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1.

B
[1]

2.

(a)

(i)

Mark the two points independently, subject to the constraint in


Reject column
Effect:
(Equilibrium) shifts to the right (1)
ALLOW: favours forward reaction / increase the amount of product
/ increase the yield (of product)
Reason:
Exothermic (in forward direction) (1)
NOTE: Just (equilibrium) shifts in the exothermic direction
scores (1)

Equilibrium shifts to left will score (0) for (a)(i)


(ii)

First mark:
Activation energy for the reaction is too high / (if cooled) molecules
would not have enough energy to react / few(er) molecules have the
required Ea/more molecules have energy Ea at higher temperatures
OR
not (technologically) feasible to cool the gases before they enter the
converter/costly to cool the gases (1)
Second mark:
(cooling the gases would make) the rate (too) slow /rate is faster if the
temperature is high (so the gases are not cooled) (1) 2
Cooling the gases decreases the yield (of products) /an
incorrect Le Chatelier argument

(iii)

Mark the two points independently, subject to the


constraint in Reject column
Effect:
(Equilibrium) shifts to the right
ALLOW: favours forward reaction / increase the amount of product /
increase the yield of product (1)
Reason:
Shifts / moves in the direction of fewer (moles of gas) molecules
ALLOW shifts in direction of fewer moles (of gas molecules) (1)
IGNORE effect on the rate

Equilibrium shifts to left will score (0) for (a)(iii)


.... fewer atoms

(b)

(i)

(In NO): +2 / 2+ (1)

(In NO3 ): +5 / 5+ (1)


NOTE:
(In NO): Just 2
AND

(In NO3 ): Just 5 scores (1)

(ii)

NO3 + 4H + 3e NO + 2H2O
ACCEPT multiples

(iii)

Ag Ag + e

()

2
()

/ Ag e

Ag

ACCEPT multiples
IGNORE state symbols, even if incorrect
Ag + e

(iv)

3Ag + NO3 + 4H

Ag+
+

3Ag + NO + 2H2O (2)

(1) for multiplication of the silver half-equation by three or cq multiple


from (b)(ii)
(1) for rest of equation correct
NOTE: Equation must be completely correct for the second mark.
IGNORE state symbols, even if incorrect

if any e are left in the final equation, second mark cannot be


scored
[13]

3.

C
[1]

4.

B
[1]

5.

C
[1]

6.

C
[1]

7.

A
[1]

(K p u u ) pCH 3 CO 2 H

8.

(a)

(i)

pCH 3 OH ( x ) pCO

Partial pressure symbol can be shown in various ways, eg pp,


pCO, (CO)p, etc
ALLOW p in upper or lower case, round brackets
IGNORE units

[]
State symbols given as (l)
+ in bottom line
(ii)

P CH3OH = 4.9 (atm) (1)


P CO = 4.9 (atm) (1)
1 mark for recognition that pressures are equal
IGNORE units

(iii)

2
2

Kp = ((22.2)/(4.9) )
= 0.925 (1)
1

atm (1) stand alone mark but must match expression used in (a)(iii)
OR
4

9.25 10 Pa / 92.5 kPa (2)


ALLOW TE from (a)(i) if inverted and/or (a)(ii)

Answers to other than 3 significant figures


(b)

(i)

CH3OH: 3.2
CO : 3.2 (1) for both values
CH3CO2H: 46.8 (1)
ALLOW TE for moles of ethanoic acid based on numbers of
methanol and carbon monoxide used, as long as moles of methanol
and carbon monoxide are equal and moles ethanoic acid +
moles methanol = 50

(ii)

46.8 32

53.2 = 28.2 / 28.1504 (atm)


IGNORE sf except 1
Value = 28.16 if mol fraction rounded
ALLOW TE from (b)(i)

28.1
46.8 32
50
= 29.95 (atm)
(iii)

(c)

(i)

exothermic as yield / pp of ethanoic acid / conversion of reactants/


Kp is higher at lower temperature / as equilibrium moves (right) at
lower temperature
ALLOW
if partial pressure of ethanoic acid < 22.2 atm in (b)(ii), endothermic
as yield / pp of ethanoic acid / conversion of reactants/ K p is lower
at lower temperature

No effect
and
other concentrations change to keep Kp constant / Kp is only affected
by temperature/ as equilibrium moves (right) to keep K p constant /
change in pressure does not change Kp

As Kp is a constant
(ii)

Yield increased to restore fraction / quotient / partial pressure ratio


back to Kp
ALLOW (equilibrium moves) to use up the methanol /answers based
on entropy or Le Chatelier
Correct prediction in (c)(i) and (c)(ii) with inadequate explanations
scores 1 mark in (c)(ii)

Just equilibrium moves to the right

(d)

Mark independently
Reaction can occur at lower temperature / has lower activation energy /
requires less energy (1)
less fuel needed / fewer emissions (from fuels) / fewer raw materials
needed / less natural resources used (1)
OR
Enables use of an alternative process with higher atom economy (1)
fewer raw materials needed / less natural resources used (1)

Answer based on car exhaust emissions


[13]

9.

