11.

Kinetics
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
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
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 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 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
[A]

then the order is 1st order

For this method to work the concentrations of the
0.030 reactants 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

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 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

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Working out orders from experimental initial rate data

The initial rate is the rate at the start of the reaction, where it is fastest. It is
often obtained by taking the gradient of the conc vs time graph.

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.
This data is normally 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

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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

5
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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
r = k [A]1[B]1[C]o The intermediate X is not one of the reactants so
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

Investigating the rate of reaction between Iodine and propanone

Propanone reacts with iodine in acidic solution (the acid is a catalyst) as shown in the equation
below.
CH3COCH3(aq) + I2(aq) → CH3COCH2I(aq) + H+(aq) + I–(aq)

This reaction can be followed by removing small samples from the reaction mixture with a
volumetric pipette. The sample is then quenched by adding excess sodium hydrogencarbonate to
neutralize acid catalyst which stops the reaction. Then the sample can be titrated with sodium
thiosulphate using a starch catalyst

2S2O32-(aq) + I2 (aq)  2I- (aq) + S4O62-(aq)

yellow/brown sol colourless sol

[I2] This reaction is zero order with respect to I2 but 1st order
with respect to the propanone and acid catalyst

The rate equation for the reaction is

Rate = k[CH3COCH3(aq)][H+(aq)]

If there is a zero order reactant there must

be at least two steps in the mechanism
because the rate determining step will not
involve the zero order reactant
Time (min)

The rate determining step of this reaction must therefore contain one propanone molecule and one H+ ion
forming an intermediate. The iodine will be involved in a subsequent faster step.

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 Example 3: SN1 or SN2?

Remember the nucleophilic substitution reaction of halogenoalkanes and hydroxide ions.

This is a one step mechanism

H CH3 H - H
δ+ δ-
H3C
-HO:
C Br  HO C Br
H3C C OH + :Br -

H
H H

CH3CH2Br + OH-  CH3CH2OH + Br- slow step

Primary halogenalkanes tend to
The rate equation is This is called SN2.
Substitution, Nucleophilic, react via the SN2 mechanism
r = k [CH3CH2Br] [OH-] 2 molecules in rate
determining step

SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes

Tertiary halogenoalkanes
CH3 CH3 CH3 undergo this mechanism as the
+
tertiary carbocation is stabilised
H3C C Br H3C C :OH- H3C C OH by the electron releasing methyl
groups around it. (see alkenes
CH3 CH3 CH3
topic for another example of this).
Also the bulky methyl groups
The Br first breaks away The hydroxide
prevent the hydroxide ion from
from the haloalkane to nucleophile then attacks
the positive carbon attacking the halogenoalkane in
form a carbocation the same way as the mechanism
intermediate
above

Overall Reaction
The rate equation is This is called SN1.
(CH3)3CBr + OH–  (CH3)3COH + Br – Substitution, Nucleophilic,
r = k [(CH3)3CBr] 1 molecule in rate
Mechanism: determining step

(CH3)3CBr  (CH3)3C+ + Br – slow Primary halogenoalkanes don’t do the SN1 mechanism

because they would only form an unstable primary
(CH3)3C+ + OH–  (CH3)3COH fast
carbocation.

Example 4
Example 5
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.

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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
the Arrhenius constant, R is the gas constant, and EA is activation energy.
temperature

Using the Arrhenius equation (equations will be given in the exam )

k = Ae-EA/RT
The Arrhenius equation is usually rearranged to (You don’t need to know how)
ln k = ln A – EA/(RT)
You should be able to do rearrangements
and substitute values into both these
Units equations.
Temperature uses the unit K
R = 8.31 J mol-1K-1
Activation energy will need to be in J mol-1 to match the units
of R
The unit of the Arrhenius constant A will be the same as the
unit of the rate constant k

Example
A reaction carried out at 30oC has a value of k = 4.26 × 10−8 s−1
The activation energy Ea = 95.8 kJ mol−1
The gas constant R = 8.31 J K−1 mol−1
Calculate a value for the Arrhenius constant, A, for the reaction.

Using Equation k = Ae-EA/RT

k = 4.26 × 10−8 = 4.26 × 10−8 4.26 × 10−8

Rearrange to A = =
e-EA/RT e-95800/(8.31x308) e-37.4 5.55× 10−17

= 7.67 × 108 s-1

Example
A reaction carried out at 25oC has a value of k = 3.3 × 10−3 mol-1 dm3 s−1
ln A = 17.1
The gas constant R = 8.31 J K−1 mol−1
Calculate a value for the activation energy in kJ mol-1
Using Equation ln k = ln A – EA/(RT)

Rearrange to EA = (ln A - ln k) x RT = (17.1 - - 5.71) x 8.31 x 298

= 56486 J mol-1
= 56.5 kJ mol-1

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 Calculating the activation energy graphically from experimental data
Using the rearranged version 1/T

ln k = ln A – 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

• the plotted points should fill all graph paper
EA = - gradient x R (8.31) (generally don’t start at the origin)
= - -5680 x8.31 • choose points far apart on the graph to
= 47200 J mol-1 calculate the gradient

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

Heterogeneous catalysis
Adsorption of reactants at active sites on the surface may lead to
A heterogeneous catalyst is in a different
catalytic action. The active site is the place where the reactants
phase from the reactants adsorb on to the surface of the catalyst. This can result in the
bonds within the reactant molecules becoming weaker, or the
Heterogeneous catalysts are usually solids whereas the
molecules being held in a more reactive configuration. There will
reactants are gaseous or in solution. The reaction also be a higher concentration of reactants at the solid surface so
occurs at the surface of the catalyst. leading to a higher collision frequency

Effect of pressure on heterogenous catalysis.

Increasing pressure has limited effect on the rate of heterogenous catalysed reactions because the reaction takes
place on surface of the catalyst. The active sites on the catalyst surface are already saturated with reactant molecules
so increasing pressure wont have an effect

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12A Entropy
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
(W) is high, then system is disordered
Substances with more ways of arranging their atoms and
and entropy (S) is high.
energy (more disordered) have a higher entropy.

