conversion of large hydrocarbons to smaller hydrocarbon molecules by breakage of C-C bonds
High Mr alkanes  smaller Mr alkanes+ alkenes + (hydrogen)
Economic reasons for cracking

• The petroleum fractions with shorter C chains (e.g. petrol and This is a chemical process
naphtha) are in more demand than larger fractions. involving the splitting of
• To make use of excess larger hydrocarbons and to supply demand strong covalent bonds so
for shorter ones, longer hydrocarbons are cracked. requires high temperatures.
• The products of cracking are more valuable than the starting
materials (e.g. ethene used to make poly(ethene), branched alkanes
for motor fuels, etc.)
There are two main types of cracking: thermal and catalytic. They need different conditions and are
used to produce different products
Thermal Cracking Catalytic Cracking
Conditions: Conditions:
High Pressure (7000 kPa) Low pressure
High Temperature (400°C to 900°C) High Temperature (450°C)
Zeolite Catalyst
produces mostly alkenes e.g. ethene used
for making polymers and ethanol Produces branched and cyclic
sometimes produces hydrogen used in the alkanes and Aromatic
Haber Process and in margarine manufacture hydrocarbons
Example Equations Used for making motor fuels
C8H18  C6H14 + C2H4 Branched and cyclic hydrocarbons burn more

C12H26  C10H22 + C2H4 cleanly and are used to give fuels a higher octane
Bonds can be broken anywhere in the molecule number
by C-C bond fission and C-H bond fission. Cheaper than thermal cracking because it saves
energy as lower temperatures and pressures are used
Alkenes
Alkenes contain a carbon-carbon
Alkenes are unsaturated hydrocarbons General formula is CnH2n double bond somewhere in their
structure.
H H H H
C C C H The arrangement of bonds around the >C=C< is

C C Ethene Propene
H H
planar and has the bond angle 120o
H
H H
H H
Numbers need to be H
H H
added to the name when But-2-ene
C C C C H But-1-ene H C C C C H
positional isomers can
occur. H H H H H H H H
π bonds are exposed and have high

C=C double covalent bond electron density.
consists of one sigma (σ) bond
and one pi (π) bond. They are therefore vulnerable to attack by
species which ‘like’ electrons: these species
are called electrophiles.
Addition reactions of alkenes

The alkenes are relatively reactive because of the relatively low bond enthalpy of the π-bond.
Addition reaction: a reaction where two molecules react

1. Reaction of Alkenes with Hydrogen together to produce one
Change in functional group: alkene  alkane H H

H H
Reagent: hydrogen
Conditions: Nickel Catalyst C C + H2  H C C H
Type of reaction: Addition/Reduction
H H H H
ethene ethane
2. Reaction of alkenes with steam to form alcohols
Industrially alkenes are converted to alcohols in one step. They are reacted with This reaction can be called
steam in the presence of an acid catalyst. hydration: a reaction where
water is added to a molecule
CH2=CH2 (g) + H2O (g)  CH3CH2OH (l) Reagent : steam

Essential Conditions
The high pressures needed mean this cannot be done in High temperature 300 to 600°C
the laboratory. It is preferred industrially, however, as
there are no waste products and so has a high atom High pressure 60 atm
economy. It would also mean separation of products is Catalyst of concentrated H3PO4 or
easier (and cheaper) to carry out. concentrated H2SO4
Electrophilic Addition Reactions of Alkenes
Definition Electrophile: an electron pair acceptor
The double bonds in alkenes are areas with high electron
density. This attracts electrophiles and the alkenes undergo
addition reactions.
3. Reaction of Bromine with Alkenes
Change in functional group: alkene  dihalogenoalkane H H
Reagent: Bromine H H
Conditions: Room temperature (not in UV light) C C + Br2  H C C H
Mechanism: Electrophilic Addition Br
H H Br
Type of reagent: Electrophile, Br+ 1,2-dibromoethane
As the Br2 molecule H H H

H H
H
approaches the alkene, the
pi bond electrons repel the + The INTERMEDIATE
C C H C C H H C C H formed, which has a
electron pair in the Br-Br
bond. This INDUCES a positive charge on a
H Brδ+ H Br carbon atom is called a
DIPOLE. Br2 becomes polar Br Br
and ELECTROPHILIC (Brδ+). :Br - CARBOCATION
Brδ-
4. Reaction of Hydrogen Bromide with Alkenes

Change in functional group: alkenehalogenoalkane H H H H H H
Reagent: HCl or HBr
H C C C C H + HBr  H C C C C H
Conditions: Room temperature
Mechanism: Electrophilic Addition H H H H H H Br H
Type of reagent: Electrophile, H+ But-2-ene 2-bromobutane
HBr is a polar
molecule because Br H H
H H H
H
is more +
H3C C C CH3
electronegative than H3C C C CH3 H3C C C CH3
H. The H δ + is δ+
attracted to the H H Br H
Br δ
electron-rich pi bond. -
:Br -
This reaction can lead to two products when

‘Markownikoff’s Rule’ :Br - the alkene is unsymmetrical
In most cases, bromine will be added to the carbon H
H H H
with the fewest hydrogens attached to it +
C CH3 Major
H C C C H product
If the alkene is H 3C 90%
unsymmetrical, δ+ δ- :Br - H Br H
addition of hydrogen H Br
H H
bromide can lead to + Minor
two isomeric products. H2C CH CH3 C C CH3 CH 2 CH2 CH 3 product
H Br 10%
H
WHY? In electrophilic addition to alkenes, the major product is formed

This carbocation intermediate is H H H
via the more stable carbocation intermediate.
more stable because the methyl
groups on either side of the In exam answers
H C C C H
positive carbon are electron + •Draw out both carbocations and identify as primary, secondary and
releasing and reduce the charge tertiary
H H
on the ion which stabilises it. •State which is the more stable carbocation e.g. secondary more stable
than primary
•State that the more stable carbocation is stabilised because the
The order of stability for carbocations is methyl groups on either (or one) side of the positive carbon are
electron releasing and reduce the charge on the ion.
tertiary > secondary >primary •(If both carbocations are secondary then both will be equally stable
and a 50/50 split will be achieved) 6
5. Reaction of cold dilute Potassium Manganate(VII) with Alkenes
Change in functional group: alkene  diol H H H H H

Reagent: KMnO4 in an acidified solution KMnO4
C C C H H C C C H
Conditions: cold dilute
Type of reaction: Oxidation
H H H OH OH H
Observation: purple colour of MnO4- ion will propene Propane-1,2-diol
decolourise to colourless
This reaction with its colour change can be used as a test for the
alkene functional group. It would not change colour with alkanes
5. Reaction of hot concentrated Potassium Manganate(VII) with Alkenes
Change in functional group: alkene  carbonyls

(mostly) A E E
KMnO4 A
Reagent: KMnO4 in an acidified solution C C C O + O C
Conditions: hot concentrated D
D G G
Type of reaction: Oxidation
General reaction – double bond breaks and two carbonyls
are formed. The products formed can be used to work out
which alkene was the reactant
Different alkenes will lead to different types of products.
H3C CH3 CH3

KMnO4 H 3C
C C C O+ O C
H3C CH3 H 3C CH3
CH3 The ethanal formed KMnO CH3

H3C CH3 KMnO4 H 3C 4
H 3C
C O+ O C in this case is also C O + O C
C C
oxidised by KMnO4
H CH3 to ethanoic acid HO CH3
H CH3
ethanal Ethanoic
propanone
acid
CH3
H CH3 CH3 KMnO4
KMnO4 H CO2 + H2O + O C
C C + O C
C O The methanal formed in this CH3
H CH3 H CH3 case is also oxidised by KMnO4
methanal to mathanoic acid, but this is
then oxidised further to finally
produce CO2 and water
Addition Polymers
Poly(alkenes) like alkanes are unreactive due to the
Addition polymers are formed from alkenes strong C-C and C-H bonds
This is called addition polymerisation
be able to recognise the repeating unit in a poly(alkene)
H H H H H H
Monomer Polymer
Ethene polyethene C C C C C C
H H H H
CH3 H CH3 H CH3 H
n C C C C
H CH3
H CH3 n
propene
poly(propene)
Add the n’s if writing an equation showing the reaction
Poly(propene) is recycled
where ‘n’ monomers become ‘n’ repeating units
H H
If asked to draw one
repeating unit, don’t add the
n on to your diagram, C C
because n represents a large
number H CH3
It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
C C C C
repeating unit for any H3C CH CH CH3 the double bond
alkene H3C H
CH3 H
H H Poly(chloroethene) is a polymer that is water proof, an electrical insulator and doesn’t

react with acids.
In its pure form it is a rigid plastic due to the strong intermolecular bonding between
C C polymer chains prevents them moving over each other. In this un-plasticised form it is
used make uPVC window frame coverings and guttering.
H Cl
Dealing with waste polymers
Most polymers (polyalkenes) are non-biodegradable and take many years to break down.
Combustion for energy production

Waste polymers can be incinerated and the heat released can be used to generate electricity.
Combustion of halogenated plastics (ie PVC) can lead to the formation of toxic, acidic waste products such as HCl.
Chemists can minimise the environmental damage of this by removing the HCl fumes formed from the combustion
process.
Hydrocarbons as fuels
Alkanes are good fuels. They burn cleanly, have high enthalpies of combustion
and are easy to transport. C H (g) + 3.5 O (g)  2CO (g) + 3 H O(l)
2 6 2 2 2
Pollution from Combustion
Incomplete Combustion Incomplete combustion produces less

energy per mole than complete
If there is a limited amount of oxygen then incomplete combustion occurs, combustion
producing CO (which is very toxic) and/or C (producing a sooty flame)
Carbon (soot) can cause global
CH4(g) + 3/2 O2(g)  CO(g) + 2 H2O(l)
dimming- reflection of the sun’s light
CH4(g) + O2(g)  C(s) + 2 H2O(l)
Nitrogen Oxides NOx

Nitrogen oxides form from the reaction between N 2 and O2 inside the car engine.
The high temperature and spark in the engine provides sufficient energy to break strong N 2 bond
N2 + O2  2NO N2 + 2O2  2NO2
Pollutant Environmental consequence

Nitrogen oxides (formed when N2 in the air reacts NO is toxic and can form acidic gas NO2
at the high temperatures and spark in the engine) NO2 is toxic and acidic and forms acid rain
Carbon monoxide toxic
Carbon dioxide Contributes towards global warming
Unburnt hydrocarbons (not all the fuel burns in the Contributes towards formation of smog
engine ) Some escapes at petrol filling stations.
soot Global dimming and respiratory problems
the exhaust gases, turning them into ‘harmless’ CO 2, N2 and H2O. Converters have a ceramic
honeycomb coated with a thin
2 CO + 2 NO  2 CO2 + N2 layer of catalyst metals Platinum,
Palladium, Rhodium – to give a
C8H18 + 25 NO  8 CO2 + 12½ N2 + 9 H2O large surface area.
Global warming
Carbon dioxide (CO2), methane (CH4) and water vapour (H2O) are all greenhouse gases. (They trap the Earth’s
radiated infra red energy in the atmosphere).
Water is the main greenhouse gas (but is natural), followed by carbon dioxide and methane.
Carbon dioxide levels have risen significantly in recent years due to The Earth is thought to be getting
increasing burning of fossil fuels. warmer, and many scientists believe it
Carbon dioxide is a particularly effective greenhouse gas and its increase is is due to increasing amounts of
thought to be largely responsible for global warming. greenhouse gases in the atmosphere.
Infrared spectroscopy
Tis type of spectroscopy can be used to measure the amounts of greenhouse gases in the atmosphere .
The bonds in CO2, methane and water vapour absorb infra-red radiation. See chapter 22 for more
details.
Aromatic Hydrocarbons / Arenes
There are two major classes of organic chemicals
All of the organic substances we have
aliphatic : straight or branched chain organic substances
looked at so far have been aliphatic.
aromatic or arene: includes one or more ring of six carbon atoms
with delocalised bonding. Benzene belongs to the aromatic class.
Benzene’s Structure Benzene is a planar molecule. The

The simplest arene is benzene. It has the molecular formula C6H6 evidence suggests all the C-C bonds are
Its basic structure is six C atoms in a hexagonal ring, with one H atom the same and have a length and bond
bonded to each C atom. energy between a C-C single and C=C
Each C atom is bonded to two other C atoms and one H atom by single double bond.
covalent σ-bonds. This leaves one unused electron on each C atom in a p
orbital, perpendicular to the plane of the ring. In formulae we draw a circle to show this
The Six p electrons are delocalised in a ring structure above and below delocalised system.
the plane of carbon atoms.
H H H H
H H H H Abbreviated
formula
H H H H
Displayed formula
The six electrons in the pi bonds are delocalised and spread out over the The H-C-C bond angle is 120o in Benzene
whole ring. Delocalised means not attached to a particular atom.
Using Enthalpies of Hydrogenation to show Thermodynamic Stability
+ H2  H = -120 kJ/mol
enthalpy
H = -152kJ/mol
cyclohexene cyclohexane x3 delocalisation energy
Theoretically because there are 3
double bonds in the theoretical -360 kJ/mol
+ 3H2  H = -360 kJ/mol cyclohexa-1,3,5-triene one might Theoretical
expect the amount of energy to be 3 value
Non delocalised times as much as cyclohexene.
structure
H = -208kJ/mol
However, in actual benzene the actual value
+ 3H2  H = -208kJ/mol amount of energy is less. The 6 pi
electrons are delocalised and not
delocalised arranged in 3 double bonds
structure
This when represented on an energy level
The increase in stability connected to delocalisation is called the diagram shows that the delocalised benzene is
delocalisation energy. more thermodynamically stable than the
theoretical structure .
In cyclohexa-1,3-diene, there would be In cyclohexa-1,4-diene, there

some delocalisation and extra stability as would not be delocalisation
the pi electrons are close together, in the as the pi electrons are too far
same plane and so overlap . The apart and so don’t overlap.
hydrogenation value would be less negative The hydrogenation value
than -240 kJ/mol (showing more stable) would be -240 kJ/mol
Halogenation of Benzene
Change in functional group: benzene  Bromobenzene This reaction can be done with chlorine.
Reagents: Bromine The catalyst can be AlCl3 or FeCl3
Conditions: iron(III) bromide catalyst FeBr3
It is possible to create the iron(III)
Mechanism: Electrophillic Substitution
bromide in situ by reacting iron with
bromine
Overall Equation for reaction Br
Equation for Formation of electrophiles: (Learn!)
+ HBr AlCl3 + Cl2  AlCl4– + Cl+
+ Br2  FeBr3 + Br2  FeBr4– + Br+
Mechanism Cl
Cl+
H Cl
+
The H+ ion reacts with the AlCl4- to H+ + AlCl4-  AlCl3 + HCl

reform AlCl3 catalyst and HCl.
Nitration of Benzene
Change in functional group: benzene  nitrobenzene
Reagents: conc nitric acid in the presence of concentrated Importance of this reaction
sulphuric acid (catalyst)
Nitration of benzene and other arenes is an
Mechanism: Electrophilic Substitution
Electrophile: NO2+ important step in synthesising useful
compounds e.g. explosive manufacture (like
Equation for Formation of electrophile: (Learn!) TNT, trinitrotoluene/ 2,4,6-
HNO3 + 2H2SO4  NO2+ + 2HSO4- + H3O+ trinitromethylbenzene) and formation of
amines from which dyestuffs are
Overall Equation for reaction manufactured. (The reaction for this is
NO2 covered in the amines section.)
+ NO2 +
 + H+
Mechanism
NO 2
NO2+ NO 2 This reaction is done at 60oC. On
using higher temperatures a
H second nitro group can be
+ substituted.
+ H+
The horseshoe shape of The H+ ion rejoins

the intermediate must not with the HSO4- to
extend beyond C’s 2 to 6 reform H2SO4
catalyst.
Friedel Crafts Acylation
Change in functional group: benzene  phenyl ketone
Reagents: acyl chloride in the presence of anhydrous Any acyl chloride can be used RCOCl where R is
aluminium chloride catalyst any alkyl group e.g. –CH3 , -C2H5. The
Conditions: heat under reflux (50OC) electrophile is the RCO+.
Equation for Formation of the electrophile.