(a)

(i)

Correct answer with or without working scores 2 marks


+

[H ] = (1 .00 10

14

/ 0.250) = 4 10

14

(1)

pH = (13.39794 =) 13.4 (1)


OR
pOH = -log 0.250 = 0.602 (1)
pH = (13.39794 =)13.4 (1)
ALLOW
+
TE in second mark if error in [H ] calculation gives pH more than 7
3 or more sf
IGNORE rounding errors e.g. accept 13.39

(ii)

[CH 3 COO ][H ]


(Ka =) [CH 3 COOH]
(1)

ALLOW
+
+
H30 instead of H
=

[A ] [H ] if key to symbols given


[HA]
IGNORE state symbols

[H ] 2
[CH 2 COOH]

(iii)

Correct answer with or without working scores 2 marks


[H ] 2
5
1.7 10 = 0.125 (1)
+

[H ] = 1.46 10
pH = 2.84/2.8 (1)

no TE from an incorrect [H ]

(iv)

pH = 4.8 / 4.77 (1)


+

pH = pKa / [H ] = Ka (when acid is half neutralized) (1)

H = Ka
(v)

Sigmoid curve starting between pH 2 and 4 (2.8), ending between


pH 12 and 14 inclusive (1)
with steep rise (may be vertical or gently sloping) of between 3
7 units between pH 6 and 12. Sloping section should not extend
3
over more than 5cm . (1)
3

When 12.5 cm , NaOH added. (1)


ALLOW tolerance for grid
Reverse curves lose first mark
(vi)

First mark
Thymolphthalein more suitable as it changes
(from colourless to blue) in steep region of titration
(pH 8.3 to 10.6)/ at the equivalence point / at the end point
OR
thymolphthalein has pH range in steep region of titration (1)
Second mark
Methyl yellow changes (from red to yellow at pH 2.9 to 4)
before equivalence point / before the end point / doesnt
change in steep section
OR
Methyl yellow has pH range before / outside steep region of titration (1)
ALLOW Thymolphthalein more suitable as it changes
at the equivalence point but methyl yellow does not.
This scores 2 marks
OR
First mark
pKin 1 must lie within vertical region on titration curve (1)
Second mark
hence thymolphthalein is suitable and methyl yellow is not (1)

(b)

Sodium ethanoate/ CH3COONa


Potassium ethanoate / CH3COOK
ALLOW
other cations as alternatives to sodium

Use of sodium hydroxide (because its in food)


[13]

10.

A
[1]

11.

(a)

(i)

2Mg(NO3)2 2MgO + 4NO2 + O2


Correct formulae (1)
Balancing (1)
ALLOW multiples or equation divided by 2 Second mark on correct
species only Ignore state symbols even if incorrect
ALLOW
N2O4
Extra oxygen molecules on both sides in a balanced equation

(ii)

Stand alone marks


2+
Mg / Magnesium ion smaller or fewer electron shells / greater
charge density (1)
OR
Magnesium ion has same charge (as calcium ion) but is smaller (1)
Causes more polarisation /distortion of nitrate / anion (electron clouds)
/ NO (bond)(1)
OR
MgO produced has stronger lattice (1)
OR
production of MgO is more exothermic (1)
OR reverse argument based on Ca

2+

Magnesium / calcium / atoms / molecules


(b)

(c)

2NaNO3 2NaNO2 + O2
ALLOW multiples or equation divided by 2 Ignore state symbols even if
incorrect
ALLOW
Extra oxygen molecules on both sides in a balanced equation

No as.
double bond would be shorter (than single bond) / shorter than dative
(covalent) bond.
ALLOW
Structure has double and single bonds (between N and O)
Double and single bonds have different lengths

Implication that the single covalent and dative covalent bonds


have different lengths

(d)

(i)

Mark independently Goes darker (brown) (1)


ALLOW
Goes browner
Ignore comments on mixture first becoming paler if volume increases
Equilibrium moves in the endothermic direction (1)
OR
Equilibrium moves left as forward reaction is exothermic (1)
For second mark ALLOW
Equilibrium moves left to counteract addition of heat / increase in
temperature(1)
OR
Reaction removes added heat by moving left (1)

Brown (gas evolved)


(ii)

Equilibrium moves right (ALLOW forwards) (so NO2 concentration


decreases) (1)
OR
Reaction reduces pressure (1)
As fewer moles / molecules(ALLOW particles) (of gas) on RHS (1)
Stand alone marks

(e)

At T2 more molecules/collisions have energy greater than (or equal to) EA (1)
This can be shown on the diagram by indicating areas to right of vertical line
Energy must be at least EA for successful collision / for reaction (1)
OR So more collisions have sufficient energy to react (1)
Ignore references to the average energy and speed of the molecules

2
[12]

12.

B
[1]

13.

C
[1]

14.

B
[1]

15.

A
[1]

16.

B
[1]

17.

A
[1]

18.

C
[1]

19.

C
[1]

20.

(a)

(i)

(pH =) log [H ]
OR
+

(pH =) log [H3O ]


OR
Accept
Definition in words
(For example: It is minus / negative log(arithm) of the hydrogen ion
concentration)
Base 10 does not have to be there, but reject ln

Just concentration of hydrogen ions


{ } curly brackets
+

-log H
(ii)

(pH = -log 0.0100) = 2(.00)

If any units given

K a [CH 3 COOH]
(b)

(i)

[H3O ] =

[CH 3 COO

OR
+ 2

[H3O ] = Ka[CH3COOH] (1)


ALLOW

[HA] for [CH3COOH] and [A ] for [CH3COO ] in rearranged expression


Accept
+
+
[H ] for [H3O ]
[H3O+] = 1.75 107
OR
[H3O+] = 4.18(3) 104 (mol dm3) (1)

pH = 3.38 / 3.4
ignore sf except one sf (1)
+

Third mark TE from [H ] only if pH less than 7


N.B. CORRECT ANSWER, WITH OR WITHOUT WORKING,
SCORES (3)
Assumption
assumes that degree of ionisation of the acid is very small/negligible
OR
[CH3COOH ]eqm =[CH3COOH ]initial
OR
+