System and Surroundings

When considering entropy it is useful to split the system

(the chemicals) from the surroundings. matter

A system will consist of reactants and then products. It does not change system
energy
temperature or pressure, and mass cannot be transferred to the
surroundings. Energy can be transferred to the surroundings.
surroundings

Entropy of the System, S˚system

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

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Predicting Change in entropy ‘∆Ssystem ’ Qualitatively

An increase in disorder and entropy will lead to a positive entropy change ∆S˚system = +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˚system 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˚system = +ve ∆S˚system = -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˚system quantitatively

Data books lists standard entropies (S˚) per mole for a Elements in their standard states do not have zero
variety of substances. It is not possible for a substance entropy. Only perfect crystals at absolute zero
to have a standard entropy of less than zero. (T = 0 K) will have zero entropy:

The unit of entropy is J K-1 mol-1 ∆S˚system = Σ S˚products - ΣS˚reactants

Example
Calculate ∆S˚ for the following reaction at 25˚C:
S [Fe2O3] = 87.4 J K-1 mol-1
2Fe2O3 (s) + 3C (s)  4Fe (s) + 3CO2 (g) Note: the entropy
S [C] = 5.7 J K-1 mol-1
change is very positive
∆S˚system = ΣS˚products - ΣS˚reactants S [Fe] = 27.3 J K-1 mol-1 as a large amount of
= (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.)

Entropy of the Surroundings Ssurrounding

The surroundings are the container, air, solvent.
In an endothermic reaction energy is transferred
In an exothermic reaction energy is given out into from the surroundings. The number of ways of
the surroundings. The number of ways of arranging the energy in the surroundings therefore
arranging the energy therefore increases and so decreases and so Ssurrounding decreases and is
Ssurrounding increases and is positive. negative.

converted into Jmol-1 by x1000

Ssurrounding = - H reaction
T in K
Convert oC into K
by +273

Total Entropy change Stotal

Stotal = Ssystem + Ssurrounding

For any reaction to be spontaneous then Stotal must be positive. If a reaction is not spontaneous
i.e. it doesn’t go, then Stotal will be negative.

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Example : Data for the following reaction, which represents the
reduction of aluminium oxide by carbon, are shown in the table. Substance ∆f H / S/
Al2O3(s) + 3C(s) → 2Al(s) + 3CO(g) kJmol–1 JK–1mol–1
Calculate the values of ∆Ssystem, ∆H , ∆Ssurroundings and ∆STotal for the
above reaction at 298 K Al2O3(s) -1669 51

1. Calculate ∆Ssystem 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

= +581 J K-1 mol-1 (3 S.F.) = +1336 kJ mol-1

3. Calculate ∆Ssurroundings 4. Calculate ∆STotal

Ssurrounding = - H reaction Stotal = Ssystem + Ssurrounding
T = 581 -4483
= -1336000/298 = -3902J K-1 mol-1
= - 4483 J K-1 mol-1
∆STotal is negative. The reaction is not feasible

Calculating the temperature a reaction will become

feasible
∆STotal during phase changes
Calculate the temperature range that this reaction will be As physical phase changes like melting and boiling are
feasible equilibria, the ∆STotal for such changes is zero.
N2(g) + O2(g)  2 NO(g)
∆ H = 180 kJ mol-1 ∆Ssystem = 25 J K-1 mol-1 What temperature would methane melt at?

The reaction will be feasible when ∆STotal ≥0 CH4(s)  CH4 (l) ∆H = 0.94 kJmol-1 ∆S = 10.3 Jmol-1K-1
Make ∆STotal = 0 in the following equation Make ∆STotal = 0 in the following equation
∆ Stotal = Ssystem + Ssurrounding ∆ Stotal = Ssystem + Ssurrounding
0 = -∆H/T + ∆Ssystem 0 = -∆H/T + ∆Ssystem
So T= ∆H / ∆Ssystem So T= ∆H / ∆Ssystem
T = 180/ (25/1000)
T= 0.94 / (10.3÷1000)
= 7200K
The T must be >7200K which is a high Temp! T= 91K

Effect of temperature on feasibility If the reaction involves an increase in entropy of the system
(∆Ssystem is +ve) then increasing temperature will make the
∆Stotal = -∆H/T + ∆Ssystem -∆H/T have a smaller magnitude and it will more likely that
∆Stotal will be positive and more likely that the reaction
Changing Temperature will change the occurs e.g. NaCl + aq  Na+(aq) + Cl-(aq)
value of - ∆H/T in the above equation

If the reaction involves an decrease in entropy If the reaction has a ∆H close to zero then
(∆Ssystem is -ve) then increasing temperature will make temperature will not have a large effect on the
it more less likely that ∆Stotal will be positive because feasibility of the reaction as - ∆H/T will be
the -∆H/T will have a smaller magnitude and will be less small and ∆ Stotal won’t change much
likely to compensate for the negative ∆Ssystem
It will be less likely for the reaction to occur. E.g.
HCl(g) + NH3 (g) ➝ NH4Cl(s)

3
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Equilibrium constants and feasibility
Values of equilibrium constants can all be used to predict the extent a reaction might occur.
Reaction Reactants equal amounts Products Reaction goes
‘does not predominate in of products and predominate in to completion
go’ an equilibrium reactants an equilibrium

Kc < 10-10 Kc  0.1 Kc = 1 Kc 10 Kc > 1010

ΔStotal increases the magnitude of the equilibrium constant increases since ΔG = - RT lnK
Where K is equilibrium constant Kc or Kp

This equation shows a reaction with a Kc >1 will therefore have a negative ΔG. Feasible
reactions with a negative ΔG will have large values for the equilibrium constant

If ΔG is negative 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 due to kinetic factors limiting the reaction.