AlCl3 + CH3COCl  CH3CO+ AlCl4-
Overall Equation for reaction These are important

O
reactions in organic
C synthesis because they
CH3CO+ AlCl4- + CH3 + AlCl3 + HCl introduce a reactive
functional group on to the
phenylethanone benzene ring
Mechanism O O
+ O
C CH3 C CH3
C
CH3
H
+
The H+ ion reacts with the AlCl4- to
H+ + AlCl4-  AlCl3 + HCl
Friedel Crafts Alkylation
Change in functional group: benzene  alkylbenzene

Reagents: chloroalkane in the presence of anhydrous Any chloroalkane can be used RCl where R is
aluminium chloride catalyst any alkyl group Eg –CH3 , -C2H5. The
Conditions: heat under reflux electrophile is the R+.
Formation of the electrophile.

AlCl3 + CH3CH2Cl  CH3CH2+ AlCl4-
Overall Equation for reaction

CH2CH3
CH3CH2+ AlCl4- + + AlCl3 + HCl
ethylbenzene
Mechanism
+CH CH
2 3 CH 2CH 3
CH2CH3
H
+
The H+ ion reacts with the AlCl4- to

H+ + AlCl4-  AlCl3 + HCl
Hydrogenation of Benzene
Reaction: benzene  cyclohexane Ni

Reagents: Hydrogen Catalyst
+ 3H2
Conditons: Nickel catalyst at 200C and 30 atm
Type of reaction: Addition and reduction
Oxidation of side chains

CH3 O OH
C
Reaction: alkylbenzene  benzoic acid
Reagents: alkaline KMnO4 (followed by H2SO4) KMnO4
Conditons: heat under reflux
Type of reaction: oxidation
CH 3
H 2C O OH
C
Different lengths of alkyl groups all
get oxidised to benzoic acid KMnO4
Reactions of Benzene
Benzene does not readily undergo addition reactions because these would involve permanently
breaking up the delocalised system. Most of Benzene’s reactions involve substituting one H for another
atom or group of atoms. It reactions are usually electrophilic substitutions.
Comparison of Benzene with alkenes: reaction with Bromine

The delocalised electrons above and below the plane of the molecule are attractive for electrophiles to
attack. But they do undergo electrophilic reactions more slowly than alkenes
Alkenes react with Bromine easily at room temperature. Benzene does not react with Bromine without
additional halogen carrier chemicals.
In benzene, electrons in π-bond(s) are delocalised. In alkenes, π-electrons are localised between two
carbons.
Benzene therefore has a lower electron density than C=C. Benzene therefore polarises bromine less and
induces a weaker dipole in bromine than an alkene would.
The electrophilic substitution mechanisms involve a temporary breaking of the delocalization to form
an intermediate. It takes energy to form this intermediate. The activation energies are therefore high,
and substitution reactions of arenes tend to be relatively slow
Effect of delocalisation on side groups with lone pairs

If a –Cl atom is directly attached to a benzene ring the delocalisation in the benzene ring will extend to
include the lone pairs on the Cl. This changes the properties and reactions of the side group.
Cl
The C-Cl bond is made stronger. Typical H H Aliphatic halogenoalkanes
halogenoalkane nucleophilic will undergo nucleophilic
substitution and elimination reactions H C C H substitution reactions to
do not occur. Also the electron rich H Cl produce alcohols
chlorobenzene benzene ring will repel nucleophiles.
Halogenation and conditions
CH3
CH3 H 2C Cl
Cl
Cl2 Cl2
AlCl3 catalyst UV light
Use the AlCl3 catalyst to Use UV light to

substitute directly on the substitute on to the side
benzene ring group
Effect of side groups on substitution

Side groups on a benzene ring can affect the position on
the ring of substitution reactions. Table 9 in the data book has
this information
Electron-donating groups such as OH, NH2 –Cl will force further
substitutions to occur on the 2- and 4- positions of the ring
OH
OH
with 4M
HNO3 NO 2 or
OH
NO 2
2 -nitrophenol
4 -nitrophenol
Electron-withdrawing groups (such as NO2 –CN – CO2H) will have a 3-directing

effect in electrophilic substitution of aromatic compounds
NO2
NO 2
AlCl3 catalyst
+ Cl2
Cl
16 Halogenoalkanes
Naming Halogenoalkanes H H H
H
H C H
H H
Based on original alkane, with a prefix indicating halogen atom:
H
H C C C H
Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I. H C C C C H
Br H H H Cl H H
Substituents are listed alphabetically
1-bromopropane 2-chloro-2-methylbutane
Classifying halogenoalkanes
Haloalkanes can be classified as primary, secondary or tertiary depending on the
number of carbon atoms attached to the C-X functional group.
H
H H H H H H
H C H
H H H
H C C C H H C C C H
H C C C C H
Br H H H Br H H Cl H H
Primary halogenoalkane Secondary halogenoalkane Two Tertiary halogenoalkane Three

One carbon attached to the carbon carbons attached to the carbon carbons attached to the carbon
atom adjoining the halogen atom adjoining the halogen atom adjoining the halogen
Reactions of Halogenoalkanes Halogenoalkanes undergo either Organic reactions are

substitution or elimination reactions classified by their
mechanisms
1. Nucleophilic substitution reactions
Substitution: swapping a halogen atom for another atom or groups of atoms
Nucleophile: electron pair donator e.g. :OH -, :NH3, CN-

:Nu represents any nucleophile – they always
The Mechanism: We draw (or outline) mechanisms to show have a lone pair and act as electron pair
in detail how a reaction proceeds donators
Nu:-
The nucleophiles
H H The carbon has a small
attack the positive H H positive charge because of
carbon atom
the electronegativity
H C C δ+ X δ- H C C Nu + X- difference between the
carbon and the halogen
H H
H H
We use curly arrows in mechanisms (with

A curly arrow will always start from
two line heads) to show the movement of
a lone pair of electrons or the centre
two electrons
of a bond
The rate of these substitution reactions depends on the strength of the C-X Bond enthalpy /
bond kJmol-1
The weaker the bond, the easier it is to break and the faster the reaction.
C-I 238
C-Br 276
The iodoalkanes are the fastest to substitute and the fluoroalkanes are
the slowest. The strength of the C-F bond is such that fluoroalkanes are C-Cl 338
very unreactive
C-F 484
Comparing the rate of hydrolysis reactions
Hydrolysis is defined as the splitting of a molecule ( in this case a Water is a poor nucleophile but it can react
haloalkane) by a reaction with water slowly with haloalkanes in a substitution
reaction
CH3CH2X + H2O  CH3CH2OH + X- + H+
Aqueous silver nitrate is added to a haloalkane and the halide CH3CH2I + H2O  CH3CH2OH + I- + H+
leaving group combines with a silver ion to form a SILVER HALIDE
Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
PRECIPITATE.
The precipitate only forms when the halide ion has left the The iodoalkane forms a precipitate with the
haloalkane and so the rate of formation of the precipitate can be silver nitrate first as the C-I bond is weakest
used to compare the reactivity of the different haloalkanes. and so it hydrolyses the quickest
The quicker the precipitate is formed, the faster the substitution AgI (s) - yellow precipitate
reaction and the more reactive the haloalkane AgBr(s) – cream precipitate forms faster
The rate of these substitution reactions depends on the strength of the AgCl(s) – white precipitate
C-X bond . The weaker the bond, the easier it is to break and the faster
the reaction.
Nucleophilic substitution with aqueous hydroxide ions

Change in functional group: halogenoalkane  alcohol H H H
H H H
Reagent: potassium (or sodium) hydroxide
H C C C Br + KOH  + KBr
Conditions: In aqueous solution; Heat under reflux H C C C OH
Mechanism:Nucleophilic Substitution H H H H H H
Role of reagent: Nucleophile, OH- 1-bromopropane propan-1-ol
The OH– is a stronger nucleophile than water as it has a full negative The aqueous conditions needed is
charge and so is more strongly attracted to the Cδ+ an important point. If the solvent is
changed to ethanol an elimination
reaction occurs
SN2 nucleophilic substitution mechanism for halogenoalkanes
H CH3 H - H
δ+ δ-
H3C C Br HO C Br H3C C OH + :Br -
-HO:
H H
H
transition state.
This mechanism occurs with primary halogenoalkanes
SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes
Tertiary haloalkanes undergo nucleophilic substitution in a different way
Tertiary halogenoalkanes
CH3 CH3 CH3 undergo this mechanism as the
+ tertiary carbocation is made
H3C C Br H3C C :OH- H3C C OH
stabilised by the electron
CH3 CH3 CH3 releasing methyl groups around it.
(see alkenes topic for another
The Br first breaks example of this).
The hydroxide Also the bulky methyl groups
away from the
nucleophile then prevent the hydroxide ion from
haloalkane to form
attacks the positive attacking the halogenoalkane in
a carbocation
carbon the same way as the mechanism
intermediate
above
Primary halogenoalkanes don’t do the SN1 mechanism because they would only form an unstable primary
carbocation.
Nucleophilic substitution with ammonia
Change in functional group: halogenoalkane 

amine H H H
H H H
Reagent: NH3 dissolved in ethanol

H C C C Br + 2NH3  H C C C NH2 + NH4Br
Conditions: Heating under pressure in a sealed
tube H H H
H H H
Mechanism: Nucleophilic Substitution propylamine

Type of reagent: Nucleophile, :NH3
Naming amines:
In the above example
H H H propylamine, the propyl shows
δ+ δ- the 3 C’s of the carbon chain.
CH3 CH2 C Br
+ :Br -
CH3 CH2 C N H Sometimes it is easier to use the
3HN: IUPAC naming for amines e.g.
H H H Propan-1-amine
:NH3
CH3 CH2 C NH2 + NH4Br

H
Further substitution reactions can occur between the haloalkane and the amines
formed leading to a lower yield of the amine. Using excess ammonia helps
minimise this.
H R
Further reactions H H
RX RX
RX R N:
H N: H N: R N:
H R R R
Nucleophilic substitution with cyanide ions
Change in functional group: halogenoalkane  H H H H H H

nitrile
Reagent: KCN dissolved in ethanol/water mixture H C C C Br + :CN-  H C C C CN + Br-
Conditions: Heating under reflux H H H
H H H
Mechanism: Nucleophilic Substitution
1-bromopropane butanenitrile
Type of reagent: Nucleophile, :CN-
Note: the H H This reaction increases the length of

mechanism is δ+ δ- the carbon chain (which is reflected in
identical to the H3C C Br H3C C CN + :Br - the name) In the above example
above one -NC: butanenitrile includes the C in the
H H nitrile group
Naming Nitriles
Nitrile groups have to be at the end of a chain. Start

numbering the chain from the C in the CN Note the naming: butanenitrile and not
butannitrile.
CH3CH2CN : propanenitrile
H3C CH CH2 C N 3-methylbutanenitrile

CH3
Elimination reaction of halogenoalkanes Elimination: removal of small molecule

(often water) from the organic molecule
Elimination with alcoholic hydroxide ions
H H H H H H
Change in functional group: halogenoalkane 
alkene H C C C H + KOH  H C C C + KBr + H2O
Reagents: Potassium (or sodium) hydroxide H H
H Br H
Conditions: In ethanol ; Heat
2-bromopropane propene
Mechanism: Elimination
Type of reagent: Base, OH-
Uses of Halogenoalkanes
chloroalkanes and chlorofluoroalkanes can be used as solvents Halogenoalkanes have also been
used as refrigerants, pesticides
CH3CCl3 was used as the solvent in dry cleaning
and aerosol propellants
Many of these uses depended on the unreactivity of Fluorine containing
compounds. They often had low flammability
Many of these uses have now been stopped due to the toxicity of
halogenoalkanes to the atmosphere and also their detrimental
effect on the atmosphere
Ozone Chemistry
The naturally occurring ozone (O3) layer in the upper Ozone in the lower atmosphere
atmosphere is beneficial as it filters out much of the sun’s is a pollutant and contributes
harmful UV radiation towards the formation of smog
Man-made chlorofluorocarbons (CFC’s) caused a hole to form in the ozone

layer.
Chlorine atoms are formed in the upper atmosphere when energy from
ultra-violet radiation causes C–Cl bonds in chlorofluorocarbons (CFCs) to CF2Cl2  CF2Cl  + Cl
break
The chlorine free radical atoms catalyse the

.
Cl + O3  ClO + O2
.
decomposition of ozone due to these reactions .
ClO + O3  2O2 + Cl
.
because they are regenerated. (They provide an
alternative route with a lower activation energy) Overall equation
2 O3  3 O2
They contributed to the formation of a hole in the
ozone layer. The regenerated Cl radical means
that one Cl radical could destroy
many thousands of ozone molecules
Legislation to ban the use of CFCs was supported by HFCs (Hydro fluoro carbons) e.g..
chemists and that they have now developed CH2FCF3 are now used for refrigerators
alternative chlorine-free compounds and air-conditioners. These are safer
as they do not contain the C-Cl bond
The C-F bond is stronger than the C-Cl bond and is not affected by UV
17 Alcohols General formula alcohols CnH2n+1OH
Naming Alcohols
OH
These have the ending -ol and if necessary the position
Butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4
O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-): OH OH
HO CH2 CH2 OH Ethane-1,2-diol
If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH
H2C OH
Bond angles in Alcohols

H The H-O- C bond is 104.5o (bent line
All the H-C-H bonds and C- H shape), because there are 2 bond
C-O are 109.5o (tetrahedral O H pairs of electrons and 2 lone pairs
shape), because there are 4
109.5O C 104.5O
C repelling to a position of minimum
bond pairs of electrons H
repulsion. Lone pairs repel more than
repelling to a position of H bond pairs so the bond angle is
minimum repulsion. H reduced.
Boiling points
The alcohols have relatively low volatility and δ- δ+ δ-