[H ] = [CH3COO ]
OR
all of the hydrogen ions come from the acid / ignore hydrogen ions
from the water (1)
IGNORE
any references to temperature

3.37 / 3 /3.39 / a correct pH value with units


just weak acid / just partially dissociates / acid does not
dissociate / [CH3COOH] constant
+

[H ] = [OH ] / [H ] = [salt]

10

(ii)

First mark:
(Dilution/addition of water) shifts the equilibrium

CH3COOH

CH3COO + H /

CH3COOH + H2O

CH3COO + H3O

to the right
OR
the above stated in words such as: degree of dissociation increases/
proportion of dissociation increases/ more dissociation (as the
ethanoic acid is diluted) (1)
Second mark:
+

so the [H ] is greater than expected/ so the decrease in [H ] is less than


+
expected / so that the decrease in [H ] is less than that for
hydrochloric acid (1)
Each mark is a stand alone mark.
ALTERNATIVE ROUTE:
First mark:
+

[H ] = Ka [HA] OR (Ka [HA])

OR
pH = pKa - log[HA] (1)
Second mark:
+

use of mathematical expression given (e.g.[H ] affected by factor of


1/10 on dilution OR substitution of numerical values into the
equation) (1)
IGNORE: any comments or calculations relating to HCl(aq)

Reject just a reference to a 0.5 increase in pH for


CH3COOH(aq) compared with a 1.0 increase in pH for
HCl(aq)
(c)

(i)

These marks are stand alone.


Maintains an almost constant pH / resists change(s) in pH (1)
+

for small addition of H or OH ions (N.B. both ions needed) / for


small additions of acid or alkali / for small additions of acid or
base (1)
IGNORE any references to named buffer mixtures

resists small change(s) in pH


OR
pH does not change
(ii)

citric acid

11

(iii)

First mark:

(buffer contains) reservoir of HA and A


OR

(buffer contains) large concentrations of [HA] and [A ]


OR
both equations:
HA

A + H+ and NaA

Na + A

Second mark:
(Addition of alkali/base)

HA + OH A + H2O
OR
+

description/equations to show that H reacts with OH (to form H2O)


+

and more acid dissociates (to replace H ) (1)


Third mark:
(Addition of acid)

A + H HA
OR
+
A reacting with H in any context described in words (e.g. by reference
to weak acid equilibrium) (1)
Fourth mark:

the ratio of [A ][HA] hardly changes / the ratio of [HA] [A ] hardly


changes
OR

[A ] nor [HA] changes significantly (1)


+

JUST NaA
Na + A
and
+

HA
H + A without correct description
+

Just [H ] remains constant


[15]

21.

(a)

Kp

p (H 2 ) 3 p (CO)
p (CH 4 ) p(H 2 O) (1)

Brackets not required

[]
Kp

(b)

(i)

p (H 2 ) 3 p (CO)
p (CH 4 ) p(H 2 O)

No effect (as Kp dependent only on temperature) (1)1

12

(ii)

(Since Kp =

X (H 2 ) 3 X (CO) PT
X (CH 4 ) X (H 2 O) PT 2

to maintain Kp constant, mole fractions of numerator must


decrease OR mole fractions of denominator
2
must increase as PT overall)
First mark:
EITHER
mole fractions/partial pressures of numerator decrease
OR
mole fractions/partial pressures of denominator increase (1)
Second mark:
PT

any mention of PT OR PT

(1)

ALLOW P for PT
NOTE:
If Le Chatelier quoted, statements such as:
Equilibrium shifts to side of fewer moles (of gas molecules)/fewer
(gas) molecules
max (1)
(iii)

Reaction takes place on surface of the catalyst (1)


Active sites/(catalyst) surface is saturated with reactant molecules
/reactants (at the pressure of the reaction) (1)
NOTE: an answer such as
... depends on the availability of active sites on
catalyst surface
scores (2)

13

(c)

CO + H2O

CO2 + H2

initial

eqm

0.25

0.25

0.75

0.75

mol
frac

0.125

0.125

0.375

0.375

pp

3.75

3.75

11.25

11.25

eqm moles all correct (1)

mole fractions all correct (1)

partial pressures and answer = 9 with no units (1)

NOTE: 3rd mark not awarded if any units shown


NOTE:

11.25 2
3.75 2
=9

scores (3)

14

15

NOTE: Mark each step CQ.


CHECK ALL WORKING
(d)

(i)

production (of hydrogen) forms CO2


OR
production (of hydrogen) forms a Greenhouse gas
OR
production (of hydrogen) forms CO
OR
CO2 is a Greenhouse gas
OR
CO is a Greenhouse gas
ALLOW production (of hydrogen) uses/requires energy
ALLOW CO is toxic/poisonous

methane produced (0)


(ii)

2KHCO3 K2CO3 + CO2 + H2O


ALLOW multiples

16

(e)

products removed
OR
not a closed system
OR
balance between rate and yield
OR
balance between time and yield
OR
recycling of reactants
OR
more product in unit time (so process more economically viable)
IGNORE any comments relating to cost

references to atom economy


dangers of maintaining high pressures
[12]

22.

(a)

1
(b)

1
[2]

23.

B
[1]

24.

D
[1]

25.

C
[1]

26.

A
[1]

17

27.