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12B: Lattice energy
Definitions of enthalpy changes for stages involved in forming an ionic lattice

Enthalpy change of formation

The standard enthalpy change of formation of a compound is the energy transferred when 1
mole of the compound is formed from its elements under standard conditions (298K and
100kpa), all reactants and products being in their standard states
Na (s) + ½Cl2 (g)  NaCl (s) [f H= - 411.2 kJ mol-1]

Enthalpy of atomisation
The enthalpy of atomisation of an element is the enthalpy change when 1 mole of
gaseous atoms is formed from the element in its standard state
Na (s)  Na(g) [atH = +148 kJ mol-1]
½ O2 (g)  O (g) [atH = +249 kJ mol-1]

First Ionisation enthalpy Second Ionisation enthalpy

The first ionisation enthalpy is the enthalpy change The second ionisation enthalpy is the enthalpy
required to remove 1 mole of electrons from 1 mole change to remove 1 mole of electrons from one mole
of gaseous atoms to form 1 mole of gaseous ions of gaseous 1+ ions to produces one mole of gaseous
with a +1 charge 2+ ions.
Mg (g)  Mg+ (g) + e- [H IE 1] Mg+ (g)  Mg 2+ (g) + e- [H IE2 ]

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

First Electron affinity values will become less exothermic as you go down Group 7 from chlorine
to iodine because the atoms get bigger and have more shielding so it becomes less easy to
attract electrons to the atom to form the negative ion

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) [LEH = -787 kJ mol-1]

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 lattice enthalpies of around –700 to -
formation (i.e. a weaker lattice). As the ions are larger the charges 1000
become further apart and so have a weaker attractive force group 2 halides (eg MgCl2) have lattice
between them. enthalpies of around –2000 to –3500
2. The charges on the ion: group 2 oxides eg MgO have lattice
The bigger the charge of the ion, the greater the attraction between enthalpies of around –3000 to –4500
the ions so the stronger the lattice enthalpy (more negative values). kJmol-1

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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)

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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)

Perfect Ionic Model

Theoretical lattice enthalpies assumes a perfect ionic model where the ions are 100% ionic and
spherical and the attractions are purely electrostatic.

Differences between theoretical and Born Haber (experimental) lattice enthalpies

The Born Haber lattice enthalpy is the real experimental value.

When a compound shows covalent character, the theoretical and the Born Haber lattice enthalpies
differ. The more the covalent character the bigger the difference between the values.

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.

Ionic with covalent

100% ionic character + -

When 100 % ionic the ions are spherical. The charge cloud is distorted .The theoretical
The theoretical and the born Haber lattice and the experimental Born Haber lattice
enthalpies will be the same enthalpies will differ

The polarising power of cation increases when: The polarizability of an anion depends
• the positive ion is small on its size. The bigger the ion the more
• the positive ion has multiple charges easily it is distorted.

When a compound has some covalent character- it tends towards giant

covalent so the lattice is stronger than if it was 100% ionic. Therefore the
born haber value would be larger than the theoretical value.

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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 8
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 Solubility of ionic substances
Enthalpy of lattice formation Enthalpy of Hydration Hhyd
The Enthalpy of lattice formation is the standard enthalpy • Enthalpy change when one mole of gaseous ions
change when 1 mole of an ionic crystal lattice is formed become hydrated such that further dilution causes no
from its constituent ions in gaseous form. further heat change
Na+ (g) + Cl- (g)  NaCl (s) [LEH = -787 kJ mol-1]
X+ (g) + aq  X+ (aq) For Li+ hydH = -519 kJ mol-1
or
Enthalpy of solution
X- (g) + aq  X- (aq) For F- hydH = -506 kJ mol-1
The enthalpy of solution is the standard enthalpy change
when one mole of an ionic solid dissolves in a large
This always gives out energy (exothermic, -ve) because
enough amount of water to ensure that the dissolved ions
bonds are made between the ions and the water molecules
are well separated and do not interact with one another.

NaCl (s) + aq  Na+ (aq) + Cl-(aq)

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 lattice enthalpies of around –700 to -
formation (i.e. a weaker lattice). As the ions are larger the charges 1000
become further apart and so have a weaker attractive force group 2 halides (eg MgCl2) have lattice
between them. enthalpies of around –2000 to –3500
2. The charges on the ion: group 2 oxides eg MgO have lattice
The bigger the charge of the ion, the greater the attraction between enthalpies of around –3000 to –4500
the ions so the stronger the lattice enthalpy (more negative values). kJmol-1

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

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Example . Calculate the enthalpy of solution of NaCl Hydration enthalpies are exothermic as energy is given
given that the lattice enthalpy of formation of out as water molecules bond to the metal ions.
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 solH tell us?

Generally solH 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 solH 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 solH 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 Ssystem can make STotal positive 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
∆S value is more positive than -∆H/T is negative
∆Stotal = -∆H/T + ∆Ssystem
∆Stotal = -∆H/T + ∆Ssystem
 Stotal is Ssystem is positive
always H is negative due to the Will dissolve
Ssystem is
positive so -∆H/T will increased disorder if Stotal is
H is positive positive due to
always be as more particles positive so -∆H/T will the increased
positive
be negative disorder

Increasing the temperature will make it more

likely that STotal will become positive, making
the reaction feasible and the salt dissolves

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 13. Chemical Equilibria
Many reactions are reversible All reversible reactions reach an
N2 + 3H2 2NH3 dynamic equilibrium state.

Dynamic equilibrium occurs when forward and backward reactions are occurring at equal rates. The
concentrations of reactants and products stays constant and the reaction is continuous.

Writing an expression for Equilibrium constant Kc

Kc = equilibrium constant
For a generalised reaction Example 1
mA + nB pC + qD
[ C]p [D]q N2 (g) + 3H2 (g) 2 NH3 (g)
m,n,p,q are the stoichiometric balancing Kc=
numbers [ A]m [B]n [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 units 1
Kc= [mol dm-3]2 Unit = [mol dm-3]-2
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

Most questions first involve having to work out the equilibrium moles and then concentrations
of the reactants and products.
Usually the question will give the initial amounts (moles) of the reactants, and some data that
will help you work out the equilibrium amounts.

Calculating the moles at equilibrium

moles of reactant at equilibrium = initial moles – moles reacted

moles of product at equilibrium = initial moles + moles formed

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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)
For the following equilibrium
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
Initial moles 1.5 4.0 0

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

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Practical: Working out equilibrium constant Kc
A common experiment is working out the equilibrium constant for an esterification reaction. Ethanol and
ethanoic acid are mixed together with a sulfuric acid catalyst.

CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O

Ethanoic acid Ethanol Ethyl Ethanoate

Method
Part 1 Preparing the equilibrium mixture
1 Use burettes to prepare a mixture in boiling tube of carboxylic acid, alcohol, and dilute sulfuric acid.
2 Swirl and bung tube. Leave the mixture to reach equilibrium for one week

Part 2 Titrating the equilibrium mixture

1 Rinse a 250 cm3 volumetric flask with distilled water.
Use a funnel to transfer the contents of the boiling tube into the flask. Rinse the boiling tube with water and
add the washings to the volumetric flask.
2 Use distilled water to make up the solution in the volumetric flask to exactly 250 cm3.
Stopper the flask, then invert and shake the contents thoroughly.
3 Use the pipette to transfer 25.0 cm3 of the diluted equilibrium mixture to a 250 cm3 conical flask.
4 Add 3 or 4 drops of phenolphthalein indicator to the conical flask.
5 Set up the burette with sodium hydroxide solution..
6 Add the sodium hydroxide solution from the burette until the mixture in the conical flask just turns pink.
Record this burette reading in your table.
7 Repeat the titration until you obtain a minimum of two concordant titres.