O H δ+
high boiling points due to their ability to form O H
hydrogen bond between alcohol molecules. H
C Hδ +
H H
C
H
H
Different types of alcohols
H
H H H O
H H H H H
H C C C H
H C C C O H H C C C H
H H H H O H H H
H C H
Propan-1-ol H
H
Primary Propan-2-ol
Secondary methylpropan-2-ol
Tertiary
Primary alcohols are alcohols Secondary alcohols are alcohols Tertiary alcohols are alcohols
where 1 carbon is attached to where 2 carbon are attached to where 3 carbon are attached to
the carbon adjoining the the carbon adjoining the oxygen the carbon adjoining the oxygen
oxygen
1. Combustion of Alcohols
Alcohols combust with a clean flame CH3CH2OH + 3O2  2CO2 + 3H2O
2. Substitution reactions of Alcohols to form Halogenoalkanes

Various halogenating compounds can be used to substitute
the –OH group for a halogen PCl5 / PCl3 / conc HCl / SOCl2 / mixture of NaCl +
H2SO4 can all be uses for substituting a Cl
Reaction with phosphorous (V) halide
This reaction with PCl5 (phosphorous(v)chloride)
CH3CH2OH + PCl5  CH3CH2Cl + POCl3 + HCl can be used as a test for alcohols. You would
observe misty fumes of HCl produced.
For Br use KBr, 50% concentrated H2SO4

CH3CH2OH + HBr  CH3CH2Br + H2O to produce HBr
Reaction with phosphorous (III) iodide

The phosphorous (III) Iodide is produced in situ by
PI3 + 3 CH3CH2OH  3CH3CH2I + H3PO3 reacting red phosphorus and Iodine.
The reaction of KI and conc H2SO4 cant be used to produce HI because the sulphuric
acid with oxidise the hydrogen halides to other products
3. Reaction of Alcohols with Sodium Observations:

Sodium reacts with alcohols • effervescence, This reaction can be
• the mixture gets hot, used as a test for
2CH3CH2OH + 2Na  2CH3CH2O-Na+ + H2 • sodium dissolves, alcohols
• a white solid is produced.
Oxidation reactions of the alcohols

Potassium dichromate K2Cr2O7 is an oxidising agent that The exact reaction, however, depends on the type
causes alcohols to oxidise. of alcohol, i.e. whether it is primary, secondary, or
tertiary, and on the conditions.
Partial Oxidation of Primary Alcohols

H
O
An aldehyde’s name ends in –
Reaction: primary alcohol  aldehyde al
Reagent: potassium dichromate (VI) solution and dilute H C C It always has the C=O bond on
sulphuric acid. the first carbon of the chain
Conditions: (use a limited amount of dichromate) warm gently Ethanal
H
H so it does not need an extra
and distil out the aldehyde as it forms: number
H H
H H H O Observation: the orange
+ [O] H C C C + H2O dichromate ion (Cr2O72-)
H C C C O H reduces to the green Cr 3+
H H H ion
H H H
OH + [O] O + H2O
CH3CH2CH2OH + [O]  CH3CH2CHO + H2O

propan-1-ol
propanal
Write the oxidation equations in a simplified form using [O] which represents O from the oxidising agent
When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO
2
Full Oxidation of Primary Alcohols
H H
O
Reaction: primary alcohol  carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute H C C C
sulphuric acid
Conditions: use an excess of dichromate, and heat H H
O H
under reflux: (distill off product after the reaction
has finished) Propanoic acid
H H H H H O
+ 2 [O] H C C C + H2O Observation: the
H C C C O H
orange dichromate
H H H H H O H
ion (Cr2O72-)
OH + 2[O] OH reduces to the
+ H2O green Cr 3+ ion
O
CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O
propan-1-ol Propanoic acid
Oxidation of Secondary Alcohols

Ketones end in -one
H O H
Reaction: secondary alcohol  ketone When ketones have 5C’s
H C C C H
Reagent: potassium dichromate(VI) solution and or more in a chain then it
dilute sulphuric acid. H H
needs a number to show
Conditions: heat under reflux the position of the double
Propanone bond. E.g. pentan-2-one
H H H
H O H
H C C C H
+ [O] Observation: the
H C C C H + H2O orange dichromate
H O H ion (Cr2O72-) reduces
H H to the green Cr 3+ ion
H
propan-2-ol Propanone
There is no further oxidation of the ketone under these conditions.
Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the OH group
Distinguishing between Aldehydes and Ketones
The fact that aldehydes can be further oxidised to carboxylic acids whereas ketones cannot be further oxidised is the
chemical basis for two tests that are commoly used to distinguish between aldehydes and ketones
Tollen’s Reagent Fehling’s solution

Reagent: Fehling’s Solution containing blue Cu 2+ ions.
Reagent: Tollen’s Reagent formed by mixing aqueous
Conditions: heat gently
ammonia and silver nitrate. The active
substance is the complex ion of [Ag(NH3)2]+ . Reaction: aldehydes only are oxidised by Fehling’s
solution into a carboxylic acid and the copper
Conditions: heat gently ions are reduced to copper(I) oxide .
Reaction: aldehydes only are oxidised by Tollen’s Observation: Aldehydes :Blue Cu 2+ ions in solution
reagent into a carboxylic acid and the silver(I) change to a red precipitate of Cu2O. Ketones do
ions are reduced to silver atoms not react
Observation: with aldehydes, a silver mirror forms
coating the inside of the test tube.
Ketones result in no visible change CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+
CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+
The presence of a carboxylic acid can be tested by addition of sodium carbonate. It will fizz and produce carbon
dioxide
Reaction of ethanol with iodine in presence of alkali
Reagents: Iodine and sodium hydroxide Only alcohols with a methyl group next to H H
Conditions: warm very gently the C-O -H bond will do this reaction. H C C H
The product tri-iodomethane CHI3 is a H OH

This reaction is called the Iodoform test
yellow crystalline precipitate with an
antiseptic smell
CH3CH(OH)CH3 + 4I2 + 6NaOH → CHI3 + CH3COONa + 5NaI +5H2O
CH3CH(OH)R + 4I2 + 6NaOH → CHI3 + RCOONa + 5NaI +5H2O
Reaction of Alcohols with Dehydrating Agents
Reaction: Alcohol  Alkene

Dehydration Reaction: removal of a
water molecule from a molecule
Reagents: Concentrated Sulphuric or Phosphoric acids
Conditions: warm (under reflux)
Role of reagent: dehydrating agent/catalyst
Type of reaction: acid catalysed elimination
H
H
H H H
H C
H C C C O H H
C C
+ H2O
H H H
H H
propan-1-ol Propene
CH3CH2CH2OH  CH2=CHCH3 + H2O
H H
H C
Some 2o and 3o Butan-2-ol But-1-ene
alcohols can give H H H H C C C H
more than one
product, when the H C C C C H H
H H
double bond H H
forms between H H O H H H
different carbon C C
atoms H
H H
C C
Butan-2-ol can form both alkenes
although more but-2-ene would be But-2-ene
H H
formed
But-2-ene could also exist as E and Z
isomers
Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong sulfuric acid catalyst, H C C C O C H methyl propanoate.
to form esters and water. H H H
H+ The bit ending in –anoate The bit ending in –yl comes from
Carboxylic Acid + Alcohol Ester + water comes from the carboxylic the alcohol that has formed it
acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.
H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate
Esterification with acyl chlorides
Change in functional group: alcohol ester This reaction for making esters is much better than
Reagent: alcohol using carboxylic acids as the reaction is much
Conditions: room temp. quicker and it is not a reversible reaction
RCOCl (l) + CH3CH2OH  RCO2CH2CH3 + HCl (g)

O H O H H
CH 3 C + CH3CH2OH  H C C O C C H + HCl
Cl H H H
Observation: Steamy white fumes of HCl

are given off
O
O C
 + HCl
OH + C O
Cl
phenol Benzoyl Phenyl

chloride benzoate
Phenols
In a phenol the OH group is directly attached to the CH2OH
benzene ring.
OH
In a phenol the lone pair of electrons on the
oxygen is delocalised with the electron
charge cloud of the arene ring.
The delocalised bonding changes the
This is not a phenol, but is
reactivity of the OH group and the arene ring.
an alcohol because the
OH group is attached to an
alkyl group rather than the
Phenols are very weakly acidic. They are weaker acids than carboxylic acids. benzene ring.
Both phenols and carboxylic acids will react with sodium metal and sodium
hydroxide. Only carboxylic acids will react with sodium carbonate as a phenol
is not strong enough an acid to react.
-
OH + Na O Na+ + ½ H2
The sodium phenoxide

- compound is more soluble
OH + NaOH O Na+ + H2O
than the original phenol. So
the solid phenol dissolves on
sodium phenoxide addition of NaOH
Reaction with Bromine
Reagents: Br2
Conditions: room temp
OH Phenol does not need a FeBr3
OH
catalyst like benzene and
Br Br undergoes multiple
substitution whereas benzene
+ 3 Br2 + 3 HBr will only add one Br.
The product in this reaction is a

Br white solid
2,4,6 –tribromophenol
In phenol the lone pair of electrons on the oxygen (p- orbital) is

partially delocalised into the ring. The electron density increases
and the Br2 is more polarised
Phenols are used in the production of plastics,

antiseptics, disinfectants and resins for paints.
Reaction of Phenol with Nitric acid
In comparison with benzene, phenol does not need the
concentrated sulphuric acid catalyst
With 4M HNO3 single substitution occurs (in comparison

to the conc HNO3 needed for benzene)
Reagent 4M HNO3
Conditions: room temp
OH
OH
with 4M
NO 2
OH HNO3
or
NO2
2 -nitrophenol 4 -nitrophenol
Reaction with diazonium ion

coupling of diazonium ion with a phenol under alkaline
conditions;
NaOH
+
N N + OH N N OH
4-hydroxyazobenzene
C6H5N2+ Cl− +C6H5OH  C6H5N2C6H4OH +HCl
Azo dyes are used for dyes, pigments and

colourings
18. Carbonyls: Aldehydes and Ketones
Carbonyls are compounds with a C=O bond.
They can be either aldehydes or ketones
H O H O H If the C=O is in the middle of

If the C=O is on the end of the
H. C C chain with an H attached it is an H C C C H the chain it is a ketone
The name will end in -one
aldehyde. H H
H H The name will end in –al
CH3COCH3 propanone
CH3CHO ethanal
Intermolecular forces in Carbonyls Solubility in water

Pure carbonyls cannot hydrogen bond, but CH3
bond instead by permanent dipole forces. The smaller carbonyls are soluble
δ- δ+ δ-
in water because they can form O H O C
hydrogen bonds with water.
H CH3
δ-
Reactions of carbonyls O
In comparison to the C=C bond in
The C=O bond is polarised because alkenes, the C=O is stronger and does
O is more electronegative than δ+ not undergo addition reactions easily.
C
carbon. The positive carbon atom
attracts nucleophiles. H3C CH3
This is in contrast to the electrophiles
that are attracted to the C=C .
nucleophile
Oxidation Reactions
Potassium dichromate K2Cr2O7 is Key point: Aldehydes

Primary alcohol  aldehydes  carboxylic acid
an oxidising agent that causes can be oxidised to
alcohols and aldehydes to Secondary alcohol  ketones carboxylic acids, but
oxidise. Tertiary alcohols do not oxidise ketones cannot be
oxidised.
Oxidation of Aldehydes
Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
dilute sulphuric acid.
Conditions: heat under reflux H H H H H O H
Full Equation for oxidation RCHO + [O]  RCO2H

3CH3CHO + Cr2O72- + 8H+  3 CH3CO2H + 4H2O + 2Cr3+
Aldehydes can also be oxidised using Fehling’s
Observation: the orange dichromate ion solution or Tollen’s Reagent. These are used
(Cr2O72-) reduces to the green Cr 3+ ion as tests for the presence of aldehyde groups
Tollen’s Reagent
Fehling’s solution
Reagent: Tollen’s Reagent formed by mixing
aqueous ammonia and silver nitrate. The
active substance is the complex ion of Reagent: Fehling’s Solution containing blue Cu 2+ ions.
[Ag(NH3)2]+ . Conditions: heat gently
Conditions: heat gently Reaction: aldehydes only are oxidised by Fehling’s
Solution into a carboxylic acid and the copper ions
Reaction: aldehydes only are oxidised by are reduced to copper(I) oxide . .
Tollen’s reagent into a carboxylic acid and Observation: Aldehydes :Blue Cu 2+ ions in solution
the silver(I) ions are reduced to silver atoms change to a red precipitate of Cu 2O. Ketones do
Observation: with aldehydes, a silver mirror forms not react.
coating the inside of the test tube. Ketones
result in no change. CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+

1
Reduction of carbonyls Reducing agents such as NaBH4 (sodium tetrahydridoborate)
Reagents: LiAlH4 In dry ether or LiAlH4 (lithium tetrahydridoaluminate) will reduce carbonyls
Conditions: Room temperature and pressure to alcohols.
Type of reaction: Reduction
Role of reagent: Reducing agent
Aldehydes will be reduced to primary alcohols Ketones will be reduced to secondary alcohols.
H H O H H H H O H H H H
H C C C + 2[H] H C C C O H H C C C H + 2[H]  H C C C H
H H H H H H H O H
H H
propanal Propan-1-ol propanone H
Propan-2-ol
Addition of hydrogen cyanide to carbonyls to form hydroxynitriles

R
Reaction: carbonyl  hydroxynitrile
When naming hydroxy
Reagent: HCN in presence of KCN NC C OH
nitriles the CN becomes
Conditions: Room temperature and pressure
part of the main chain
Mechanism: nucleophilic addition
H
hydroxynitrile
CH3COCH3+ HCN  CH3C(OH)(CN)CH3 CH3
NC C OH
2-hydroxy-2-methylpropanenitrile The extra KCN increases the
CH3 concentration of the CN- ion
CH3
CH3CHO + HCN  CH3CH(OH)CN nucleophile needed for the
NC C OH first step of the mechanism
2-hydroxypropanenitrile H
Nucleophilic Addition Mechanism