C
[1]

28.

C
[1]

29.

A
[1]

30.

C
[1]

31.

(a)

(b)

(c)

1
[3]

32.

(a)

(b)

(c)

1
[3]

33.

(a)

methyl butanoate
Accept Methyl butaneoate

Reject an missing
(b)

the other three substances can form


intermolecular hydrogen bonds with themselves but the ester cannot.

Reject Discussion of London Forces

18

(c)

Hydrolysis

(d)

QWC

Must cover advantages and disadvantages. Must not be contradictory


Advantages to manufacturers: (any two)
not dependent on weather, seasons etc
consistent taste /concentration/more consistent
quality
or alternative ideas
Disadvantages to consumers : (any two)

some people put off by non-natural food

may not taste the same as natural product which may contain
other impurities

unable to describe the product as organic

or alternative ideas

Reject cost with no justification

(e)

[C 3 H 7 COOH(l)][CH 3 OH(l)]
Kc = [C 3 H 7 COOCH 3 (l)][H 2 O(l)] (1)
Accept eq subscripts

butanoic acid = 4.4/88 =


methanol
ester (methyl butanoate)
water

Moles at
equilibrium

Concentration /
3
mol dm

0.05
0.05
0.05
0.95

1.67
1.67
1.67
31.7

all four equilibrium moles = (1)


Conc at equilibrium = equilibrium moles 0.030 (1)

1.67 1.67
Kc = 1.67 31.7 (1) = 0.053 (1)
ignore significant figures unless value given to 1 s.f.
The units cancel because both the top and bottom of the fraction
have units of concentration squared.
Or same number of moles on both sides of the equation (1)

Reject absence of square brackets


[12]

34.

(a)

Value of equilibrium constant increases (1)

19

(b)

QWC
If the equilibrium constant increases then more products will be formed (1)
And the position of equilibrium will move to the right (1)

2
[3]

35.

(a)

(b)

(i)

(ii)

(iii)

(c)

2+

Mg(s) + 2H (aq) Mg (aq) + H2(g)


Accept state symbols omitted

(i)

(ii)

Positive because a gas is given off (1)


which is more disordered and so has more entropy (1)

Positive because the reaction is exothermic (1)


and = H/T (1)

Positive because the reaction occurs / total entropy change


is the sum of the two positive values above.

Surface coated with magnesium oxide (which would react to


form water rather than hydrogen).

QWC
Initial number of moles of HCl = 20 1 /1000 = 0.02
Number of moles of Mg = 0.1 / 24 = 0.00417 (1)
number of moles of HCl which reacts is 0.00834 (1)
Therefore number of moles of HCl left = 0.01166 (1)
Ignore sig figs
so the concentration nearly halves which would significantly
reduce the rate and so make the assumption that the initial
rate is proportional to 1/time invalid / inaccurate. (1)
3

Increase the volume of acid to (at least) 50 cm (1)


Or measure the time to produce less than the full amount of gas
Or use a smaller piece of magnesium. (1)

20

(iii)

Energy given out = 467 000 0.1/24 J = 1 946 J


20 4.18 T = 1 946 (1)
(o)
T = 23.3 (1)
Accept units of degrees celsius or Kelvin
This temperature change would significantly increase
the rate of the reaction (1)
Carry out the reaction in a water bath of constant
temperature/use a larger volume of more dilute acid (1)

(iv)

At 329 time 4s 1/time = 0.25 s ln(rate) = 1.39 (1)


1

At 283 time 124s 1/time = 0.00806 s ln(rate) = 4.82 (1)


[graph to be drawn]
Plot line with new gradient = 3.43 / 0.00049
= 7 000 (1)
Accept 6800 to 7200
Activation energy = + 7 000 8.31
1
= + 58.2 kJ mol (1)
(v)

QWC
Rate of reaction reduced because less surface area in contact
with the acid. (1)

(vi)

Any two
Repeat the experiment at each of the temperatures
obtain an initial rate eg by measuring the volume of gas
given off before the reaction is complete.
Other sensible suggestions.

(vii) The rate should be lower, since ethanoic acid is a weaker acid
(compared to hydrochloric acid) and so there will be a lower
concentration of hydrogen ions present.

1
[24]

21

36.

QWC
Answer must be given in a logical order, addressing all the points using precise
terminology
Collision frequency increases as particles moving more quickly (1)
More collisions have sufficient energy to overcome activation energy /
more molecules on collision have energy activation energy (1)
A greater proportion of collisions result in reaction (1)
Collision energy has greater effect (1)
Homogeneous all in same phase and heterogeneous in different
phases / gas and solid (1)
No need to separate products from catalyst (1)

Reject more collisions


Reject more successful collisions
[6]

37.

A
[1]

38.

A
[1]

39.

C
[1]

40.

D
[1]

41.

(a)

(b)

1
[2]

22

42.