The sodium hydroxide will react with the sulfuric acid catalyst and any unreacted carboxylic
acid in the equilibrium mixture

There are many different calculations that can be based on this experiment.
Let’s look at general stages. Not all calculations will use all the stages.

Working out initial amount of moles of reactants

The amount of moles of alcohol and carboxylic acid can be calculated from the
densities and volumes of liquids added
Mass = density x volume
then
Moles = mass / Mr
The initial amount of moles of acid catalyst used is usually determined by titrating a
separate sample of catalyst with sodium hydroxide

Working out equilibrium amount of moles of acid present from the titre results
39.0 cm3 of 0.400 mol dm-3 sodium hydroxide was used in the above titration. The initial moles of sulphuric acid
was 5x10-4 mol. Calculate the moles of ethanoic acid present at equilibrium

Amount of NaOH = vol X conc

= 0.039 x 0.400
= 0.0156 mol
So total amount of H+ present in 25cm3 = 0.0156 mol
So total amount of H+ present in 250cm3 = 0.156 mol

Total mol acid present = moles of carboxylic acid + moles of acid catalyst
So X 2 because H2SO4
Amount of carboxylic acid at equilibrium = 0.156 – (5x10-4 x 2) has 2 H+
= 0.155 mol

The pink colour of the phenolphthalein in the titration can fade after the end-point of
the titration has been reached because the addition of sodium hydroxide may make
the equilibrium shift towards the reactants

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Working out equilibrium amount of moles of other substances
Calculate the equilibrium amount of ethanol, ethyl ethanoate and water if there were initially 0.400 mol of
ethanol and 0.500 mol of ethanoic acid and at equilibrium there were 0.155 mol of ethanoic acid.

Amount of ethanoic acid that reacted = initial amount – equilibrium amount

= 0.5 – 0.155
= 0.344mol
Amount of ethanol at equilibrium = initial amount - amount that reacted
= 0.400 – 0.344
= 0.056 mol
Amount of ethyl ethanoate at equilibrium = initial amount + amount that formed
= 0 + 0.344
= 0.344 mol
Amount of water at equilibrium = initial amount + amount that formed The amount of water at
= 0 + 0.344 equilibrium would not really be
= 0.344 mol 0 as there would be water
present in the acid catalyst

Calculating the equilibrium constant

Finally calculate the equilibrium constant.
To work out equilibrium concentrations divide the equilibrium amounts by the total volume. Then put in
Kc expression

Kc = [CH3CO2CH2CH3 ] [H2O]
[CH3CO2H] [CH3CH2OH]

In order to confirm that one week was sufficient time for

equilibrium to be established in the mixture from Part 1,
several mixtures could be made and left for different
amount of time. If the resulting Kc is the same value then
it can be concluded the time is sufficient

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 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 : A mixture contains 0.2 moles N2, 0.5 moles O2 and 1.2 moles of CO2. If the total pressure is 3atm.
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(atm) into the Kp equation

atm2
Unit = However, if the equation is
p 2 NH
Kp= 3 (g) atm atm3 written the other way round, the
pN2 (g) p 3H2 (g) value of Kp will be the inverse of
1 above and the units will be atm2.
Cancel out units Unit =
It is important therefore to write
atm2
an equation when quoting
Unit = atm-2 values of Kp.

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Example 4
N2 (g) + 3H2 (g ) 2 NH3 (g)
For the following equilibrium

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 2atm 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
Initial moles 1.0 3.0 0

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

Kc
= 0.2222 = 0.0469 atm-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 atm

Equilibrium constants and feasibility

Values of equilibrium constants can all be used to predict the extent a reaction might occur.
Reaction Reactants equal amounts Products Reaction goes
‘does not predominate in of products and predominate in to completion
go’ an equilibrium reactants an equilibrium

Kc < 10-10 Kc  0.1 Kc = 1 Kc 10 Kc > 1010

ΔStotal increases the magnitude of the equilibrium constant increases since ΔS = R lnK
Where K is equilibrium constant Kc or Kp

This equation shows a reaction with a Kc >1 will therefore have a positive ΔStotal

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Application of rates and equilibrium
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 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 Temperature on rate

As the temperature increases a significantly bigger proportion of particles have energy greater than the activation
energy, so the frequency of successful collisions increases

Effect of Concentration on position of equilibrium and Kc

H2 (g) +Cl2 (g) 2HCl (g)
Changing concentration would
shift the position of equilibrium
but the value of Kc would not Increasing concentration of H2 would move equilibrium to the right lowering
change. concentration of H2 and Cl2 and increasing concentration of HCl. The new
concentrations would restore the equilibrium to the same value of Kc

Effect of Concentration and pressure on rate

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.

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 bottom Kp=
p N 2 p 3 H2
of Kp expression more than the top. The system is now no
longer in equilibrium so the equilibrium shifts to the right x 2 NH3 . P2
increasing mole fractions of products and decreases the mole Kp= Where P is total
fractions of reactants. The top of Kp expression therefore x N2.P x3 H2.P3 pressure and x
increases and the bottom decreases until the original value of mole fraction
Kp is restored x 2 NH3 . P2
Kp=
x N2 x3 H2. P4
Effect of catalysts on position of equilibrium and Kc

A catalyst has no effect on the position of equilibrium or values of Kc and Kp, 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.

Catalysts speeds up the rate allowing lower temperatures to be used (and hence lower energy costs) but have no
effect on equilibrium.
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7
14. Acid Base 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.

