MS Acids Bases Buffers ALL PPQ

5.1.3 Acids, Bases and Buffers PhysicsAndMathsTutor.
com
Mark scheme – Acids, Bases and Buffers
Questi Mark
Answer/Indicative content Guidance
on s
IGNORE state symbols (even if wrong)

HCOOH + CH3COOH ⇌ HCOO– + CH3COOH2+ ✓
IF proton transfer is wrong way around

A1 B2 B1 A2
ALLOW 2nd mark for idea of acid–base
OR
2 pairs, i.e.
A2 B1 B2 A1 ✓
(AO HCOOH + CH3COOH ⇌ HCOOH2+ +
1 a
1.2×2 CH3COO–
CARE:
) B2 A1 A2 B1
Both + and – charges required for products in equilibrium
NOTE For the 2nd marking point (acid–base

DO NOT AWARD the 2nd mark from an equilibrium
pairs), this is the ONLY acceptable ECF
expression that omits either charge
i.e. NO ECF from impossible chemistry
ALLOW 2SF up to calculator value of

[H+] = 10–2.72 OR 1.905 × 10–3 (mol dm–3) ✓ 2 1.905460718 x 10-3
(AO
b i
2.4×2 ALLOW use of [HA]
(= 0.204 mol dm–3) )
Mark is for working.
ALLOW ECF
FIRST CHECK THE ANSWER ON ANSWER LINE
If answer = 2.4 × 10–2 (mol dm–3) award 4 marks
ALLOW [HA] and [A–] in working
-----------------------------------------------------------------
4
(AO
3.3×3
Calculation of H+ in buffer
)
[H+] buffer = 10–4.00 OR 1 × 10–4 (mol dm–3) ✓
Calculation of CH3COOH in buffer

n(CH3COOH) OR [CH3COOH]buffer
Calculation of [CH3COO–] in buffer (in 1 dm3)
ALLOW 1.5 × 10–2 up to calculator value

ii
OR 1.5 × 10–2 (mol dm–3) ✓ 1.45248 × 10–2 (mol dm–3)
Calculation of original [CH3COO–] (in 600 cm3)

ALLOW 2.4 × 10–2 up to calculator value
= 2.4 × 10–2 (mol dm–3) ✓ 2.4208 × 10–2 (mol dm–3)
COMMON ERRORS BUT CHECK

WORKING
(AO [CH3COO–]initial = 8.7 × 10–3
3 marks
600 and 1000 inverted
3.4×1
[CH3COO–]initial = 3.6 × 10–6
) 3 marks
-------------------------------------------------- [CH3COOH] : [H+] inverted
[CH3COO ]initial = 1.3 × 10
– –6
[CH3COOH] : [H+] inverted 2 marks

ALLOW alternative approach based on Henderson– AND 600 and 1000 inverted
5.1.3 Acids, Bases and Buffers PhysicsAndMathsTutor.com
Hasselbalch equation (ALLOW –logKa for pKa) e.g. No volumes used = 3.6 x 10-2 2 marks
ALLOW –logKa for pKa
log[CH3COO–] = 4 – 4.75 – 1.09 = –1.84 ✓
[CH3COO–]buffer = 1.5 × 10–2 ✓ ------------------------------------------
[CH3COO–]initial = 2.4 × 10–2 ✓ Examiner’s Comments
This question required the candidate to

calculate the original concentration of
ethanoate ions in the buffer. Higher-attaining
students gained full credit. Most students
calculated the concentration in the buffer
solution but did not factor for the original
solution. Lower-attaining candidates often
scored the first two marking points but did
not use the buffer equation.
Total 8
ALLOW → for ⇌
ALLOW acid–base pairs labelled other way

4 round.
(AO
2.1×2
ALLOW small slip
)
If ONE charge is missing from equilibrium.

ALLOW ECF for acid–base pairs mark
For an equilibrium shown using CH3COOH instead of H2O,

IGNORE ‘more acidic’
mark acid–base pairs by ECF, i.e.
Response needs strength/dissociation
ALLOW maths explanation for final 2

marks, e.g.
2 Ka(CH3COOH) = 10–(4.76) = 1.74 × 10–5
CH3SO2OH dissociates more (than CH3COOH)
OR CH3SO2OH is a stronger acid ✓ [H+] = √(1.74 × 10–5) × 1) = 4.17 × 10–3
(AO pH = –log 4.17 × 10–3 = 2.38 ✓
3.1)
ORA in terms of CH3COOH being a weaker acid Ka(CH3SO2OH) = 10–(–1.90) = 79.4
[H+] = √(79.4) × 1) = 8.91
Student is correct pH = –log 8.91 = –0.95 ✓
AND BOTH pH calcs subsumes ‘Student is
correct’
(sulfonic acid has) lower pKa/higher Ka OR greater [H+]
ORA ✓
(AO
3.2)
Examiner’s Comments
Most candidates completed a correct

equilibrium equation and assigned the
correct acid-base pairs. A significant number
of candidates used ethanoic acid instead of
water in the equation. The examiners
allowed error carried forward in this case for
the acid-base pairs.
Candidates found it much more difficult to

explain whether the sulfonic acid had a
lower pH value. The higher-attaining
candidates answered concisely. They
usually identifying that the sulfonic acid
would have a lower pH as the pKa value was
lower (or the Ka value greater), leading to
more dissociation than ethanoic acid.
Lower-attaining candidates often produced
unfocussed and lengthy responses,
sometimes relating increased dissociation in
an acid to a higher, rather than a lower, pH.
Some candidates approached their

explanation mathematically, calculating pH
values for ethanoic acid and sulfonic acid
from their concentrations and pKa values. If
correct, this approach was fully credited.
Total 4
ALLOW ECF throughout
ONLY ALLOW pH mark by ECF if Ka AND

0.080 used and AND pH <7
Common errors (Must be to 2 DP)

One mark for pH = 5.97 (No square root):
If answer = 2.98 award 2 marks
2
(AO One mark for pH = 0.92 OR pH = 5.15
3 a --------------------------------------
2.2 (Using incorrect Ka values)
[H+] = √(Ka × [C2H5COOH])= 1.039 × 10–3 (mol dm–3) ✓
×2)
pH = –log 1.039 × 10–3 = 2.98 (Must be to 2 DP) ✓
Most candidates could calculate the pH of a

weak acid although a significant number
gave the answer as 3.0, presumably
confusing the demand for two decimal
points with two significant figures.
ALLOW 0.02 dm3 if unit given

n(C2H5COOH) = (0.0800 ×
Mark is for WORKING which could all be
1
shown as 1 step
b i (AO
AND 2.5)
ALLOW method showing 20cm3 NaOH
contains the same moles as acid
× 1000 = (= 20(.0) n(C2H5COOH) = 0.08(00) x 0.025(0) = 0.002
cm3 ) ✓ (mol)
and
n(NaOH) = 0.02(00) x 0.1 = 0.002(00) (mol)
Showing by calculation something already

known is a skill that some candidates find
challenging. Many responses included rows
of figures with ‘20 cm3’ appearing at the end.
Clarity of working is essential and in

questions such as this, candidates are
advised to include word descriptions of what
they are calculating, even if it is
abbreviations such as ‘n’ for number of
moles.
ALLOW ECF throughout

For first mark ALLOW
(Excess volume of NaOH = 25(.0) cm3)
n(OH–)excess = 0.100 ×
Common errors
------------------------------------------
If initial V(NaOH) = 45 cm3
Excess mol of NaOH:
[OH–] = 0.0643 (mol)
[H+] = 1.56 × 10–13 (mol dm–3)
n(OH–)excess = n(OH–) – n(C2H5COOH)
pH = 12.81 award three marks (no 1st mark)
4
If n(OH–)excess is used in [H+] calculation
= (0.100 × – (0.0800 ×
n(OH–)excess = 0.0025 (mol)
= 0.0045 – 0.002 = 0.0025 (mol) ✓ =4.(00) × 10–12 (mol dm–3)

ii
(AO
Concentration of OH–:
1.2
×1) pH = 11.40 award three marks (no 2nd mark)
= 0.0357 (mol dm–3) ✓ (AO
2.6 ALLOW pOH method for last two marks
×3) pOH = – log[OH–] =1.447
Concentration of H+:
pH = 14 – 1.447 = 12.55
= 2.8 × 10–13 (mol dm–3) ✓

ALLOW ECF for conversion from [H+] to pH
provided value calculated is above 7 and
from derived [H+]
Conversion to pH:
pH = (–log 2.8 × 10–13) = 12.55 ✓ Examiner’s Comments
This calculation proved difficult with once

again, many figures and sums appearing
with little indication as to their relevance.
Responses to 20bi/ii often featured rows of

figures and random sums without a single
word about what the figures were or sums
were set to calculate. Candidates should
remember to provide written indications of
what it is they’re working out – presenting
the calculations without any annotations can
make it harder for error carried forward
marks to be given if there is an error in their
calculation.
If pH curves wrong way round (i.e. adding

acid to alkali),
ONLY award mark for End point (~ 20
cm3)
This weak acid / strong alkali titration curve

required candidates to apply their
knowledge. Some candidates found it
difficult to draw an adequate titration curve.
The key points to titration curves are:
• A ‘vertical’ section at the end point

• The vertical section with pH range
correct to relative to the strength of
Shape acid/alkali
Slight rise/flat, AND (near) vertical, AND then slight rise/flat ✓ • A correct equivalence point relative
3 to pH 7 with respect to the strength
pH (AO of acid/alkali
Vertical section within the extremes of pH 5 to 12 and a 2.3 • A ‘shallow curve’ leading from 0
ii
minimum range of three pH units ×1) cm3 to vertical section
i
AND middle of vertical section (equivalence point) needs to be (AO • A ‘shallow curve’ leading from the
above pH 7 ✓ 2.4 vertical section to the total volume
×2) added
End point
Vertical section at ~ 20 cm3 NaOH ✓ For this reaction:
• The vertical section was at 20 cm3

(given in 20bi)
• As it was a weak acid and strong
alkali reacting, the vertical section
should start above pH 5 and finish
around pH 11
• The equivalence point (half-way up
the vertical section) for a weak acid
/ strong alkali titration should be
above pH 7
• The starting pH should be that of
the weak acid, C2H5COOH (answer
to 20(a))
• The final pH should be that of the
final solution (answer to 20(b)(ii))
ALLOW pH range (of the indicator) matches

equivalence point
ALLOW end point/colour change matches
equivalence point
IGNORE colour change matches end point
cresol purple
Colour change is the same as end point
AND 1
i Examiner’s Comments
pH range matches vertical section/rapid pH change (AO
v
OR 3.3)
Some candidates realised that the most
end point/colour change matches vertical section/rapid pH
suitable indicator for a weak acid / strong
change ✓
alkali titration would be cresol purple. For
incorrect responses, other indicators
appeared to be selected at random,
suggesting that candidates were unclear on
the criteria for selected a suitable indicator.
End point must not refer to same pH
ALLOW different equivalence point

similarity: end point / volume (20 cm of NaOH needed to
3) IGNORE different starting pH
neutralise
OR 2 Examiner’s Comments
final pH / shape of curve after end point ✓ (AO
v
3.2 When identifying a similarity, many
difference: HCN higher starting pH ×2) candidates confused the term ‘equivalence
OR point’ with the term ‘end point’.
HCN shorter vertical section ✓
For differences, many candidates realised
that HCN had a different Ka to C2H5COOH
but often did not appreciate that this would
lead to a starting point with a higher pH.
ALLOW use of HA
Ignore [HIO3]equilibrium < [HIO3 ]initial/undissociated
ALLOW
[HIO3]equilibrium ~ [HIO3]undissociated is no longer
a valid assumption
ALLOW
HIO3 dissociation is not negligible / dissociates to a significant [HIO3] has a larger Ka so the assumption
extent that [HIO3] at equilibrium = [HIO3] initially so
1
OR assumption is not valid
c (AO
Large Ka and HIO3 is ‘stronger’ (weak) acid
3.3)
OR Examiner’s Comments
[HIO3 ]eqm is significantly lower than [HIO3 ]initial/undissociated ✓
Very few candidates scored the mark for this
question.
The most common error was to write ‘HIO3

dissociates’. While correct, this is true of all
weak acids.
The subtlety in this question was to realise

that because Ka was relatively high, the

resultant acid strength would mean that the
degree of dissociating was significant
enough so initial [HIO3] was significantly
less than [HIO3] at equilibrium. In other
words, the assumption [HIO3]initial =
[HIO3]equilibrium is not valid in this case.
Total 14
Indicative scientific points may include:

Please refer to the marking instructions on page 4 of this (State symbols not required in equations)
mark scheme for guidance on how to mark this question.
Equilibrium and equilibrium shifts
Level 3 (5–6 mark)
Detailed explanation of equilibrium, the action of the buffer and • H2CO3(aq) ⇌ H+(aq) + HCO3–(aq)
correct calculation of [HCO3–] : [H2CO3] ratio. • Addition of H+ causes ⇌ to shift to
left
There is a well-developed line of reasoning which is clear and • Addition of OH– causes ⇌ to shift to
logically structured. The information presented is relevant and right
substantiated.
Action of buffer
Level 2 (3–4 marks)
Detailed explanation of equilibrium and the action of the buffer.
• Increase in H+ / addition of acid
OR
leads to:
Detailed explanation of equilibrium and correct calculation of
H+(aq) + HCO3–(aq) → H2CO3(aq)
[HCO3–] : [H2CO3] ratio.
OR HCO3– reacts with added acid
OR
• Increase in OH– / addition of alkali
Detailed explanation of the action of the buffer and correct
leads to:
calculation of [HCO3–] : [H2CO3] ratio. 6
H+(aq) + OH–(aq) → H2O(l)
(AO1.
OR
OR 1 ×2)
H2CO3(aq) + OH–(aq) → HCO3–
Partial explanations of equilibrium, and the action of the buffer (AO1.
(aq) + H2O(l)
4 and attempt calculation of [HCO3–] : [H2CO3] ratio. 2 ×2)
OR
(AO3.
H2CO3 reacts with added alkali
There is a line of reasoning presented with some structure. 1 ×1)
The information presented is relevant and supported by some (AO3.
Calculation of [HCO3–] : [H2CO3] ratio
evidence. 2 ×1)
• Ka = 10–6.38 OR 4.17 × 10–7 (mol

Level 1 (1–2 marks)
dm–3)
Detailed explanation of equilibrium.
• [H+] = 10–7.40 OR 3.98 x 10–8 (mol
OR
dm–3)
Correct calculation of [HCO3–] : [H2CO3] ratio.
OR • OR
Detailed explanation of the action of the buffer. • ratio = 10.47(:1) OR 10.48(:1)
OR ALLOW 10.5 OR 10(:1) (after
Partial explanations of equilibrium and the action of the buffer.’ working shown)
OR
Partial explanation of equilibrium and attempt at calculation of
[HCO3–] : [H2CO3] ratio.’
ALLOW
OR
Partial explanation of the action of the buffer and attempt at
calculation of [HCO3–] : [H2CO3] ratio.
There is an attempt at a logical structure with a line of And ratio = 10.5 OR 11 (after working
reasoning. The information is in the most part relevant. shown)
0 marks ALLOW OR
No response or no response worthy of credit.
And ratio = 1 : 0.095 ..
This Level of Response question was
generally well answered with many
candidates achieving maximum marks by
simply considering what was required in the
question.
The calculation of the [HCO3–] : [H2CO3]

ratio was well described although
sometimes the final expression of the ratio
left ambiguity as it was hard to tell whether
the ratio given referred to the [HCO3–] :
[H2CO3] ratio or the [H2CO3] : [HCO3–] ratio
The buffer reactions on separate addition of

acid (H+ ions) and alkali (OH– ions) were
explained and, better still, shown in equation
form.
The direction of shift on the H2CO3 ⇌ H+ +

HCO3– equilibrium was invariably correct,
but many candidates did not achieve credit
for responses such as ‘Addition of H+ ions
shifts the equilibrium to the left’ because
they did not give the equilibrium which was
undergoing shift.
An example of a complete answer gaining

L3 (6 marks) is given.
Exemplar 5
The candidate clearly writes the equilibrium

at the top.
The first bullet point gives a chemical

equation for the reaction occurring when H+

ions are added as well as the shift in
equilibrium.
The second bullet point gives a chemical

equation for the reaction occurring when
OH– ions are added as well as the shift in
equilibrium.
The steps in the calculation are clearly

shown and the ratio is clear.
Total 6
This part tested an understanding of pH as a

logarithmic scale and the relationship
between rates and order. This part
discriminated extremely well. A pH of 3
meant that the H+ concentration would be
100 times less than at a pH of 1. Being a
first order reaction with respect to H+, the
initial rate is simply 100 times less than at a
pH of 1: 2.4 × 10–5 mol dm–3 s–1.
Initial rate = 10–2 × 2.4 × 10–3 s–1 1

The higher-ability candidates identified the
5 AO
relationships and often wrote the correct
= 2.4 × 10–5 (mol dm–3 s–1) ✓ 2.2
answer on the answer line with no visible
working (presumably doing the calculation in
their head). Others used their well-learnt
equations to calculate the same correct
answer.
Many candidates found the calculation

difficult and 7.2 × 10–3 (3 × (2.4 × 10–3)) was
a very common incorrect answer. If
candidates had fully scrutinised this answer,
they may have realised that a more dilute
solution cannot produce a faster rate.
Total 1
ALLOW
CO32– + 2H2O → 2OH– + H2CO3
IGNORE state symbols
ALLOW inclusion of Na+ as spectator ion,

CO32– + H2O → OH– + HCO3– 1
e.g.
6 a OR AO
2Na+ + CO32– + H2O → 2OH– + 2Na+ + CO2
CO32– + H2O → 2OH– + CO2 ✓ 1.2
IGNORE
Na2CO3 + H2O → 2NaOH + CO2
Ionic equation required
IGNORE equation with H+ or H3O+

e.g. CO32– + H+ → OH– + CO2

Question asks for reaction with H2O
This equation presented problems for many

candidates, despite the question asking for
an equation between carbonate ions and
water. An acceptable equation had to be
ionic and needed to produce OH– (for the
alkaline solution) and either HCO3– or CO2.
Many candidates wrote an equation with H+

instead of H2O, with lower ability candidates
showing the carbonate ion with the wrong
charge as CO3–.
Many candidates wrote full equations

despite the question asking for an ionic
equation. Candidates do need to read the
instructions in the question.
ALLOW suitable equation, e.g.

C6H5COO– + H+ → C6H5COOH
IGNORE responses purely in terms of

neutralisation of alkali, e.g. Acid/H+/HCl
neutralises / reacts with/removes alkali /
OH– / CO32– / Na2CO3
Acid/H+/HCl reacts with OR protonates
Candidates found this part extremely

• benzoate / C6H5COO–
1 difficult. The question was aimed to stretch
• carboxylate / salt
b AO and challenge.
2.3
Many candidates followed on directly from
part (a), stating in simple terms that the
(to form benzoic acid) ✓
alkaline solution needed to be neutralised to
remove hydroxide ions. However,
candidates were expected to recognise that
the alkaline conditions would lead to
benzoate ions rather than benzoic acid
being present in the mixture. The mixture is
acidified to protonate the benzoate. The hint
in the question was about making the
benzoic acid appearing when acid is added.
ALLOW molecular, structural, displayed

formulae, etc
e.g. molecular:
1
C7H8O + 2[O] → C7H6O2 + H2O
c C6H5CH2OH + 2[O] → C6H5COOH + H2O ✓ AO
2.6
This part discriminated well with many

candidates being able to write a correct

equation using their knowledge of the
oxidation of alcohols. Mistakes usually
resulted in the balancing with either [O]
instead of 2[O] or 2H2O instead of H2O.
Written equations always need to be

checked for the atoms balancing.
ALLOW ECF for each step
Calculator = 0.03851851852
Calculator = 0.01303278689
------------------------------------------------
Alternative method using mass

1. Theoretical moles = 0.0385 mol
If answer = 33.8 OR 33.9 (%) award 3 marks 2. Mass = 0.0385 × 122.0 = 4.70 g
-----------------------------------------------
Theoretical moles
n(C6H5COOH) OR n(C6H5CH2OH) 3.
3
OR 0.0385….. (mol) ✓
----------------------------------------------
Common errors
Actual moles AO2. 35.2% → 2 marks
8×1
d
n(C6H5COOH) OR 0.013(0)…. AO2.
•
8×1
(mol) ✓
(no use of density)

AO1.
= 33.8% OR 33.9 2 36.5 OR 36.6% → 2 marks
(3 sig fig) ✓
Answer depends on some intermediate roundings to 3SF
(÷ density instead of × density)
Candidates are well practised with

percentage yield calculations with about half
obtaining the correct percentage yield of
33.8 or 33.9% to secure all 3 marks. Many
were able to secure partial credit for
incorrect answers, provided that the working
was laid out clearly.
Some responses showed a simple

percentage of the two masses with no
consideration of moles or molar masses.
Such a response received no credit.
ALLOW any solvent
DO NOT ALLOW use of drying agent (e.g.