(a)

(i)

Fe[Ar] 3d 4s in either order, allowing superscripts to be subscripts


6
6 0
Fe[Ar] 3d or 3d 4s in either order, allowing
superscripts to be subscripts
Letter d must be lower case

Reject any other letters


(ii)

O H

Fe

2+

O H

H 2O

O H

H 2O

O H

O R

H 2O
H 2O

O H

Fe

2+

O H

O H
O H

O R
H 2O

H 2O
Fe

H 2O

O H

2+

H 2O

O H

In s te a d o f d o tte d lin e

ALLOW bond to H of H2O (accept on left side if OH2 is given)


IGNORE charge unless incorrect

(iii)

[Fe(H2O)6]

2+

+ 2OH [Fe(OH)2(H2O)4] + 2H2O

2+

+ 2OH Fe(OH)2 + 6H2O

OR
[Fe(H2O)6]
(iv)

Green precipitate/solid Foxy-red/red-brown/


brown/orange
Both colours and precipitate/solid needed

Reject just Darkens

23

(b)

(i)

QWC
Emf of cell/ potential difference of cell containing Fe (1)
3

dipping into a 1 mol dm Fe

2+

solution (1)

And standard hydrogen electrode/half cell


3 +
OR hydrogen electrode and 1 mol dm H and 1 atm
H2
OR description of standard hydrogen electrode (1)
IGNORE temperature

RejectSHE
(ii)

QWC
Emf of hydrogen electrode is zero stated or implied
e.g. if calculate Ecell = +0.44 V (1)

(iii)

Potential for the reaction is positive so reaction is feasible


OR Fe half cell has more negative electrode potential
+
OR H and ()H2 has a more positive electrode potential (1)

High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions

1
[10]

43.

(a)

QWC
enthalpy/heat/energy change when 1 mole (of a substance) (1)
Accept evolved instead of change
Accept sulphur or element or species instead of
substance
Reject heat/energy required
Reject compound instead of substance
is completely burned in oxygen /
burned in excess oxygen (1)
Reject reacts completely with oxygen
Any mention of specific products or specific amounts of
nd
products, other than SO2, negates 2 mark
(all species) at 1 atm/100 kPa/105Pa/1 Bar and a specified temperature (1)

Accept .298 K/ 25 C /101 kPa


Or
..a specified temperature e.g. any value
Reject just 273 K
Reject any mention of concentration negates third mark

24

(b)

(i)

QWC
Temperature
More molecules/collisions/ particles have
E Eact /sufficient energy to react (1)
Accept E > Eact
energy barrier instead of Eact/activation energy
Reject more atoms.
a greater proportion of collisions are successful
Or
More of the collisions are successful (1)
Accept collisions more likely to be successful
Accept greater chance of successful
Accept more successful collisions per second
Reject just more successful collisions
Reject ..fruitful collisions
IGNORE greater frequency of collision
nd

st

2 mark dependent on 1 mark


st
UNLESS 1 mark is not awarded through use of atoms
Catalyst
EITHER:
provides alternative route of lower activation energy (1)
Accept energy barrier instead of Eact/activation energy
more molecules have E > Ecat / a greater proportion of collisions
are successful (1)
Accept collisions more likely to be successful
Accept greater chance of successful
Accept more successful collisions per second
Reject just more successful collisions
N.B. Penalise more collisions are successful only once
Reject ..fruitful collisions
nd

2 mark dependent on mention of lowered activation energy


Do not penalise use of atoms again
OR:
provides (active) sites (1)
where reactant molecules can bond/be adsorbed (1)

Reject where reaction can take place

25

(ii)

QWC
reaction exothermic (1)
equilibrium shifts to the left decreasing the yield (1)
nd
st
2 mark is dependent on the 1 and is not consequential.
IGNORE Le Chatelier explanations

Accept H negative/reverse reaction is endothermic


Reject just equilibrium shifts to the left
Reject just yield decreases
(iii)

QWC
fewer (gaseous) molecules /particles/moles on the right (1)
equilibrium shifts to the right increasing the yield (1)
Reject just equilibrium shifts to the right
Reject just yield increases
nd

st

2 mark is dependent on the 1 and is not consequential.


IGNORE Le Chatelier explanations
N.B do not penalise omission of either equilibrium shifts
or change of yield if already penalised in (ii)

Reject arguments based on volume


(c)

H = Hf (products) Hf
(reactants)
Or (814 2) (286 2) (1)
1

= 1056 (kJ mol ) (1)


IGNORE units
Correct answer with no working (2)
Omission of either or both of 2 max 1. Hence
242 with some working (1)
1342 with some working (1)
528 with some working (1)
(+)1056 with some working (1)

Reject Hf values added scores zero overall


[13]

26

Kp
44.

(a)

2
p NO
2

p N 2O4

IGNORE UNITS HERE

Reject [ ]

(b)

(i)

p NO2

= 0.8 1.1
= 0.88 (atm)
and
p N 2 O2

= 0.2 1.1
= 0.22 (atm) (1)
(0.88) 2
K = (0.22)
p

Kp = 3.52 (1)
atm (1)
SECOND MARK IS CQ ON PARTIAL PRESSURES
AS CALCULATED
(ii)

First mark:
X N 2 O4
= 0.10
X NO2
= 0.90 (1)
Reject B
Second mark:
Kp constant or
use of Kp = 3.52 or
use of Kp calculated in (b)(i) (1)
Third mark:
Value of PT with some working e.g.

( X NO2 PT ) 2
3.52 =

X N 2O4 PT

0.81
3.52 = 0.10 PT
PT = 0.435 (atm) (1)
Mark CQ on first and second answers to (b)(ii)
Accept in range 0.43 to 0.44
THIRD MARK NOT AVAILABLE IF Kp EXPRESSION
2

DOES NOT CONTAIN A p TERM

27

(c)

(i)

Increases / gets larger/ gets bigger/ goes up/greater

Reject more
(ii)

First mark:
2
p NO
2

p
Fraction/quotient/ N 2O4 /numerator has to increase
(to equal new Kp) (1)
Second mark (can only be awarded for an answer that refers
to the fraction/quotient above):
EITHER
p
p
so shifts to RIGHT hand side (as NO2 and N 2O4 ) /
p
p
goes in forward direction (as NO2 and N 2O4 )
OR
so (more) N2O4 changes to NO2
OR
so (equilibrium) yield of NO2 increases (1)

Mark consequentially on decreases in (i)


Le Chatelier argument scores (0)
[10]

45.