δ-
O
O:
- -
H CN O H
δ+ H3C C CH3
C H3C C CH3
H3C CH3
CN CN
:CN-
Reaction of carbonyls with iodine in presence of alkali
Reagents: Iodine and sodium hydroxide Only carbonyls with a methyl group next to O
Conditions: warm very gently the C=O bond will do this reaction. Ethanal
is the only aldehyde that reacts. More H3C C H
The product CHI3 is a yellow crystalline commonly is methyl ketones.
precipitate with an antiseptic smell
CH3COCH3 + 3I2 + 4NaOH → CHI3 + CH3COONa + 3NaI +3H2O
CH3COCH2CH3+ 3I2 + 4NaOH → CHI3 + CH3CH2COONa + 3NaI +3H2O
Reaction with 2,4-dinitro phenylhydrazine
2,4-DNP reacts with both aldehydes and ketones. The Use 2,4-DNP to identify if the compound is a
product is an orange precipitate, It can be used as a test carbonyl. Then to differentiate an aldehyde
for a carbonyl group in a compound. from a ketone use Tollen’s reagent.
The melting point of the crystal formed can be used to help identify which carbonyl was used. Take the melting
point of orange crystals product from 2,4-DNP. Compare melting point with known values in database
H O 2N You don’t need to

learn these equations
H3C C
..
H2N NH NO2
for the exam
+
O 2,4-DNP
addition
O 2N H O 2N
H
elimination of
water
H3C C NH NH NO2 H3C C N NH NO2
orange precipitate
OH
19 Carboxylic Acids and Derivatives
Naming Carboxylic acids
H H
These have the ending -oic O
If there are carboxylic acid groups on both ends of the
acid but no number is
chain then it is called a - dioic acid
necessary for the acid group H C C C
as it must always be at the O O
Ethanedioic acid
end of the chain. The H H
O H
C C
numbering always starts from
the carboxylic acid end Propanoic acid HO OH Note the e in this name
Solubility in Water

Acidity The smaller carboxylic (up to C4) H
 
The carboxylic acid are only weak acids acids dissolve in water in all O H O
in water and only slightly dissociate, but proportions but after this the solubility 
H3C C
they are strong enough to displace rapidly reduces. They dissolve   H
carbon dioxide from carbonates. because they can hydrogen bond to 

O H O
the water molecules.
H
CH3CO2H(aq) CH3CO2-(aq)+ H+(aq)
Delocalisation
The delocalised ion has equal C-O bond lengths. If
The carboxylic acid salts are stabilised by delocalisation, which delocalisation did not occur, the C=O bond would be shorter
makes the dissociation more likely. than the C-O bond.
O O The pi charge cloud has delocalised O

delocalised and spread out. The delocalisation
H3C C H3C C
makes the ion more stable and H3C C
OH O therefore more likely to form.
O
Strength of carboxylic acids
O O Increasing chain length pushes

delocalised electron density on to the COO- ion,
H3C CH2 C H3C CH2 C
making it more negative and less
OH O stable. This make the acid less
strong.
Alkyl groups electron releasing
Propanoic acid less acidic than ethanoic acid
Cl O Cl O Electronegative chlorine atoms

H C C delocalised withdraw electron density from the
H C C COO- ion, making it less negative
OH and more stable. This make the acid
H O
H more strong.
Chlorine electron withdrawing chloroethanoic acid more acidic than ethanoic acid
O H H
O O OH In a dibasic acid the second HO2C- group
C C C C C C - withdraws electron density from the
COO- ion, making it less negative and
H O H O H H O OH
H more stable and weakens the O-H bond.
This make the acid more strong.
HO2C- group electron withdrawing
Methods of preparing carboxylic acids
Full Oxidation of Primary Alcohols
Reaction: primary alcohol  carboxylic acid Observation: the

Reagent: potassium dichromate(VI) solution and dilute sulphuric acid orange dichromate
Conditions: use an excess of dichromate, and heat under reflux: (distill off ion (Cr2O72-) reduces
product after the reaction has finished) to the green Cr 3+ ion
H H H H H
O
H C C C O H + 2 [O] H C C C + H2O
H H H O H
H H
CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O

propan-1-ol Propanoic acid
Oxidation of Aldehydes
Reaction: aldehyde  carboxylic acid H H O H H O

Reagent: potassium dichromate (VI) solution and H C C C + [O]  H C C C
dilute sulphuric acid.
Conditions: heat under reflux H H H H H O H
Full Equation for oxidation RCHO + [O]  RCOOH

3CH3CHO + Cr2O72- + 8H+  3 CH3COOH + 4H2O + 2Cr3+
Hydrolysis of Nitriles
Reaction: Nitrile  carboxylic acid
Reagent: dilute hydrochloric/ sulphuric acid.
Conditions: heat under reflux
CH3CH2CN + H+ + 2H2O  CH3CH2COOH + NH4+
The Reactions of Carboxylic Acids
Salt formation reactions of carboxylic acids

Carboxylic acids can form salts with metals, alkalis and
carbonates.
acid + metal (Na)  salt + hydrogen The effervescence caused by production of CO2
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2 with carboxylic acids with solid Na2CO3 or
aqueous NaHCO3 can be used as a functional
acid + alkali (NaOH)  salt + water group test for carboxylic acids
CH3CO2H + NaOH  CH3CO2-Na+ + H2O
acid + carbonate (Na2CO3)  salt + water + CO2

2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2
Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong acid catalyst, to form H C C C O C H methyl propanoate.
esters and water. H H H
H+ The bit ending in –anoate The bit ending in –yl comes from
Carboxylic Acid + Alcohol Ester + water comes from the carboxylic the alcohol that has formed it
acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.
H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate
Reduction of carboxylic acids to alcohols

Lithium tetrahydridoaluminate (LiAlH4) is a
Carboxylic acids will be reduced to primary alcohols
strong reducing agent
H H O H H H
Reagents: LiAlH4 In dry ether
Conditions: Room temperature and pressure H C C C + 4[H] H C C C O H + H2O
Type of reaction: Reduction H H O H H H H

Propanoic acid Propan-1-ol
Role of reagent: Reducing agent
Reaction of carboxylic acid with phosphorous (V) chloride
Reaction: carboxylic acid  acyl chloride This reaction with PCl5 (phosphorous(v)chloride)
Reagent: PCl5 phosphorous(v)chloride can be used as a test for carboxylic acids. You would
Conditions: room temp observe misty fumes of HCl produced.
CH3COOH + PCl5  CH3COCl + POCl3 + HCl
O O
+ PCl5  + POCl3 + HCl
H3C C H3C C
OH Cl
Oxidation of methanoic acid O O It forms carbonic acid

(H2 CO3 ) which
Carboxylic acids cannot be oxidised by using H C + [O]  H O C decomposes to give
oxidising agents but methanoic acid is an O H O H CO2 + H2O
exception as its structure has effectively an
aldehyde group. It can be oxidised by Fehling’s
solution and Tollen’s Reagent
Oxidation of ethanedioic acid
Ethanedioic acid can be oxidised by potassium manganate (VII). The
The reaction between MnO4- and
ethanedioic acid is oxidised to carbon dioxide gas. This reaction can be
C2O42- is slow to begin with (as
done as a quantitative titration.
the reaction is between two
negative ions). To do as a titration
Ox H2C2O42-  2CO2 + 2H+ + 2e- the conical flask can be heated to
Red MnO4-(aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O 60o C to speed up the initial
Overall 2MnO4-(aq) + 6H+(aq) + 5C2O42-(aq)  10CO2(g) + 2Mn2+(aq) + 8H2O(l) reaction.
Relative acidities of carboxylic acids, phenols and alcohols

Carboxylic acids are acidic enough to react with sodium, sodium hydroxide, and O
sodium carbonate. As mentioned earlier the carboxylic acid salts are stabilised by
delocalisation, which makes the formation of the salts more likely. Delocalisation H3C C
spreads out the negative charge which makes it more stable
O
2CH3CO2H + 2Na  2CH3CO2-Na+ + H2
CH3CO2H + Na  CH3CO2-Na+ + H2
Phenols are very weakly acidic. They are weaker acids than carboxylic acids.
Phenols will react with sodium metal and sodium hydroxide, but are not strong
enough an acid to react with sodium carbonate. In phenol the lone pair of
electrons on the oxygen is delocalised with the electron charge cloud of the
arene ring. The delocalised bonding stabilises the formation of the phenoxide
ion. The delocalisation is less effective than that in a carboxylate ion
-
OH + Na O Na+ + ½ H2
-
OH + NaOH O Na+ + H2O
sodium phenoxide
Alcohols have almost no acidity. The do not react with sodium hydroxide or sodium
carbonate. They can react with sodium metal.
There is no delocalisation within an alcohol so the formation of a stable ethoxide
ion from ethanol is not possible except with the reaction with sodium. The negative
charge stays on the oxygen atom which makes it very unstable
2CH3CH2OH + 2Na  2CH3CH2O -Na+ + H2
4
Carboxylic acid derivatives: Acyl Chlorides
Acyl Chlorides
Acyl chlorides are The Cl groups are classed as good leaving
O
much more reactive groups (to do with less effective delocalisation.)
CH3 C than carboxylic acids This makes acyl chlorides more reactive than
carboxylic acids and esters
Cl
ethanoyl chloride
Reaction with water Reaction with alcohol
Change in functional group: acyl chloride  Change in functional group: acyl chloride  ester
carboxylic acid Reagent: alcohol
Reagent: water Conditions: room temp.
Conditions: room temp.
RCOCl (l) + CH3CH2OH  RCO2CH2CH3 + HCl (g)
RCOCl (l) + H2O  RCO2H + HCl (g)
O H O H H
O O CH 3 C + CH3CH2OH  H + HCl
C C O C C H
CH3 C + H2O  CH3 C + HCl (g) Cl H H H
Cl OH
Observation: Steamy white fumes of HCl are
Observation: Steamy white fumes of HCl
given off
are given off
This reaction for making esters is much better than using

carboxylic acids as the reaction is much quicker and it is
not a reversible reaction
Reaction with phenol
Change in functional group: acyl chloride  ester

Reagent: phenols
Conditions: room temp.
O
O C
 + HCl
OH + C O
Cl
phenol Benzoyl Phenyl

chloride benzoate
Reaction with ammonia

Reaction with primary amines
Change in functional group: acyl chloride  Change in functional group: acyl chloride 
primary amide secondary amide
Reagent: ammonia Reagent: primary amine
Conditions: room temp. Conditions: room temp.
RCOCl (l) +2NH3  RCONH2 + NH4Cl (s) RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-
O O O
O + CH3NH3+Cl-
CH3 C + 2NH3  CH3 C + NH4Cl (s) CH3 C + 2CH3NH2  CH3 C NH CH3
Cl NH2 Cl
N-methylethanamide
Observation: white smoke of NH4Cl is given off
5
Nucleophilic Addition Elimination Mechanism
Oδ- :O - O
O
CH3 C δ+ + +
H3C C OH H3 C C OH CH3 C
Cl δ-
:OH H H OH
Cl
H
Relative ease of hydrolysis

Acyl chlorides hydrolyse at room temperature with both water and sodium hydroxide. The carbon in the acyl
chloride is particularly electron deficient as it is attached to two electronegative atoms (O and Cl) so it
attractive to nucleophiles such as water. Also the C-Cl bond is weakest in the acyl chloride
H H
Alkyl halogenoalkanes will undergo nucleophilic substitution hydrolysis
H C C H reactions to produce alcohols . They won’t do this at room temperature
H Cl though so are less reactive than acyl chlorides. The carbon attached to the Cl is
positive due to the electronegativity difference but is less positive than the
carbon in the acyl chloride. They will hydrolyse if heated with water or sodium
Cl
hydroxide.
Aryl halogenoalkanes will not undergo nucleophilic substitution hydrolysis

reactions. The delocalisation in the benzene ring will extend to include the
lone pairs on the Cl. This strengthens the C-Cl bond and stops it from breaking
chlorobenzene
Hydrolysis of esters Esters can be hydrolysed and split up by either heating with acid or with sodium hydroxide.
i) with acid
This reaction is the reverse reaction of ester formation. When an ester
reagents: dilute acid (HCl)
is hydrolysed a carboxylic acid and an alcohol are formed.
conditions: heat under reflux
H+
This reaction is reversible and does not
CH3CH2CO2CH2CH3 + H2O CH3CH2CO2H + CH3CH2OH
give a good yield of the products.
ethyl propanoate
ii) with sodium hydroxide

reagents: dilute sodium hydroxide CH3CH2CO2CH3 + NaOH  CH3CH2CO2- Na+ + CH3OH
conditions: heat under reflux methyl propanoate sodium propanoate methanol
The carboxylic acid salt product is the anion of the carboxylic acid.
This reaction goes to completion. The anion is resistant to attack by weak nucleophiles such as alcohols, so the
reaction is not reversible.
Uses of Esters
Esters can have pleasant smells
Esters are sweet smelling
compounds that can be used in For use in perfumes they need to be non toxic, soluble in solvent such as
perfumes and flavourings. ethanol, volatile (turns into gas easily), and not react with water.
Although polar, they do not form hydrogen bonds (reason: there is no

Esters can be used as solvents for
hydrogen bonded to a highly electronegative atom)
polar organic substances thus, they have much lower b.p. than the hydrogen-bonded carboxylic acids
Ethyl ethanoate is used as a solvent they came from. They are also almost insoluble in water
in glues and printing inks
20 Nitrogen compounds
Primary Amines
Formation of amines
Forming a primary amine in a one step reaction of halogenoalkanes with ammonia
Change in functional group: halogenoalkane  amine Ammonia dissolved in ethanol is the initial nucleophile
Reagent: NH3 dissolved in ethanol
CH3CH2Br + 2NH3  CH3CH2NH2 + NH4Br
Conditions: Heating under pressure in a sealed tube
Mechanism: Nucleophilic Substitution
Using an excess of Ammonia can limit the further
Type of reagent: Nucleophile, :NH3 subsequent reactions and will maximise the amount of
primary amine formed
Primary amines can be formed by the nucleophilic substitution reaction between halogenoalkanes and ammonia in
a one step reaction. However, as the lone pair of electrons is still available on the N in the amine formed, the
primary amine can react in the same nucleophilic way in a successive series of reactions forming secondary, tertiary
amines and quaternary ammonium salts.
This is therefore not a good method for making a primary amine because of the further reactions. It would mean the
desired product would have to be separated from the other products.
Preparing Amines from Nitriles

Using the method above of reacting halogenoalkanes and ammonia is not an efficient method for preparing a
high yield of the primary amine because of the further substitution reactions that occur.
A better method is to use the following 2 step reaction scheme

Step 1. convert halogenoalkane to nitrile by using KCN in ethanol (heat under reflux)
CH3CH2Br + CN-  CH3CH2CN + Br -

Step 2. reduce nitrile to amine by using LiAlH4 in ether or by reducing with H2 using a Ni catalyst
CH3CH2CN + 4[H] CH3CH2CH2NH2 A disadvantage of this method is that it is a two step reaction
that may therefore have a low yield. Also KCN is toxic.
Reduction of amides with LiAlH4 reduce an amide to amine by using LiAlH4 in ether
O This reaction is then followed by reaction with a dilute acid,
CH3 C + 4[H]  CH3CH2NH2 + H2O such as dilute sulfuric or hydrochloric acid.
NH2
Reducing nitroarenes to aromatic amines See the hydrocarbon chapter for how to
form nitrobenzene from benzene.
The nitro group on an arene can be reduced an amine group as follows
Reagent: Sn and HCl or Fe and HCl NO 2 NH2

Conditions: Heating + 6[H] + 2H2O
Mechanism:reduction
phenylamine
nitrobenzene
As the reaction is carried out in HCl the salt C6H5NH3+Cl- will be formed. Reacting
this salt with NaOH will give phenylamine.
Ionic ½ equation for reduction: C6H5NO2 + 6 e– + 6 H+  C6H5NH2 + 2 H2O
Base Properties
Primary aliphatic amines act as Bronsted-Lowry Bases because the

lone pair of electrons on the nitrogen is readily available for forming a CH3NH2 +H2O  CH3NH3+ +OH-
dative covalent bond with a H+ and so accepting a proton.
Primary aliphatic amines are stronger bases than ammonia as the

alkyl groups are electron releasing and push electrons towards the NH3 (aq) +H2O (l)  NH4+(aq) +OH-(aq)
nitrogen atom and so make it a stronger base.
Secondary amines are stronger bases than primary amines because they have more alkyl groups that are
substituted onto the N atom in place of H atoms. Therefore more electron density is pushed onto the N atom (as
the inductive effect of alkyl groups is greater than that of H atoms).
One might expect using the same trend that tertiary amine would be the strongest amine base but the trend does
not hold. The tertiary amines and corresponding ammonium salts are less soluble in water and this makes them
less strong bases than the secondary amines. (This point will not be examined)
Base strength of aromatic amines NH2

Primary aromatic amines such as Phenylamine do not form basic solutions because the
lone pair of electrons on the nitrogen delocalise with the ring of electrons in the benzene
ring. This means the N is less able to accept protons. phenylamine
Overall order of base strength

Aromatic amines < ammonia< primary amines< tertiary amines< secondary amines
Weaker bases Stronger bases
Reactions with acids
All amines will react with acids to become ammonium salts

CH3NH2 (aq) + H+ (aq)  CH3NH3+(aq)
(CH3CH2)2 NH (aq) + H+ (aq)  (CH3CH2)2NH2+(aq)
(CH3CH2)3 N (aq) + H+ (aq)  (CH3CH2)3NH+(aq)
Amines as bases react with acids to form ammonium salts.