HNO3 + HNO2 ⇌ NO3– + H2NO2+ HCOOH + CH3(CH2)2COOH ⇌ HCOO– + CH3(CH2)2COOH2+

Acid 1 Base 2 Base 1 Acid 2 Acid 1 Base 2 Base 1 Acid 2

In these reactions the substance with bigger Ka will act as

the acid

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 1
[H+] = 1x 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
value is constant and make a new
Rearrange to 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
pKw the [OH- (aq)] ions and vice versa.
Sometimes Kw is quoted as pKw values
pKw = -log Kw so Kw = 10-pKw
If Kw = 1x10-14 then pKw =14

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 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 2 : Calculate the pH of water at 50ºC given that Kw =
pure water changes. Le Chatelier’s
5.476 x 10-14 mol2 dm-6 at 50ºC
principle can predict the change. The
[H+(aq) ] = √ Kw = √ 5.476 x 10-14 =2.34 x 10-7 mol dm-3
dissociation of water is endothermic so
pH = - log 2.34 x 10-7 = 6.6
increasing the temperature would push the
It is still neutral though as [H+ (aq) ] = [OH- (aq)]
equilibrium to the right giving a bigger
concentration of H+ ions and a lower pH.

Calculating pH of Strong Base

For bases we are normally given the Example 3: 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 4 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 [CH3CH2CO2H(aq)]
dm-3.
pKa
The larger ka the stronger the acid 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

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 Example 5 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

Example 6 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

Working out pH of a weak acid at half equivalence

Example 7
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
25cm3 of 0.1M NaOH is added to 50cm3 of
simplified considerably.
0.1M CH3COOH (ka 1.7 x 10-5 )
ka = [H+] [CH3CO2- ] At half neutralisation we can make From the volumes and concentrations spot it
[ CH3CO2H ] the assumption that [HA] = [A-] is half neutralisation (or calculate)

So [H+(aq)] = ka pH = pka = -log (1.7 x 10-5 ) = 4.77

And pH = pka

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 8 Calculate the new pH when 50.0 cm3 of 0.150 mol dm-3 HCl is mixed with 500 cm3 of water.
[H+(aq)] = 0.0136
[H+] = [H+]old x old volume 0.05
[H+(aq)] = 0.150 x
new volume 0.55 pH = – log [H+]
= -log 0.0136
= 1.87

Comparing the pH of a strong acid and a weak acid after dilution 10, 100 and 1000 times
Because pH is a logarithmic scale, diluting a strong acid 10 times will increase its pH
by one unit, and diluting it 100 times would increase its pH by two units
Weak acids would not change in the same way as when they are diluted. They increase by less than 1 unit
CH3CH2CO2H +H2O H3O+ + CH3CH2CO2-
Diluting the weak acid pushes the equilibrium to the right so the degree of dissociation increases and
more H+ ions are produced meaning pH increases less than expected

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 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, CH3CO2- (aq) + H+ [CH3CO2H (aq)]
[H+(aq)] = Ka
(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

Normally we
[H+ (aq)][A- (aq)] But here we assume the [A-] [H+(aq)] = Ka
[HA(aq)]
Ka= rearrange to
concentration is due to the
[HA (aq)] [A- (aq) ]
added salt only

We also assume the Initial concentration of

the acid has remained constant, because
amount that has dissociated or reacted is
The salt content can be added in several ways: a salt solution
small.
could be added to the acid or some solid salt added. A buffer can
also be made by partially neutralising a weak acid with alkali and
therefore producing salt.

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 Example 9: 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 10 : making a buffer by adding a solid salt

We can enter moles of
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
[H+(aq)] = 1.7 x 10-5 x [H+(aq)] = 5.07x 10-5 pH = – log [H+]
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 11 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 NaOH = conc x vol = 0.35 x 0.025 = 0.00875

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

Buffering action in blood

Equilibrium
A carbonic acid– hydrogencarbonate equilibrium acts H2CO3 ⇌ H+ + HCO3 –
as a buffer in the control of blood pH
Adding alkali reacts with H+ so the above Equilibrium
The H2CO3/HCO3– buffer is present in would shift right forming new H+ and more HCO3 –
blood plasma, maintaining a pH between
7.35 and 7.45.

Buffers can be found naturally in some foods to prevent deterioration due to pH change (caused by
bacterial or fungal activity). The pH of the food tends to be acidic which prevents the growth of
bacteria. The buffer prevents the pH of the food increasing to a point where bacteria can thrive

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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 12: 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
We can enter moles of
[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
[H+(aq)] = 1.7 x 10-5 x [H+(aq)] = 1.24x 10-5 pH = – log [H+]
0.130 = -log 1.24x 10-5
= 4.91

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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
1. Strong acid and strong base
pH
2. Weak acid and strong base
13 3. Strong acid and weak base
Long vertical part 4. Weak acid and weak base
from around 3 to 9
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 titration calculations. The equivalence point lies at the
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

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

Steep part of curve >7 If we know the Ka we can then work

(around 7 to 9) out the pH at ½ V or vice versa
pH
starts 1

near 3 V cm3 of base

½V
N Goalby chemrevise.org 7
 Weak acid – Weak base
Strong acid – Weak base
e.g. HCl and NH3
e.g. CH3CO2H and NH3
pH
pH
13
13
No vertical part of the curve

Vertical 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

Indicators can be considered as weak acids. The acid must HIn (aq) In- (aq) + H+ (aq)
have a different colour to its conjugate base
colour A colour B
An indicator changes colour from HIn to In-
over a
narrow range. Different indicators change colours We can apply Le Chatelier to give us the colour.
over different ranges. In an acid solution the H+ ions present will push
this equilibrium towards the reactants.
The end-point of a titration is defined as the point when Therefore colour A is the acidic colour.
the colour of the indicator changes colour In an alkaline solution the OH- ions will react
The end-point of a titration is reached when [HIn] = [In-]. and remove H+ ions causing the equilibrium to
To choose a correct indicator for a titration one should shift to the products. Colour B is the alkaline
pick an indicator whose end-point coincides with the colour.
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
bases but not weak bases-
13

Colour change: colourless acid  pink alkali pH range for

weak base phenolphthalein
7
Use methyl orange with titrations with weak acid pH range for methyl
strong acids but not weak acids orange
Colour change: red acid  yellow alkali 1
strong acid
(orange end point)
3
25 cm of base

8
N Goalby chemrevise.org
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.

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 changes of neutralisation are always exothermic. For reactions involving strong acids and alkalis, the
values are similar, with values between -56 and -58 kJ mol-1 because the same reaction is occurring H+ + OH-
H2O

Weak acids have a less exothermic enthalpy change of neutralisation because energy is absorbed to ionise the
acid and break the bond to the hydrogen in the un-dissociated acid.