(a)

(i)

H2O(l)

H (aq) + OH (aq)

OR
+

2H2O(l)

H3O (aq) + OH (aq)

IGNORE STATE SYMBOLS

Reject if a full arrow is shown in the equation

(ii)

KW = [H

(aq)][OH (aq)]

OR
+

(aq)][OH (aq)]

KW = [H3O

IGNORE STATE SYMBOLS

If [H2O] included (0).


+ 2

Reject Kw = [H ]

28

(iii)

pH = log10[H ]
OR
+

pH = log10[H3O ]
OR
in words

1
+

Accept pH = lg 1/[H ]

(iv)

KW = [H ][OH ]
5.48 10

14

+ 2

= [H ] (1)

14
+
[H ] = 5.48 10
+
7
3
[H ] = 2.34 10 (mol dm )
pH = 6.6(3) (1)
correct answer with no working (2)

pH = 13.3/13.6 scores (0)


(v)

(b)

(In pure water)


+

[H ] = [OH ]
OR
+

equal concentrations of H and OH

(i)

12.5

(ii)

4.8 / 4.9
[no consequential marking from (i)]

Reject 5 or 5.0

(iii)

[CH 3 COO ][ H ]
Ka
[CH 3 COOH ]

OR
Ka

[CH 3 COO ][ H 3 O ]
[CH 3 COOH ]

Reject expressions containing [H2O]


OR
Reject HA
generic equations

29

(iv)

(at half-neutralised point so)


pKa = 4.8
Mark CQ on (ii)
Reject just pH = 4.8 as already credited in (b)(ii)
OR
pH = pKa (1)
Ka = antilog10(4.8)
5

Ka = 1.6 10 (mol dm ) (1)


Mark CQ on pKa
5
Accept if pKa = 4.9, Ka = 1.3 10
Reject answers to other than 2 s.f.
Must be to two sig figs
CORRECT ANSWER WITH OR WITHOUT WORKING (2)

Reject 2.5 10 scores (0)


(c)

Phenolphthalein:
changes colour (OWTTE) in vertical part of the graph
OR
changes colour within a stated range anywhere from 7 to 11 (1)
Reject if colour change pink to colourless
Methyl orange
changes colour at a low(er) pH
OR
has already changed colour
OR
changes colour before the vertical (section) (1)
Allow range for methyl orange of 3 to 6 or colour change takes
place below pH = 7
Reject just methyl orange changes colour outside the vertical
range
[NB There must be a statement about methyl orange for second mark]

2
[13]

30

46.

(a)

e.m.f. of a half cell relative/compared to a (standard) hydrogen electrode


OR
voltage produced from a half cell joined to a hydrogen electrode (1)
Accept potential (difference) /voltage for emf
Accept emf of a cell with standard hydrogen as the left
electrode
Accept a description of the half cell e.g. a metal dipping into a
solution of its ions
Reject SHE
3

(solutions at) 1 mol dm concentration, (gases at) 1 atm/100 kPa/


105Pa/ 1 Bar pressure and stated temperature (1)
all 3 conditions needed STAND ALONE

Accept 101 kPa


Accept 298 K or 25 C
If any other temperature is quoted it must be as an example of a
stated temperature
Reject constant pressure STP
Reject room temperature
Reject just 273 K
(b)

Can only measure a potential difference/emf


(if a reference electrode is present)
OR
voltmeter needs 2 connections
OR
Cannot measure the potential difference between a metal and a
solution of its ions

Reject just electron source and sink


Reject to make comparisons between half cells

31

(c)

(i)

st

1 mark
(simultaneous) oxidation and reduction of a (single) species/
substance/ reactant/compound/chemical
Reject oxidation and reduction occur at the same time
Or the oxidation state/number is both increased and
decreased of a (single) species/ substance/ reactant/
compound/chemical
Reject oxidation states are
Or a (single) species/ substance/ reactant/compound/
chemical both loses and gains electrons (1)
nd

2 mark
For a given type of atom within an ion/ molecule
Or Illustrated by a suitable example in which the
individual atom is identified (1)
(ii)

2H2O2 2H2O + O2 (1)


+

Reject 2H on both sides of equation


Ecell = (+) 1.09 (V) (1)
Reject greater than any other stated number
Ecell is positive/greater than 0 so the reaction is feasible (1)
rd

3 mark must be cq on sign of Ecell


(iii)

activation energy of the reaction may be high


OR
reaction too slow to be observed

Reject just Not enough energy to overcome the activation


energy
Reject conditions are non-standard
Reject just kinetically stable
[9]

47.

(a)

(i)

The activation energy for the reaction is high


or to ensure that more molecules have E Ea.