CH3NH2 (aq) +HCl (aq)  CH3NH3+Cl-(aq) Addition of NaOH to an ammonium salt
Methylamine methylammonium chloride will convert it back to the amine
The ionic salts formed in this reaction means that the These ionic salts will be solid crystals, if
compounds are soluble in the acid. the water is evaporated, because of the
e.g. Phenylamine is not very soluble in water but strong ionic interactions.
phenylammonium chloride is soluble
Reaction of phenylamine with aqueous bromine
The lone pair of electrons on the nitrogen in the amine group delocalise with the ring of
electrons in the benzene ring. This makes the benzene ring more reactive. Phenylamine
reacts with aqueous bromine at room temperature. (Remember Benzene would not do
this)
NH2 NH2
+ 3 Br2 Br Br
+ 3 HBr
phenylamine
Br
2,4,6-tribromophenylamine
Synthesis of azo dyes

Step 1: reaction of an aromatic amine with nitrous acid, HNO2, at <10 °C, Nitrous acid is generated in
forming a diazonium ion, situ from NaNO2/HCl.
NH2 NaNO2 + HCl <10oC Below 0oC the temperature is too

+ low and the reaction would be
N N too slow
diazonium ion If the diazonium ion is allowed to heat

above 10oC it reacts with water to form
C6H5NH2 + HNO2 + HCl C6H5N2+ Cl− + 2H2O phenol and N2 gas
C6H5N2+ + H2O  C6H5OH + N2 + H+
If this reaction is wanted then heat the
diazonium ion
Step 2: coupling of diazonium ion with a phenol under

alkaline conditions;
NaOH
N
+
N + OH N N OH
4-hydroxyazobenzene
C6H5N2+ Cl− +C6H5OH  C6H5N2C6H4OH +HCl
Azo dyes are used for dyes, pigments and

colourings
Amides
Amides are neutral
O
O
CH3 C
CH3 C NH CH3
NH2
Secondary amide
Primary amide
N-methylethanamide
ethanamide
Formation of amides
Reaction of acyl chloride with ammonia Reaction of acyl chloride with primary amines
Change in functional group: acyl chloride  primary Change in functional group: acyl chloride 
amide secondary amide
Reagent: ammonia Reagent: primary amine
Conditions: room temp. Conditions: room temp.
RCOCl (l) +2NH3  RCONH2 + NH4Cl (s) RCOCl +2CH3NH2  RCONHCH3 + CH3NH3+Cl-
O O O
O + CH3NH3+Cl-
CH3 C + 2NH3  CH3 C + NH4Cl (s) CH3 C + 2CH3NH2  CH3 C NH CH3
Cl NH2 Cl
N-methylethanamide
Observation: white smoke of NH4Cl is given off
Amide hydrolysis
primary amides can be hydrolysed by aqueous acids or alkalis.
With HCl an amide will be hydrolysed and split up in to a carboxylic acid and an ammonium salt
With NaOH an amide will be hydrolysed and split up into ammonia and the carboxylic acid salt
O O
CH3 C + H2O + HCl  CH 3 C + NH4+Cl-
NH2
OH
CH3CONH2 + H2O + NaOH  CH3COO-Na+ + NH3

Secondary amides can be hydrolysed by aqueous acids or alkalis.
With HCl an amide will be hydrolysed and split up in to a carboxylic acid and an amine salt
With NaOH an amide will be hydrolysed and split up into the amine and the carboxylic acid salt
O O
CH3 C NH CH3 + H2O + HCl  CH 3 C + CH3NH3+Cl-
OH
O
O
CH3 C NH CH3 + H2O + NaOH + CH3NH2
CH 3 C
-
O Na+
Reduction of amides with LiAlH4 reduce an amide to amine by using LiAlH4 in ether
This reaction is then followed by reaction with a dilute acid,
such as dilute sulfuric or hydrochloric acid.
O
CH3 C + 4[H]  CH3CH2NH2 + H2O
NH2
Amino Acids
General structure of an α amino acid The simplest amino acid is NH2 CH2 CO2H
NH2 CH CO 2H glycine, where the R is an H
R Optical Activity
The R group can be a variety of different All amino acids, except glycine, H H
things depending on what amino acid it is. are chiral because there are
four different groups around C C
The alpha in ‘α’ amino acid means both H2N
the C CO2H HO2C
NH2 and COOH groups are joined to the CH3 CH3
NH2
same C. They rotate plane polarised light.
Naming amino acids CO2H

CO2H Some amino acids have an extra
You do not need to know any carboxylic acid or an amine CH2
common names for the 20 CH2 group on the R group. These are
essential amino acids. You NH2 C CO2H classed as acidic or basic NH2 C CO2H
should, however, be able to H 2-aminobutanedioic (respectively) amino acids H
name given amino acids using acid Aspartic acid
IUPAC organic naming OH
CO2H
CH2
H C (CH2)4 NH2
NH2 CH2 CO2H NH2 C CO2H Lycine (basic)
H 2-amino-3- H2N 2,6-diaminohexanoic acid
(2-)aminoethanoic acid
hydroxypropanoic acid
Zwitterions
R R
The no charge form of an amino acid never occurs. + -
The amino acid exists as a dipolar zwitterion. H2N C CO2H H3N C CO2
H H
Amino acids are often solids Zwitterion
The ionic interaction between zwitterions explains the relatively high melting points of amino acids as
opposed to the weaker hydrogen bonding that would occur in the no charge form.
Acidity and Basicity

The amine group is basic and the carboxylic acid group is acidic. Amino acids act as weak buffers and will
only gradually change pH if small
R OH- R H+ R amounts of acid or alkali are added to the
- + - +
H2N C CO2 H3N C CO2 H3N C CO2H amino acids.
+NH -CH -CO - + HCl  Cl- NH3+-CH2-CO2H
H H H 3 2 2
H+ OH-
+NH -CH -CO - + NaOH  NH2-CH2-CO2-Na+ +H2O
Species in Species in Species in 3 2 2
alkaline solution neutral solution acidic solution
High pH Low pH
-
COO
The extra carboxylic acid or amine groups
Aspartic acid in high pH
on the R group will also react and change CH2
-
form in alkaline and acid conditions NH 2 C COO
H
OH
O
Skeletal formula of lycine in low pH

+
H 3N
+
NH 3
Dipeptides
Dipeptides are simple combination molecules of For any two different amino acids there are two possible
two amino acids with one amide (peptide) link. combinations of the amino acids in the dipeptide.
HO HO
HO
CH3 H
Can make CH3 H CH2 CH2 CH3
CH2 or
H2N C CO2H +
H2N C C N C CO2H H2N C C N C CO2H
H H2N C CO2H
H H H O H
O
H
Other reactions of amino acids

The carboxylic acid group and amine group in amino acids can undergo the usual reactions of these functional groups met
in earlier topics. Sometimes questions refer to these.
e.g. Esterification reaction
CH3 CH3 O
Strong acid
+
catalyst H3N C C O CH3 + H2O
H2N C CO2H + CH3OH
H H
CO 2 H O
If the R group contains
CO2H H C (CH 2) 4 NH C CH 3 a amine or carboxylic
H C (CH2)4 NH2 + 2CH3COCl NH acid then these will do
H2N the same reactions as
C O the α amine and
CH3 carboxylic groups
Electrophoresis of Amino Acids
A mixture of amino acids can be separated by electrophoresis
The mixture of amino acids is put at the
Dc power supply start point.
A gel or filter paper soaked in a buffer
solution is used.
The pH of the buffer solution makes a big
difference to the results.
-ve electrode
+ve Amino acids are transparent and cannot be
electrode seen.
filter paper soaked in If ninhydrin is sprayed on an amino acid and
buffer solution
Start point then heated for 10 minutes then red to blue
spots appear.
Different amino acids will move by different amounts depending on their size, charge and the pH of
the buffer solution.
If buffer is alkaline pH>7
R Amino acids with smaller sized R groups will

In alkaline conditions the amino acids will - move further towards the positive plate.
be negatively charged and therefore will H2N C CO2
If the R group contains a –CO2H group (such as
move towards the positive plate H aspartic acid) then as it will have two CO2-
groups. It will move further than if it was a
similar sized neutral R group.
If buffer is acidic pH<7
Amino acids with smaller sized R groups will

In acidic conditions the opposite will R move further towards the negative plate.
occur. The amino acids will be positively + If the R group contains a –NH2 group (such as
charged and therefore will move towards H3N C CO2H
lysine) then as it will have two NH3+ groups. It
the negative plate H will move further than if it was a similar sized
neutral R group.
If buffer is neutral pH=7

CH 3 O
If an amino acid has a non-polar R group, it will exist in + -
zwitterion form and it will not move. H 3N CH C O
-
CO2
If an amino acid has a R group that contains a –CO2H group CH2
(such as aspartic acid) ) then as it will have two CO2- groups. -
+H2N C CO2
It will move towards the positive plate
H
-
O
If an amino acid has a R group that contains a –NH2 group O

(such as lysine) then as it will have two NH3+ groups. It will
move towards the negative plate +
H 3N
+
NH 3
21. Polymers
There are two types of polymerisation: addition and condensation
Addition Polymerisation
An addition polymer forms when unsaturated Poly(alkenes) are chemically inert due to the strong C-C and C-H
monomers react to form a polymer bonds and non-polar nature of the bonds and therefore are
Monomers contain C=C bonds non-biodegradable.
Chain forms when same basic unit is
repeated over and over.
It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
H3C CH CH CH3 C C C C
repeating unit for any the double bond
alkene H3C H
CH3 H n
Condensation Polymerisation
In condensation polymerisation there are two different monomers that
The two most common types of add together and a small molecule is usually given off as a side-product
condensation polymers are polyesters e.g. H2O or HCl.
and polyamides which involve the
formation of an ester linkage or an The monomers usually have the same functional group on both ends of the
amide linkage. molecule e.g. di-amine, di carboxylic acid, diol, diacyl chloride.
Forming polyesters and polyamide uses these reactions we met earlier in the course
Carboxylic Acid + Alcohol  Ester + water Carboxylic Acid + Amine  amide + water
Acyl chloride + Alcohol  Ester + HCl Acyl chloride + Amine  amide + HCl
If we have the same functional group on each end of molecule we can make polymers so we have the analogous
equations:
dicarboxylic acid + diol  poly(ester) + water dicarboxylic acid + diamine  poly(amide) + water
diacyl dichloride + diol  poly(ester) + HCl diacyl dichloride + diamine  poly(amide) + HCl
Using the carboxylic acid to make the ester or amide would need an acid catalyst and would only give an equilibrium
mixture. The more reactive acyl chloride goes to completion and does not need a catalyst but does produce hazardous HCl
fumes.
Terylene- a common polyester

O O
O O
n + n HO CH CH OH C C O CH2 CH2 O + 2n-1 H2O
C C 2 2
n
HO OH Ethane-1,2-diol
The -1 here is because at
Benzene-1,4-dicarboxylic acid
each end of the chain the H
Terylene fabric is used in clothing, tire cords and OH are still present
O O O O
n C (CH2)3 C + n HO OH + 2n-1 HCl
C (CH2)3 C O O
Cl Cl n
Pentanedioyl dichloride Benzene-1,4-diol
Nylon 6,6 - a common polyamide
O O
O O H H
N (CH2)6 N
n C (CH2)4 C +n C (CH2)4 C N (CH2)6 N + 2n-1 H2O
H H
HO OH
hexanedioic acid Hexane-1,6-diamine H H
n
The 6,6 stands for 6 carbons in each of the monomers. Different length carbon chains produce different
polyamides
Kevlar- a common polyamide
O O
n HO2C CO2H + n H2N NH2 + 2n-1 H2O
N N C C
H H n
Note on classification for condensation polymers

If asked for type of polymer: It is polyamide or polyester
Whereas type of polymerisation is condensation
It is also possible for polyamides and polyesters to form from one monomer, if that monomer
contains both the functional groups needed to react
O O O O
HO (CH2)3 C O (CH2)3 C O (CH2)3 C O (CH2)3 C
Cl
4-hydroxybutanoyl chloride 3 repeating units
O O O
O
H2N C N C N C N C
OH H H H
3 repeating units
H O H O H O
HO O
CH C HO C C O C C O C C OH
H 3C OH CH3 CH3 CH3

2-hydroxypropanoic acid (lactic acid) 3 repeating units poly(lactic acid)
OH
2 lactic acid molecules
can also form a ring O O
diester
O
OH 1 repeating unit
4-hydroxypentanoic acid
O
O
It is possible for some of these compounds to form O
O O various cyclic esters under different conditions from
forming the polymer.
You do not need to learn these but may be asked to
O deduce structures from information given
Properties of polymers
Low density (LD) and high density (HD) poly(ethene) are produced from ethene, using different catalysts and reaction
conditions. In HDPE the polymer chains are single strands and can closely line up in parallel (called a crystalline
structure). In LDPE, the chains are irregularly packed, branched chain polymers therefore they cannot get as close
together. The polymer chains in HDPE can form stronger van der waals forces between them.
H H Poly(chloroethene) is a polymer that is water proof, an electrical insulator and doesn’t

react with acids.
C C In its pure form it is a rigid plastic. The strong permanent-dipole intermolecular
bonding between polymer chains prevents them moving over each other. In this un-
H Cl plasticised form it is used make uPVC window frame coverings and guttering.
F F Polytetrafluoroethene (PTFE, or “Teflon”) is very resistant to heat and

chemical corrosion. It is used on nonstick cookware. It has strong van der
C C waals forces between chains
F F n
Intermolecular bonding between condensation polymers chains