MgSO4)
IGNORE
• Initial filtering
• hot filtration to remove insoluble
impurities
Dissolve in the minimum quantity of hot water/solvent ✓
Many candidates produced thorough
responses, showing that they had
Cool 2 encountered recrystallisation as a technique
e AND AO in their practical work.
Filter 3.3 x2
AND Most candidates were aware that the impure
(leave to) dry ✓ product is dissolved in a minimum volume of
All three needed hot solvent, although ‘minimum’ was
sometimes omitted.
The subsequent stages were sometimes

incomplete or in the wrong order. Many
were aware that the hot solution can be
passed through fluted filter paper to remove
solid impurities. (This is beyond the
specification requirements for A Level but
good practice).
Most candidates were aware of the need to

filter (usually under reduced pressure) but
the necessary cooling stage to form the
crystals was sometimes omitted.
Finally, many responses omitted the need to

dry the crystals. Candidates did sometimes
dry the crystals by adding an anhydrous salt
(e.g. CaCl2 or MgSO4), a clear confusion
with drying an organic liquid. Others
described the purification of an organic

liquid for their response, including use of a
separating funnel, drying and distillation.
Total 8
ALLOW 3-hydroxybutan-1-al
IGNORE lack of hyphens or addition of

commas
ALLOW 4-oxobutan-2-ol OR 1-oxobutan-3-

ol
DO NOT ALLOW
• 3-hydroxybutal
• 3-hydroxylbutanal
7 i 3-hydroxybutanal ✓ 1
Most candidates made good attempts at the

name, the difficulty being that hydroxyl
group needed to be shown as a hydroxy-
prefix, rather than the suffix -ol.
Common errors included 2-hydroxybutanal

(counting the carbon chain from the wrong
end) and 2- or 3-hydroxybutanoic acid
(reading the aldehyde group as a carboxylic
acid).
IGNORE nucleophilic OR electrophilic OR

radical
DO NOT ALLOW addition–elimination,

condensation, polymerisation
ii Addition ✓ 1
This part was answered well with most

choosing nucleophilic addition. Credit was
given just for ‘addition’.
Throughout, IGNORE ‘connectivity in any

ALLOW any formula provided that number and type of atoms
formula or structures shown.
and charge are correct,
Examples in Answer column and in 6a(iv)
e.g. For CH3CHO, ALLOW CH3COH, C2H4O, etc.
guidance below
_________________________________
______________________________
Step 1:
ii
3
i Step 1: ALLOW H+ transfer from OH−,
• Correct equation ✓
i.e.
One correct acid–base pair ✓
• i.e. A1 and B1 OR A2 and B2
CH3CHO + OH− ⇌ CH3CH2O+ + O2−
✓
CH3CHO + OH− ⇌ −CH2CHO + H2O

CH3CHO + OH− ⇌ CH3CO− + H2O ✓ B1
OR B2 A1 A2
B2
OR B1 A2 A1
A2
A1 B2 B1
Step 2:
A1
OR A2 B1 B2
CH3CHO + CH3CH2O+ + O2−
Step 2: → CH3CHOHCH2CHO + OH− ✓
CH3CHO + −CH2CHO + H2O →
For CH3CH2O+: ALLOW CH3CHOH+,
CH3CHOHCH2CHO + OH− ✓
C2H5O+
For −CH2CHO: ALLOW CH2CHO−; CH3CO−; C2H3O−

For CH3CHOHCH2CHO, ALLOW C4H8O2

This novel question linked together acid–
base equilibria with a multi-step process.
Many candidates completed an equation to
generate acid–base pairs, which were then
usually assigned correctly. The final
equation was challenging but the highest
ability candidates were able to combine
together all the information with their earlier
responses to arrive at the correct equation.
See Exemplar 15.
Exemplar 15
ALLOW correct structural OR displayed

OR skeletal formulae
OR a combination of above as long as
unambiguous
For connectivity,
ALLO
W
i
1
v (Connectivity not being assessed)
This part was one of the most challenging

on the paper.
Candidates needed to link the earlier

information for combining two ethanal
molecules to derive the product for
combining two propanone molecules.
Despite the challenge, the highest ability
candidates were able to come up with the

correct structure.
Total 6
Must be square brackets
IGNORE expressions with HA or with [H+]2
8 a i 1
Almost universally known.
Common errors were the use of [HA], [A−] or

[H+]2.
ALLOW use of HA and A−
ALLOW 3 SF up to calculator value of:

FIRST, CHECK ANSWER ON ANSWER LINE
3.89045145 × 10−3 correctly rounded
IF answer = 4.76 award 3 marks
--------------------------------------------------------
Ka 1.739725573 × 10−3
[H+] = 10−pH
NOTE: 1.74 × 10−5 is same from unrounded
[H+] calculator value and 3 SF [H+] value
= 10−2.41 = 3.89 × 10−3 (mol dm−3) ✓
ii 3
Ka
2 DP required
= 1.74 × 10−5 (mol dm−3) ✓
pKa
This three-step calculation was successfully
= −log Ka = −log 1.74 × 10−5 = 4.76 ✓
completed by almost all candidates.
The common errors were to omit giving the

final answer to 2 decimal places or to use
[H+] rather than [H+]2 in the calculation,
leading to a pKa of 2.35.
3 SF required
This proved a more difficult calculation than

ii
1 expected, but higher ability candidates
i
realised that [H+] (determined from the pH)
divided by the given concentration of
CH3COOH was required. Answers had to be
expressed to three significant figures in
order to receive credit.
FIRST, CHECK ANSWER ON ANSWER LINE

b 2
IF answer = 95.9(%) award 4 marks
-------------------------------------------------------- ALLOW ECF throughout

[H+] = 10−pH
IGNORE rounding errors beyond 3rd SF
= 10−13.48 = 3.31 × 10−14 (mol dm−3) ✓ throughout
ALLOW 3.3 × 10−14 (mol dm−3)
[OH−] from Kw ALLOW 0.30

ALLOW 0.303 if 3.3 × 10−14 used in the first
marking point
ALLOW pOH method:,
pOH = 14 − 13.48 = 0.52

Mass of (NaOH)
[OH−] = 10−0.52 = 0.302 (mol dm−3)
% of NaOH to 3 SF ALLOW [OH−] × 0.1 × 40
Rounding [OH−] to 0.3(0) gives 1.2/1.26 =

95.2%
Award 4 marks
Rounding [OH−] to 0.303 gives 1.212/1.26 =
96.2%
Award 4 marks
To help candidates, on this occasion early

rounding was ignored and consequently
most candidates scored full marks in this
multi-step calculation. However, candidates
should be advised not to round in the early
stages of calculations such as this, as this
introduces rounding errors into the final
answer.
Candidates should be encouraged to

indicate what they are attempting to
calculate in unstructured calculations such
as this.
The first step was frequently seen as 10−13.48

= 3.31… × 10−14 which most examiners
could take to be [H+]. However, it is clearer
to write [H+] = 10−13.48 = 3.31… × 10−14 mol
dm−3. Even inclusion of units would help
some candidates achieve partial credit as
this might allow examiners to determine
what a candidate is attempting to do.
Total 9
FIRST, CHECK THE ANSWER ON ANSWER LINE

9 a 3
IF answer = 0.753, award 3 marks
..............................................................
[H+] m= 10−pH = 10−2.440 = 3.63 × 10−3 ALLOW use of HA and A−
(mol dm−3) ✓ ALLOW 3 SF up to calculator value of
NOTE: Answer is same from unrounded [H+]

= 0.753 (mol dm−3) ✓
calculator value and 3 SF [H+] value
ALLOW 0.749 if [H+] has been subtracted

from [CH3COOH] for greater accuracy at
end
Most candidates coped with this commonly
seen type of calculation and were able to
correctly calculate the concentration of the
weak acid
Watch for opposite order on RHS, i.e.:
FCH2COO− + CH3COOH2+
Take great care matching labels
ALLOW ECF for incorrect proton transfer as

below. This is the ONLY ECF
CH3COOH + FCH2COOH ⇌CH3COO−

+ FCH2COOH2+ ×
CH3COOH + FCH2COOH ⇌ CH3COOH2+

+ FCH2COO− ✓ A1 B2 B1 A2
OR
b 2
B2 A1 A2 B1 A2 B1 B2 A1 ✓ECF
OR
i.e. labels other way round
B1 A2 A1 B2 ✓
i.e. labels other way round Examiner’s Comments

For the able candidate, this question was
quite straightforward but for the weaker
candidate, there were many pitfalls.
Candidates struggled with the idea that the
equilibrium needed a positive ion and a
negative ion on the product side. Others
were unable to use Ka values in order to
decide which of the two starting acids
should become protonated. Finally, the
assigning of the conjugate acid-base pairs
was also challenging.
ALLOW 2 sig fig

ALLOW use of HA and A−
Mark by ECF
.....................................................
[CH3COO-]
.........
Alternative method
(If both methods are attempted, mark the
method which produces the higher mark)
[H+]
[H+] = 10−pH = 10−4.50
= 3.16 × 10−5 (mol dm−3) ✓
[CH3COO−]
mass of CH3COONa
c i 5
(must come from calculated [H+])
pH
pH = −log (3.16 × 10−5) = 4.50 ✓
..............................................................
LAST 3 marks are NOT available using .....................................................
.........
• Ka square root approach (weak acid pH)
• Kw/10−14 approach (strong base pH)
Common errors
.............................................................. 4.64 Use of M(CH3COONa) = 60 4 marks

Henderson-Hasselbalch (HH) alternative 2.40 Use of Ka of FCH2COOH 4 marks
pKa = −log 1.75 × 10−5 = 4.757 (or 4.756961951..)
This question caused difficulty for all but the
more able. For many weaker candidates
getting beyond a concentration of
CH3COONa was a problem. Once again,
candidates should be advised to show every
step in their calculation. This would allow
method marks to be applied in the absence
of a correct final answer.
M2 is dependent upon M1
pH is the same/constant ✓ ALLOW Change in [HA] and [A−] is

ii 2 proportional
ratio/proportion [HA]/[A−] is the same ✓
Only the very able were able to explain that

the ratio of concentrations of acid and salt
would remain constant and as Ka is
constant, [H+] and therefore pH would
remain constant.
Total 12
ALLOW correct structural OR skeletal OR

displayed formula OR mixture of the above
as long as non- ambiguous
Examiner’s Comment:
1 This part was very well answered.
i 1
0 Square brackets required Candidates responded with either near
molecular formulae, such as C4H9SH,
structural formulae or with skeletal formulae.
Some candidates made careless errors
such as omitting the negative charge or
showing [H+]2 as numerator rather than
[C4H9S–] [H+].
ALLOW correct skeletal OR displayed

formula OR mixture of the above as long as
non-ambiguous
ALLOW C4H9SH
ALLOW CH3COOH
Thioester functional group must be fully

displayed, OR as a skeletal formula
but allow SC4H9 in thioester
ii 2
In this part, candidates were expected to
apply their knowledge and understanding of
Structure of thioester ✓ esterification to thiols and thioesters. Over
half the candidates obtained a correct
Complete equation ✓ structure of the thioester. Most of these
candidates constructed a balanced equation
although some omitted the water product.
Common errors included formation of a
conventional ester and H2S, and retaining
the O atom from the OH in the carboxyl
group to form –COOS–. As with 4(b)(i),
structural and skeletal formulae were used.
Candidates are less likely to omit H atoms if
the skeletal formula is used.
IF correct skeletal formula is shown,

ii
The image part with relationship ID rId54 was not found in the file.
1 IGNORE displayed formula in a second

i
structure
Just over half the candidates drew the
correct structure, displaying a good
understanding of interpreting organic
nomenclature when drawing a structure.
Common errors included omission of the

CH2 adjacent to the terminal –SH group and
placing the branch or double bond in wrong
positions. Some candidates spoilt an
otherwise good response by showing a
structural formula or a mixture of skeletal
and structural formulae.
ALLOW correct structural OR skeletal

OR displayed formula OR mixture of the
above as long as non- ambiguous
In this part, candidates were expected to
i apply their knowledge and understanding of
2
v Reactants ✓ condensation to an entirely new context.
One mark was allocated for the reactants
Products AND balanced equation ✓ and this was usually scored. The second
mark for the novel cyclic compound and
water was much more difficult, aimed at
stretch and challenge. A significant number
of candidates interpreted the information to
obtain a correct cyclic structure but this
mark was the domain of the most able
candidates.
Total 6
Complete dissociation would give [H+] = 0.2 (mol dm −3) ✓
pH from complete dissociation = −log 0.2 = 0.7

1 OR actual [H+] = 10−0.96 = 0.11 (mol dm−3)✓
i 3
1
Stage 1 is complete dissociation
AND
Stage 2 is partial dissociation ✓
IGNORE Stage 1 is a strong acid
AND Stage 2 is a weak acid.
Observation: fizzing ✓
ii H+ reacts with carbonate 2 ALLOW effervescence/‘bubbling’

AND
(Stage 2) equilibrium shifts to the right ✓
Total 5
✓ ALLOW [H3O+] for [H+]
1 ALL species MUST have square brackets State symbols not IGNORE state symbols, even if wrong
a i 1
2 required
TAKE CARE that ‘H’ is different on top and bottom of
IGNORE
expression
ii pKa = −log Ka = −log (6.76 × 10−5) = 4.17 ✓ 1 Answer required to two DP

...........................................................
n(vitamin C)
= 8.52(2) × 10−3 (mol) ✓ ALLOW ECF from incorrect n(vitamin C)
ii [vitamin C]
4
i
= 0.0341 (mol dm−3) ✓
[H+] = √(Ka × [C6H8O6]) OR

√(6.76 × 10−5 × 0.0341) OR
1.52 × 10−3 mol dm−3 ✓ ALLOW ECF from incorrect [vitamin C]
must be derived from √(Ka × [C6H8O6])
pH = −log(1.52 × 10−3) = 2.82 ✓
Answer required to two DP ALLOW ECF from incorrect [H+]
but ONLY if derived from √(Ka × [C6H8O6])
IF there is an alternative answer, check to

see if there is any ECF credit possible using
working below
FIRST, CHECK THE ANSWER ON ANSWER LINE .....................................................
IF ratio = 0.708 award 3 marks ......
........................................................... ANNOTATIONS MUST BE USED
ALLOW ALTERNATIVE using
[H+] = 10−pH = 10−4.02 = 9.55 × 10−5 (mol dm−3) ✓ Henderson−Hasselbalch equation
.....................................................
......
ALLOW 9.55 × 10−5 up to calculator value
b i 3 of 9.54992586 × 10−5 correctly rounded
ALLOW ECF from incorrect [H+]
= ✓
ALLOW 0.71 (2 SF) up to calculator value

correctly rounded
mass of C6H7O6Na =
ii 1 ALLOW ECF from answer to (i)
= 239 OR 240 (mg) ✓
ALLOW alternative approach via pOH

FIRST, CHECK THE ANSWER ON ANSWER LINE pOH = 14 − 12.72 = 1.28 ✓
IF answer = 0.0524 (mol dm−3) award 2 marks [NaOH] / [OH−(aq)] = 10−pOH
........................................................... = 0.0524 (mol dm−3) ✓
[H+(aq)] = 10−pH = 10−12.72
c = 1.91/1.9 × 10−13 (mol dm−3) ✓ 2
[NaOH] / [OH−(aq)] = ALLOW any value between 0.052 and

0.053 answer depends on degree of
= 0.0524 (mol dm−3) ✓ rounding for H+ but 2 SF minimum
calculator: 0.052480746
Total 12
ALLOW H3O+ for H+
Square brackets required
1 Examiner's Comments
a 1
3
IGNORE state symbols Almost all candidates successfully wrote the
expression for Ka. Responses using
[H+(aq)]2 were not credited. Rarely, the
expression was shown inverted or square
brackets were omitted from one or more of
the terms. For most candidates, this was an
easy mark.

...............................................
ALLOW intermediate value from 3 SF (7.50
up to calculator value of 7.501999733 × 10−3
...............................................
ALLOW 1 mark for 2.1 OR answer > 2 DP
b 2 (i.e. not 2 DP)
ONLY ALLOW pH mark by ECF if Ka AND

0.120 used and AND pH < 7
pH = −log 7.502 × 10−3 = 2.12 ✔
...............................................
pH to 2 DP
COMMON ERRORS (MUST be to 2 DP)
pH = 4.25 No square root:1 mark

[H+] = (4.69 × 10−4 × 0.120) = 5.628 × 10−5
(mol dm−3)
pH = −log 5.628 × 10−5 = 4.25 ✔

pH = 0.92 no Ka used:
zero marks
pH = −log 0.120 = 0.92
pH = 13.08 Kw / pOH used:

zero marks
Examiner's Comments
Most candidates calculated [H+] as the

square root of Ka × [HNO2], and then the
correct pH value. The commonest errors
were incorrect rounding of the pH value (e.g.
2.13) and missing out the square root
(giving 4.25).
Answer: pH = 2.12
FULL ANNOTATIONS MUST BE USED

...............................................

IF answer = 3.43, AWARD 4 marks ALLOW just
...............................................
expression
Expression: Ka × acid / base ratio
Using correct concs / mol in expression Mark by ECF from

inverted expression
Calculation of [H+]
[H+] = 3.752 × 10−4 (mol dm−3) ✔ Mark by ECF from incorrect [HNO2] and
[NO2−]
pH to 2 DP (From 3.42573717) ONLY award marks for a pH calculation via
c i 4
pH = −log 3.752 × 10−4 = 3.43 ✔ Ka AND using concentrations / mol derived
from the question
NO marks are available using
Ka square root approach (weak acid pH) DO NOT ALLOW final pH mark by ECF if
Kw/10−14 approach (strong base pH) pH > 7
............................................... ...............................................
ALLOW alternative approach based on Henderson– COMMON ERRORS BUT CHECK
Hasselbalch equation (ALLOW −logKa for pKa) WORKING
pH = 2.82 3 marks
initial concs: 0.200 and 0.0625
pH = 3.23 3 marks
0.0400 and 0.0500 acid / base ratio inverted
pH = 3.83 2 marks
pH = 3.329 + 0.097 = 3.43 ✔
initial concs: 0.200 and 0.0625 and ratio
inverted
pH = 2.73 3 marks
Incorrect [NO2−] = 0.01 and correct [HNO2] =
0.04
pH = 4.03 3 marks
correct [NO2−] = 0.05 and incorrect [HNO2] =
0.01
Examiner's Comments
This buffer calculation was easier than some

on recent papers as the equilibrium moles
had been provided. Some candidates tried
to mimic the approach for a more complex
calculation, introducing errors where there
were none.
The simpler problem allowed more

candidates to obtain the correct value for the
pH of the buffer solution than in recent
examinations.
Answer: pH = 3.43

...............................................
IGNORE HA ⇌ H+ + A−
Equilibrium sign essential

Equilibrium: 1 mark BUT ALLOW small slips in its appearance if
HNO2 ⇌ H+ + NO2− ✔ it is obviously an attempt to show an
(ignore state symbols) equilibrium sign rather than an arrow
QWC: Quality of written communication
DO NOT ALLOW HA and A− for HNO2 and

NO2−
Control of pH: 2 marks (QWC) IGNORE just acid reacts with added alkali
Added HCl
NO2− reacts with added acid / HCl / H+ IGNORE just conjugate base / salt / base
OR NO2− + H+ → reacts with added acid
ii 4
OR more HNO2 forms ✔ DO NOT ALLOW salt / base reacts with
added acid
Added NaOH
HNO2 reacts with added alkali / NaOH / OH−
OR HNO2 + OH− →
OR more NO2− forms
OR H+ reacts with added alkali / NaOH AWARD ‘shift mark’ ONLY if correct
OR H+ + OH− → ✔ equilibrium equation has been given
IGNORE any other equilibria in response
Equilibrium shift:
1 mark for shifts in HNO2 ⇌ H+ + NO2− (See 1st mark) Examiner's Comments
Equilibrium for added acid → left
AND Equilibrium for added alkali → right ✔ (QWC) The role of buffers in controlling pH is a
common question and most candidates had
prepared their rehearsed answers.
Consequently these candidates could obtain
the four marks easily. As always, candidates
who had not learnt the work produced
muddled responses that made little sense

and could not be credited.
Endothermic and reason required for the

mark
ALLOW Endothermic AND increasing

temperature shifts equilibrium / reaction to
the right / favours forward reaction
Endothermic AND Kw increases with temperature

DO NOT ALLOW breaking hydrogen bonds
OR
OR intermolecular bonds / forces
d i Endothermic AND dissociation increases with temperature 1
OR
Examiner's Comments
Endothermic AND (dissociation) involves breaking bonds ✔
Candidates were expected to predict the

type of energy change using the provided
information. Credit was given for responses
linking an endothermic change with the
increase of Kw with temperature or breaking
bonds during dissociation.
H+ OR OH− concentration (neutral pH)