Accept E > Ea
Reject to overcome Ea alone
Reject reactants kinetically stable;
reactants thermodynamically stable

32

(ii)

protonates the alcohol (1)


Reject as a catalyst alone
providing H2O as the leaving group which is more easily displaced
by the bromide ion/is a better leaving group than hydroxide (1)
OR
reacts with NaBr (1)
to give HBr (which is the attacking reagent) (1)

(iii)

H-bonding between water and the alcohol not strong


enough to overcome hydrophobic interactions /effect of
alkyl group (1)
+

acid and alcohol form ionic species/C4H9OH2 which


is more soluble (1)

Accept butyl group


(iv)

Removes acid

Accept neutralises HCl /HBr


Accept neutralises acid
(v)

Removes water

Accept absorbs water


Accept dries the product
(vi)

Electric heating mantle or sand bath or oil bath (1)


Accept water bath
Reject heat under reflux
Reject no naked flame
Reject fume cupboard
because the alcohol/reaction mixture/bromobutane is
flammable or because the heating is uniform and less
likely to crack the flask (1)
This mark is conditional on the first being scored.

Reject volatile for flammable

33

(b)

QWC
EITHER
Intermediate (ion) in SN1 is planar (1)
Accept intermediate carbocation is a planar molecule
intermediate molecule alone loses this mark
equal attack (by hydroxide ions) from either side (1)
produces a racemic mixture (1)
Reject attack by bromide ions
Note: Statement that the SN2 mechanism is consistent with
the information cannot score any marks.
OR
SN2 involves attack from one side (1)
so configuration of the product would be inverted (1)
leading to retention of optical activity so must be SN1 (1)
Accept forms one optical isomer only

(c)

Statement that the reaction is SN1 alone scores zero.

(i)

Orange green

(ii)

Cr2O7 + 6e + 14H 2Cr

3+

+ 7H2O (1)
+

(3CH3CH(OH)CH2CH3 3CH3COCH2CH3 + 6H + 6e )
2

Cr2O7 + 3CH3CH(OH)CH2CH3 + 8H 2Cr


3CH3COCH2CH3 (1)

3+

+ 7H2O +

No consequential marking on incorrect equations.

Accept C4H9OH and C4H8O


+

Accept equation having non-cancelled H ions


Reject equation having non-cancelled electrons

(iii)

The broad peak/absorption/trough around 3400 cm due to OH (1)


Accept 3230 3550
Reject broad transmission
1

has disappeared in the product to be replaced by C=O at 1700 cm (1)


Accept 1680 1750
If no reference to both groups responsible for the peaks then max (1)
OR
If no reference to both wavenumbers responsible for the
peaks then max (1)

34

(d)

(i)

Addition of barium ions pulls equilibrium to r.h.s. (1)


+

increases [H ] and so lower pH/the pH falls (1) stand-alone mark

Reject ..so gets more acidic


(ii)

lower pH/pH falls

Reject mixture is more acidic for lower pH


[20]

48.

(a)

(i)

Liquids are more disordered than solids/ solids are more


ordered than liquids/ solids are less disordered than liquids /
liquids are less ordered than solids

Accept more ways of arranging energy in a liquid because of


translation/rotation energy
Reject just more ways of arranging energy

(ii)

(165 + 217.1 166.5 =) + 215.6 OR +216 (J mol

K )

+ sign essential

1
1

Accept +(0).2156 kJ mol K


1 1
OR +0.216 kJ mol K
1

Reject 215 J mol K


1 1
Reject 0.215 kJ mol K
(iii)

Yes because
The products include a gas (1)
Accept solid goes to liquid and gas for first mark
One mole/molecule goes to two moles/molecules (1)

nd

1 reactant goes to 2 products does not get 2 mark

35

(b)

S surroundings = T
OR
123800
298
(1)
1

= 415 J mol K (1)

2
1

Accept 0.415 kJ mol K


1

Accept 415.4 J mol K

Accept final answer with no working (2)


Allow j for J
Reject full calculator display eg 415.4362416
Reject more than 2 dp e.g. 415.436
(c)

(i)

Stotal = 415 + 216 = 199


1

or 199.8 or 200) (J mol K )


th
IGNORE 4 significant figure
1

Accept 0.199 kJ mol K

ALLOW TE from(a)(ii) and (b)


(ii)

reactants predominate / equilibrium lies well to the left


OR
Equilibrium completely to the left

ALLOW TE from (c)(i)

Kp
(d)

(i)

p PCl3 p CL2
p PCl5

(1)

IGNORE state symbols or lack of them unless (s) or (l)


Units atm (1)

Accept capital P
Accept use of ( )
If expression the wrong way up allow second mark if units
1
given as atm
Reject use of [ ]

36

(ii)
Substance

PCl5(g)

Moles at
start

Moles at
equilibrium

Peq /atm

0.15
0.25 4.32
= 2.592

0.20
(1)

PCl3(g)

0.05

0.05
0.25 4.32
= 0.864

Cl2(g)

0.05

0.864

Total number of moles at equilibrium


All three(1)

0.25
All three(1)

Allow consequential marking across columns

If moles at eqm are given as 0.025 for PCl3(g) and for Cl2(g)
th

then 4 column should be 3.24, 0.54 and 0.54


and gets 2 (out of 3)

Kp
(iii)

0.864 0.864
( 2.592) )

(
= 0.288 (atm)

ALLOW TE from di and from dii


Common wrong values above gives 0.090
ALLOW 0.29
Reject 0.3
reject 0.28
(iv)

A No change because Kp depends only on temperature /


number of moles would change in same proportion (1)
B Increase because reaction is endothermic (1)
OR
entropy arguments

If both changes correct but no explanations then 1 (out of 2)


[16]

37

49.