Polyesters have permanent dipole forces between the Cδ+=Oδ- groups in the different chains in addition to
the instantaneous temporary dipole forced between the chains.
δ-
:
:
Oδ-
Polyamides (and proteins) have hydrogen bonding O
δ-
O
between the lone pairs on oxygen in Cδ+=Oδ- groups N C

δ+
N
δ+
C Nδ- C
and the H in the Nδ- —Hδ+ groups in the different H H δ+ H δ+
chains.
There are also instantaneous temporary dipole
:
:
O δ- Oδ- O
forces which are large because there are many
electrons in the molecule N δ+
C N
δ-
C N
δ-
C
Polyamides will therefore have higher melting
δ+
H H Hδ+
points than polyesters. δ+
Hydrogen bonding between Kevlar chains

causes chains to line up into very strong sheets.
It is used to make bullet proof clothing.
Proteins
Primary Structure of Proteins
Proteins are polymers made from The primary structure of proteins is the sequence of the
combinations of amino acids. 20 different naturally occurring amino acids joined
The amino acids are linked by peptide links, together by condensation reactions with peptide links
which are the amide functional group.
CH3
H3C CH3 S
O O O CH HS CH2
CH3 O CH2 O CH2 O CH2 O
NH CH C NH CH C NH CH C
H N CH C N CH C N CH C N CH C O H
R R R
H H H H
Secondary Structure of a Protein.
Secondary Structure: α-helix

The 3D arrangement of amino acids with the
polypeptide chain in a corkscrew shape is held in
place by Hydrogen bonds between the H of –Nδ-
—Hδ+ group and the –O of Cδ+=Oδ- of the fourth
amino acid along the chain

The R-groups on the amino acids are all pointed to the
outside of the helix
:
O δ- O
δ-
N CH C N CH C
δ+
H R H δ+ R
:
δ-
O O
δ-
N CH C N CH C
δ+
H R H R
Secondary Structure: β-Pleated Sheet Structure of Proteins
The secondary structure can also take the form of a β–

pleated sheets
The protein chain folds into parallel strands side by side
The protein chain is held into a the pleated shape by

Hydrogen bonds between the H of –N-H group and the –
O of C=O of the amino acid much further along the chain
in the parallel region .
Tertiary Structures of Proteins
The tertiary structure is the folding of the secondary

structure into more complex shapes. It is held in place
by interactions between the R- side groups in more
distant amino acids . These can be a variety of
interactions including hydrogen bonding, sulphur-
sulphur bonds and ionic interactions
By Elizabeth Speltz (SpeltzEB) (Own work) [Public domain], via
Wikimedia Commons
Hydrogen bonds
OH
CH2 O
CH3 H2N C C
O CH2 OH
H
H
O Hydrogen bonds could form between two
CH2 H serine side chains in different parts of the
H3C folded chain. (Other amino acids chains
can also hydrogen bond)
ionic interactions
Ionic interactions could form between acidic

amino acids such as aspartic acid and basic
O + amino acids such as lysine. There is a transfer
H 3N CH 3 of a hydrogen ion from the -COOH to the -
C -
CH2 O NH2 group to form zwitterions just as in simple
amino acids.
H3C
Sulphur bridges
CH3 CH3
HS CH2 S CH2
SH S
CH2 CH2
H3C H3C
SH
If two cysteine side chains end up near each other due to folding in the protein chain, they CH2 O
can react to form a sulphur bridge, which is a covalent bond. H2N C C
H OH
cysteine (cys)
You don’t need to learn the details of these interactions
on this page but understand the principles of how the
tertiary structure is held in place.
DNA
Key molecules in DNA

HO OH HO CH2
O O OH
O
H H
HO P OH
H H
-
O OH H
OH
phosphate ion
2-deoxyribose (a pentose sugar)
The 4 bases
NH 2 O O NH 2
N H 3C
N NH NH
N N
NH N NH 2
NH NH O NH O
N
Guanine (G) Thymine (T)
Adenine (A) Cytosine (C)
The structures of these substances are given in the Chemistry Data Booklet.
Nucleotides O
H 3C
OH
A nucleotide is made up from a phosphate ion bonded to - NH
O P O
2-deoxyribose which is in turn bonded to one of the four
bases adenine, cytosine, guanine and thymine O N O
O
base
phosphate NH 2 OH
NH 2 O
OH OH OH
- N - N - N
O P O N O P O NH
O P O
O N O O O N
O O N N O N NH 2
sugar OH
OH OH
Although the structures will be given in the data sheet you need to learn which atoms on the base
joins on to the sugar and how the sugar attaches to the phosphate ions
Sugar- phosphate chain
NH 2
NH 2 A single strand of DNA
OH (deoxyribonucleic acid) is a polymer
N OH
-
O P O - N of nucleotides linked by covalent
O P O bonds between the phosphate group
O N O
O O
of one nucleotide and the 2-
N O
O deoxyribose of another nucleotide.
-H2O
This results in a sugar-phosphate-
OH sugar- phosphate polymer chain
NH 2
NH 2 with bases attached to the sugars in
OH O the chain.
- N
- N O P O N
O P O N
O O N
O N N
O N
Carefully learn how these join
together
OH OH
DNA exists as two complementary strands of the sugar

phosphate polymer chain arranged in the form of a
double helix.
Hydrogen bonding between base pairs leads to

the two complementary strands of DNA.
OH
- N O: H NH
O P O
O N :N
O N H
OH
N N
:O Guanine pairs with cytosine by 3
NH H
hydrogen bonds
OH
O O
-
O P O
OH
HN H :O CH 3
OH
- N
O P O N: H N OH
Adenine pairs with thymine by 2
O N hydrogen bonds
O N N
O
O
O
-
OH O P O
OH
Non-solvent based adhesives
Most adhesives are solvent based. They harden when the solvent evaporates. The following harden in a different way.
Epoxy resin glues

The glues have two components: one containing O CH 3 O
polymers chains and the other a hardener (which is a H 2C CH CH 2 O C O CH2 HC CH 2
cross-linking agent). They are mixed together when CH 3
the glue is applied. As the glue sets the hardener forms
cross links between the polymer chains forming a pre-polymer with epoxy group
strong thermosetting structure.
O O
HC CH 2 H 2C CH OH OH
H H
CH CH 2 CH 2 H C
N
Diamine is N
polymer chains cross linked
crosslinking R
R into a strong thermosetting
hardener N
structure
H
N
H
HC CH2 H2C CH HC CH 2 CH 2 CH
O O OH OH
Ends of polymer chains

You don’t need to remember the details of
the substances here- just the process of
Cross links in thermosetting polymers tend to be
crosslinking.
covalent bonds which are strong and not easy to break.
Once formed the polymer cannot be melted
Polymers with only weaker intermolecular forces between chains can generally be heated up to melt and change
their shape. These are called thermosoftening polymers.
Superglue N
N N N
The monomer in superglue

polymerises on exposure to
moisture in the atmosphere to O
O O O
form a strong addition polymer O O O
O
monomer
ethyl 2-cyanoprop-2-enoate You don’t need to remember the details of
the substances here
Conducting polymers –poly(ethyne)

Ethyne has a triple bond. It can form
CH CH CH CH3
an addition polymer that has H C C H
H3C CH CH CH
alternate double single bonds. Ethyne
Poly(ethyne) also known
as polyacetylene
Poly(ethyne) conducts electricity. It conducts through its long chain of delocalised electrons. It
can delocalise because the polymer chain is planar so the π bonds overlap with each other.
Degradable polymers
Poly(alkenes) are chemically inert due to the strong C-C and C-H
Poly(alkenes) are chemically inert and can therefore bonds and non-polar nature of the bonds and therefore are
be difficult to biodegrade non-biodegradable.
Some condensation polymers may be photodegradable as the C=O bond absorbs radiation.
Chemical reactivity of condensation polymers The reactivity can be explained by the presence of polar
polyesters and polyamides can be broken down by bonds which can attract attacking species such as
hydrolysis and are, therefore, biodegradable nucleophiles and acids
Hydrolysis
Polyesters and polyamides can be hydrolysed by acid and alkali
The hydrolysis will result in the original monomers forming- although the carboxylic acid or amine group
will be in salt form depending on whether the conditions are alkaline or acidic
O O
O
+
HCl OH H 3N +
C (CH2)4 C N (CH2)6 N
HO
+ NH 3
H H O
n
NaOH O
-
-CO(CH2)4CONHC(CH3)2CH2O- - O
O + H2N
This polymer has both an amide and O
OH
ester link
Hydrolysis of di-peptides/proteins
If proteins are heated with dilute acid or alkali they can be The composition of the protein
hydrolysed and split back into their constituent amino acids. molecule may then be deduced by
using TLC chromatography
H3C CH3
CH H3C CH3
CH
CH3 O CH2 O CH3 O
H+
H N CH C N CH C O H + CH2 O
H3N CH C O H + +
H3N CH C O H
H H
O H 3C CH 3
CH
C OH O H 3C CH 3
CH2 O H 2C O - CH
C O
NaOH
H N CH C N CH C O H CH2 O H 2C O
+
- -
H 2N CH C O H 2N CH C O
H H
22.Analytical Techniques
Chromatography
Chromatography is an analytical technique that separates The mobile phase may be a liquid or a gas.
components in a mixture between a mobile phase and a The stationary phase may be a solid (as in thin-layer
stationary phase. chromatography, TLC) or either a liquid or solid on a
solid support (as in gas chromatography, GC)
Types of chromatography include:
• thin-layer chromatography (TLC) – a plate is coated with a
solid and a solvent moves up the plate
• column chromatography (CC) – a column is packed with a In gas-liquid chromatography GC the mobile phase
solid and a solvent moves down the column is a inert gas such as nitrogen, helium, argon.
• gas chromatography (GC) – a column is packed with a solid The Stationary phase is a liquid on an inert solid.
or with a solid coated by a liquid, and a gas is passed
through the column under pressure at high temperature.
If the stationary phase was polar and the moving

Separation by column chromatography depends on phase was non- polar e.g. Hexane. Then non-polar
the balance between solubility in the moving phase compounds would pass through the column more
and retention in the stationary phase. quickly than polar compounds as they would have a
greater solubility in the non-polar moving phase.
A solid stationary phase separates by adsorption, (Think about intermolecular forces)
A liquid stationary phase separates by relative solubility
Retention times and Rf values are used to identify different substances.
Method: Thin-layer chromatography

Wear plastic gloves to prevent contamination
a) Wearing gloves, draw a pencil line 1 cm above the bottom of a from the hands to the plate
TLC plate and mark spots for each sample, equally spaced along line.
b) Use a capillary tube to add a tiny drop of each solution to a pencil line –will not dissolve in the solvent
different spot and allow the plate to air dry.
c) Add solvent to a chamber or large beaker with a lid so that is no tiny drop – too big a drop will cause different
more than 1cm in depth spots to merge
d) Place the TLC plate into the chamber, making sure that the level Depth of solvent– if the solvent is too deep it
of the solvent is below the pencil line. Replace the lid to get a tight will dissolve the sample spots from the plate
seal.
e) When the level of the solvent reaches about 1 cm from the top of lid– to prevent evaporation of toxic solvent
the plate, remove the plate and mark the solvent level with a pencil. Will get more accurate results if the solvent is
Allow the plate to dry in the fume cupboard. allowed to rise to near the top of the plate but
f) Place the plate under a UV lamp or if using amino acids spray with the Rf value can be calculated if the solvent
ninhydrin in order to see the spots. Draw around them lightly in front does not reach the top of the plate
pencil.
g) Calculate the Rf values of the observed spots. dry in a fume cupboard as the solvent is toxic
UV lamp used if the spots are colourless and
not visible
Rf value = distance moved by amino acid

distance moved by the solvent
Column chromatography (CC)
Simple column chromatography
• A glass tube is filled with the stationary phase usually silica or solvent
alumina in powder form to increase the surface area.
• A filter or plug is used to retain the solid in the tube. Solvent is glass tube filled
added to cover all the powder. with slica
• The mixture to be analysed is dissolved in a minimum of a
solvent and added to the column.
• A solvent or mixture of solvents is then run through the column.
components
• The time for each component in the mixture to reach the end of
the column is recorded (retention time)
HPLC stands for high performance liquid chromatography and

it type of column chromatography commonly used in
filter
industry.
HPLC: stationary phase is a solid silica
HPLC: mobile phase a liquid
Gas-Liquid Chromatography
Gas-liquid chromatography can be used to separate mixtures In gas-liquid chromatography, the mobile
of volatile liquids. phase is a gas such as helium and the stationary
phase is a high boiling point liquid absorbed
The time taken for a particular compound to travel onto a solid.
from the injection of the sample to where it leaves
the column to the detector is known as its Sample in
retention time. This can be used to identify a Flow
substance. control oven
Some compounds have similar retention times so

display
will not be distinguished.
Waste
column outlet
Basic gas-liquid chromatography will tell us how
many components there are in the mixture by the Carrier gas detector
number of peaks. It will also tell us the abundance of
each substance. The area under each peak will be
proportional to the abundance of that component.
It is also possible for gas-liquid chromatography

machine to be connected to a mass spectrometer, IR Most commonly a mass spectrometer is combined with
or NMR machine, enabling all the components in a GC to generate a mass spectra which can be analysed or
mixture to be identified. compared with a spectral database by computer for
positive identification of each component in the
GC-MS is used in analysis, in forensics, environmental mixture.
analysis, airport security and space probes.
Infrared spectroscopy
Complicated spectra can be obtained than provide
Certain bonds in a molecule absorb infra-red radiation at information about the types of bonds present in a
characteristic frequencies causing the covalent bonds to molecule
vibrate
ABOVE 1500 cm-1 – “Functional group identification”