[H+] = [OH−] = √(9.311 × 10−14) = 3.05 × 10−7
(mol dm−3) ✔
Explanation (dependent on 1st mark)

pH = −log (3.05 × 10−7) = 6.5 →
OH− concentration 6.515501837 (calc)
AND
Alkaline ✔
ii Explanation (dependent on 1st mark) 2 Examiner's Comments

9.311 × 10−7 > 1.(00) × 10−7 OR [OH−] > [H+] OR OH− in
excess Most candidates calculated a value for [H+]
AND using the Kw value at 60°C. Many
Alkaline ✔ recognised that [OH−] > [H+] giving an
alkaline solution. An alternative and equally
valid method seen was to calculate the pH
of a neutral solution at 60°C as 6.52 and
then to relate water at a pH of 7 as being
alkaline. Many using this approach thought
that water would be acidic rather than
alkaline, presumable because 6.52 < 7.00.
ONLY correct answer
Examiner's Comments
ii
pKw = 13.03 ✔ 1
i
Despite the novel context, almost all
candidates obtained the correct pKw value of
13.03.
FIRST, CHECK THE ANSWER ON ANSWER LINE FULL ANNOTATIONS MUST BE USED
i
IF answer = 10.76, award 3 marks 3 ...............................................
v
...............................................
Dilution 1 mark ALLOW dilution AFTER calculation of

[H+(aq)]
[H+] 1 mark After dilution, [H+] = 3.45 × 10−12 × 5 = 1.72

× 10−11 (mol dm−3) ✔
pH = −log 1.72 × 10−11 = 10.76 ✔
Calculator: 1.724259259 × 10−11 ALLOW ECF from incorrect [H+(aq)]
pH 1 mark provided that pH > 7
pH = −log 1.72 × 10−11 = 10.76 ✔ ...............................................
............................................... COMMON ERRORS (MUST be to 2 DP)
ALLOW pOH method for 2nd and 3rd mark: pH = 11.73 At 25°C (1.00 × 10−14): 2
marks
pOH = −log 0.00540 = 2.27 ✔ (calculator 2.26760624) pH = −log 1.85 × 10−12 = 11.73
pH = 13.03 − 2.27 = 10.76 ✔ pH = 11.46 No dilution at 60°C (9.311 ×

10−14) 2 marks
pH = −log(3.45 × 10−12) = 11.46
pH = 12.43 No dilution AND 25°C (1.00 ×

10−14) 1 mark
pH = −log(3.70 × 10−13) = 12.43
pH = 12.16 × 5 instead of ÷ 5 at 60°C (9.311

× 10−14) 2 marks
pH = −log(6.879 × 10−13) = 12.16
pH = 13.13 × 5 instead of ÷ 5 at 25°C (1.00

× 10−14) 1 mark
pH = −log(7.407 × 10−14) = 13.13
NOTE: Attempts at dilution → 0.0270 with

error in powers of 10 → 12.46 from 0.00270,
etc may give 2 marks by ECF
Examiner's Comments
The majority of candidates correctly

calculated the pH via Kw but many had
problems in initially deriving the
concentration of the diluted solution of
NaOH. Some candidates did not consider
the dilution at all; others produced long
calculations of this simple dilution, obtaining
an array of concentrations. Provided that
this concentration was then converted to a
pH by a correct method, credit could still be
given for the second part of the problem.
Answer: pH = 10.76
Total 18
State symbols NOT required

1 ALLOW CNH and HO− (i.e. any order)
i 1
4
ALLOW 1 and 2 labels the other way
around.
ALLOW ‘just acid’ and ‘base’ labels
throughout if linked by lines so that it is
clear what the acid-base pairs are.
Examiner's Comments
The majority of candidates were able to

complete the equation for acid–base
equilibrium and to identify the acid–base
pairs. Candidates are advised to use
numbers to label the acid–base pairs, such
as ‘acid 1’ and ‘base 1’. Attempts at using
‘acid’ and ‘conjugate base’ are ambiguous
when more than one acid–base pair is
involved. Although credited, it was strange
to see hydrogen cyanide often written as
CNH.
ALLOW Acid reacts with / removes OH−

ions (to form HCN)
ALLOW CNH (i.e. any order)
H+ reacts with CN− OR HCN forms
IGNORE other equilibrium comments

ii OR equation: H+ + CN− → HCN (ALLOW ⇌) 1
OR CN− accepts a proton / H+
Examiner's Comments
OR equilibrium shifts right AND CN− is removed ✔
The majority of candidates recognised that

acid conditions would lead to protonation of
CN−forming toxic HCN.
Total 2
Examiner's Comments
Proton / H+ donor
1
a AND 1
5 For most candidates, this was an easy
Partially dissociates / ionises ✔
mark, although some only responded for a
weak acid (partial dissociation) or for a
Brønsted–Lowry acid (proton donor).

IF answer = 13.7(0), award 2 marks
b
...........................................................
For pOH method:,

ALLOW pOH = −log[OH−] = 0.3(0) ✔
(calculator 0.301029995)
ALLOW pH = 14 − 0.3 = 13.7 ✔
pH = −log 2(.00) × 10−14 = 13.7(0) ✔ 2

ALLOW 13.7 up to calculator value of
13.69897 correctly rounded.
ALLOW ECF from incorrect [H+(aq)]

provided that pH > 7
Examiner's Comments

calculated the pH via Kw. Another less
popular but successful approach was via
pOH. Either approach could result in both
marks. Weaker candidates sometimes
calculated the pH as 0.30 (from −log 0.500).
This gained no credit.
Answer: pH = 13.70
ALLOW [H3O+] for [H+]
Examiner's Comments
c i 1 Almost all candidates successfully wrote the

expression for Ka. Responses using
[H+(aq)]2 were not credited. Rarely, the
expression was shown inverted or square
brackets were omitted from one or more of
the terms. Candidates are recommended to
carefully check the formulae as this easy
mark was sometimes not awarded for a
missing C atom within a formula (even in the
scripts of able candidates).

...........................................................
ALLOW HA for C2H5COOH and A− for
ii [C2H5COOH] = 0.12(0) mol dm−3 ✔
C2H5COO−
ALLOW ECF from incorrectly calculated
[C2H5COOH]
OR 1.27 × 10−3 (mol dm−3) ✔
ALLOW 1.27 × 10−3 to calculator value of
ALLOW 2.9(0) × 10−3 to calculator value of

pH = −log 1.27 × 10 −3 = 2.9(0) ✔ 2.895242493 correctly rounded
ii 3
NOTE: The final two marks are ONLY available from ALLOW use of quadratic equation which
attempted use of Ka AND [C2H5COOH] gives same answer of 2.90 from 0.120 mol
dm−3
....................................................
.......
COMMON ERRORS (MUST be to AT

LEAST 2 DP unless 2nd decimal place is
0)
pH = 2.59 2 marks
−log√(1.35 × 10−5 × 0.480) Original conc
pH = 5.79 2 marks
−log(1.35 × 10−5 × 0.120) No √
pH = 5.19 1 mark
−log (1.35 × 10−5 × 0.480) Original conc,
no √
pH = 4.87 0 marks
−log(1.35 × 10−5) = 4.87 −log Ka
Examiner's Comments
This part discriminated extremely well. The

added stage of an initial dilution to a stock
weak acid pH calculation created problems
for many candidates. Although most were
able to use the correct square root
expression to obtain a value for [H+(aq)], the
concentration used was often incorrect.
Although just a four times dilution from
0.480 mol dm−3 to 0.120 mol dm−3, many
candidates obtained 0.120 using learnt
equations rather than the simple ratio.
Others used the original concentration of
0.480 mol dm−3 or incorrectly calculated
concentrations, commonly seen as 0.0480,
0.0120 or even 0.192 (from × 4). Some
candidates calculated [H+(aq)] using 0.480
mol dm−3 but then divided by 4 before
calculating the pH. Able candidates
invariably obtained the correct pH but many
obtained pH values from the values above
such as a pH of 2.59 (from 0.480 mol dm−3),
for which partial credit could be awarded.
Answer: pH = 2.90
ONLY correct answer

DO NOT ALLOW 4.9 (Question asks for 2
DP)
Examiner's Comments
d i pH = −log 1.35 × 10−5 = 4.87 ✔ 1
Some candidates correctly calculated the

pH here as −log Ka but most used the
standard buffer pH method, using a 1:1
acid–base ratio. Weak candidates often first
took the square root of the Ka value,

obtaining a pH of 2.43. Unfortunately, some
candidates rounded a correct pH to 4.9,
despite a two decimal place requirement
being emphasised in the question.
Answer: pH = 4.87
Added ammonia
C2H5COOH removes added NH3 / alkali / base
ALLOW use of HA / weak acid / acid for
OR C2H5COOH + NH3 / OH− →
ii C2H5COOH;
OR NH3 / alkali reacts with / accepts H+
OR H+ + NH3 →
OR H+ + OH− → ✔
ALLOW use of NH4OH for NH3
ALLOW A− for C2H5COO−
ASSUME that equilibrium applies to that

supplied in the question, i.e. IGNORE any
other equilibria
Examiner's Comments
The role of buffers in controlling pH is a

ii Equlibrium → C2H5COO− OR Equilibrium → right ✔ 2 common recall question and most
candidates had prepared their rehearsed
answers. Although this question asked for
the addition of ammonia as a specific base,
all but the weakest candidates identified that
this was a question about addition of a base.
The commonest and best answers stated
that NH3 accepts a proton to form NH4+ (with
many ionic equations seen). The correct
equilibrium shift was usually included.
CHECK WORKING CAREFULLY AS CORRECT

NUMERICAL ANSWER IS POSSIBLE FROM WRONG FULL ANNOTATIONS MUST BE USED
VALUES
........................................................... .....................................................
ALLOW HA and A− throughout ......
Amount of Mg (1 mark) For n(Mg), 1 mark
ALLOW ECF for ALL marks below from
incorrect n(Mg)
...........................................................
ECF ONLY available from concentrations
ii Moles / concentrations (2 marks)
4 that have
i
n(C2H5COOH) = 1.00 − (2 × 0.25) = 0.50 (mol) ✔
n(C2H5COO−) = 1.00 + (2 × 0.25) = 1.50 (mol) ✔ • subtracted 0.50 OR 0.25 from 1 for
[C2H5COOH]
........................................................... • added 0.50 OR 0.25 to 1 for
[C2H5COO−]
[H and pH
+] (1 mark)
i.e.
For moles / concentration 1 mark (1 mark
pH = −log 4.5 × 10−6 = 5.35 2 dp required ✔ lost)
NOTE: IF there is no prior working,

1. n(C2H5COOH) = 0.75 AND
n(C2H5COO−) = 1.25
2. n(C2H5COOH) = 0.50 AND
IF the ONLY response is pH = 5.35, award 1 mark ONLY n(C2H5COO−) = 1.25
........................................................... 3. n(C2H5COOH) = 0.75 AND
Award a maximum of 1 mark (for n(Mg) = 0.25 mol) for: n(C2H5COO−) = 1.50
pH value from Ka square root approach (weak acid pH)
pH value from Kw / 10−14 approach (strong base pH) .....................................................
......
........................................................... ALLOW ECF ONLY for the following giving
ALLOW alternative approach based on 1 additional mark and a total of 3 marks
Henderson−Hasselbalch equation for final 1 mark
1.
2.
3.
Examiner's Comments
This buffer calculation was aimed as stretch

and challenge and the majority of
candidates struggled to derive the
concentrations of CH3CH2COOH and
CH3CH2COO−. An easy mark for the amount
of magnesium added was available for
almost all candidates. The problem was
then to derive the amount and concentration
of CH3CH2COOH that would be obtained
0.500 mol−3. Many did not identify that Mg
and CH3CH2COOH react in a 1:2 molar
ratio, subtracting 0.25, instead of 0.50, from
the original concentration. Rarely did
candidates realise that the CH3CH2COO−
concentration would increase from the initial
concentration of 1 mol dm−3. Others
assumed that no CH3CH2COO− was present
at the start. Consequently, candidates often
used a variety of acid–base ratios in their
buffer calculation. Instead of the correct ratio
of 0.5/1.5, it was very common to see
0.75/1.25, 0.75/0.25, and especially 0.5/1,
0.75/1 and 0.25/1.0.
The very best candidates tackled the

problem with apparent ease but this was
seen comparatively rarely in scripts of other
candidates.
Answer: pH = 5.35
Total 14
1 CH3COOH + H2O ⇌ H3O+ + CH3COO− ✔ IGNORE state symbols (even if incorrect)

a 2
6 Acid 1 Base 2 Acid 2 Base 1 ✔
ALLOW 1 AND 2 labels the other way

around.
ALLOW ‘just acid’ and ‘base’ labels if linked
by lines so that it is clear what the acid—
base pairs are
ALLOW A and B for ‘acid’ and ‘base’

ALLOW 2nd mark for idea of acid—base
pairs, i.e.
CH3COOH + H2O ⇌ CH3COOH2+

+ OH− ✗
Base 2 Acid 1 Acid 2 Base 1 ✔
NOTE For the 2nd marking point (acid—

base pairs),
this is the ONLY acceptable ECF
i.e., NO ECF from impossible chemistry
Examiner's Comments
Most candidates showed an acid-base

equilibrium involving proton transfer and
then identified the acid-base pairs. The acid-
base pairs were usually correctly identified
but the proton transfer was sometimes
shown the wrong way round. Common
errors included omission of a positive
charge on H3O+ and an equilibrium involving
OH− ions rather than water. Neither
approach could be credited.
ALLOW Kw = [H+] [OH−]

OR [H+] [OH−] = 10−14 (mol2 dm−6)
IGNORE breaking for dissociation
IGNORE water contains H+ and OH−
Water dissociates / ionises

IGNORE H2O → H+ + OH− i.e. no
OR
equilibrium sign
b i H2O ⇌ H+ + OH− 1
IGNORE 2H2O → H3O+ + OH− i.e. no
OR
equilibrium sign
2H2O ⇌ H3O+ + OH− ✔
Examiner's Comments
The key required feature was the

dissociation of water but many instead
discussed dissociation of the acid.
FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer, check to
see if there is any
IF answer = 1.15 × 10−11, award 2 marks ECF credit possible using working below.
ii 2
.......................................... ..........................................
[H+] = 10−3.06 = 8.71 × 10−4 (mol dm−3) ✔ ALLOW 2 SF: 8.7 × 10−4 up to calculator
value of
✔
ALLOW alternative approach using pOH:

ALLOW answer to two or more significant figures
2SF: 1.1 × 10−11; 4SF: 1.148 × 10−11;
pOH = 14 − 3.06 = 10.94 ✔
calculator 1.148153621 × 10−11
[OH−] = 10−10.94 = 1.15 × 10−11 (mol dm−3) ✔
Examiner's Comments

calculated the hydroxide ion concentration
via Kw. Another less popular but successful
approach was via pOH. Either approach
could result in both marks. Weaker
candidates were successful in calculating
the hydrogen ion concentration but this was
then often shown also as the hydroxide ion
concentration in the final answer.
Answer: 1.15 × 10−11 mol dm−3

ALLOW ⇌ provided that reactants on LHS
For CO2 + H2O, ALLOW H2CO3
ALLOW Ca(CH3COO)2
ALLOW (CH3COO−)2Ca2+
BUT DO NOT ALLOW if either charge is
missing or incorrect
Examiner's Comments
c i 1
2CH3COOH + CaCO3 → (CH3COO)2Ca + CO2 + H2O ✔ The equations seen were certainly better
than in previous sessions, perhaps as
candidates will have practised similar
questions from past papers. Ionic signs
within the formula of calcium ethanoate
were allowed but both were then needed.
Common errors included an incorrect
formula of calcium ethanoate with one
ethanoate group only and an unbalanced
ethanoic acid on the left-hand side of the
equation.
ALLOW names: ethanoic acid for

CH3COOH
ethanoate for CH3COO−
ii 1 ALLOW calcium ethanoate OR

solution contains CH3COOH AND CH3COO− ✔ (CH3COO)2Ca for CH3COO−
IGNORE ‘acid, salt, conjugate base;

responses must identify the acid and
conjugate base as ethanoic acid and

ethanoate
IGNORE ethanoic acid is in excess (in

question)
BUT DO ALLOW some ethanoic acid is left
over / present / some
ethanoic acid has reacted
IGNORE equilibrium: CH3COOH ⇌ H+ +

CH3COO−
Dissociation of ethanoic acid only
Examiner's Comments
The mark scheme was specific in wanting

the names or formulae of the components of
the buffer solution and also the idea that
some ethanoic acid remains. More general
responses in terms of an acid and its
conjugate base were not credited.

.....................................................
....................
Note: If there is no equilibrium equation
then the two subsequent equilibrium
marks are not available: max 2
Quality of written communication, QWC
2 marks are available for explaining how the equilibrium
DO NOT ALLOW HA ⇌ H+ + A−
system allows the buffer solution to control the pH on addition
DO NOT ALLOW more than one equilibrium
of H+ and OH− (see below)
equation.
..........................................
..........................................
CH3COOH ⇌ H+ + CH3COO− ✔
ALLOW response in terms of H+, A− and HA
..........................................
IF more than one equilibrium shown, it must
be clear which one is being referred to by
labeling the equilibria.
ii
CH3COOH reacts with added alkali 5
i
OR CH3COOH + OH− →
ALLOW weak acid reacts with added alkali
OR added alkali reacts with H+
DO NOT ALLOW acid reacts with added
OR H+ + OH− → ✔
alkali
Equilibrium → right OR Equilibrium → CH3COO− ✔ (QWC)
ALLOW conjugate base reacts with added

acid
CH3COO− reacts with added acid ✔
DO NOT ALLOW salt / base reacts with
added acid
Equilibrium → left OR Equilibrium → CH3COOH ✔ (QWC)
Examiner's Comments
The role of buffers in controlling pH is a

common recall question and most
candidates had prepared their rehearsed
answers. Well-prepared candidates were

thus able to collect full or nearly full marks
for this part. There was a significant minority
of candidates who had obviously not learnt
this part of the specification and, despite
their best efforts to invent answers, there
was rarely anything that the examiners
could credit. This was a great pity because
marks were effectively being thrown away.
Candidates are recommended to construct
their responses using the weak acid
equilibrium equation only. Some candidates
shown both the correct relevant equilibrium
but also others, including for calcium
ethanoate. Subsequent explanations in
terms of equilibrium were then ambiguous
as the examiner could not tell which
equilibrium was being discussed. Some
candidates thankfully did label and
reference multiple equilibria so that some
credit could be awarded.