N Goalby chemrevise.org 9
15. Carbonyls, Carboxylic Acids and chirality

prefix / suffix
homologous functional group example
(* = usual use)
series
H H

alkenes C C suffix -ene C C ethene

H H

suffix* -ol H H H
alcohols C OH
prefix hydroxy-
H C C C O H Propan-1-ol
H H H

H H H
halogenoalkane C halogen
prefix chloro- H C C C Cl
bromo- 1-chloropropane
H H H
iodo-

O H O
suffix -al
aldehydes C H H C C H
prefix formyl- ethanal
H

H O H
O suffix* -one
ketones prefix oxo- H C C C H
C Propanone
H H

O H O
suffix -oic acid
carboxylic acids C OH H C C OH
Ethanoic acid
H

H H
suffix -nitrile
nitriles H C C C N
prefix cyano- Propanenitrile
C N
H H

suffix* -amine H H H
amines C NH2 prefix amino- Propylamine
H C C C NH2
Or propan-1-amine
H H H

H O H
O
esters H C C O C H Methyl ethanoate
C O
-yl –oate
H H
O
O
Acyl chloride CH 3 C ethanoylchloride
C -oyl chloride
Cl Cl

O
O
Amide
C -amide CH3 C ethanamide
NH2 NH2

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 H
Aldehydes O
Ketones H O H
An aldehyde’s name ends in –al
It always has the C=O bond on the H C C
Ketones end in -one H C C C H
first carbon of the chain so it does
When ketones have 5C’s or more
not need an extra number. It is by H H
H
in a chain then it needs a number
default number one on the chain H Propanone
to show the position of the double
Ethanal bond. E.g. pentan-2-one
H O H O H
If two ketone groups then
Carboxylic acids H H di is put before –one and H C C C C C H
O
These have the ending -oic an an e is added to the H H H
acid but no number is stem
H C C C
necessary for the acid group Pentane-2,4-dione
as it must always be at the
end of the chain. The H H
O H O
The prefix oxo- should be
numbering always starts used for compounds that H3C C C
from the carboxylic acid end propanoic acid
contain a ketone group in O OH
addition to a carboxylic acid
If there are carboxylic acid groups on both ends of the or aldehyde 2-oxopropanoic acid
chain then it is called a - dioic acid
O O
Ethanedioic acid
C C
HO OH Note the e in this name

Nitriles H H H OH
These end in –nitrile, but the C of the H3C
CN group counts as the first carbon of H C C C CN C
the chain. Note the stem of the name is C
H3C N
different : butanenitrile and not H H H
butannitrile. butanenitrile 2-hydroxy-2-methylpropanenitrile

Carboxylic acid derivatives

Esters H
H H O
Esters have two parts to their names
H C C C O C H
The bit ending in –yl comes from the alcohol that has
formed it and is next to the single bonded oxygen.
H H H
The bit ending in –anoate comes from the carboxylic acid.
(This is the chain including the C=O bond) Methyl propanoate

Acyl Chlorides H3C O O

O O
add –oyl chloride to the stem CH3 C CH C C (CH2)3 C
name Cl
Cl H3C Cl Cl
ethanoyl chloride 2-methylpropanoyl chloride Pentanedioyl dichloride

Amides O Secondary and tertiary amides O

are named differently to show the
Add –amide to the stem CH3 C two (or three) carbon chains.
H3C CH2 C NH CH3
name NH2 The smaller alkyl group is
ethanamide preceded by an –N which plays N-methylpropanamide
the same role as a number in
positioning a side alkyl chain CH3 O CH3
O CH3
H3C CH C N CH3
H3C CH2 C N CH3 N,N,2-trimethylpropanamide
N,N-dimethylpropanamide

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 15A Chirality
A carbon atom that has
Optical isomerism occurs in carbon compounds with 4 H H H H
four different groups
different groups of atoms attached to a carbon (called
attached is called a chiral
an asymmetric carbon). H C C C C H
(asymmetric) carbon
H H O H atom
These four groups are arranged H
tetrahedrally around the carbon.

OH OH This causes two

A mixture containing a 50/50 mixture of the
different isomers that
C C two isomers (enantiomers) is described as
are not superimposable
CH3 H3C being a racemate or racemic mixture.
H5 C2 C2 H5 to be formed. They are
H H mirror images

Many naturally occurring molecules

contain chiral C atoms, but are usually
Two compounds that are optical isomers of
found in nature as a pure enantiomer
each other are called enantiomers.
Different systems of nomenclature are is
Optical isomers have similar physical and chemical properties, existence for optical isomers. D/L or +/- are
but they rotate plane polarised light in different directions. commonly used, but both have been
superseded by the more useful and informative
One enantiomer rotates it in one direction and the other enantiomer R/S system (this is not on the syllabus – for
rotates it by the same amount in the opposite direction. information only).

One optical isomer will rotate light clockwise (+)(called

dextrorotatory). The other will rotate it anticlockwise(-)(called
laevorotatory).
Racemate
A racemic mixture (a mixture of equal amounts of the two -ve enantiomer +ve enantiomer
no rotation
optical isomers) will not rotate plane-polarised light. Anticlockwise clockwise
rotation rotation

Chemical Reactions and Optical Isomers

Formation of a racemate
CH3
A racemate will be formed in a reaction H
mechanism when a trigonal planar reactant or C
intermediate is approached from both sides by NC:
:CN
an attacking species
O
Nucleophilic addition of HCN to aldehydes
H
and ketones (unsymmetrical) when the H H3 C CN
trigonal planar carbonyl is approached from NC CH3
both sides by the HCN attacking species: There is an equal chance of C
C
results in the formation of a racemate either enantiomer forming so
a racemate forms. No
OH OH
optical activity is seen

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 Formation of a racemate with SN1 mechanism H

Br CH C
H3C + CH2 3
H3C C CH2 CH3 C H3C C2H5
H H :OH- OH
H
The Br first breaks Because a
The OH- ion can then attack C racemate forms
away from the
from either side resulting in there will be no
haloalkane to form a H5C2 CH3
different enantiomers and a optical activity in
planar carbocation
racemate forms HO the products
intermediate