BELOW 1500 cm-1 – “Fingerprinting”
Complicated and contains many signals

– picking out functional group signals
difficult.
This part of the spectrum is unique for

every compound, and so can be used as
a "fingerprint".
e.g. C=O 1640 – 1750 cm-1 A computer will compare the IR spectra
against a database of known pure
O-H (acid) 2500- 3300 cm-1 compounds to identify the compound
Use the IR absorption table provided in the
data book to deduce presence or absence
of particular bonds or functional groups use spectra to identify particular functional groups limited to data
presented in wavenumber form e.g. an alcohol from an absorption peak
Bond Wavenumber of the O–H bond,
C-O 1000-1300
C=O 1640-1750 Spectra for

butanal
C-H 2850 -3100
O
O-H 2500-3300
Carboxylic acids Very broad H3C CH2 CH2 C
H
N-H 3200-3500
2000 1500
O-H 3200- 3550
Acohols, phenols broad C=O
Absorption or trough in between 1640-1750 cm-1 range indicates
presence of C=O bond
Always quote the wave number range from the data sheet
Spectra for
O-H absorptions tend ethanoic acid
to be broad
O
Absorption or trough in
between 2500-3300 cm-1 range H3C C
indicates presence of O-H OH
bond in an acid
C=O
Mass spectrometry
Spectra for C4H10
Measuring the Mr of an organic molecule
If a molecule is put through a mass spectrometer it Mass spectrum for butane

will often break up and give a series of peaks caused
by the fragments. The peak with the largest m/z, 43
Molecular ion
however, will be due to the complete molecule and
C4H10+
will be equal to the Mr of the molecule. This M peak is
called the molecular ion 29
58
M+1 peak
A small peak will often occur in a mass spectrum next to the
molecular ion peak. This is due to the presence of the C 13 isotope in Example
the molecule. A hydrocarbon showed a ratio of heights of the M
The relative height of this M+1 peak compared to the M peak can : M+1 peaks of 9.3 : 0.5.
be used to calculate the number of carbons in a molecule Calculate the number of carbon atoms present in
Use the following equation to calculate the number (n) of carbons one molecule of this hydrocarbon
in a molecule n = 100 x height of M+1 peak
1.1 x height of M peak
n = 100 x height of M+1 peak Learn this equation n = 100 x 0.5
1.1 x height of M peak 1.1 x 9.3
=4.89
Round to 5 carbons
M+2 peak
If a compound contains a chlorine or a bromine atom then a M+2 peak Chlorine exists as Cl35 (75%) and Cl37 (25%)
will occur due to the two naturally occurring isotopes of chlorine or Bromine exists as Br79 (50%) and Br81 (50%)
bromine.
CH3Cl will have a m/z value of M of 50 CH3Cl 35 and M+2 of 52 CH3Cl 37

The ratio of heights M:M+2 will be 3:1
CH3Br will have m/z value of M of 94 CH3Br79 and M+2 of 96CH3Br81

The ratio of heights M:M+2 will be 1:1
If a compound contains two chlorine or bromine atoms then a M+2 and a M+4 peak will occur
Relative abundances
C2H4Cl2 will have a m/z value of M of 98 C2H4Cl 35Cl 35 , a Cl35Cl35 = 0.75 x0.75 = 0.5625 =>9
M+2 of 100 C2H4Cl 35Cl 37 and a M+4 of 102 C2H4Cl 35Cl 37 Cl35Cl37 = 0.75 x0.25x2= 0.375 =>6
The ratio of heights M:M+2: M+4 will be 9:6:1 Cl37Cl35
Cl37Cl37 = 0.25 x0.25 =0.0625 =>1
C2H4Br2 will have a m/z value of M of 186 C2H4Br79Br79 , a
÷ smallest to get
M+2 of 188 C2H4Br79Br81 and a M+4 of 190 C2H4Br81Br81
whole number ratio
The ratio of heights M:M+2: M+4 will be 1:2:1
Relative abundances
C2H3Cl3 will have a m/z value of M of 132 C2H4Cl35Cl35Cl 35 , a
Cl35Cl35Cl35 = 0.75 x0.75x0.75 = 0.4219 =>27
M+2 of 134 C2H4Cl35Cl35 Cl 37 , a M+4 of 136 C2H4Cl35Cl 37Cl 37
Cl35Cl35Cl37 = 0.75 x0.75x0.25x3= 0.4219 =>27
and a M+6 of 138 C2H4Cl37Cl 37Cl 37
Cl35Cl37Cl37 = 0.75 x0.25x0.25x3= 0.1406 =>9
The ratio of heights M:M+2:M+4:M+6 will be 27:27:9:1
Cl37Cl37Cl37 = 0.25 x0.25x0.25 =0.0156 =>1
÷ smallest to get
whole number ratio
Fragmentation
Molecular ion formed: M → [M]+. + e–
When organic molecules are passed through a mass spectrometer,
it detects both the whole molecule and fragments of the molecule. The molecule loses an electron and
becomes both an ion and a free radical
Several peaks in the mass spectrum occur due to fragmentation. This process produces an ion
The Molecular ion fragments due to covalent bonds breaking: [M]+. → X+ + Y. and a free radical. The ion is
responsible for the peak
Relatively stable ions such as carbocations R+ such as CH3CH2+ and acylium ions
[R-C=O]+ are common. The more stable the ion, the greater the peak intensity.
The peak with the highest mass/charge ratio will be normally due to the
original molecule that hasn’t fragmented (called the molecular ion) . As the
charge of the ion is +1 the mass/ charge ratio is equal to Mr.
Equation for formation molecular ion

Mass spectrum for butane
C4H10  [C4H10]+. + e– m/z 58
43
Equations for formation of fragment ions from molecular ions
[C4H10]+.  [CH3CH2CH2]+ + .CH3 m/z 43

29 C4H10 = 58
[C4H10]+.  [CH3CH2]+ + .CH2CH3 m/z 29
Equation for formation molecular ion

Mass spectrum for butanone
CH3CH2COCH3  [CH3CH2COCH3]+. + e– m/z 72
The high peak at 43
43 due to stability [CH3CO]+ Equations for formation of fragment ions from molecular ions
of acyl group
[CH3CH2COCH3]+.  [CH3CH2CO]+ + .CH3 m/z 57
29 [CH3CH2CO]+ [CH3CH2COCH3]+.  [CH3CO]+ + .CH2CH3 m/z 43

57 [CH3CH2COCH3]
+.
[CH3CH2]+ [CH3CH2COCH3]+.  [CH3CH2]+ + .COCH3 m/z 29
72
NMR spectroscopy
Different types of NMR
NMR spectroscopy involves interaction of materials with the low-energy

radiowave region of the electromagnetic spectrum
NMR spectroscopy is the same technology as that used in ‘magnetic resonance

imaging’ (MRI) to obtain diagnostic information about internal structures in body scanners
There are two main types of NMR There is only around 1% C13 in organic molecules but modern NMR
1. C13 NMR machines are sensitive enough to give a full spectra for C13
2. H (proton) NMR The C13 spectra is a simpler spectrum than the H NMR
The radio waves used in proton nmr cause the hydrogen nucleus to
change its spin state.
Equivalent Carbon atoms.

In a C13 NMR spectrum, there is one signal (peak) for each set of equivalent C atoms.
O
H H H H H H b
a b c
O H O H H a b c d CH3 Ca
a b
c d H C C C C H
H C C C O
H C C O C C H
H H H H a H H b a
H CH3 C
H H H C H
4 peaks
3 peaks 4 peaks O
H
2 peaks
1,2 dinitrobenzene 1,3 dinitrobenzene 1,4 dinitrobenzene
NO 2 a
CH3 a CH
1 3
2 2 a b
b
H3C C Cl c c
2 a
2 CH3 d d
1 e
2 peaks
NO 2 NO2
3 peaks
4 peaks
2 peaks 5 peaks
Equivalent Hydrogen atoms.
In addition the intensity (integration value) of
In an H NMR spectrum, there is one signal for
each signal is proportional to the number of
each set of equivalent H atoms.
equivalent H atoms it represents.
Ha H b 3 Ha Hb Hc H d
a
a H Hd
H C C O C C C C
c aH Hc H
H Hb H H C Ha d
a 2 a
4sets of equivalent H’s:
Ha
Ethanol has 3 groups ratio 6:1:2:3
1
of different hydrogen
atoms O
H3C C CH3 1 signal
a a
a b O c
CH3c H3C CH2 C O CH3
O
a b c
H3C CH2 C O C CH3
3 sets of equivalent H’s: ratio 3:2:3
c
CH3
Br
3 sets of equivalent H’s: ratio 3:2:9
a b c
H3C CH CH2 CH3 CH CH2 CH3
a b c d
3 sets of equivalent H’s: 4 sets of equivalent H’s: ratio 3:1:2:3
ratio 3:1:2
Solvents
This means that in the H NMR the
Samples are dissolved in solvents without any 1H atoms, e.g. CCl4, CDCl3.
solvent will not give any peaks
The same solvent is used in C13 NMR and in this case there will be one peak due to the solvent that will
appear on the spectrum. However, it is known where this peak is so it can be ignored.
In the exam it is likely this peak will not occur on the spectra.
Calibration and shift
A small amount of TMS (tetramethylsilane) is added to the

The same calibration compound is
sample to calibrate the spectrum
used for both H and C NMR
TMS is used because: CH3
•its signal is away from all the others The spectra are recorded on a
•it only gives one signal H3C Si CH3 scale known as the chemical shift
•it is non-toxic (δ), which is how much the field
•it is inert CH3 has shifted away from the field for
•it has a low boiling point and so can be removed tetramethylsilane TMS..
from sample easily
The δ is a measure in parts per million (ppm) is a relative scale 10 9 8 7 6 5 4 3 2 1 0

of how far the frequency of the proton signal has shifted away d chemical shift (ppm)
from that for TMS.
7
H NMR shift
The δ depends on what other

atoms/groups are near the H –
more electronegative groups
gives a greater shift.
3
H3C H
O
H3C CH2 C O CH3 O
C CH 3
H
3
H3C H
δ ppm
3
H H O
H C C C
H H O H
2
δ ppm
Proton exchange using D2O
If D2O is added to a sample then a process of proton Addition of D2O to the sample of Propanoic acid
exchange happens with the H in any O-H and N-H bonds. would make the peak at δ = 11.7 (ppm) in the
This has the effect of removing the peaks from the H- above spectrum disappear
NMR spectra. This can help with the identification of O–H
and N–H peaks on the spectra.
8
C13 NMR shift
H O H H H
H C C O C C C H
0-45
H H H H 50-90 It will not be possible to
identify the exact carbon
160-220 0-45
corresponding to each peak if
several carbons are in the
same range
ppm
It is not possible to distinguish

O between similar shifts for each
carbon in a benzene ring. In this
C CH 3
H 3C example it should be possible to
work out there are four different
carbons in the benzene ring and
these correspond to the four
peaks between 120-145
4 peaks
between
110-160
Spin-Spin coupling in H NMR
Nuclei in identical chemical
In high resolution H NMR each signal in the spectrum can be split into further environments do not show coupling
lines due to inequivalent H’s on neighbouring C atoms. amongst themselves!
Splitting of peak = number of inequivalent H’s on neighbouring C atoms + 1

a b O c
signal singlet doublet triplet quartet quintet H3C CH2 C O CH3
The peak due to group a will be
a triplet as it is next to b (a
appearance carbon with 2 H’s)
The peak due to group b will be
a quartet as it is next to a (a
Split number
1 2 3 4 5 carbon with 3H’s)
of peaks
The peak due to group c will be
number of a singlet as it is next to a carbon
neighbouring
0 1 2 3 4 with no H’s)
inequivalent
H atoms
For 6 split peaks use the term
relative size 1:1 1:2:1 1:3:3:1 1:4:6:4:1 hextet or multiplet
H O H H The peak due to group c will

a
be a triplet as it is next to a
H C C O C C H
carbon with 2 H’s
a H Shift 0.7-1.2
b H H c
c Integration trace 3
The peak due to group a The peak due to group b
b
will be a singlet as it is next will be a quartet as it is next
to a carbon with 0 H’s to a carbon with 3 H’s
Shift 2.1-2.6 Shift 3.7 -4.1
Integration trace 3 Integration trace 2
ppm
Hydrogens bonded to a Nitrogen or Oxygen usually

do not couple with other protons and appear as
singlets on the NMR spectra
The peak due to group a will be a triplet

Ethanol
as it is next to a carbon with 2 H’s
Shift 0.7-1.2
Integration trace 3 H3C CH2 OH
a b c
The peak due to group b will be a quartet
as it is next to a carbon with 3 H’s a
Shift 3.7 -4.1 b
Integration trace 2 c
The peak due to group c will be a singlet as the
Hydrogen is bonded to an oxygen and this does not
split
Shift 0.5-5.0
Integration trace 1
You will not be asked to interpret splitting patterns for the protons attached to a benzene ring
Bringing it all together
C H O
1. Work out empirical formula
66.63/12 11.18/1 22.19/16
Elemental analysis C 66.63% H 11.18% O 22.19%
=5.5525 =11.18 =1.386875
=4 =8 =1
2. Using molecular ion peak m/z value from mass

spectrum calculate Molecular formula Mr empirical formula C4H8O = 72
molecular ion peak m/z value= 144 If Mr molecular formula 144 then
compound is C8H16O2
3. Use IR spectra to identify main C8H16O2 could be an ester, carboxylic acid or combination of
bonds/functional group alcohol and carbonyl. Look for IR spectra for C=O and O-H
bonds
There is a C=O but no

O-H absorptions, so
must be an ester.
C-H
C=O
CH3
4. Use NMR spectra to give details of carbon chain singlet of area 9 H3C C H
At δ =0.9 CH3
4 peaks – only 4 different environments. Means 3 CH3 groups
9
Peak at δ 4 shows H–C–O Peak at δ 1.2

Peak at δ 2.2 shows H–C=O
shows R-CH3
Area 2 suggests CH2 Area 2 suggests CH2 Area 3 means CH3
Quartet means next to a Singlet means adjacent to Triplet means next
CH3 C with no hydrogens to a CH2
H H3C CH3
H O
H3C O C H
H3C O C C H 2
2 3
H
H
5 4 δ ppm 3 2 1
Put all together to give final structure
CH3 O
H3C C CH2 C O CH2 CH3
CH3
23 Synthetic Routes
Chirality in pharmaceutical synthesis

Molecules prepared synthetically in the laboratory
The synthesis of pharmaceuticals often requires the
often contain a mixture of optical isomers, whereas
production of a single optical isomer
molecules of the same compound produced naturally
by enzymes in
Drug action and optical isomers living systems will often be present as one optical
Drug action may be determined by the stereochemistry of isomer only
the molecule. Different optical isomers may have very
different effects
Thalidomide Ibuprofen
H CH3
H O
C H H H3C HC CH CH CH3
C C H
C
C C H
C N CH2 C C HC
H C C
C C C
H O CH CH C O
C N
H O
O HO
H
Chiral carbon
One enantiomer of thalidomide causes birth defects in

unborn children whilst the other had useful sedative
problems. Unfortunately it was given in a mixture of the
two when first used.
Modern synthesis of a pharmaceutical with a