..........................................
see if there is any
ECF credit possible.
Incorrect use of [H+] = √ ( [CH3COOH] ×

IF answer = 11.48 OR 11.5 (g), award 5 marks
Ka ) scores zero
BUT IGNORE if an alternative successful
.......................................... method is present
[H+] = 10−5 (mol dm−3) ✔
Incorrect use of Kw, 1 max for [H+] = 10−5

(mol dm−3)
BUT IGNORE if an alternative successful
method is present
..........................................
d 5 ALLOW n(CH3COONa / CH3COO−)
..........................................
= ✔ × 0.08 = 0.14(0) (mol) ✔✔
[CH3COO−] = ✔ × 0.200 = 0.350 mol dm−3 ✔
n(CH3COONa / CH3COO−) in 400
cm3 ✔
Note: There is no mark just for
n(CH3COOH) in 400 cm3 = 0.200 × =

.......................................... 0.08 (mol)
mass CH3COONa = 0.140 × 82.0 = 11.48 OR 11.5 (g) ✔ ..........................................
As alternative for the 4th and 5th marks,
ALLOW:
For ECF, n(CH3COONa/CH3COO−) must have been mass of CH3COONa in 1 dm3 = 0.350 ×
calculated in step before 82.0 = 28.7 g ✔
mass of CH3COONa in 400 cm3 = 28.7 ×
= 11.48 g ✔
..........................................
COMMON ECF 4.592 OR 4.6 g AWARD 4
marks
use of 400 / 1000 twice
ALLOW variants of Henderson—

Hasselbalch equation.
pKa = −log(1.75 × 10−5) = 4.757 ✔ Calc:

4.75696. … .
log = pH − pKa = 5 − 4.757
= 0.243
= 100.243 = 1.75 ✔
[CH3COO−] = 1.75 × 0.200 = 0.350 mol dm−3

✔
n(CH3COONa/CH3COO−) in 400 cm3
= 0.350 × = 0.14(0) (mol) ✔

..........................................
mass CH3COONa = 0.140 × 82.0 = 11.48
OR 11.5 (g) ✔
Examiner's Comments
Able candidates answered this question with

comparative ease, collecting all five marks
for a carefully constructed answer. This was
in contrast to weaker candidate who
struggled, often resorting to the ‘square root’
method for calculating the pH of a weak
acid.
The calculation started off with an easy
mark for calculating the hydrogen ion
concentration from the pH. Unfortunately,
this ‘square root’ method then resulted in
another hydrogen ion concentration which
contradicted the original. Other weak
candidates resorted to use of Kw. The result
was that weaker candidates would often
score no marks at all for this part.
Many candidates were aware of the
importance of the acid/base ratio in buffer
calculations and were able to gain at least
some marks for this part. The commonest
error in partially successful responses was
with the scaling factor of 400/1000, being
either omitted to give an answer of 28.7 g,
or used twice to give an answer of 4.952 g
Answer: 11.48 g
Total 17
1
a i Using a pH probe on a data logger OR pH meter 1
7

FIRST CHECK THE ANSWER ON THE ANSWER LINE see if there is any ECF credit possible using
IF answer = 0.11(0) (mol dm−3), award 2 marks working below.
........................................................... .....................................................
......
ii 2
ANNOTATE WITH TICKS AND CROSSES,

etc
= 0.11(0) (mol dm−3) ALLOW ECF: n(NaOH) × 1000/25.00
ALLOW pH range (of the indicator) matches

Brilliant yellow equivalence point
AND ALLOW end point / colour change matches
b i 1
Vertical section / rapid pH change matches the pH range / end equivalence point
point / colour change (of the indicator) IGNORE colour change matches end point
(colour change is the same as end point)
Explanation:
Acid / H+ reacts with A− AND equilibrium (position) shifts ALLOW direction of equilibrium shift if
ii 4
towards HA (to give a red colour) equilibrium shown: HA ⇌ H+ + A−
i.e. ‘towards HA’ is equivalent to ‘to left’
i.e. ‘towards A−’ is equivalent to ‘to right’
Alkali / OH− reacts with HA/H+ AND equilibrium (position) shifts
towards A− (to give a yellow colour)
At end point, equal amounts of HA and A−

AND orange colour
ALLOW yellow−red colour
FIRST CHECK THE ANSWER ON THE ANSWER LINE

Ka = 10−3.40 = 3.98 × 10−4 (mol dm−3)
c i 4
= 0.0556 (mol dm−3)

pH = −log 4.70 × 10−3 = 2.33 ALLOW ECF
ALLOW ECF only from [H+] calculation

using
[H+] = √(Ka × [HA])
ii Salts are ionic AND attracted to polar H2O 1
COO− reacts with H+ forming COOH

ii
2 ALLOW equilibrium shifts to left
i
Aspirin precipitates out
Total 15
[H+] = 10−pH = 10−2.19 = 6.46 × 10−3 (mol dm−3)
= 0.0302(mol dm−3)
1 Mass of CH3CH(OH)COOH = 0.0755 × 90 = 6.80 g

a 8
8 ALLOW 5 marks for 6.80 g through any
Dissolve 6.80 g of the solid in distilled water (less than 250 calculation.
cm3) in a beaker
ALLOW ECF for incorrect calculation of
(then) transfer the solution to a 250 cm3 volumetric flask AND mass. Mass used must be linked to
ensure that all solution is washed out of beaker (washings calculation.
transferred to volumetric flask)
(then) make solution up to 250 cm3 with distilled water AND

ensure thorough mixing by inverting the flask several times
CH3CH(OH)COO− + CH3CH2CH2COOH2+
State symbols NOT required
b CH3CH(OH)COOH AND CH3CH(OH)COO− 2

ALLOW labels ‘acid 1’, ‘base 1’ etc.
CH3CH2CH2COOH AND CH3CH2CH2COOH2+
ALLOW ECF for second mark
Both pairs identified
ALLOW 5.405405405 × 10–14 and correct

rounding to 5.4 × 10–14
ALLOW alternative approach using pOH:

c i (Use of Kw) 2 pOH = –log(0.185) = 0.73
pH = 14 – 0.73 = 13.27
pH = −log(5.405 × 10−14) = 13.27 Correct answer scores BOTH marks
ALLOW 13.267
n(A−) = 9.25 × 10−3 (mol) ALLOW HA / acid and A−/salt throughout for
butanoate and butanoic acid
ii n(HA) = 0.0165 − 9.25 × 10−3 = 7.25 × 10−3 (mol) 4
ALLOW pKa = −log Ka OR −log 1.5 ×

10−3 OR 4.82
ALLOW ECF from incorrect values of n(A−)

or n(HA)
Final mark also via Henderson-Hasselbalch equation:
Total 16
1
2
9 1 mark for correct reactants AND products AND correct
positioning of + and − charges on products
1 mark for two correct curly arrows

AND H2O curly arrow starting from O lone pair
Total 2
2
i 1 state symbols not required
0
ALLOW ECF from calculated [H+] provided

that
BOTH
OR 0.0245 (mol dm−3)
ii 2 6.0 x 10−3 AND 0.100 only have been used
pH = −log 0.0245 = 1.61

ALLOW calculation via quadratic equation
→ pH 1.66
Total 3
Actual Kw = 2.38 × 10−14 mol2 dm−6
ALLOW ECF only if candidate uses a value

Kw value from graph from 2.2 to 2.4 × 10−14 (mol2 dm−6) between 2.0 and 2.6 × 10−14 (mol2 dm−6),
i.e. from the approximately correct region of
2 Using 2.4 × 10−14, the graph
3
1 OR 1.55 × 10−7
ALLOW 6.8 (1DP) up to calculator value
pH = −log (1.55 × 10 −7) = 6.81 (using Kw = 2.4 × 10−14) ALLOW ECF only if candidate has
generated a value of [H+] by attempting to
take a square root of a value between 2.0
and 3.0 × 10−14
Total 3
ALLOW HNO3 completely dissociates AND

HNO2 partially dissociates
ALLOW HNO3 → H+ + NO3− AND HNO2 ⇌
2
a i HNO3 is a strong acid AND HNO2 is a weak acid 1 H+ + NO2−
2
IGNORE HNO3 is a stronger acid ORA

IGNORE HNO3 produces more H+
ii pH = −log 0.0450 = 1.35 (2 DP required) 1
ALLOW 2 SF to calculator value:

FIRST CHECK THE ANSWER ON ANSWER LINE 4.466835922 × 10−4, correctly rounded
IF answer = 2.35, award all three calculation marks IGNORE HNO3 in working
Ka = 10−3.35 OR 4.47 × 10−4 (mol dm−3) Always ALLOW calculator value irrespective
ii of working as number may have been kept
3
i [H+] = √(Ka × [HNO2]) OR √(Ka × [HA]) in calculator.
OR √(Ka × 0.0450)
OR 4.48 × 10−3 (mol dm−3) Note: pH = 2.35 is obtained from all three
values above
pH = 2.35 (2 DP required) From no square root, pH = 4.70. Worth Ka
mark only.
Always ALLOW calculator value

irrespective of working as number may have
been kept in calculator.
IF answer = 0.810 (g) award 4 marks ALLOW alternative approach using pOH:
pOH = 14.000 − 12.500 = 1.500
[H+] = 10−12.500 = 3.16 × 10−13 (mol dm−3)
[OH−] = 10−1.500 = 0.0316
b 4 ALLOW ECF from [H+] derived using Kw

and [OH−]
BUT DO NOT ALLOW an acid pH.
ALLOW 0.81 g, up to calculator value but

take care as rounding could be from any
mass RbOH = 7.91 × 10−3 × 102.5 = 0.810 (g) stage.
Last 3 SF figure is zero and is treated as a
‘trailing zero’ as specific number of SF has
not been asked for.
Total 9
Equilibria, Energetics and Elements
Acids, Bases & Buffers
1. (i) H+/proton donor (1) 1

(ii) partially dissociates/ionises (1) 1
[2]
2. C6H5OH(aq) + OH–(aq) C6H5O–(aq) + H2O(l)

acid 1 base 2 base 1 acid 2 (1)
[1]
3. (i) Ka = [C6H5O–(aq)] [H+(aq)] / [C6H5OH(aq)] (1) 1

(ii) Mr C6H5OH = 94 (1)
[C6H5OH(aq)] 4.7/94 = 0.050 mol dm–3 (1)
1.3 × 10–10 ≈ [H+(aq)]2 / 0.050 mol dm–3 (1) (‘=’ sign is acceptable)
[H+] = √{(1.3 × 10–10) × (0.050) } = 2.55 × 10–6 mol dm–3 (1)
pH = –log[H+] = –log 2.55 × 10–6 = 5.59 (1)
3 marks: [H+]; pH expression ; calc of pH from [H+] 5
[6]
4. [H+(aq)] = 1.99 × 10–9 mol dm–3 (1)

[C6H5O–(aq)] = Ka [C6H5OH(aq)] / [H+(aq)](1)
[C6H5O–(aq)] = 0.13 mol dm–3 (1)
Calculation should use half the original concentration of
phenol to find the concentration of sodium phenoxide in the
buffer. This should then be doubled back up again.
Do not penalise an approach that uses the original
concentration of phenol in the expression above.
[3]
5. (a) (i) Ionic product (1) 1

(ii) Kw = [H+(aq)] [OH–(aq)] (1) state symbols not needed 1
PhysicsandMathsTutor.com 1
5 × 10 −3 × 21.35
(b) moles of HCl = = 1.067 × 10–4 mol (1)
1000
1.067 × 10 4
moles of Ca(OH)2 = = 5.34 × 10–5 mol (1)
2
concentration of Ca(OH)2 = 40 × 5.34 × 10–5
= 2.136 × 10–3 mol dm–3 (1)
2 marks for 4.27 × 10–3/ 8.54 × 10–3 mol dm–3
(no factor of 4) 3
(c) [OH–] = 2 × 2.7 × 10–3 = 5.4 × 10–3 mol dm–3 (1)

Kw 1.0 × 10 −14
[H+(aq)] = = −3
= 1.85 × 10–12 mol dm–3 (1)
[OH (aq)]
−
5.4 × 10
pH = –log (1.85 × 10–12) = 11.73/11.7 (1) 3

ecf is possible for pH mark providing that the [H+]
value has been derived from Kw/[OH–]
If pOH method is used, pOH = 2.27. would get 1st mark,
pH = 14 – 2.27 = 11.73 gets 2nd mark.
Commonest mistake will be to not double OH-- and to use 2.7 × 10–3
This gives ecf answer of 11.43/11.4, worth 2 marks.
pH = 11.13 from dividing by 2: worth 2 marks
(d) 8 (1) 1
[9]
6. (a) Ca3(PO4)2 + 2H2SO4 → Ca(H2PO4)2 + 2CaSO4 (1) 1
(b) H2PO4–(aq) H+(aq) + HPO42–(aq) /
H2PO4–(aq) 2H+(aq) + PO43–(aq) (1)
(or equivalent with H2O forming H3O+) 1
(c) (i) HPO42– (1) 1
(ii) H3PO4 (1) 1
(iii) H2PO4– produced Ca(H2PO4)2 or on LHS of an attempted

equilibrium equation (1)
2 equations/equilibria to shown action of buffer (1)(1)
from:
H2PO4– + H+ H3PO4 /
–
H2PO4 H + HPO42–/
+
H2PO4– + OH– H2O + HPO42– /

H+ + OH– H2O 3
[7]
7. proton donor
partially dissociates
[2]
[HCOO – ] [H + ] [H + ] 2
8. Ka = / /[H + ] = ( Ka × [HA]) /
[HCOOH] [HCOOH]
[H + ] 2
1.58 × 10–4 = /
0.025
[H+] = √{(1.58 × 10–4) × (0.025) } = 1.99 × 10–3 mol dm−3
pH = −log[H+] = −log 1.99 × 10–3 = 2.70
5.4034 (no square root) with working would score 1 mark.
[3]
9. (i) A solution that minimises pH changes/resists pH

changes/opposes pH changes
(not pH is kept constant/pH maintained/pH cancelled out. 1
(ii) HCOONa/HCOO–/ NaOH

HCOO– is the conjugate base/
HCOONa is the salt of the weak acid or HCOOH/
HCOONa supplies HCOO– 2
(iii) Two points from:
Ka /pKa /acid strength/amount of dissociation
temperature (but not “temperature & pressure”)
ratio/amounts/concentrations of weak acid and
conjugate base/salt (or reverse ratio)
(not ………. concentration of base as it could imply
NaOH) 2 max
[5]
1400 × 65
10. Mass of HNO3 = / 910g
100
910
Moles of HNO3 = = 14.4
63
pH = –log[H+] = –log 14.4 = –1.16/1.2 calc –1.15836
pH from ignoring 65% pH = –1.35: with working, 2 marks.
[3]
11. → ………… CO2 + H2O

Complete correct balanced equation for 2nd mark:
2HNO3 + CaCO3 → Ca(NO3)2 + CO2 + H2O /
2H+ + CaCO3 → Ca2+ + CO2 + H2O /
2H+ + CO2–3 → CO2 + H2O
[2]
12. Two species differing by H+ …. AW

one pair: HNO3 and NO3–
other pair: HCOOH and HCOOH2+
[3]
0.1263 × 23.75
13. moles of NaOH = / 3.00 × 10–3 mol
1000
moles of acid = 3.00 × 10–3 mol
moles of acid in flask = 10 × 3.00 × 10–3 = 3.00 × 10–2 mol
mass 2.58
molar mass of compound = = = 86 4
n 3.00 × 10 – 2
Molecular formula = C4H6O2
A 4 carbon carboxylic acid
(e.g. butanoic acid) shown (bod)
Any 2 possible isomers from:
CH2 = C(CH3)COOH
CH2 = CHCH2COOH
cis CH3CH = CHCOOH
trans CH3CH = CHCOOH 4
Accept structural formulae that are unambiguous.
[8]
14. (a) partial dissociation: HCOOH H+ + HCOO– (1) 1
(b) (i) pH = –log (1.55 × 10–3) = 2.81/2.8 (1)

[H+] deals with negative indices over a very wide range/
pH makes numbers manageable
/removes very small numbers (1) 2
[ H + (aq)][HCOO − (aq)]
(ii) Ka = (1) (state symbols not needed) 1
[ HCOOH(aq)]
[ H + (aq)] 2 (1.55 × 10 −3 ) 2
(iii) Ka = = (1)
[HCOOH(aq)] 0.015
= 1.60 × 10–4 (mol dm–3)(1)
pKa = –log Ka = –log (1.60 × 10–4) = 3.80 (1) 3
(1.55 × 10 −3 ) × 100
(iv) Percentage dissociating = = 10.3 % /
0.015
10% (1) 1
(working not required)
[8]
15. (i) HCOOH + NaOH → HCOONa + H2O (1) 1

state symbols not needed
(ii) n(HCOOH) = 0.0150 × 25.00/1000 = 3.75 × 10–4 (1)
volume of NaOH(aq) that reacts is 30 cm3 (1)
so [NaOH] = 3.75 × 10–4 × 1000/30 = 0.0125 mol dm–3 (1) 2
(iii) Kw = [H+(aq)][OH–(aq)] (1)
pH = –log(1 × 10–14/0.0125) = 12.10/12.1 (1)
(calc 12.09691001) 3
(iv) metacresol purple (1)

pH range coincides with pH change during sharp rise OR
pH 6-10 /coincides with equivalence point/end point (1) 2
[8]
16. (a) strength of acid/extent of dissociation/ionisation (1) 1
(b) (i) H2SO3(aq) + CH3COOH(aq) HSO3–(aq) + CH3COOH2+(aq)

acid 1 base 2 (1) base 1 acid 2 (1) 2
1 mark for labels on each side of equation
(ii) CH3COOH is the stronger acid/

Ka CH3COOH is greater/
CH3COOH is more acidic ORA (1)
C6H5OH(aq) + CH3COOH(aq) C6H5OH2+(aq) + CH3COO–(aq) (1) 2
(c) For HCl, pH = –log[H+] (1) (or with values).

Could be awarded below
= –log 0.045 = 1.35 (1) (accept 1.3)
For CH3COOH, [H+] = √(Ka × [CH3COOH]) /
√(1.70 × 10–5 × 0.045) (1)
[H+] = 8.75 × 10–4 mol dm–3 (1)
pH = –log 8.75 × 10–4 = 3.058/3.06 (1) (accept 3.1) 5
[10]
17. HCl and CH3COOH have same number of moles/
release same number of moles H+ /
1 mole of each acid produce ½ mol of H2 (1)
[H+] in CH3COOH < [H+] in HCl/

CH3COOH is a weaker acid than HCl (ora) (1)
Mg + 2HCl → MgCl2 + H2 (1)
Mg + 2CH3COOH → (CH3COO)2Mg + H2 (1)
or
Mg + 2H+ → Mg2+ + H2 (1)(1) 4
[4]
18. amount of NaOH in titration = 0.175 x 22.05/1000

or 3.86 × 10–3 (1) (calc: 3.85875 x 10–3)
amount of A in 25.0 cm3 = 0.5 × mol NaOH
or 1.93 × 10–3 (1) (calc: 1.929375 × 10–3)
amount of A in 250 cm3 = 10 × 1.93 × 10–3 or 1.93 × 10–2 (1)
1.93 × 10–2 mol A has a mass of 2.82 g
molar mass of A = 2.82/1.93 × 10–2 = 146 g mol–1 (1)
(or Mr of A is 146)
Therefore A is adipic acid / HOOC(CH2)4COOH (1) 5
[5]
19. (i) proton donor (1) 1

(ii) partially dissociates (1) 1
[2]

acid 1 base 2 (1) base 1 acid 2 (1)
1 mark for each acid-base pair
[2]
[C 6 H 5 O − ][H + ]
21. (i) Ka = (1) 1
[C 6 H 5 OH]
(ii) concentration = 38/94 (1) = 0.40 mol dm–3 (1)

(first mark for Mr of phenol – incorrect answer here will give
ecf for remainder of question)
[ H + (aq)] 2
1.3 × 10–10 ≈ (1)
0.40
(‘=’ sign is acceptable)
[H+] = √{(1.3 × 10–10) × (0.40)} = 7.2 × 10–6 mol dm–3 (1)

pH = –log[H+] = –log 7.2 × 10–6 = 5.14 (1) 5
3 marks: [H+] (1); pH expression (1); calc of pH from [H+] (1)
Common errors:
Without square root, answer = 10.28 (1)(1)(0)
Use of 38 as molar concentration does not score 1st 2 marks.
This gives an answer of 4.15 for 3 marks (1)(1)(1)
[6]
22.
O-Na+
O-Na+
CH2(CH2)4CH3
/ NaOH /Na (1)
weak acid/base pair mixture formed (1) 2
On structure, 1 mark for O Na on either or both phenol groups.
[2]
23. (i) completely dissociates/ionised (1)

proton donor (1) 2
(ii) NO3– (1) 1

[3]
24. (i) pH = –log[H+] / –log(0.015) (1) = 1.82 / 1.8 (1) (Not 2) 2
(ii) [H+] = 0.0075 mol dm–3
pH = –log(0.0075) = 2.12 / 2.1 (1) 1
[3]
25. (i) Kw = [H+(aq)] [OH–(aq)] (1) 1

(ii) [H+(aq)] = 10–pH = 10–13.54 = 2.88/2.9 × 10–14 mol dm–3 (1)

Kw 1.0 × 10 −14
[NaOH] / [OH–(aq)] = =
[H + (aq)] 2.88 × 10 −14
= 0.347 / 0.35 mol dm–3 (1) 2
[3]
26. (i) a solution that minimises/resists/opposes pH changes (1) 1
(ii) The buffer must contain both CH3COOH and CH3COONa /

CH3COO– /weak acid and conjugate base(*) (1)
Solution A is a mixture of CH3COOH(*) and CH3COONa(*) /
/ has an excess of acid /is acidic (1)
Solution B, contains only CH3COONa/ only CH3COO–
/only the salt/ is neutral (1)
CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l) /
acid/alkali has been neutralised/
CH3COOH(aq) and NaOH react together (1) 4
[5]
27. [H+] increases (1)

H2O ionises more /
for H2O H+ + OH–, equilibrium moves to the right (1) 2
exo/endo is ‘noise’
[2]
PMT
1. (i) O3: Exp 2 has 4 times [H2] as Exp 1

and rate increases by 4 (1),
so order = 1 with respect to O3 (1)
C2H4: Exp 3 has 2 × [C2H4] and 2 × [O3] as Exp 2;
and rate has increased by 4 (1),
so order = 1 with respect to C2H4 (1)
rate = k [O3] [C2H4] (1) 5
(ii) use of k = rate / [O3] [C2H4] = 1.0 × 10–12 / (0.5 × 10–7 × 1.0 × 10–8)
to obtain a calculated value (1)
k = 2 × 103 (1)
units: dm3 mol–1 s–1 (1) 3
(iii) rate = 1.0 × 10–12 /4 = 2.5 × 10–13 (mol dm–3 s–1) (1) 1
(iv) rate increases and k increases (1) 1

[10]
2. 1½O2(g) → O3(g)/
O2(g) + ½O2(g) → O3(g) (1)
NO is a catalyst (1) as it is (used up in step 1 and) regenerated in step 2/
not used up in the overall reaction(1)
allow 1 mark for ‘O/NO2 with explanation of regeneration.’ 3
[3]
3. (i) H+/proton donor (1) 1