Comparison with SN2 mechanism

In the SN2 mechanism no intermediates are formed and the reaction occurs via a transition state.
-
CH3 H
Br OH
H3C C CH2 CH3 HO C Br H3C C CH2 CH3
H :OH- CH 2CH 3 H

If the reactant was chiral then during the reaction the opposite enantiomer would form.
The product will rotate light in the opposite direction to the reactant

A racemate can also be formed in the AS reaction of the

electrophilic addition of HBr to an unsymmetrical alkene

:Br - H
H The bromide can H
+ attack this planar
δ+ δ- C CH2 carbocation from C
C
H Br both sides leading to CH2 Br CH2
H3C CH3 a racemate H3C Br
CH3 CH3
CH3
H2C CH CH2 CH3
:Br - Major product s 90%
If the alkene is H H
unsymmetrical, addition of +
hydrogen bromide can C C CH2 CH3
CH2 CH2 CH2 CH3 Minor
lead to isomeric products. H product
H
Br 10%

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Compounds with C=O group
Carbonyls are compounds with a C=O bond.
15B Carbonyls: Aldehydes and Ketones 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

Solubility in water
CH3
The smaller carbonyls are soluble Pure carbonyls cannot hydrogen bond, but
in water because they can form O H O C bond instead by permanent dipole bonding.
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+

CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+

5
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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

This reaction is called the Iodoform test

CH3COCH3 + 3I2 + 4NaOH → CHI3 + CH3COONa + 3NaI +3H2O

CH3COCH2CH3+ 3I2 + 4NaOH → CHI3 + CH3CH2COONa + 3NaI +3H2O

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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

15C Carboxylic Acids

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)

Hydrogen bonding in solid ethanoic acid

δ- Hydrogen bonding
δ - between dimer in
δ+
solid ethanoic acid
O H O
C CH3
H3C C δ -
Solid Ethanoic
δ- δ+
O H O appears to have Mr
of 120

Delocalisation
The delocalised ion has equal C-O bond lengths. If
The carboxylic acid salts are stabilised by delocalisation, delocalisation did not occur, the C=O bond would be
which makes the dissociation more likely. shorter than the C-O bond.

O O The pi charge cloud has O

delocalised H3C C delocalised and spread out. The
H3C C delocalisation makes the ion C
H3C
OH O more stable and therefore more
likely to form.
O

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Strength of carboxylic acids

O O Increasing chain length pushes

delocalised electron density on to the COO-
H3C CH2 C H3C CH2 C
ion, making it more negative and
OH O less 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
H C C the COO- ion, making it less
OH negative and more stable. This
H O
H make the acid more strong.
Chlorine electron withdrawing
chloroethanoic acid more acidic than ethanoic acid

O H O H
O OH In a dibasic acid the second HO2C-
C C C C C C - group withdraws electron density
O O H
from the COO- ion, making it less
H H H O H OH
negative and more stable and
weakens the O-H bond. This make
HO2C- group electron withdrawing the acid more strong.

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 ion
Conditions: use an excess of dichromate, and heat under reflux: (distill off product after (Cr2O72-) reduces to
the reaction has finished) the green Cr 3+ ion

H H H H H O
+ 2 [O] H C C C + H2O
H C C C O H
H H H H H O 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 dilute
H C C C + [O]  H C C C
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+

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 The Reactions of Carboxylic Acids

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

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

Oxidation of methanoic acid O O It forms carbonic acid

Carboxylic acids cannot be oxidised by using (H2 CO3 ) which can
oxidising agents but methanoic acid is an H C + [O]  H O C decompose to give
exception as its structure has effectively an O H O H CO2
aldehyde group

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

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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

Uses of Esters
Esters can have pleasant smells
Esters are sweet smelling
For use in perfumes they need to be non toxic, soluble in solvent such as
compounds that can be used in
ethanol, volatile (turns into gas easily), and not react with water.
perfumes and flavourings.

Esters can be used as solvents Although polar, they do not form hydrogen bonds (reason: there is no
for polar organic substances hydrogen bonded to a highly electronegative atom)
thus, they have much lower b.p. than the hydrogen-bonded carboxylic
Ethyl ethanoate is used as a acids they came from. They are also almost insoluble in water
solvent in glues and printing inks

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
reagents: dilute acid (HCl)
ester is hydrolysed a carboxylic acid and an alcohol are formed.
conditions: heat under reflux
H+
This reaction is reversible and does
CH3CH2CO2CH2CH3 + H2O CH3CH2CO2H + CH3CH2OH
not 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.

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Carboxylic acid derivatives: Acyl Chlorides

Acyl Chlorides
O Acyl chlorides are The Cl group is classed as a good leaving
much more reactive groups (to do with less effective delocalisation.)
CH3 C
than carboxylic acids This makes acyl chlorides and acid anhydrides
Cl much more reactive than carboxylic acids and
ethanoyl chloride esters

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 C C O C C H + HCl
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 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

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Polyesters

There are two types of polymerisation: addition and condensation

Condensation Polymerisation
In condensation polymerisation there are two different monomers
The two most common types of that add together and a small molecule is usually given off as a
condensation polymers are side-product e.g. H2O or HCl.
polyesters and polyamides which
involve the formation of an ester The monomers usually have the same functional group on both ends
linkage or an amide linkage. of the molecule e.g. di-amine, di carboxylic acid, diol, diacyl chloride.

Forming polyesters uses these reactions we met earlier in the course

Carboxylic Acid + Alcohol  Ester + water Acyl chloride + Alcohol  Ester + 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 diacyl dichloride + diol  poly(ester) + 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

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 It is also possible for polyamides and polyesters to form from one monomer, if that monomer
contains both the functional groups needed to react
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
O O

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

Chemical reactivity of condensation polymers

The reactivity can be explained by the presence of
polyesters can be broken down by hydrolysis and polar bonds which can attract attacking species
are, therefore, biodegradable such as nucleophiles and acids

Polyesters can be hydrolysed by acid and alkali

With HCl a polyester will be hydrolysed and split up in to the original dicarboxylic acid and diol
With NaOH an polyester will be hydrolysed and split up into the diol and dicarboxylic acid salt.