Synthesis of a pharmaceutical that is a single optical single optical isomer is often carried out:
isomer is more expensive because separation of the (i) using enzymes or bacteria which promote
single isomer is difficult. stereoselectivity,
However one of the isomers may be more (ii) using chemical chiral synthesis or chiral
pharmacologically active and one of the isomers might catalysts,
have adverse side effects . (iii) using natural chiral molecules, such as L-
amino acids or sugars, as starting materials.
KOH aqueous
dihalogenoalkane heat under reflux
Nucleophilic substitution
poly(alkene) diol
Br2, Cl2 KMnO4
room temp oxidation
Electrophilic addition
high pressure
alkane
Catalyst Br2, Cl2
H2, Nickel Catalyst
polymerization UV light
addition/reduction
alkene HBr, HCl
Free radical Substitution
room temp
Electrophilic addition
KOH alcoholic heat
halogenoalkane
conc. H3PO4 under reflux
H2O (g) Elimination
Catalyst: Elimination,
dehydration
Conc H3PO4 CN– and
PCl5, NaBr/H2SO4 P + I2
,
ethanol
Heat under reflux Nucleophilic
substitution KOH aqueous Alcoholic NH3 substitution
heat under reflux heat under pressure
Nucleophilic substitution Nucleophilic
LiAlH4
alcohol substitution
Reduction Caboxylic acid + H2SO4

heat amine LiAlH4
nitrile
LiAlH4 K2Cr2O7/H+ esterification
Reduction
Reduction
LiAlH4
If primary If secondary Reduction haloalkane
heat gently and distill heat under reflux NuSub
partial oxidation oxidation
Acyl chloride
2o amine room temp
3o amine Nu add/elim
aldehyde ketone LiAlH4
HCN + KCN secondary Reduction
Nucleophilic addition amide
K2Cr2O7/H+
heat under reflux + Esters and amides
excess oxidising agent can be hydrolysed
Oxidation hydroxynitrile by NaOH and acids
1o amine
Alcohol + H2SO4 room temp Primary
heat ester amide
carboxylic acid esterification
Alcohol
PCl5 room temp NH3 room temp
H2O room
temp Acyl chloride
Acid hydrolysis
Heat with HCl
Aromatic synthetic routes
Br N N OH
CH2CH3
chloroalkane and
+ OH
NaOH
anhydrous AlC3
Hydrogen Electrophilic catalyst
Nickel substitution
catalyst Br2
FeBr3
+
N N
conc nitric acid +

conc sulphuric acid
Electrophilic NO
2 NaNO2 + HCl <10oC
substitution
Sn and HCl
reduction
NH2
NH CH3
CH3Cl
Nu sub
acyl chloride in the presence
of anhydrous aluminium
chloride catalyst Br2
Electrophilic substitution
O NH2 CH3COCl
Br Br O
C
CH3 NH C CH3
NaCN + H2SO4
Nu Add
Br
LiAlH4 H
Red Nu Add
O
H
C CN
O
CH CH 3
CH3
HCl/heat
H
O O
CH3CO2H + H2SO4
heat C C
esterification OH
CH3
O
H3C CH O C CH3
Organic techniques
It’s important to be able to

Distillation draw and label this apparatus
In general used as separation technique to separate an thermometer accurately. Don’t draw lines
organic product from its reacting mixture. Need to between flask, adaptor and
collect the distillate of the approximate boiling point condenser.
range of the desired liquid.
Note the bulb of the thermometer should be Liebig condenser

at the T junction connecting to the
condenser to measure the correct boiling
point
Note the water goes in the bottom of the Water

condenser to go against gravity. This allows more out
efficient cooling and prevents back flow of water.
Round Water in
Electric heaters are often used to heat organic bottomed
chemicals. This is because organic chemicals are flask
normally highly flammable and could set on fire Heat
with a naked flame.
Reflux
Reflux is used when heating organic reaction mixtures for long Water out
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.
condenser
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated including the distillation
set up
Water in
Anti-bumping granules are added to the flask in both distillation and
reflux to prevent vigorous, uneven boiling by making small bubbles
form instead of large bubbles
Round
bottomed
flask
It’s important to be able to draw and label this apparatus
accurately.
• Don’t draw lines between flask and condenser.
• Don’t have top of condenser sealed
Heat
• Condenser must have outer tube for water that is sealed at
top and bottom
• Condenser must have two openings for water in and out
that are open
Fractional Distillation: In the laboratory
Fractional distillation is used
• Heat the flask, with a Bunsen burner or electric
to separate liquids with
mantle
different boiling points
• This causes vapours of all the components in the
mixture to be produced.
• Vapours pass up the fractionating column.
• The vapour of the substance with the lower boiling
point reaches the top of the fractionating column
first.
• The thermometer should be at or below the boiling
point of the most volatile substance.
• The vapours with higher boiling points condense
back into the flask.
condenser
• Only the most volatile vapour passes into the
condenser.
fractionating column
• The condenser cools the vapours and condenses to
a liquid and is collected.
flask
Measuring boiling point

Purity of liquid can be determined by measuring a boiling point. This can be
done in a distillation set up or by simply boiling a tube of the sample in an To get a correct measure
heating oil bath. of boiling point the
thermometer should be
Pressure should be noted as changing pressure can change the boiling above the level of the
point of a liquid surface of the boiling liquid
and be measuring the
temperature of the
Measuring boiling point is not the most accurate method of identifying a saturated vapour.
substance as several substances may have the same boiling point.
Purifying an organic liquid General method
• Put the distillate of impure product into a separating

funnel
• wash product by adding either Sodium hydrogencarbonate will
• sodium hydrogencarbonate solution , shaking neutralise any remaining reactant acid.
and releasing the pressure from CO2 produced. Sodium chloride will help separate the
• Saturated sodium chloride solution organic layer from the aqueous layer
•Allow the layers to separate in the funnel, and then run and The layer with lower density will Separating
discard the aqueous layer. be the upper layer. This is usually funnel
the organic layer
•Run the organic layer into a clean, dry conical flask and add
three spatula loads of drying agent (e.g. anhydrous sodium
The drying agent should
sulphate, calcium chloride) to dry the organic liquid. When
•be insoluble in the organic liquid
dry the organic liquid should appear clear.
• not react with the organic liquid
• Carefully decant the liquid into the distillation flask
Decant means carefully pour off organic liquid
•Distill to collect pure product leaving the drying agent in the conical flask
Purifying an organic solid: Recrystallisation Used for purifying aspirin
Step Reason
1. Dissolve the impure compound in a minimum An appropriate solvent is one which will dissolve both
volume of hot (near boiling) solvent. compound and impurities when hot and one in which
the compound itself does not dissolve well when cold.
The minimum volume is used to obtain saturated
solution and to enable crystallisation on cooling
2. Hot filter solution through (fluted) filter paper This step will remove any insoluble impurities and
quickly. heat will prevent crystals reforming during filtration
3. Cool the filtered solution by inserting beaker in ice Crystals will reform but soluble impurities will remain
in solution form because they are present in small
quantities so solution is not saturated. Ice will
increase the yield of crystals
4. Suction filtrate with a Buchner flask to separate The water pump connected to the Buchner flask
out crystals reduces the pressure and speeds up the filtration.
5 Wash the crystals with distilled water To remove soluble impurities
6. Dry the crystals between absorbent paper
Loss of yield in this process

• Crystals lost when filtering or washing
• Some product stays in solution after recrystallisation
• other side reactions occurring
buchner flask
If the crystals are not dried properly the mass will be larger
than expected which can lead to a percentage yield >100%
Measuring melting point
One way of testing for the degree of purity is to determine the melting
“point”, or melting range, of the sample.
Thermometer with
If the sample is very pure then the melting point will be a capillary tube
sharp one, at the same value as quoted in data books. strapped to it
containing sample
If impurities are present (and this can include solvent from the
recrystallisation process) the melting point will be lowered and Heating oil- needs
the sample will melt over a range of several degrees Celsius to have boiling point
higher than samples
melting point and
Melting point can be measured in an electronic melting point machine low flammability
or by using a practical set up where the capillary tube is strapped to a
thermometer immersed in some heating oil.
In both cases a small amount of the sample is put into a capillary tube.
The tube is heated up and is heated slowly near the melting point
Heat
Comparing an experimentally determined melting point
value with one quoted in a data source will verify the
degree of purity.
Sometimes an error may occur if the temperature on the thermometer is not the same as the temperature in
the actual sample tube.
Summary of Organic Analysis
Tests for alcohol, aldehyde, alkene and carboxylic acid
Functional group test for an Alkene
To 0.5 cm3 of bromine water in a test tube add a few drops of the unknown and shake.
Observation: alkenes should decolourise bromine water
Reaction with 2,4-dinitro phenylhydrazine

2,4-DNP reacts with both aldehydes and ketones. The product Use 2,4-DNP to identify if the compound is a
is an orange precipitate, It can be used as a test for a carbonyl carbonyl. Then to differentiate an aldehyde
group in a compound. from a ketone use Tollen’s reagent.
The melting point of the crystal formed can be used to help

identify which carbonyl was used. Take the melting point of
orange crystals product from 2,4-DNP. Compare melting point
with known values in database
Functional group tests for an Aldehyde
Tollen’s Reagent
Reagent: Tollen’s Reagent formed by mixing aqueous ammonia and silver
nitrate. The active substance is the complex ion of [Ag(NH 3)2]+ .
Conditions: heat gently
Reaction: aldehydes only are oxidised by Tollen’s reagent into a carboxylic
acid and the silver(I) ions are reduced to silver atoms
Observation: with aldehydes, a silver mirror forms coating the inside of the
test tube. Ketones result in no change.
Tollen's reagent method
Place 1 cm3 of silver nitrate solution in each of two clean boiling tubes.
Then add one drop of sodium hydroxide solution to form a precipitate of
silver oxide. Add ammonia solution dropwise until a clear, colourless
solution is formed. Add a few drops of the unknown and leave in the
water bath for a few minutes.
Fehling’s solution
Reagent: Fehling’s Solution containing blue Cu 2+ ions. Fehling's solution method
Conditions: heat gently Place 1 cm3 of Fehling's A into each of
two boiling tubes, and then add Fehling's
Reaction: aldehydes only are oxidised by Fehling’s Solution
into a carboxylic acid and the copper (II) ions are B until the blue precipitate redissolves.
reduced to copper(I) oxide . Add a few drops of the unknown and
Observation: Aldehydes :Blue Cu 2+ ions in solution change leave in the water bath for a few
to a red precipitate of Cu2O. Ketones do not react minutes.
CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+
Reaction of carbonyls with iodine in presence of alkali
Reagents: Iodine and sodium hydroxide H H

Only alcohols with a methyl group next to
Conditions: warm very gently the C-O -H bond will do this reaction. H C C H
The product CHI3 is a yellow crystalline H OH
precipitate with an antiseptic smell This reaction is called the Iodoform test
Only carbonyls with a methyl group next to the O

C=O bond will do this reaction. Ethanal is the
only aldehyde that reacts. More commonly is H3C C H
methyl ketones.
Functional group test for a Carboxylic acid

To 0.5 cm3 of your unknown solution in a test tube add a The presence of a carboxylic acid can be tested by
small amount of sodium carbonate solid and observe. addition of sodium carbonate. It will fizz and produce
Result carboxylic acids will fizz with sodium carbonate due carbon dioxide
to CO2 produced 2CH3CO2H + Na2CO3  2CH3CO2-Na+ + H2O + CO2
Summary of Identification of Functional Groups by test-tube reactions
Functional group Reagent Result
Alkene Bromine water Orange colour

decolourises
Alcohols + carboxylic acids PCl5 Misty fumes of HCl
produced
Alcohols, phenols, Sodium metal Efferevesence due to H2
carboxylic acids gas
Carbonyls 2,4,DNP Orange/red crystals
produced
Aldehyde Fehlings solution Blue solution to red
precipitate
Aldehyde Tollens Reagent Silver mirror formed
Carboxylic acid Sodium carbonate Effervescence of CO2

evolved
1o 2o alcohol and Sodium dichromate and Orange to green colour
aldehyde sulphuric acid change
chloroalkane Warm with silver nitrate Slow formation of white
precipitate of AgCl
Acyl chloride Silver nitrate Vigorous reaction- steamy
fumes of HCl- rapid white
precipitate of AgCl

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1 Atoms, molecules and stoichiometry try

DEFINITION: Relative Isotopic mass is the mass of one isotope compared to

The term molecule should only be

The mole Avogadro's Number

1 mole of copper atoms will contain 6.022 x 1023 atoms

No of particles = moles of substance (in mol) X Avogadro's constant (L)

Fig: spectra for

R.A.M =  (isotopic mass x % abundance) Use these equations to

For above example of Mg

R.A.M =  (isotopic mass x relative abundance)

R.A.M = [(124x2) + (126x4) + (128x7) + (130x6)]

%abundance 63-Cu =72.5% %abundance 65-Cu = 27.5%

Molecular formula from empirical formula

C3H6O has a mass of 58

So molecular formula is C6H12O2

be a whole number multiple of the empirical formula

Work out moles of CO2 = Mass of CO2/Mr of CO2

Moles of H in compound = 2 x moles of H2O Mass of H in = mol of H x 1

Work out mass of O = mass of compound – mass of C – mass of H

Work out moles of O = Mass of O /Ar of O

Work out molar ratio

empirical formula = C5H6O

Molar Gas Volume Example 10 : Calculate the volume in dm3 at room

1 mole of any gas at room pressure amount = mass/Mr

moles = mass Gas Volume (dm3)= amount x 24 Concentration = moles

A Hydrated salt contains water of crystallisation Example 13

This method could be used for measuring mass loss in various

Large amounts of hydrated calcium sulphate, such as 50g,

Calculate the mass of H2O = 3.51 – 1.97 = 1.54g

Calculate moles = 1.97 Calculate = 1.54

Calculate ratio of mole of 0.0122 = 0.085

Concentration = moles Unit of concentration: mol dm-3 or M

A m3 is equivalent to a cube A dm3 is equivalent to a cube A cm3 is equivalent to a cube

1dm3 = 1litre 1cm3 = 1 ml

1 m3 = 1000 dm3 or 1000L 1 dm3 = 1000 cm3 or 1000mL

cm3  dm3 ÷ 1000

• Add 100cm3 of distilled water to the beaker. Use a glass rod to

•Sometimes the substance may not dissolve well in cold water so

so new diluted concentration = original concentration x Original volume

Moles original solution = conc x vol

Safety and hazards

Step 1: work out moles of sodium hydrogencarbonate

First calculate maximum mass of Fe that could be produced

Step 3: work out mass of Fe

Step 4 : calculate %yield

Indicators are generally weak acids so we

Common Titration Equations Titrating mixtures

Safely dealing with excess acid

Calculating Apparatus Uncertainties

Reducing uncertainties in a titration If looking at a series of measurements in

To reduce the uncertainty in a burette reading it is necessary to make

Reducing uncertainties in measuring mass

If the %uncertainty due to the apparatus <

Behaviour of beams of protons, neutrons and electrons in electric fields

+ The negatively charged electron is

p The positively charged proton is

An atom of Lithium (Li) can be represented as follows:

Proton (atomic) Number 3

The A-level model

Writing electronic structure using letters and numbers •s sublevels are

Number of main Name of

For Calcium 1s2 2s2 2p6 3s2 3p6 4s2

Using spin diagrams

The arrows going in the