(ii) partially dissociates/ionises (1) 1
[2]

acid 1 base 2 base 1 acid 2 (1) 1
[1]
PMT
5. (i) Ka = [C6H5O–(aq)] [H+(aq)] / [C6H5OH(aq)] (1) 1

(ii) Mr C6H5OH = 94 (1)
[C6H5OH(aq)] 4.7/94 = 0.050 mol dm–3 (1)
1.3 × 10–10 ≈ [H+(aq)]2 / 0.050 mol dm–3 (1) (‘=’ sign is acceptable)
[H+] = √{(1.3 × 10–10) × (0.050) } = 2.55 × 10–6 mol dm–3 (1)
pH = –log[H+] = –log 2.55 × 10–6 = 5.59 (1)
3 marks: [H+]; pH expression ; calc of pH from [H+] 5
[6]
6. [H+(aq)] = 1.99 × 10–9 mol dm–3 (1)

[C6H5O–(aq)] = Ka [C6H5OH(aq)] / [H+(aq)](1)
[C6H5O–(aq)] = 0.13 mol dm–3 (1) 3
Calculation should use half the original concentration of
phenol to find the concentration of sodium phenoxide in the
buffer. This should then be doubled back up again.
Do not penalise an approach that uses the original
concentration of phenol in the expression above.
[3]
7. (a) rate of forward reaction = rate of reverse reaction (1)

concentrations of reactants and products are constant but they are
constantly interchanging (1) 2
(b) (i) Kc = [CH3OH] / [CO] [H2]2 (1) 1
(ii) use of Kc = [CH3OH] / [CO] [H2]2 and moles to

obtain a calculated value (1)
convert moles to concentration by +2: [CO] = 3.10 × 10–3 mol dm–3;
[H2] = 2.60 × 10–5 mol dm–3; [CH3OH] = 2.40 × 10–2 mol dm–3 (1)
Kc = [2.60 × 10–5] / [3.10 × 10–3] [2.40 × 10–2]2 = 14.6 / 14.56 (1)

If moles not converted to concentration, calculated Kc value = 3.64
(scores 1st and 3rd marks)
units: dm6 mol–2 (1) 4
(c) (i) fewer moles of gas on right hand side (1) 1

(ii) None (1) 1
PMT
(d) (i) moved to left hand side/reactants increase/less products (1) 1

(ii) ∆H negative because high temperature favours the
endothermic direction (1) 1
(e) (i) CH3OH + 1½ O2 → CO2 + 2H2O(1) 1

(ii) adds oxygen/oxygenated (1) 1
[13]
8. (i) H2: Exp 2 has 2.5 times [H2] as Exp 1

and rate increases by 2.5 (1),
so order = 1 with respect to H2 (1) 2
NO: Exp 3 has 3 x [NO] as Exp 2;
and rate has increased by 9 = 32 (1),
so order = 2 with respect to NO (1) 2
QWC At least two complete sentences where the meaning is clear. 1
(ii) rate = k[NO]2 [H2] (1) 1
rate 2.6
(iii) k= / (1)
[NO] [H 2 ] 0.10 2 × 0.20
2
= 1300 (1) units: dm6 mol–2 s–1 (1)

allow 1 mark for 7.69 × 10–4 or 1.3 × 10x (x not 3) 3
[9]
9. (i) 1½O2(g) → O3(g)/

O2(g) + ½O2(g) → O3(g) (1)
NO is a catalyst (1) as it is (used up in step 1 and)
regenerated in step 2/
not used up in the overall reaction(1)
allow 1 mark for ‘O/NO2 with explanation of regeneration.’ 3
(ii) Rate = k[NO] [O3] (1)

Species in rate equation match those reactants in the slow
step / rate determining step (1) 2
[5]
[PCl 3 ][Cl 2 ]
10. (a) Kc = (1) 1
[PCl 5 ]
PMT
(b) (i) PCl5 > 0.3 mol dm–3 ; PCl3 and Cl2 < 0.3 mol dm–3 (1) 1
(ii) At start, system is out of equilibrium with too much PCl3
and Cl2 and not enough PCL5 /
0.3 × 0.3
= 0.3 is greater than Kc = 0.245 mol dm–3 (1) 1
0.3
(c) (i) Kc does not change as temperature is the same (1) 1

(ii) Fewer moles on left hand side (1)
system moves to the left to compensate for increase in
pressure by producing less molecules (1) 2
(d) (i) Kc decreases (as more reactants than products)(1) 1
(ii) Forward reaction is exothermic/

reverse reaction is endothermic (1)
equilibrium → left to oppose increase in energy/
because Kc decreases (1) 2
[9]
11. (a) (i) Ionic product (1) 1

(ii) Kw = [H+(aq)] [OH–(aq)] (1) state symbols not needed 1
5 × 10 −3 × 21.35
(b) moles of HCl = = 1.067 × 10–4 mol (1)
1000
1.067 × 10 4
moles of Ca(OH)2 = = 5.34 × 10–5 mol (1)
2
concentration of Ca(OH)2 = 40 × 5.34 × 10–5
= 2.136 × 10–3 mol dm–3 (1)
2 marks for 4.27 × 10–3/ 8.54 × 10–3 mol dm–3
(no factor of 4) 3
PMT
(c) [OH–] = 2 × 2.7 × 10–3 = 5.4 × 10–3 mol dm–3 (1)

Kw 1.0 × 10 −14
[H+(aq)] = −
= −3
= 1.85 × 10–12 mol dm–3 (1)
[OH (aq)] 5.4 × 10
pH = –log (1.85 × 10–12) = 11.73/11.7 (1) 3

ecf is possible for pH mark providing that the [H+]
value has been derived from Kw/[OH–]
If pOH method is used, pOH = 2.27. would get 1st mark,
pH = 14 – 2.27 = 11.73 gets 2nd mark.
Commonest mistake will be to not double OH-- and to use 2.7 × 10–3
This gives ecf answer of 11.43/11.4, worth 2 marks.
pH = 11.13 from dividing by 2: worth 2 marks
(d) 8 (1) 1
[9]
12. (a) Ca3(PO4)2 + 2H2SO4 → Ca(H2PO4)2 + 2CaSO4 (1) 1
(b) H2PO4–(aq) H+(aq) + HPO42–(aq) /
H2PO4–(aq) 2H+(aq) + PO43–(aq) (1)
(or equivalent with H2O forming H3O+) 1
(c) (i) HPO42– (1) 1

(ii) H3PO4 (1) 1
(iii) H2PO4– produced Ca(H2PO4)2 or on LHS of an attempted

equilibrium equation (1)
2 equations/equilibria to shown action of buffer (1)(1)
from:
H2PO4– + H+ H3PO4 /
–
H2PO4 H + HPO42–/
+
H2PO4– + OH– H2O + HPO42– /

H+ + OH– H2O 3
[7]
13. Correct equation for a metal (1)

Correct equation for a carbonate (1)
Correct equation for a base (1) 3
[3]
PMT
14. (a) partial dissociation: HCOOH H+ + HCOO– (1) 1
(b) (i) pH = –log (1.55 × 10–3) = 2.81/2.8 (1)

[H+] deals with negative indices over a very wide range/
pH makes numbers manageable
/removes very small numbers (1) 2
[H + (aq)][HCOO − (aq)]
(ii) Ka = (1) (state symbols not needed) 1
[HCOOH(aq)]
[H + (aq)] 2 (1.55 × 10 −3 ) 2
(iii) Ka = = (1)
[HCOOH(aq)] 0.015
= 1.60 × 10–4 (mol dm–3)(1)
pKa = –log Ka = –log (1.60 × 10–4) = 3.80 (1) 3
(1.55 × 10 −3 ) × 100
(iv) Percentage dissociating = = 10.3 % /
0.015
10% (1) 1
(working not required)
[8]
15. (i) HCOOH + NaOH → HCOONa + H2O (1) 1

(ii) n(HCOOH) = 0.0150 × 25.00/1000 = 3.75 × 10–4 (1)

volume of NaOH(aq) that reacts is 30 cm3 (1)
so [NaOH] = 3.75 × 10–4 × 1000/30 = 0.0125 mol dm–3 (1) 2
(iii) Kw = [H+(aq)][OH–(aq)] (1)
pH = –log(1 × 10–14/0.0125) = 12.10/12.1 (1)
(calc 12.09691001) 3
(iv) metacresol purple (1)

pH range coincides with pH change during sharp rise OR
pH 6-10 /coincides with equivalence point/end point (1) 2
[8]
[HI] 2
16. (a) Kc = (1) 1
[H 2 ][I 2 ]
(b) (i) H2 I2 HI
0.30 0.20 0
PMT
0.14 0.04 0.32

(1) (1) 2
0.32 2
(ii) Kc = = 18.28571429 (1)
0.14 × 0.04
= 18 (to 2 sig figs) (1)
no units (1)
(or ecf based on answers to (i) and/or (a)) 3
(c) Kc is constant (1)

Composition of mixture is the same (1) 2
[8]
17. (i) I2(aq) + H2S(g) → 2HI(aq) + S(s)

species and balance (1)
state symbols: accept (s) for I2; (aq) for H2S (1) 2
(ii) amount I2 reacted = 1.89 mol / HI formed = 3.44 mol (1)

theoretical amount HI produced = 3.78 mol/484 g (1)
3.44 × 100 440 × 100
% yield = or = 91.0 % (1) 3
3.78 484
3.44 × 1000
(iii) [HI] = = 4.58/4.59 mol dm–3 (1)
750
pH = –log 4.59 = –0.66 (1) 2
[7]
18. From graph, constant half-life (1)

Therefore 1st order w.r.t. [CH3COCH3] (1) 2
From table, rate doubles when [H+] doubles (1)

Therefore 1st order w.r.t. [H+] (1) 2
From table, rate stays same when [I2] doubles (1)
Therefore zero order w.r.t. [I2] (1)
Order with no justification does not score. 2
rate = k[H+][CH3COCH3] (1)
(from all three pieces of evidence)
rate 2.1 × 10 −9
k= / (1)
[H + ][CH 3COCH 3 ] 0.02 × 1.5 × 10 − 3
= 7.0 × 10–5 (1) dm3 mol–1 s–1 (1) 4
accept 7 × 10–5
PMT
rate determining step involves species in rate equation (1)

two steps that add up to give the overall equation (1)
The left hand side of a step that contains the species in rate-determining step (1)
i.e., for marking points 2 and 3:
CH3COCH3 + H+ → [CH3COHCH3]+
[CH3COHCH3+] + I2 → CH3COCH2I + HI + H+ 3
organises relevant information clearly and coherently,
using specialist vocabulary where appropriate
Use of the following four words/phrases:
constant, half-life, order, doubles/x2 (1) 1
[14]
19. (a) (i) (+)1 (1) 1

(ii)
N N O N N O
or
Look for atoms bonded together.
AND other lone pairs. 1
(b) (i) C13H18O2 (1)

(ii) any chemical that reacts to produce gas:
e.g. carbonate and CO2 (1)
accept: metal more reactive than Pb and H2
balanced equation to match chemical added (1) 3
(c) Mr(Lidocaine) = 236 (1)

Moles Novocaine = 100 × 10-3/236 = 4.24 × 10–4 (1)
Concentration of Novocaine = 4.24 × 10–4 × (1000/5)
= 0.0847/0.0848/0.085 mol dm–3 (1) 3
PMT
3.74
(d) mass C = 12 × = 1.02 g /
44.0
3.74
moles CO2 = = 0.085 mol (1)
44
2
mass H = × 0.918 = 0.102 g /
18
0.918
moles H2O = = 0.051 mol (1) 2
18
1.02 0.102
ratio C : H = : = 0.0850 : 0.102 = 5 : 6 / 10 : 12/
12 1
ratio CO2 : H2O = 5 : 3 / 10 : 6 (1)
mass O = 1.394 – (1.020 + 0.102) = 0.272 g
/ using 1.394 g eugenol and Mr = 164, shows that 1
molecule contains 2 atoms of O (1) 2
∴ molecular formula = C10H12O2 (1) 1
[13]
20. (a) (change in) concentration/mass/volume with time 1
(b) (i) O2:

Exp 2 has 4 × [O2] as Exp. 1: rate increases by 4 (1),
so order = 1 with respect to O2 (1)
NO:
Exp 3 has 3 × [NO] as Exp. 3: rate has increases by 9 (1),
so order = 2 with respect to NO (1) 4
(ii) rate = k[O2] [NO]2 (1) 1
rate 7.10
(iii) k= = = 7.10 × 109 (1)
[O 2 ][ NO] 2
0.0010 × 0.0010 2
units: dm6 mol–2 s–1 (1) 2

[8]
21. (i) The slowest step (1) 1

(ii) 2NO2 → NO + NO3 (1)
NO3 + CO → NO2 + CO2 (1) 2
(or similar stage involving intermediates)
[3]
22. (a) strength of acid/extent of dissociation/ionisation (1) 1

PMT
(b) (i) H2SO3(aq) + CH3COOH(aq) HSO3–(aq) + CH3COOH2+(aq)

acid 1 base 2 (1) base 1 acid 2 (1) 2
1 mark for labels on each side of equation
(ii) CH3COOH is the stronger acid/

Ka CH3COOH is greater/
CH3COOH is more acidic ORA (1)
C6H5OH(aq) + CH3COOH(aq) C6H5OH2+(aq) + CH3COO–(aq) (1) 2
(c) For HCl, pH = –log[H+] (1) (or with values).

Could be awarded below
= –log 0.045 = 1.35 (1) (accept 1.3)
For CH3COOH, [H+] = √(Ka × [CH3COOH]) /
√(1.70 × 10–5 × 0.045) (1)
[H+] = 8.75 × 10–4 mol dm–3 (1)
pH = –log 8.75 × 10–4 = 3.058/3.06 (1) (accept 3.1) 5
[10]
23. HCl and CH3COOH have same number of moles/

release same number of moles H+ /
1 mole of each acid produce ½ mol of H2 (1)
[H+] in CH3COOH < [H+] in HCl/

CH3COOH is a weaker acid than HCl (ora) (1)
Mg + 2HCl → MgCl2 + H2 (1)
Mg + 2CH3COOH → (CH3COO)2Mg + H2 (1)
or
Mg + 2H+ → Mg2+ + H2 (1)(1) 4
[4]
PMT
24. amount of NaOH in titration = 0.175 x 22.05/1000

or 3.86 × 10–3 (1) (calc: 3.85875 x 10–3)
amount of A in 25.0 cm3 = 0.5 × mol NaOH
or 1.93 × 10–3 (1) (calc: 1.929375 × 10–3)
amount of A in 250 cm3 = 10 × 1.93 × 10–3 or 1.93 × 10–2 (1)
1.93 × 10–2 mol A has a mass of 2.82 g
molar mass of A = 2.82/1.93 × 10–2 = 146 g mol–1 (1)
(or Mr of A is 146)
Therefore A is adipic acid / HOOC(CH2)4COOH (1) 5
[5]
p(SO 3 ) 2
25. (a) Kp = (1)(1)
p(SO 2 ) 2 × p(O 2 )
1 mark for correct powers but wrong way up.
1 mark for square brackets 2
(b) An increase in pressure moves equilibrium to the right because

there are less gaseous moles on the right hand side (1)
Increased pressures are expensive to generate/safety problems
with walls of containers/enables gases to flow (1)
Kp gets less with increasing temperature (1)
SO2 and O2 increase/SO3 decreases (1)
Equilibrium → left to oppose increase in temperature (1)
Forward reaction is exothermic or ΔH is –ve /reverse
reaction is endothermic or ΔH is +ve because Kp gets less
with increasing temperature (1) 6
QoWC: organises relevant information clearly and
coherently, using specialist vocabulary where appropriate (1) 1
p(SO 3 ) 2
(c) 3.0 × 102 = (1)
10 2 × 50
p(SO3) = √(3.0 × 102 × 102 × 50) = 1225 kPa (1)
%(SO3) = 100 × 1225 /(1225 + 10 + 50) = 95% (1) 3
PMT
(d) (i) 2ZnS + 3O2 → 2ZnO + 2SO2 (1)(1)

ZnS, O2 as reactants and SO2 as a product: 1st mark.
ZnO and balance: 2nd mark 2
(ii) ZnS is more available than S. (1) 1
[15]
26. (a) (i) O3: 1

and C2H4 (1) 1
(ii) 2 (1) 1
(iii) rate = k[O3] [C2H4] (1) 1
(b) (i) measure gradient/tangent (1)

at t = 0/start of reaction (1) 2
rate
(ii) k= (1)
[O 2 ][C 2 H 4 ]
1.0 × 10 −12
k= −7 −8
= 2 × 103 (1) dm3 mol–1 s–1 (1) 3
0.5 × 10 × 1.0 × 10
(iii) 2 mol CH2O forms for every 0.5 mol O2 /

stoichiometry of CH2O : O2 is not 1:1 (1) 1
(iv) rate increases (1)
k increases (1) 2
[11]
27. (i) each atom has two unpaired electrons (1) 1

(ii) 2 oxygen atoms bonded by double bond (1)
third oxygen bonded by a covalent bond and outer shells correct (1)
For 2nd mark, all O atoms must have an octet.
A triangular molecule would have 3 single covalent bonds
for 1st mark but the origin of each electron must be clear for 2nd mark 2
(iii) amount of O3 in 150 kg = 150 × 103/48 = 3.13 × 103 mol (1)
amount of Cl radicals in 1 g = 1 /35.5 = 2.82 × 10–2 mol (1)
1 mol Cl destroys 3.13 × 103/2.82 × 10–2 = 1.11 × 105 mol O3
1 Cl radical destroys 1.11 × 105 O3 molecules (1)
(calculator: 110937) 3
[6]
PMT
28. (i) proton donor (1) 1

(ii) partially dissociates (1) 1
[2]

acid 1 base 2 (1) base 1 acid 2 (1)
1 mark for each acid-base pair
[2]
[C 6 H 5 O − ][H + ]
30. (i) Ka = (1) 1
[C 6 H 5 OH]
(ii) concentration = 38/94 (1) = 0.40 mol dm–3 (1)

(first mark for Mr of phenol – incorrect answer here will give
ecf for remainder of question)
[H + (aq)] 2
1.3 × 10–10 ≈ (1)
0.40
(‘=’ sign is acceptable)
[H+] = √{(1.3 × 10–10) × (0.40)} = 7.2 × 10–6 mol dm–3 (1)
pH = –log[H+] = –log 7.2 × 10–6 = 5.14 (1) 5
3 marks: [H+] (1); pH expression (1); calc of pH from [H+] (1)
Common errors:
Without square root, answer = 10.28 (1)(1)(0)
Use of 38 as molar concentration does not score 1st 2 marks.
This gives an answer of 4.15 for 3 marks (1)(1)(1)
[6]
PMT
31.
O-Na+
O-Na+
CH2(CH2)4CH3
/ NaOH /Na (1)
weak acid/base pair mixture formed (1) 2
On structure, 1 mark for O Na on either or both phenol groups.
[2]
32. moles HCl in 23.2 cm3 = 0.200 × 23.2/1000 = 4.64 × 10–3 (1)
moles B in 25 cm3 = moles HCl = 4.64 × 10–3 (1)
moles B in 250 cm3 = 4.64 × 10–3 × 10 = 4.64 × 10–2 (1)
4.64 × 10–2 mol B has a mass of 4.32 g
molar mass of B = 4.32/4.64 × 10–2 = 93 g mol–1 (1)
93 – 16 = 77 (1)
Therefore B is phenylamine / C6H5NH2 (1) 6
There may be other valid structures that are amines. These can
be credited provided that everything adds up to 93.
Answer could be a primary, secondary or tertiary amines.
[6]
33. (a) (i) constant half-life (1) 1

(ii) rate = k[N2O5] (1) 1
Common error will be to use ‘2’ from equation.
(iii) curve downwards getting less steep (1)

curve goes through 1200,0.30; 2400,0.15; 3600,0.075 (1) 2
(iv) tangent shown on graph at t = 1200 s (1) 1
(v) 3.7(2) × 10–4 (1) mol dm–3 s–1 (1)

ecf possible from (ii) using [N2O5]x
(2nd order answer: 2.2(3) × 10–4) 2
[7]
34. (i) slow step (1) 1

PMT
(ii) (CH3)2C=CH2 + H2O → (CH3)3COH (1) 1
(iii) H+ is a catalyst (1)

H+ used in first step and formed in second step/
regenerated/ not used up (1) 2
(iv) rate = k [(CH3)2C=CH2] [H+] (1)
common error will be use of H2O instead of H+ 1
[5]
35. (a) High Pressure