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 15E. Spectroscopy and chromatography
The effect of different types of radiation on molecules
i infrared in analysis – infra red energy causes bonds to vibrate. This can be used to identify the types
of bond in a molecule
ii microwaves for heating- certain molecules absorb the microwaves causing them to rotate
iii radio waves in nmr – can cause the hydrogen nucleus to change its spin state. This can give us
information about the arrangements of hydrogens in a molecule.
iv ultraviolet in initiation of reactions – UV energy can break bonds such as the Cl-Cl bond or C-Cl
bond

NMR spectroscopy

NMR spectroscopy involves interaction of materials with the low- The radio waves used in
energy radiowave region of the electromagnetic spectrum proton nmr cause the
hydrogen nucleus to change
NMR spectroscopy is the same technology as that used in ‘magnetic its spin state.
resonance imaging’ (MRI) to obtain diagnostic information about
internal structures in body scanners e.g. scanning for brain disorders

Equivalent Hydrogen atoms.

In addition the intensity (integration value)
In an H NMR spectrum, there is one
of each signal is proportional to the number
signal for each set of equivalent H atoms.
of 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
Ha
4sets of equivalent H’s:
Ethanol has 3 ratio 6:1:2:3
1
groups 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 4 sets of equivalent H’s: ratio 3:1:2:3
H’s: 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

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Calibration and shift

A small amount of TMS (tetramethylsilane) is added

to the sample to calibrate the spectrum

CH3 The spectra are recorded on a

TMS is used because:
scale known as the chemical
•its signal is away from all the others
H3C Si CH3 shift (δ), which is how much the
•it only gives one signal
field has shifted away from the
•it is non-toxic
field for TMS..
•it is inert CH3
•it has a low boiling point and so can be removed tetramethylsilane
from sample easily

The δ is a measure in parts per million (ppm) is a relative 10 9 8 7 6 5 4 3 2 1 0

scale of how far the frequency of the proton signal has δ chemical shift (ppm)
shifted away from that for TMS.

H NMR shift
The δ depends on what other atoms/groups are near the
H – more electronegative groups gives a greater shift.

3
O
H3C CH2 C O CH3

δ ppm

H H O
H C C C
H H O H
2

δ ppm

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Spin-Spin coupling in H NMR
Nuclei in identical chemical
In high resolution H NMR each signal in the spectrum can be split into environments do not show
further lines due to inequivalent H’s on neighbouring C atoms. coupling 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
appearance (a carbon with 2 H’s)
The peak due to group b will
be a quartet as it is next to a
Split number (a carbon with 3H’s)
1 2 3 4 5
of peaks
The peak due to group c will
number of be a singlet as it is next to a
neighbouring carbon with no H’s)
0 1 2 3 4
inequivalent
H atoms
For 6 split peaks use the
relative size 1:1 1:2:1 1:3:3:1 1:4:6:4:1 term 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
Integration trace 3
c
The peak due to group a will The peak due to group b will
b
be a singlet as it is next to be a quartet as it is next to
a carbon with 0 H’s a carbon with 3 H’s
Shift 2.1-2.6 Shift 3.7 -4.1
Integration trace 3 Integration trace 2

ppm

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Mass spectrometry
Measuring the Mr of an organic molecule Spectra for C4H10

If a molecule is put through a mass spectrometer Mass spectrum for butane

it will often break up and give a series of peaks
caused by the fragments. The peak with the 43
Molecular ion
largest m/z, however, will be due to the complete
C4H10+
molecule and will be equal to the Mr of the
molecule. This peak is called the parent ion or 29
molecular ion
58

Fragmentation
Molecular ion formed: M → [M]+. + e–
When organic molecules are passed through a mass
spectrometer, it detects both the whole molecule and The molecule loses an electron and
fragments of the molecule. 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 43
at 43 due to [CH3CO]+ Equations for formation of fragment ions from molecular ions
stability of acyl
group [CH3CH2COCH3]+.  [CH3CH2CO]+ + .CH3 m/z 57

29 [CH3CH2CO]+ [CH3CH2COCH3]+.  [CH3CO]+ + .CH2CH3 m/z 43

+.
[CH3CH2]+ 57 [CH3CH2COCH3] [CH3CH2COCH3]+.  [CH3CH2]+ + .COCH3 m/z 29
72

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 Chromatography
The mobile phase may be a liquid or a gas.
The stationary phase may be a solid (as in thin-
Chromatography is an analytical technique that separates
layer chromatography, TLC) or either a liquid or
components in a mixture between a mobile phase and a
solid on a solid support (as in gas
stationary phase.
chromatography, GC)

Separation by column chromatography depends on

the balance between solubility in the moving phase If the stationary phase was polar and the moving
and retention in the stationary phase. phase was non- polar e.g. Hexane. Then non-
polar compounds would pass through the column
more quickly than polar compounds as they would
A solid stationary phase separates by adsorption, have a greater solubility in the non-polar moving
A liquid stationary phase separates by relative solubility phase.
(Think about intermolecular forces)

HPLC stands for high performance liquid

In gas-liquid chromatography GC the mobile phase is
chromatography.
a inert gas such as nitrogen, helium, argon.
HPLC: stationary phase is a solid silica
The Stationary phase is a liquid on an inert solid.
HPLC: mobile phase a liquid

Gas-Liquid Chromatography

Gas-liquid chromatography can be used to separate In gas-liquid chromatography, the mobile

mixtures of volatile liquids. phase is a gas such as helium and the
stationary phase is a high boiling point
The time taken for a particular compound to liquid absorbed onto a solid.
travel from the injection of the sample to where
it leaves the column to the detector is known as Sample in
its retention time. This can be used to identify Flow
a substance. control oven

Some compounds have similar retention times so

will not be distinguished. display

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 Most commonly a mass spectrometer is combined
spectrometer, IR or NMR machine, enabling all with GC to generate a mass spectra which can be
the components in a mixture to be identified. analysed or compared with a spectral database by
computer for positive identification of each
component in the mixture.
GC-MS is used in analysis, in forensics, environmental
analysis, airport security and space probes.

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TLC Chromatography (thin-layer A mixture can be separated by chromatography and
chromatography) identified from the amount they have moved. (Can be
used with mixtures of amino acids)

Method: Thin-layer chromatography

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

If using amino acids then ninhydrin spray can be used instead of

UV lamp to locate the spots

Rf value = distance moved by amino acid

distance moved by the solvent

Each substance has its own Rf value

Measure how far each spot travels relative

to the solvent front and calculate the Rf
value.
Compare Rf values to those for known
substances.
Some substances won't separate because similar
compounds have similar Rf values. So some spots may
contain more than one compound

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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

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