Equilibrium → right as fewer moles on right hand side
and the shift reduces number of molecules/compensates
for increasing pressure (1)
Rate increases/ more collisions (1) 2
High temperature
Equilibrium → left as equilibrium goes to the left to
compensate for increased temperature/absorbs the
energy/in endothermic direction (ora) (1)
Rate increases/ more successful collisions (1) 2
Other effect
High pressures expensive/ high temperatures expensive
/high pressures cause safety problems (1) 1
QWC: One correct statement followed by correct explanation (1) 1
(b) (i) CO H2 CH3OH

1.0 2.0 0.0
0.9 1.8 (1) 0.1 (1)
0.9/2.8 or 0.321 or 0.32/0.3 1.8/2.8 or 0.643 or
0.64/0.6 0.1/2.8 or 0.036 or 0.04 (1)
3.21 (MPa) 6.43 (MPa) 0.36 (MPa) (1)
In 3rd and 4th rows, ecf from previous row 4
p(CH 3 OH)
(ii) Kp = (1)(1)
p(CO) × p(H 2 ) 2
1 mark for Kc / use of any [ ] /inverted/power missing. 2
(iii) Kp stays the same (1)

Equilibrium position moves to the right/yield increases (1)
in response to increase in reactants (1)
0.261
Kp = = 2.71 × 10–3 (1) MPa–2 (1) 3
3.70 × 5.10 2
(iv) calc value 2.7120546 × 10–3; answer and/or units ecf from (ii) 2
(c) CH3OH + 1.5O2 → CO2 + 2H2O (1) 1

[18]
PMT
36. (i) completely dissociates/ionised (1)

proton donor (1) 2
(ii) NO3– (1) 1

[3]
37. (i) pH = –log[H+] / –log(0.015) (1) = 1.82 / 1.8 (1) (Not 2) 2

(ii) [H+] = 0.0075 mol dm–3
pH = –log(0.0075) = 2.12 / 2.1 (1) 1
[3]
38. (i) Kw = [H+(aq)] [OH–(aq)] (1) 1

(ii) [H+(aq)] = 10–pH = 10–13.54 = 2.88/2.9 × 10–14 mol dm–3 (1)
Kw 1.0 × 10 −14
[NaOH] / [OH–(aq)] = =
[H + (aq)] 2.88 × 10 −14
= 0.347 / 0.35 mol dm–3 (1) 2
[3]
39. (i) a solution that minimises/resists/opposes pH changes (1) 1
(ii) The buffer must contain both CH3COOH and CH3COONa /

CH3COO– /weak acid and conjugate base(*) (1)
Solution A is a mixture of CH3COOH(*) and CH3COONa(*) /
/ has an excess of acid /is acidic (1)
Solution B, contains only CH3COONa/ only CH3COO–
/only the salt/ is neutral (1)
CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l) /
acid/alkali has been neutralised/
CH3COOH(aq) and NaOH react together (1) 4
[5]
PMT
40. [H+] increases (1)

H2O ionises more /
for H2O H+ + OH–, equilibrium moves to the right (1) 2
exo/endo is ‘noise’
[2]
Question Answer Marks Guidance
1 (a) +
Proton/H donor
AND
Partially dissociates/ionises  1
(b) FIRST, CHECK THE ANSWER ON ANSWER LINE
---------------------------------------------------------------------------------
1.00 × 10 –14 For pOH method:,
[H+] = OR 2(.00) × 10–14 (mol dm–3)  ALLOW pOH = –log[OH–] = 0.3(0) 
0.5(00)
(calculator 0.301029995)
pH = –log 2(.00) × 10–14 = 13.7(0)  2 ALLOW pH = 14 – 0.3 = 13.7 
ALLOW 13.7 up to calculator value of 13.69897 correctly

rounded.
ALLOW ECF from incorrect [H+(aq)] provided that pH >7

(c) (i) [H+ ] [C2H5COO – ] [H+ ]2 [H+ ] [A – ]
(Ka =)  1 IGNORE OR
[C2H5COOH] [C2H5COOH] [HA]
ALLOW [H3O+] for [H+]
PhysicsAndMathsTutor.com
(c) (ii) FIRST, CHECK THE ANSWER ON ANSWER LINE
---------------------------------------------------------------------------------
–3
[C 2H5COOH] = 0.12(0) mol dm  ALLOW HA for C2H5COOH and A– for C2H5COO–
[H+] = K a × [C2H5COOH] = 1.35 ×10−5 × 0.12(0)

ALLOW ECF from incorrectly calculated [C2H5COOH]
OR 1.27 × 10–3 (mol dm–3)  ALLOW 1.27 × 10–3 to calculator value of 1.272792206 ×
10–3 correctly rounded
pH = –log 1.27 × 10–3 = 2.9(0)  3
ALLOW 2.9(0) × 10–3 to calculator value of 2.895242493
NOTE: The final two marks are ONLY available from attempted correctly rounded
use of Ka AND [C2H5COOH]
ALLOW use of quadratic equation which gives same
answer of 2.90 from 0.120 mol dm–3
--------------------------------------------------------------------------
COMMON ERRORS (MUST be to AT LEAST 2 DP
unless 2nd decimal place is 0)
pH = 2.59 2 marks
–log√ (1.35 x 10–5 × 0.480) Original conc
pH = 5.79 2 marks
–log(1.35 x 10–5 × 0.120) No √
pH = 5.19 1 mark
–log (1.35 x 10–5 × 0.480) Original conc, no √
pH = 4.87 0 marks
–log(1.35 x 10–5) = 4.87 –log Ka
(d) (i) 2C2H5COOH + Na2CO3 → 2C2H5COONa + CO2 + H2O  1 IGNORE state symbols and use of equilibrium sign
FOR CO2 + H2O ALLOW H2CO3
ALLOW C2H5COO–Na+ OR C2H5COO– + Na+
BUT BOTH + and – charges must be shown
ALLOW NaC2H5COO
(d) (ii) H+ + OH– → H2O  1 ALLOW C2H5COOH + OH– → C2H5COO– + H2O
(e) (i) pH = –log 1.35 × 10—5 = 4.87  1 ONLY correct answer
DO NOT ALLOW 4.9 (Question asks for 2 DP)
(e) (ii) Added ammonia

C2H5COOH removes added NH3/alkali/base ALLOW use of HA/weak acid/acid for C2H5COOH;
OR C2H5COOH + NH3 / OH– →
OR NH3/alkali reacts with/accepts H+
OR H+ + NH3 → ALLOW use of NH4OH for NH3
OR H+ + OH– → 
Equlibrium → C2H5COO– OR Equilibrium → right  2 ALLOW A– for C2H5COO–
ASSUME that equilibrium applies to that supplied in the

question, i.e. IGNORE any other equilibria
(e) (iii) CHECK WORKING CAREFULLY AS CORRECT NUMERICAL FULL ANNOTATIONS MUST BE USED
ANSWER IS POSSIBLE FROM WRONG VALUES
================================================== -----------------------------------------------------------------------------
ALLOW HA and A– throughout For n(Mg), 1 mark
Amount of Mg (1 mark) ALLOW ECF for ALL marks below from incorrect n(Mg)
6.075
n(Mg) = 24.3 = 0.25(0) mol  ECF ONLY available from concentrations that have
------------------------------------------------------------------------------------ • subtracted 0.50 OR 0.25 from 1 for [C2H5COOH]
Moles/concentrations (2 marks) • added 0.50 OR 0.25 to 1 for [C2H5COO–]
i.
n(C2H5COOH) = 1.00 – (2 × 0.25) = 0.50 (mol)  For moles/concentration 1 mark (1 mark lost)
1. n (C2H5COOH) = 0.75 AND n(C2H5COO–) = 1.25
(C2H5COO–) = 1.00 + (2 × 0.25) = 1.50 (mol)  2. n(C2H5COOH) = 0.50 AND n(C2H5COO–) = 1.25
3. n(C2H5COOH) = 0.75 AND n(C2H5COO–) = 1.50
-n--------------------------------------------------------------------------------------- ----------------------------------------------------------------------------
[H+] and pH (1 mark) ALLOW ECF ONLY for the following giving 1 additional
0.50 mark and a total of 3 marks
+
] = 1.35 × 10 × 1.50 OR 4.5 × 10–6 (mol dm–3)
–5
0.75
[H 1. [H +] = 1.35 × 10–5 × 1.25 pH = –log 8.1 × 10–6 = 5.09
pH = –log 4.5 × 10–6 = 5.35 2 dp required  4
0.50
2. [H +] = 1.35 × 10–5 × 1.25 pH = –log 5.4 × 10–6 = 5.27
NOTE: IF there is no prior working,
0.50
ALLOW 4 MARKS for [H+] =1.35 × 10–5 × 1.50 AND pH = 5.35 0.75
3. [H +] = 1.35 × 10–5 × 1.50 pH = –log 6.75 × 10–6 = 5.17
IF the ONLY response is pH = 5.35, award 1 mark ONLY
Award a maximum of 1 mark (for n(Mg) = 0.25 mol) for:
pH value from Ka square root approach (weak acid pH)
pH value from Kw /10–14 approach (strong base pH)
---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
ALLOW alternative approach based on Henderson–Hasselbalch equation for final 1 mark
1.5 0.5
pH = pKa + log OR pKa – log pH = 4.87 + 0.48 = 5.35  ALLOW –log Ka for pKa
0.5 1.5
Total 16
2 (a) CH3COOH + H2O ⇌ H3O+ + CH3COO–  IGNORE state symbols (even if incorrect)
Acid 1 Base 2 Acid 2 Base 1 
2 ALLOW 1 AND 2 labels the other way around.
ALLOW ‘just acid’ and ‘base’ labels if linked by lines so that it is
clear what the acid–base pairs are
ALLOW A and B for ‘acid’ and ‘base’

ALLOW 2nd mark for idea of acid–base pairs, i.e.
CH3COOH + H2O ⇌ CH3COOH2+ + OH– 
Base 2 Acid 1 Acid 2 Base 1 
NOTE For the 2nd marking point (acid–base pairs),

(b) (i) Water dissociates/ionises ALLOW Kw = [H+] [OH–]

OR OR [H+] [OH–] = 10–14 (mol2 dm–6)
H2O ⇌ H+ + OH– IGNORE breaking for dissociation
OR
IGNORE water contains H+ and OH–
2H2O ⇌ H3O+ + OH–  1
IGNORE H2O → H+ + OH– i.e. no equilibrium sign
IGNORE 2H2O → H3O+ + OH– i.e. no equilibrium sign
(b) (ii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer, check to see if there is any
ECF credit possible using working below.
IF answer = 1.15  10–11, award 2 marks
-------------------------------------------------------------
--------------------------------------------------------------------–
ALLOW 2 SF: 8.7  10–4 up to calculator value of
+ –3.06 –4 –3
[H ] = 10 = 8.71  10 (mol dm )  8.7096359  10–4 correctly rounded
1.00  10–14 ALLOW alternative approach using pOH:

[OH–] = = 1.15  10–11 (mol dm–3)  2
8.71  10–4
pOH = 14 – 3.06 = 10.94 
ALLOW answer to two or more significant figures [OH–] = 10–10.94 = 1.15  10–11 (mol dm–3) 
2SF: 1.1  10–11; 4SF: 1.148  10–11;
calculator 1.148153621  10–11
(c) (i) IGNORE state symbols
2CH3COOH + CaCO3 → (CH3COO)2Ca + CO2 + H2O  1 ALLOW ⇌ provided that reactants on LHS
For CO2 + H2O, ALLOW H2CO3
ALLOW Ca(CH3COO)2
ALLOW (CH3COO–)2Ca2+
BUT DO NOT ALLOW if either charge is missing or incorrect
(c) (ii) ALLOW names: ethanoic acid for CH3COOH
solution contains CH3COOH AND CH3COO–  1 ethanoate for CH3COO–
ALLOW calcium ethanoate OR (CH3COO)2Ca for CH3COO–
IGNORE ‘acid, salt, conjugate base; responses must identify the

acid and conjugate base as ethanoic acid and ethanoate
IGNORE ethanoic acid is in excess (in question)

BUT DO ALLOW some ethanoic acid is left over/present/some
ethanoic acid has reacted
IGNORE equilibrium: CH3COOH ⇌ H+ + CH3COO–

Dissociation of ethanoic acid only
(c) (iii) Quality of written communication, QWC FULL ANNOTATIONS MUST BE USED
2 marks are available for explaining how the equilibrium --------------------------------------------------------------------------------
system allows the buffer solution to control the pH on addition Note: If there is no equilibrium equation then the two
of H+ and OH- (see below) subsequent equilibrium marks are not available: max 2
------------------------------------------------------
CH3COOH ⇌ H+ + CH3COO–  DO NOT ALLOW HA ⇌ H+ + A–
DO NOT ALLOW more than one equilibrium equation.
----------------------------------------------------- -----------------------------------------------------
ALLOW response in terms of H+, A– and HA
CH3COOH reacts with added alkali
OR CH3COOH + OH–  IF more than one equilibrium shown, it must be clear which one
OR added alkali reacts with H+ is being referred to by labeling the equilibria.
OR H+ + OH–  
Equilibrium  right OR Equilibrium  CH3COO–  (QWC) ALLOW weak acid reacts with added alkali
DO NOT ALLOW acid reacts with added alkali
CH3COO– reacts with added acid 
Equilibrium  left OR Equilibrium  CH3COOH  (QWC) 5

ALLOW conjugate base reacts with added acid
DO NOT ALLOW salt/base reacts with added acid
(d) FULL ANNOTATIONS MUST BE USED
--------------------------------------------------------------------------------
FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer, check to see if there is any
ECF credit possible.
IF answer = 11.48 OR 11.5 (g), award 5 marks
Incorrect use of [H+] = √( [CH3COOH]  Ka ) scores zero
--------------------------------------------------------------------– BUT IGNORE if an alternative successful method is present
[H+] = 10–5 (mol dm–3) 
Incorrect use of Kw, 1 max for [H+] = 10–5 (mol dm–3)
BUT IGNORE if an alternative successful method is present
-------------------------------------------------------------------------- ------------------------------------------------------------------------
1.75  105 ALLOW n(CH3COONa/CH3COO–)
[CH3COO–] =   0.200 = 0.350 mol dm–3 
10 –5
1.75 105
=   0.08 = 0.14(0) (mol) 
10–5
n(CH3COONa/CH3COO–) in 400 cm3
400 Note: There is no mark just for
= 0.350  = 0.14(0) (mol) 
1000 400
n(CH3COOH) in 400 cm3 = 0.200  = 0.08 (mol)
1000
------------------------------------------------------------------------ -----------------------------------------------------------
mass CH3COONa = 0.140  82.0 = 11.48 OR 11.5 (g)  As alternative for the 4th and 5th marks, ALLOW:
5
mass of CH3COONa in 1 dm3 = 0.350  82.0 = 28.7 g 
For ECF, n(CH3COONa/CH3COO–) must have been 400
calculated in step before mass of CH3COONa in 400 cm3 = 28.7  = 11.48 g 
1000
-------------------------------------------------------------
COMMON ECF
4.592 OR 4.6 g AWARD 4 marks
use of 400/1000 twice
ALLOW variants of Henderson–Hasselbalch equation.
pKa = –log(1.75 x 10–5) = 4.757  Calc: 4.75696…..
[CH3COO ]
log = pH – pKa = 5 – 4.757 = 0.243
[CH3COOH]
[CH3COO ]
= 100.243 = 1.75 
[CH3COOH]
[CH3COO–] = 1.75  0.200 = 0.350 mol dm–3 
n(CH3COONa/CH3COO–) in 400 cm3

400
= 0.350  = 0.14(0) (mol) 
1000
------------------------------------------------------------------------
mass CH3COONa = 0.140  82.0 = 11.48 OR 11.5 (g) 
Total 17
Question
uest er Marks Guidance
3 (a) 5 ANNOTATE WITH TICKS AND CROSSES, etc
HCl is a strong acid AND HClO is a weak acid  ALLOW HCl completely dissociates
AND HClO partially dissociates
HCl:
pH = –log 0.14 = 0.85 (2 DP required)  ALLOW HCl  H+ + Cl AND HClO ⇌ H+ + ClO–
IGNORE HCl is a stronger acid than HClO

IGNORE HCl produces more H+
HClO:
CHECK THE ANSWER ON ANSWER LINE
IF answer = 4.14, award all three calculation marks
IF there is an alternative answer, check to see if there is
--------------------------------------------------------------------
any ECF credit possible using working below
-------------------------------------------------------------
Ka = 10–7.43 OR 3.7 x 10–8 (mol dm–3) 
ALLOW 2 SF to calculator value: 3.715352291 x 10–8,
correctly rounded
[H+] = K a  [HClO] OR K a  [HA]
IGNORE ‘HCl’ if it is clear that it is a ‘slip’
OR K a  0.14 OR 3.7 x 108 x 0.14 
Always ALLOW calculator value irrespective of working as
pH = 4.14 (2 DP required)  number may have been kept in calculator.
Note: pH = 4.14 is obtained from all three values above
From no square root, pH = 8.28. Worth Ka mark only
Question
(b) 2 IGNORE state symbols
2Al + 6CH3COOH  2(CH3COO)3Al + 3H2  ALLOW correct multiples, e.g.:
Al + 3CH3COOH  (CH3COO)3Al + 1.5H2
ALLOW any unambiguous formula for (CH3COO)3Al,
i.e. (CH3CO2)3Al, Al(CH3CO2)3, (CH3COO–)3Al3+, etc.
Note: IF charges are shown, they must be correct with
both – and 3+ shown
2Al + 6H+  2Al3+ + 3H2  ALLOW multiples, e.g.:

Al + 3H+  Al3+ + 1.5H2
(c) FIRST, CHECK THE ANSWER ON ANSWER LINE 2

--------------------------------------------------------------------
Kw 1.0  10 14 1.0  10 14 ALLOW alternative approach using pOH:

[H+] = OR OR pOH = 0.4(0) 
[OH ] [OH ] 0.4(0)
OR 2.5 x 10 (mol dm–3) 
–14
pH = 14 – 0.40 = 13.6(0) 
Correctly calculates pH = –log 2.5 x 10–14 = 13.6(0)  ALLOW ECF from [H+] derived using Kw and [OH–]
BUT DO NOT ALLOW an acid pH.
ALLOW one or more decimal places
Question
(d) (i) 7 ANNOTATE WITH TICKS AND CROSSES, etc
A buffer solution minimises pH changes  ALLOW resists pH changes

ALLOW buffer solutions maintains a nearly/virtually
on addition of small amounts of acid/H+ or alkali/OH–/base  constant pH
DO NOT ALLOW a response that implies that the pH is
actually constant, e.g. does not change pH; maintains pH
-------------------------------------------------------------------------------- --------------------------------------------------------------------------
HCOOH ⇌ H+ + HCOO–  DO NOT ALLOW COOH– OR CHOOH OR COOH
Equilibrium sign essential DO NOT ALLOW HA ⇌ H+ + A–
For effect of acid and alkali, Quality of written communication, QWC

ALLOW wrong carboxylic acid (e.g. CH3COOH) OR HA; 2 marks are for explaining how the equilibrium system allows
ALLOW CHOOH for acid (effectively ECF) the buffer solution to control the pH on addition of H+ and OH–
ALLOW COOH– for base
ALLOW responses based on COOH ⇌ H+ + COO–
DO NOT ALLOW other incorrect formula, e.g. CH3OOH
Added alkali
HCOOH reacts with added alkali/base/OH– ALLOW HA OR weak acid reacts with added alkali
OR added alkali/OH– reacts with H+ 
QWC: Equilibrium shifts forming HCOO– OR H+ DO NOT ALLOW this mark if there is no equilibrium
OR (HCOOH) Equilibrium  right  system shown, e.g. HCOOH ⇌ H+ + HCOO– is absent
Added acid ALLOW A– OR conjugate base reacts with added acid

HCOO– reacts with added acid/H+  IGNORE salt reacts with added acid
QWC: Equilibrium shifts forming HCOOH DO NOT ALLOW this mark if there is no equilibrium
OR (HCOOH) Equilibrium  left  system shown, e.g. HCOOH ⇌ H+ + HCOO– is absent
Question
(d) (ii) HCOOH reacts with NaOH forming HCOO–/HCOONa 6 ANNOTATE WITH TICKS AND CROSSES, etc
OR DO NOT ALLOW just ‘methanoate/HCOO– forms’
HCOOH + NaOH  HCOONa + H2O  formulae or names of reactants also required
Equilibrium sign allowed
ALLOW HCOOH + OH–  HCOO– + H2O 
IGNORE conjugate base/salt forms
(Some) HCOOH/(weak) acid remains
OR HCOOH/(weak) acid is in excess  IGNORE HCOOH has been partially neutralised
Calculation
CHECK THE ANSWER IF answer = 3.99, award all four calculation marks
n(HCOOH) OR [HCOOH] Note: There must be a clear statement that 0.24 and 0.4
= 0.24(0) (mol / mol dm–3)  apply to moles or concentrations of HCOOH and HCOO–.
DO NOT ALLOW these values if unlabelled
n(HCOO–) OR [HCOO–] OR [HCOONa]
= 0.4(00) (mol / mol dm–3) 
[HCOOH] ALLOW HA/acid and A–/salt for HCOOH and HCOO–

[H+] = K a  
[HCOO– ]
DO NOT ALLOW ECF for this mark:

0.24
pH = –log [H+] = –log( 1.70  10 –4  ) = 3.99  3.99 is the ONLY correct answer
0.4 ---------------------------------------------------------------
---------------------------------------------------------- ALLOW HA/acid and A–/salt for HCOOH and HCOO–
OR use of Henderson–Hasselbalch equation: [HCOOH]
[HCOO ]
ALLOW pH = pKa – log
pH = pKa + log [HCOO ]
[HCOOH] [HCOOH]
[HCOO ]
OR pH = –logKa – log
OR pH = –logKa + log  [HCOO ]
[HCOOH]
ALLOW = 3.77 – (–0.22) = 3.99
= 3.77 + 0.22 = 3.99  DO NOT ALLOW ECF for this mark:
3.99 is the ONLY correct answer
Total 22
4 (a) (i) +
[H ][CH3 (CH2 )2COO ] – ALLOW CH 3 CH 2 CH 2 COOH OR C 3 H 7 COOH in expression
(K a =)  1
[CH3 (CH2 )2COOH] DO NOT ALLOW use of HA and A– in this part.
DO NOT ALLOW:
[H+ ][CH3 (CH2 )2COO – ] [H+ ]2
= : CON
[CH3 (CH2 )2COOH] [CH3 (CH2 ) 2COOH]
(ii) pK a = –logK a = 4.82  1 ALLOW 4.82 up to calculator value of 4.821023053
DO NOT ALLOW 4.8
(iii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF alternative answer to more or fewer decimal places, check
IF answer = 2.71 award 3 marks calculator value and working for 1st and 2nd marks
-------------------------------------------------------------------- ------------------------------------------------------------
ALLOW use of HA and A– in this part
[H+] = [K a ][CH3 (CH2 )2COOH] OR 1.51 10 5  0.250
Calculator: 1.942935923 x 10–3
 ALLOW use of calculated K a value, either calculator value or
rounded on script.
[H+] = 1.94 x 10–3 (mol dm–3)  pH must be to 2 decimal places
3 ALLOW ECF from incorrectly calculated [H+] and pH ONLY

pH = –log[H+] = 2.71  when values for both K a AND [CH 3 CH 2 CH 2 COOH] have been
used, i.e. 1.5 x 10–5 AND 0.250. e.g.:
pH = 5.42 2 marks –log(1.51 x 10–5 x 0.250) No √

5
1.51 10
pH = 2.11 2 marks –log( )
0.250
1.51 105
pH = 4.22 1 mark –log( ) No √
0.250
DO NOT ALLOW just –log(1.51 x 10–5) = 4.82 NO MARKS
(b) (i) Mg + 2H+  Mg2+ + H 2  1 IGNORE state symbols
ALLOW Mg + 2 CH 3 (CH 2 ) 2 COOH 
2CH 3 (CH 2 ) 2 COO– + Mg2+ + H 2
DO NOT ALLOW on RHS: (CH 3 (CH 2 ) 2 COO–) 2 Mg2+
Ions must be shown separately
(ii) CO 3 2– + 2H+  H 2 O + CO 2  1 IGNORE state symbols

ALLOW CO 3 2– + 2 CH 3 (CH 2 ) 2 COOH 
2 CH 3 (CH 2 ) 2 COO– + H 2 O + CO 2
ALLOW as product H 2 CO 3
(c) (i) CH 3 (CH 2 ) 2 COONa OR CH 3 (CH 2 ) 2 COO– forms ALLOW names throughout
OR ALLOW ‘sodium salt of butanoic acid’
CH 3 (CH 2 ) 2 COOH + OH–  CH 3 (CH 2 ) 2 COO– + H 2 O  ALLOW CH 3 (CH 2 ) 2 COOH + NaOH  CH 3 (CH 2 ) 2 COONa +
H2O
CH 3 (CH 2 ) 2 COOH is in excess OR acid is in excess DO NOT ALLOW just ‘forms a salt/conjugate base’
OR some acid remains  2 i.e. identity of product is required
(c) (ii) Moles (2 marks) ANNOTATIONS MUST BE USED
amount CH 3 (CH 2 ) 2 COOH = 0.0100 (mol)  --------------------------------------------------------------------------------
ALLOW HA and A– throughout
amount CH 3 (CH 2 ) 2 COO– = 0.0025 (mol)  2
Mark by ECF throughout
Concentration (1 mark)
[CH 3 (CH 2 ) 2 COOH] = 0.100 mol dm–3
AND
[CH 3 (CH 2 ) 2 COO–] = 0.025 mol dm–3  1
[H+] and pH (2 marks) ONLY award final 2 marks via a correct pH calculation via
0.100 [CH3 (CH2 ) 2COOH]
[H+] = 1.51 105  = 6.04 x 10-–5 (mol dm–3) Ka  using data derived from that in the
0.025 [CH3 (CH2 )2COO ]
 2 question (i.e. not just made up values)
-–5
pH = –log 6.04 x 10 = 4.22  pH to 2 DP
ALLOW alternative approach based on Henderson–Hasselbalch equation for final 2 marks
0.025 0.100
pH = pK a + log OR pK a – log  pH = 4.82 – 0.60 = 4.22  ALLOW –logK a for pK a
0.100 0.025
TAKE CARE with awarding marks for pH = 4.22 Common errors
There is a mark for the concentration stage. pH = 4.12
If this has been omitted, the ratio for the last 2 marks use of initial concentrations: 0.250 and 0.050 given in question.
will be 0.0100 and 0.0025. 4 marks max. Award last 3 marks for:
0.250/2 AND 0.050/2 = 0.125 AND 0.025 
Common errors 0.125
pH = 5.42 1.51 105  = 7.55 x 10-–5 (mol dm–3) 
0.025
As above for 4.22 but with acid/base ratio pH = –log[H+] = 4.12 
inverted.
Award 4 OR 3 marks Award last 2 marks for:
0.250
Award zero marks for: 1.51 105  = 7.55 x 10-–5 (mol dm–3) 
4.12 from no working or random values 0.050
pH value from K a square root approach (weak acid pH) pH = –log[H+] = 4.12 
pH value from K w /10–14 approach (strong base pH) pH = 5.52
As above for 4.12 but with acid/base ratio inverted.
Award 2 OR 1 marks as outlined for 4.12 above
(d) HCOOH + CH 3 (CH 2 ) 2 COOH ⇌ State symbols NOT required
HCOO– + CH 3 (CH 2 ) 2 COOH 2 + ALLOW 1 and 2 labels the other way around.
 ALLOW ‘just acid’ and ‘base’ labels throughout if linked by
lines so that it is clear what the acid-base pairs are
acid 1 base 2
base 1 acid 2  2 For 1st mark, DO NOT ALLOW COOH–
(i.e. H at end rather than start)
CARE: but within 2nd mark ALLOW COOH– by ECF
Both + and – charges are required for the products in
the equilibrium IF proton transfer is wrong way around then
DO NOT AWARD the 2nd mark from an equilibrium ALLOW 2nd mark for idea of acid–base pairs, i.e.
expression that omits either charge HCOOH + CH 3 (CH 2 ) 2 COOH ⇌
HCOOH 2 + + CH 3 (CH 2 ) 2 COO– 
base 2 acid 1
acid 2 base 1 
For H 2 COOH+ shown with wrong proton transfer,

DO NOT ALLOW an ECF mark for acid–base pairs
Total 16
Quest
Question er Mark Guidance
1 (a) (i) proton donor  1 ALLOW H+ donor
(ii) (the proportion of) dissociation  ALLOW a weak acid partly dissociates
ALLOW a strong acid totally dissociates
ALLOW ionisation for dissociation
ALLOW the ability to donate a proton
Correct equation for any of the four acids:

C6H5COOH ⇌ H+ + C6H5COO– Equilibrium sign required
ALLOW equilibria involving H2O and H3O+
OR CH3COOH ⇌ H+ + CH3COO–
e.g. C6H5COOH + H2O ⇌ H3O+ + C6H5COO– , etc
OR CH3COCOOH ⇌ H+ + CH3COCOO–
2 DO NOT ALLOW HA ⇌ H + A + –
OR CH3CHOHCOOH ⇌ H+ + CH3CHOHCOO– 
(iii) weakest: CH3COOH acetic acid ALLOW correct order using any identifier from the table,
C6H5COOH benzoic acid ie, common name, systematic name, structural formula OR pKa
CH3CHOHCOOH lactic acid value
strongest: CH3COCOOH  pyruvic acid 1
(iv) C6H5COOH2+ + CH3CHOHCOO–  BOTH products AND correct charges required for mark
1 Mark ECF from incorrect order in (iii)
See response from (iii) below response to (iv)
Quest
(b) (i) All species AND balancing required for the mark
2CH3COCOOH + Ca(OH)2 → (CH3COCOO)2Ca + 1 ALLOW (CH3COCOO–)2Ca2+
2H2O ALLOW equation showing 2CH3COCOO– + Ca2+
IF charges shown, charges must balance,
Note: pyruvic acid must have been used here and e.g. DO NOT ALLOW (CH3COCOO–)2Ca
formula of pyruvic acid and pyruvate must be correct IGNORE state symbols if shown
ALLOW multiples ALLOW equilibrium sign
(ii) H+ + OH– ⎯→ H2O 1 ALLOW multiples but not same species on both sides
ALLOW equilibrium sign
IGNORE state symbols if shown
ALLOW H3O+ + OH– ⎯→ 2H2O
ALLOW CH3COCOOH + OH– ⎯→ CH3COCOO– + H2O
(c) FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer, check to see if there is any ECF
IF answer = 2.11, award 4 marks credit possible using working below
-------------------------------------------------------------------- -------------------------------------------------------------
IF ECF, ANNOTATE WITH TICKS AND CROSSES, etc
Ka = 10–pKa
= 10–2.39 OR 0.00407  ALLOW 0.0041 to calculator value: 0.004073802
+ –
Ka = [H ] [CH3COCOO ] (ALLOW use of HA,H+ and A–)
[CH3 COCOOH] IF the pKa of a different weak acid has been used
use ECF from 2nd marking point
OR [H+] = √(Ka x [HA])

OR [H+] = 0.00407 × 0.0150  ALLOW 0.0078 to calculator value
(subsumes 1st marking point) (depending on previous rounding)
[H+] = 0.00782 (mol dm–3)  ALLOW ONLY 2.11
4 (This is to take into account poor previous rounding)
pH = –log 0.00782 = 2.11 
IF candidate has used 0.0150 mol dm–3 (ie assumes strong acid)
ALLOW final mark ONLY by ECF for a pH of 1.82
IF no square root used, pH = 4.21 3 marks
Quest
(d) (i) O O 1 ALLOW correct structural OR displayed OR skeletal formula OR
recognisable mixture of formulae
C C
DO NOT ALLOW molecular formula but
H O O H ALLOW (COOH)2 OR (CO2H)2
O O
C C
OH
ALLOW OH BUT not O–H–C
(ii) C2H2O4 ⇌ H+ + C2HO4–  2 ALLOW in either order

ALLOW arrow instead of equilibrium sign
C2HO4– ⇌ H+ + C2O42–  ALLOW molecular formulae for this part
ALLOW equilibria involving H2O and H3O+
ALLOW equations using structures
Quest
(e) Chemicals (1 mark) ANNOTATE WITH TICKS AND CROSSES, etc
lactic acid / CH3CHOHCOOH AND
(sodium) lactate / CH3CHOHCOO– (Na+)  ALLOW any lactate salt
ALLOW lactic acid AND NaOH
OR lactic acid AND OH–
---------------------------------------------------------------
FOR ALTERNATIVE using Henderson–Hasselbalch equation,
Concentrations (4 marks) SEE PAGE 11
--------------------------------------------------------------
If another weak acid has been selected and salt has been
selected, allow ECF for remainder of question SEE PAGE 12
EITHER --------------------------------------------------------------
[H+(aq)] = 10–3.55 OR 2.8 x 10–4 ALLOW 2.8 x 10–4 up to calculator value of 2.81838 x 10–4
OR 2.82 x 10–4 (mol dm–3) separate marking point ALLOW 0.00028, etc
Ka = 10–3.86 OR 1.4 x 10–4 OR 1.38 x 10–4 (mol dm–3) ALLOW 1.4 x 10–4 up to calculator value of 1.38038 x 10–4
 ALLOW 0.00014, etc
separate marking point
ALLOW use of CH3CHOHCOOH AND CH3CHOHCOO–(Na+)
ALLOW use of acid AND salt
[HA] [H+ ] [A − ] K
= OR = +a  calculated value of [H+ ]
[A − ] Ka [HA] [H ] ALLOW value from
calculated value of K a
[HA] 2.8 × 10–4 2 [A − ] 0.5 ALLOW 2SF up to calculator value of 2.041742129 correctly
−
= OR OR 2 OR = OR rounded but ALLOW 2 if 2.8 x 10–4 and 1.4 x 10–4 used
[A ] 1.4 × 10 –4
1 [HA] 1
ALLOW 2 mol dm–3 HA AND 1 mol dm–3 A–
0.5 OR any concentration ratio of 2(acid) : 1(salt)
This marking point subsumes previous marking point
ONLY ALLOW 2SF up to calculator value of 0.489778819 correctly
Comment (1 mark) rounded but ALLOW 0.5 if 2.8 x 10–4 and 1.4 x 10–4 used
Magic tang/taste could come from other 6
chemicals/substances in the sweet
OR
The buffer would have the same taste/tang as the
magic tang 
Quest
ALTERNATIVE approach for concentrations using
Henderson–Hasselbalch equation (4 marks) ALLOW use of CH3CHOHCOOH AND CH3CHOHCOO–(Na+)
ALLOW use of acid AND salt
[A − ] [A − ] [HA] [HA]
pH = pKa + log OR –logKa + log  ALLOW pH = pKa – log − OR –logKa – log −
[HA] [HA] [A ] [A ]
[A − ] [HA]
log = 3.55 – 3.86  (subsumes previous ALLOW log = 3.86 –3.55 (subsumes previous mark)
[HA] [A − ]
mark)
[HA]
− ALLOW log = 0.31 (subsumes previous mark)
log
[A ]
= –0.31  (subsumes previous mark) [A − ]
[HA]
[HA] 2.04 2
ALLOW = 100.31 = OR OR 2
[A − ] 0.490 −
[A ] 1 1
= 10–0.31 = OR 0.490 
[HA] 1 [A − ]
For , ALLOW 2 SF up to calculator value of 0.48978819
[HA]
[HA]
For , ALLOW 2 SF up to calculator value of 2.041737945
[A − ]
but ALLOW 2 if 10–0.31 used
Quest
(e) SUMMARY OF 4(e) MARKING POINTS FOR EACH POSSIBLE ACID CHOSEN
FIRST, CHECK THE ANSWER ON ANSWER LINE: IF answer is correct for weak acid chosen, award MP2–MP5
IF there is an alternative answer, check to see if there is any ECF credit possible using working below
lactic
a yruvic acetic benzoic
pKa 3.86
.86 4.19
lactic AND lactate
MP1 No mark No mark No mark
OR lactic acid AND OH–
MP2: [H+] 10–3.55 OR 2.82 x 10–4 ( calc: 2.81838 x 10–4 )
MP3: Ka 10–3.86 OR 1.38 x 10–4 10–2.39 OR 4.07 x 10–3 10–4.76 OR 1.74 x 10–5 10–4.19 OR 6.46 x 10–5
calc: 1.380384265 x 10–4 4.073802778 x 10–3 1.737800829 x 10–5 6.45654229 x 10–5
MP4: ratio [HA] [H+ ] [A − ] K

= OR = +a
expression [A − ] Ka [HA] [H ]
MP5:
[HA] 2.82 × 10 –4 2.82 × 10 –4 2.82 × 10 –4 2.82 × 10 –4
OR 2.04 OR 0.0693 OR 16.2 OR 4.37
[A − ] 1.38 × 10 –4 4.07 × 10 –3 1.74 × 10 –5 6.46 × 10 –5
calc: 2.041737945 calc: 0.069183097 calc: 16.21810097 calc: 4.365158322
[A − ] 1.38 × 10 –4 4.07 × 10 –3 1.74 × 10 –5 6.46 × 10 –5

OR OR 0.489 OR 14.4 OR 0.0617 OR 0.229
[HA] 2.82 × 10 –4 2.82 × 10 –4 2.82 × 10 –4 2.82 × 10 –4
calc: 0.489778819
.489778819 0.0616595 0.229086765
TAKE CARE: Calc values are completely unrounded and may differ between brands of calculator
Use actual candidate values at each stage using rounding to 2 or more SF.
MP5: calculated using 3 SF from MP2 and MP3
calc values for MP5 are completely unrounded (using calculator values from MP2 and MP3)
Be slightly flexible as candidates may have written down rounded values but carried on with calculator values
– This appr ach is ACCEPTABLE
Total 20
Question Expected Answers Marks Additional Guidance
2 a 4 ALLOW C2H5 throughout question
measured pH > 1 OR [H+] < 0.1 (mol dm–3)  ALLOW [H+] < [CH3CH2COOH] OR [H+] < [HA]
ALLOW measured pH is higher than expected
ALLOW measured pH is not as acidic as expected
ALLOW a quoted pH value or range > 1 and < 7
OR between 1 and 7
[H+] = 10–pH  ALLOW [H+] = antilog –pH OR [H+] = inverse log –pH
Ka = [H+][CH3CH2COO–] OR [H+]2  ALLOW [H+][A–] OR [H+]2

[CH3CH2COOH] [CH3CH2COOH] [HA] [HA]
[H+ ]2 [H+ ]2
Calculate Ka from  IF Ka is NOT given and Ka = is shown, award mark for Ka also
0.100 0.100
[H+ ]2
(i.e. Ka = is automatically awarded the last 2 marks)
0.100
b Marks are for correctly calculated values. 2 ALLOW 3.467368505 × 10–14 and correct rounding to 3.5 × 10–14
Working shows how values have been derived.
[H+] = 10–13.46 = 3.47 x 10–14 (mol dm–3)  ALLOW 0.28840315 and correct rounding to 0.29,
i.e. ALLOW 0.288
[OH–] = 1.0 × 10–14 = 0.29 (mol dm–3) 
3.47 × 10–14 ALLOW alternative approach using pOH:
pOH = 14 – 13.46 = 0.54 

[OH–] = 10–0.54 = 0.29 (mol dm–3) 
Correct answer gets BOTH marks
c 7 ANNOTATIONS MUST BE USED
Propanoic acid reacts with sodium hydroxide ALLOW C2H5 throughout question
forming propanoate ions/sodium propanoate ALLOW Adding NaOH forms propanoate ions/sodium propanoate
OR (imples that the NaOH is added to the propanoic acid)
CH3CH2COOH + NaOH  CH3CH2COONa + H2O 
Some propanoic acid remains

OR
propanoic acid AND propanoate (ions)
/ sodium propanoate present  ALLOW: weak acid AND its conjugate base/salt present
Throughout, do not penalise comments that imply that pH is constant in

presence of buffer
equilibrium: CH3CH2COOH ⇌ H+ + CH3CH2COO– DO NOT ALLOW HA and A– in this equilibrium expression
For description of action of buffer below,

ALLOW HA for CH3CH2COOH; ALLOW A– for CH3CH2COO–
Equilibrium responses must refer back to a written equilibrium.

IF no equilibrium shown, use the equilibrium as written in expected
answers (which is also written on page 6 of the paper)
Added alkali
CH3CH2COOH reacts with added alkali
ALLOW weak acid reacts with added alkali
OR CH3CH2COOH + OH– 
OR H+ + OH–  
 CH3CH2COO– OR Equilibrium  right 
Added acid
CH3CH2COO– reacts with added acid ALLOW conjugate base reacts with added acid
OR [H+] increases  DO NOT ALLOW salt reacts with added acid
 CH3CH2COOH OR Equilibrium  left 
5
d HNO3 + CH3CH2COOH ⇌ CH3CH2COOH2+ + NO3 
– 2 State symbols NOT required
acid 1 base 2 acid 2 base 1  ALLOW 1 AND 2 labels the other way around.
ALLOW ‘just acid’ and ‘base’ labels throughout if linked by lines so that
it is clear what the acid–base pairs are.
IF proton transfer is wrong way around then ALLOW 2nd mark for idea
of acid–base pairs, i.e.
HNO3 + CH3CH2COOH ⇌ CH3CH2COO– + H2NO3+ 
base 2 acid 1 base 1 acid 2 
e i 2CH3CH2COOH + Mg  (CH3CH2COO)2Mg + H2  1 IGNORE state symbols

ALLOW ionic equation: 2H+ + Mg  Mg2+ + H2
IGNORE any random charges in formula of (CH3CH2COO)2Mg

as long as the charges are correct (charges are treated as working)
i.e. (CH3COO–)2 Mg OR (CH3COO)2– Mg should not be penalised
However, Mg2+ instead of Mg on the left side of equation is obviously
wrong
ii 2H+ + CO32–  H2O + CO2 1 State symbols NOT required

OR 2H+ + CO32–  H2CO3
OR H+ + CO32–  HCO3–
Total 17
Question Expected answers Marks Additional guidance
3 a A strong acid completely dissociates ALLOW ionises for dissociates
AND
a weak acid partially dissociates  1
ii [H+ ] [NO2– ] [H+ ]2

(Ka =)  1 DO NOT ALLOW
[HNO2 ] [HNO2 ]
Square brackets are required
iii FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer to more decimal places,
IF answer = 1.89 award 2 marks check calculator value
IF answer = 1.9 award 1 mark
-------------------------------------------------------------------- -------------------------------------------------------------
Working to get to 0.0129 (mol dm–3)
Not required and no credit
[H+] = K a  [HNO2 ] = 4.43  10 4  0.375
pH = –log 0.0129 = 1.89 
OR
pH = –log 0.0129 = 1.9  not two decimal places 2 ALLOW 1 mark for an answer with more than 2 decimal
places that rounds back to 1.89
iv HNO + HNO2 ⇌ NO3– + H2NO2+  State symbols NOT required

3
Acid 1 Base 2 Base 1 Acid 2  2
ALLOW 1 AND 2 labels the other way around.
ALLOW ‘just acid’ and ‘base’ labels if linked by lines so that
it is clear what the acid–base pairs are

ALLOW 2nd mark for idea of acid–base pairs, i.e.
HNO3 + HNO2 ⇌ H2NO3+ + NO2– 
Base 2 Acid 1 Acid 2 Base 1 
NOTE For the 2nd marking point (acid–base pairs),

b Proton acceptor  1 ALLOW H+ acceptor
ii Marks are for correctly calculated values.

Working shows how values have been derived.
[OH–] = 2 × 0.04(00) = 0.08(00) (mol dm–3) 

+ 1.00  10 –14 –13 –3
1.00  1014
[H ] = OR 1.25 × 10 (mol dm )  ALLOW by ECF
0.08(00) calculated value of [OH ]
pH = –log 1.25 × 10–13 = 12.90  DO NOT ALLOW 12.9 not two decimal places
--------------------------------------------- ---------------------------------------
pOH variation (also worth 3 marks) 3 COMMON ERRORS
[OH–] = 2 × 0.04(00) = 0.08(00) (mol dm–3)  12.60  no × 2 for [OH–]
12.6  no × 2 for [OH–] AND 1 DP only
pOH –log 0.08(00) = 1.10  12.30  ÷ 2 [OH–]
12.3  ÷ 2 [OH–] AND 1 DP only
pH = 14.00 – 1.10 = 12.90  1.40 NO marks
c Ca(OH)2 + 2HNO2  Ca(NO2)2 + 2H2O 
H+ + OH–  H2O  2 ALLOW: 2H+ + 2OH–  2H2O
d ANNOTATIONS MUST BE USED
Equilibrium Equilibrium sign is required
H2CO3 ⇌ H+ + HCO3–  IGNORE HA ⇌ H+ + A–
DO NOT ALLOW H2CO3 ⇌ 2H+ + CO32–
DO NOT ALLOW NaHCO3 ⇌ Na+ + HCO3–
IGNORE H2O + CO2 ⇌ H2CO3
Action of buffer IF HA ⇌ H+ + A– OR H2CO3 ⇌ 2H+ + CO32– have been

used above:
ALLOW all marks that meet marking alternatives as written
NOTE The 1st ‘added acid’ mark cannot then be accessed
Equilibrium responses must refer back to a written

equilibrium
BUT IF H2CO3  H+ + HCO3– shown above, assume that
any equilibrium comments apply to the correct equilibrium
Added alkali IF more than one equilibrium shown, it must be clear which
H2CO3 reacts with added alkali equilibrium is being referred to
OR H2CO3 + OH– 
OR added alkali reacts with H+ ALLOW added alkali reacts with weak acid
OR H+ + OH–  
Quality of Written Communication
Mark is for linking the action of the buffer in controlling
added alkali and hence pH
Equilibrium  right
OR equilibrium shifts forming H+ OR HCO3– 
Added acid 5 HCO3– is required for this mark BUT …
HCO3– reacts with added acid  ALLOW added acid reacts with conjugate base ONLY if
HCO3– is present in equilibrium with H2CO3
Equilibrium  left DO NOT ALLOW salt reacts with added acid
OR equilibrium shifts forming H2CO3 
d ii FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer, check to see if there is any
IF answer = 6.6 : 1 OR 1 : 0.15 ECF credit possible using working below
CHECK ratio is HCO3– : H2CO3 and award 5 marks. -----------------------------------------------------------
IF answer = 0.15 : 1 , ANNOTATIONS MUST BE USED
CHECK ratio is H2CO3 : HCO3– and award 4 marks FOR ALTERNATIVE using Henderson–Hasselbalch
-------------------------------------------------------------------- equation below
In blood at pH 7.40, --------------------------------------------------------------
[H+] = 10–pH = 10–7.40 = 3.98 × 10–8 (mol dm–3)  ALLOW 3.98 × 10–8 up to calculator value of
[H+ ] [HCO3– ] 3.98  10 –8  10.5 3.981071706 × 10–8 correctly rounded
Ka = =
[H2CO3 ] 1
OR Ka = 4.18 × 10 (mol dm–3) 
–7
In blood at pH 7.20, ALLOW 6.31 × 10–8 up to calculator value of

[H+] = 10–pH = 10–7.20 = 6.31 × 10–8 (mol dm–3)  6.309573445 × 10–8 correctly rounded
[HCO3– ] Ka 4.18  10 7 -----------------------------------------------------------------------------
 OR  Common errors
[H2CO3 ] [H+ ] 6.31 10 –8
0.15 : 1  Inverse ratio of H2CO3 : HCO3–
6.6 5 16.6 : 1 OR 0.06 : 1  10.5/1 swapped over in 2nd
= OR 6.6 : 1  (up to calc. value, see below)
1 mark giving Ka value of 3.79 x 10–9
ALLOW any answer with > 1 decimal place that ALLOW answer with > 1 decimal place that rounds back to
rounds back to 6.62 OR 6.63 16.64 OR 16.65
ALTERNATIVE approach for concentrations using Henderson–Hasselbalch equation (5 marks)
[HCO3– ] [HCO3– ]
pH = pKa + log OR –logKa + log 
[H2CO3 ] [H2CO3 ]
[HCO3– ] 10.5
pKa = pH – log = 7.40 – log = 6.38  (subsumes previous mark) Calculator: 6.378810701
[H2CO3 ] 1
–
[HCO ]
At pH = 7.20, log 3
= pH – pKa = 7.20 – 6.38 = 0.82  (subsumes previous mark)
[H2CO3 ]
[HCO3– ] 6.6
= 100.82  = OR 6.6 : 1 
[H2CO3 ] 1
Total 22
Question Answer Mark Guidance
1 (a) (i) HOCH 2 COOH + NaOH  HOCH 2 COONa + H 2 O 1 ALLOW: HOCH 2 COOH + OH–  HOCH 2 COO– + H 2 O
 ALLOW: H+ + OH–  H 2 O
DO NOT ALLOW molecular formulae
(cannot see which OH has reacted)
(ii) FIRST, CHECK THE ANSWER ON ANSWER LINE IF there is an alternative answer, check to see if there is any
IF answer = 0.142 (mol dm–3), award 2 marks ECF credit possible using working below
-------------------------------------------------------------------- -------------------------------------------------------------
25.0 ANNOTATE WITH TICKS AND CROSSES, etc
amount of HOCH 2 COOH = 0.125 
1000
= 0.003125 (mol)  ALLOW 3.125 × 10–3 mol
1000 1000
concentration NaOH = 0.003125 × ALLOW ECF: answer above ×
22.00 22.00
= 0.142 (mol dm–3)  2 ALLOW 2 SF: 0.14 to calculator value: 0.142045454
--------------------------------------------------------------------- -----------------------------------------------------------------------------
If candidate has written in (a)(i): HOCH 2 COOH + 2NaOH,
mark by ECF:
1000
concentration NaOH = 2 × 0.003125 ×
22.00
= 0.284 (mol dm–3)
(iii) Vertical section matches the (pH) range (of the ALLOW stated pH range for vertical section at about
indicator) 7–10, 6–10, etc
OR colour change (of the indicator) 1 ie ALLOW ‘pH range must be about 7–10’
OR end point (of the indicator)  ALLOW ‘pH changes rapidly’ for vertical section
ALLOW ‘equivalence point’ for vertical section,
ie ALLOW equivalence point matches the (pH) range, etc
DO NOT ALLOW just ‘end point matches (pH) range’

DO NOT ALLOW just ‘indicator matches vertical section’
Response must link either the pH range or colour change or

end point with the vertical section / pH range ~ 7–10
Quest
(b) (i) H  HOCH2COO 
+ – IGNORE state symbols
(K a =)     
1 2
HOCH2COOH H+ 
IGNORE   in (i) but ALLOW in (ii)
HOCH2COOH
IF answer = 1.46 x 10–4, award 2 marks ECF credit possible using working below
THEN IF units are mol dm–3, award 1 further mark UNITS can be credited with no numerical answer
--------------------------------------------------------------------- ----------------------------------------------------------------------
ANNOTATE WITH TICKS AND CROSSES, etc
[H+] = 10–2.37 = 0.00427 (mol dm–3)  ALLOW 4.27 x 10–3 (mol)

ALLOW 2 SF: 0.0043 up to 0.0042 5795188 (calc value)
2
K a = 0.00427 = 1.46 × 10–4 
0.125 2 IF candidate has rounded to 0.00427 (mol dm–3) in 1st
response, credit
EITHER
2 SF: 1.5 x 10–4 up to 1.458632 × 10–4 (from 0.00427)
OR
2 SF: 1.5 x 10–4 up to 1.455760687 × 10–4 (from unrounded
calculator value of 0.004265795188)
ALLOW calculation based on equilibrium conc of glycolic acid

as 0.125 – [H+]:
0.00427 2
Using [H+] = 0.00427, K a = = 1.51 × 10–4
units: mol dm  –3 1 0.125  0.00427
For UNITS this is the ONLY correct answer
(iii) ALLOW ECF using calculated [H+] from b(ii),

% dissociation = 0.00427  100 = 3.4 (%) 
0.125 1 ALLOW 2 SF: 3.4 % up to calculator value
+
Assume working from EITHER from a rounded [H ]
OR unrounded calculator value of b(ii) [H+] Note: [H+] from b(ii) displayed at top of answer window
DO NOT MARK THIS TWICE!
(c) ONE mark for equilibrium expression ANNOTATE WITH TICKS AND CROSSES, etc
equilibrium: HOCH 2 COOH ⇌ H+ + HOCH 2 COO– 1 DO NOT ALLOW H+, A– and HA
ALLOW < – > as alternative for equilibrium sign
--------------------------------------------------------------------- ---------------------------------------------------------------------
Four marks for action of buffer ALLOW response in terms of H+, A– and HA
Equilibrium responses must refer back to a written equilibrium:
IF more than one equilibrium shown, assume correct one
HOCH 2 COOH reacts with added alkali ALLOW weak acid reacts with added alkali
DO NOT ALLOW acid reacts with added alkali
OR HOCH 2 COOH + OH– 
OR H+ + OH–  
 HOCH 2 COO–
OR Equilibrium  right 
HOCH 2 COO– reacts with added acid  ALLOW conjugate base reacts with added acid
 HOCH 2 COOH DO NOT ALLOW salt/base reacts with added acid
OR Equilibrium  left  4
--------------------------------------------------------------------- ---------------------------------------------------------------------
Two marks for preparation of buffer
Ammonia reacted with an excess of glycolic acid
OR some glycolic acid remains  ALLOW as products HOCH 2 COO– + NH 4 +
HOCH 2 COOH + NH 3  HOCH 2 COONH 4  2 ALLOW ⇌ sign instead of 
(d) Base 1 + Acid 2 ⇌ Acid 1 + Base 2 ALLOW: Base 2 + Acid 1 ⇌ Acid 2 + Base 1
1st mark for identifying acids and bases. 
2nd mark for correct pairing (ie numbers)  2
(e) 2HSCH 2 COO– + R–S–S–R ALLOW (SCH 2 COO–) 2
 –OOCCH 2 S–SCH 2 COO– + 2 SH  ALLOW equation with ammonium salt, ie:
2R–SH + H 2 O 2  R–S–S–R + 2H 2 O  2 2HSCH 2 COONH 4 + ………

 H 4 NOOCCH 2 S–SCH 2 COONH 4 + ………
Total 20
2 (a) (i) (K w = ) [H+(aq)] [OH–(aq)]  1 IGNORE state symbols
ALLOW [H 3 O+(aq)] [OH–(aq)]
IF answer = 2.3 × 10–10 (mol dm–3), award 2 marks ECF credit possible using working below
IF answer = 2.34 × 10–10 (mol dm–3) , award 1 mark ANNOTATE WITH TICKS AND CROSSES, etc
--------------------------------------------------------------------- ----------------------------------------------------------------------
------ ALLOW 4.3 × 10–5 up to calculator: 4.265795188 × 10–5
[H+] = 10–pH = 4.27 × 10–5 (mol dm–3)  ALLOW 0.0000427
1.0  1014 Answer MUST be to 2 SF (in question)

[OH–] = ALLOW = 2.3 ×10–x (mol dm–3) for 1 mark
4.27  10 5
= 2.34 × 10–10 (must be a negative power)
= 2.3 × 10–10 (mol dm–3)  2
ALLOW alternative approach based on pOH:
pOH = 14 – 4.27 = 9.63  (DO NOT ALLOW 9.6)
[OH–] = 10–pOH = 10–9.63 = 2.3 × 10–10 (mol dm–3) 
(b) (i) Endothermic because K w increases with 1 Endothermic AND reason required for the mark
temperature  ALLOW Endothermic because increasing temperature shifts
equilibrium/reaction to the right
(ii) ANNOTATE WITH TICKS AND CROSSES, etc

K w value from graph from 2.2 to 2.6 × 10–14 (mol2 Actual K w = 2.38 × 10–14 mol2 dm–6
dm–6)
For this mark, candidate must use a value between 2.0 and
Using 2.4 × 10–14, 3.0 × 10–14 (mol2 dm–6), ie from the approximately correct
[H+] = 2.4  1014 OR 1.55 × 10–7  region of the graph,
3 ALLOW 6.8 up to calculator value

–7
pH = –log (1.55 × 10 ) = 6.81 Note: You will need to calculate the pH value from the
(using K w = 2.4 × 10–14)  candidate’s estimate of K w at 37 ºC before awarding the 3rd
marking point
ONLY award an ECF pH mark if candidate has generated a
value of [H+] by attempting to take a square root of a value
between 2.0 and 3.0 × 10–14
(b) (iii) (Work is) inaccurate OR invalid Response requires reason for inaccuracy/invalidity in terms of
because K w varies with temperature  1 Kw
ALLOW incorrect with reason
IGNORE unreliable
ALLOW inaccurate because wrong K w was used
For K w varies with temperature, ALLOW equilibrium shifts with
temperature
(c) ANNOTATE WITH TICKS AND CROSSES, etc
Acid and alkali mixed  ALLOW ‘base’ for ‘alkali throughout

ALLOW if mentioned anywhere which could be within a
definition for enthalpy change of neutralisation
Amounts of acid AND alkali stated  Amounts could be expressed as amounts, moles, volumes OR
concentrations
Temperature taken at start AND finish  ALLOW temperature change
energy, Q = mc∆T OR in words m = mass/volume of solution/reactants/mixture, etc

AND meaning of m, c AND ∆T given  (but NOT surroundings)
c = (specific) heat capacity (of solution/water) OR 4.18/4.2
∆T = temperature change
Energy scaled up to form 1 mol of water  ALLOW divide energy by moles
Q
∆H neut = –energy change  6 ALLOW ‘–‘ sign shown in earlier part, ie ∆H neut = 
n
ALLOW a statement linking ∆H with temperature change, ie:
IF temperature increases, ∆H neut is –ve
OR IF temperature decreases, ∆H neut is +ve
(d) ANNOTATE WITH TICKS AND CROSSES, etc
Throughout question, ORA in terms of Rb+

Throughout question, ALLOW energy for enthalpy
Ionic radius
Potassium ion OR K+ OR K ion is smaller DO NOT ALLOW potassium OR K OR reference to atoms
OR K+ has greater charge density  (ie reference to ions is required throughout a response)
Lattice enthalpy
Lattice enthalpy of KF is more negative than RbF  ALLOW lattice enthalpy of KF > lattice enthalpy of RbF
OR
K+ has greater attraction for F– ALLOW more energy needed to separate K+ AND F–
IGNORE KF has stronger bonds
Hydration enthalpy
∆H(hydration) of K+ is more negative than Rb+  ALLOW ∆H(hydration) of K+ > ∆H(hydration) of Rb+
OR
K+ has greater attraction for H 2 O ALLOW more energy needed to separate K+ AND H 2 O
IGNORE K+ has a stronger bond to H 2 O
Enthalpy change of solution
Idea that ∆H(solution) is affected more by lattice ALLOW a correct attempt to link the contribution of lattice
enthalpy than by hydration enthalpy  4 enthalpy and hydration enthalpy to ∆H(solution), ie lattice
enthalpy is a more important factor than hydration enthalpy
(e) (During dissolving,) entropy/disorder increases ALLOW entropy change is positive

OR disorder increases  OR ∆S is positive
OR T∆S is positive
T∆S > ∆H ALLOW ∆S(system) > ∆H/T

OR T∆S is more positive than ∆H ALLOW ∆S(system) is more positive than ∆H/T 
OR ∆H – T∆S is negative  2 ALLOW ∆S(system) + ∆S(surroundings) is positive
ALLOW Energy contribution from increase in entropy is greater

than decrease in energy from enthalpy change
OR entropy change outweighs enthalpy change
IGNORE ∆G is negative
Total 20

MS Acids Bases Buffers ALL PPQ

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5.1.3 Acids, Bases and Buffers PhysicsAndMathsTutor.

Mark scheme – Acids, Bases and Buffers

IGNORE state symbols (even if wrong)

IF proton transfer is wrong way around

NOTE For the 2nd marking point (acid–base

ALLOW 2SF up to calculator value of

Calculation of CH3COOH in buffer

Calculation of [CH3COO–] in buffer (in 1 dm3)

ALLOW 1.5 × 10–2 up to calculator value

Calculation of original [CH3COO–] (in 600 cm3)

COMMON ERRORS BUT CHECK

[CH3COOH] : [H+] inverted 2 marks

ALLOW –logKa for pKa

log[CH3COO–] = 4 – 4.75 – 1.09 = –1.84 ✓

[CH3COO–]buffer = 1.5 × 10–2 ✓ ------------------------------------------

[CH3COO–]initial = 2.4 × 10–2 ✓ Examiner’s Comments

This question required the candidate to

ALLOW acid–base pairs labelled other way

If ONE charge is missing from equilibrium.

For an equilibrium shown using CH3COOH instead of H2O,

ALLOW maths explanation for final 2

Most candidates completed a correct

Candidates found it much more difficult to

Some candidates approached their

ALLOW ECF throughout

ONLY ALLOW pH mark by ECF if Ka AND

Common errors (Must be to 2 DP)

Most candidates could calculate the pH of a

ALLOW 0.02 dm3 if unit given

Showing by calculation something already

Clarity of working is essential and in

ALLOW ECF throughout

= 0.0045 – 0.002 = 0.0025 (mol) ✓ =4.(00) × 10–12 (mol dm–3)

= 2.8 × 10–13 (mol dm–3) ✓

This calculation proved difficult with once

Responses to 20bi/ii often featured rows of

If pH curves wrong way round (i.e. adding

This weak acid / strong alkali titration curve

The key points to titration curves are:

• A ‘vertical’ section at the end point

• The vertical section was at 20 cm3

ALLOW pH range (of the indicator) matches

End point must not refer to same pH

ALLOW different equivalence point

The most common error was to write ‘HIO3

The subtlety in this question was to realise

that because Ka was relatively high, the

Indicative scientific points may include:

• Ka = 10–6.38 OR 4.17 × 10–7 (mol

And ratio = 1 : 0.095 ..

The calculation of the [HCO3–] : [H2CO3]

The buffer reactions on separate addition of

The direction of shift on the H2CO3 ⇌ H+ +

An example of a complete answer gaining

The candidate clearly writes the equilibrium

The first bullet point gives a chemical

equation for the reaction occurring when H+

The second bullet point gives a chemical

The steps in the calculation are clearly

This part tested an understanding of pH as a

Initial rate = 10–2 × 2.4 × 10–3 s–1 1

Many candidates found the calculation

IGNORE state symbols