(a)

(i)

[ H ][HCO 3 ]
[CO 2 ]
Ka =
(1)
3

mol dm (1)
If H2O is included as denominator then allow only the 2
mark if no units suggested
(ii)

pKa = log Ka / lg Ka / log10 Ka


Accept Ka = 10

(b)

nd

2
1

pKa

A solution which does not change its pH value (significantly) (1)


May be shown using an equation

(c)

(d)

When some/small amount of acid or alkali is added (1)

Acting as a base because it is accepting


a proton (to form H2CO3/CO2 + H2O)

(i)

[acid]
Before race 7.4 = 6.5 log [base]
[acid]
Log [base] = 0.9 (1)
[acid]
[base] = 0.126 (1)

Accept 0.13
Reject 0.12
(ii)

Before race
3
[CO2] = 0.126 0.0224 = 2.82 10
OR
2
2
3
2.52 10 2.24 10 = 2.8 10

38

(iii)

Hypothesis I would result in an increase in

[CO2] / [HCO3 ] / [CO2 + HCO3 ]


OR
Hypothesis II would produce greater acidity without

additional [CO2] / [HCO3 ] / [CO2 + HCO3 ] (1)

The table shows a fall in [CO2] / [HCO3 ] / [CO2 + HCO3 ]


and therefore Hypothesis II must be favoured. (1)

2
[11]

50.

(a)

N/N2 goes from 0 to 3 = reduction (1)


H/H2 goes from 0 to (+)1 = oxidation (1)

If the oxidation number of N goes down hence reduced and the


oxidation number of H goes up and hence oxidised (max 1)
If all O.N. correct but fails to state which is oxidation and
which is reduction scores 1.
If all O.N. correct but both reactions misclassified, scores zero.
Any answer not referring to nitrogen or hydrogen scores zero.
(b)

(i)

Calculation of bonds broken 463 3 + 944/ (= 2252) (1)


Calculation of bonds made 3886/ (= 2328) (1)
1
H = 76 (kJ mol ) (1)
mark consequential on numerical values calculated above

Correct answer with some working scores 3 marks


Correct answer alone scores 2 marks
(ii)

Average / mean bond enthalpy used for NH bond / ammonia

Reject just average bond enthalpies used


(iii)

Thermodynamic:
energy level of products lower than that of reactants
OR
energy released in bond formation > energy used to break bonds (1)
Accept H negative / reaction exothermic
kinetic:
high activation energy (1)
because strong NN (1)
[confusion between thermodynamic and kinetic loses first 2 marks].

Accept because NN is 944/ total bond breaking energy is


1
high/2252(kJ mol )

39

(c)

(i)

QWC
One way
temperature increase therefore molecules have greater (average
kinetic) energy (1)
Accept moving faster
more molecules/collisions have E Eact (1)
Therefore a greater proportion of/ more of the collisions are
successful (1)
Ignore greater frequency of collision
Accept E > Eact particles for molecules
greater frequency of successful collisions/ more successful
conditions per unit time
Reject just more successful collisions
Another way
addition of (iron) catalyst (1)
Accept platinum catalyst
Reject incorrect catalyst
provides alternative route of lower activation energy (1)
EITHER:
A greater proportion of /more of the molecules/collisions have E E cat/
a greater proportion of collisions are successful
Reject just more successful collisions
OR provides (active) sites (where reactant molecules can
bond / be adsorbed) (1)

(ii)

Ignore any answers referring to pressure or concentration.


Do not penalise just more collisions are successful more
than once

QWC
Decrease temperature (1)
because (forward) reaction exothermic (1)
increase pressure (1)
because more moles (of gas) on left (1)

Accept low temperature H is negative


Answer based on endothermic reaction scores 0
Accept high pressure
Accept molecules for moles
[19]

40

51.

(a)

(i)

To slow down the reaction/to stop the reaction


OR to quench the reaction
OR to freeze the (position of) equilibrium OWTTE (1)
so that the (equilibrium) concentrations/amounts do not change (1)

Accept to stop equilibrium shifting to the left


(ii)

First mark:
[ H 2( g ) ] [ I 2 ( g ) ]

OR
4 2

Use of (5.0 10 ) (1)


If [HI] not squared, first mark only.
Second mark:
[ HI ( g ) ] 2

(5.0 10 4 ) 2
0.019

OR
(5.0 10 4 ) 2
0.019 =

[HI (g) ] 2

OR

[HI(g)] =

(5.0 10 4 ) 2

0.019

(1)

Third mark:
3

[HI(g)] = 3.6 10 (mol dm ) (1)


Correct answer scores 3 marks.
Ignore state symbols.
Ignore units unless wrong.
Ignore s.f.

If first mark not awarded, total (0)

Kp
(b)

(i)

2
p HI
p H2 p I2

Ignore position of any ( )

[ ] scores (0)

41

(ii)

Each step of this calculation must be looked at.


st
1 mark is for calculating equilibrium moles
2 = 0.2
2 = 0.2
= 1.6 (1)
Mark consequentially
nd

2 mark is for dividing these by 2 (to get mole fractions)


0.2
xH 2
0.1
2.0
0.2
xI2
0.1
2.0
1.6
x HI
0.8
2.0
(1)
Mark consequentially
rd

3 mark is for multiplying by 1.1 (to get partial pressures)


0.2
PH 2
1.1
2. 0
= 0.11 (atm)
0. 2
PI 2
11
2.0
= 0.11 (atm)
1.6
PHI
11
2.0
= 0.88 (atm) (1)
Mark consequentially
th

4 mark is for substituting into their expression and calculating Kp


(0.88) 2
(0.11) (0.11)
= 64 (1)
Kp

Ignore s.f.
Correct answer with no working scores (1)

If moles HI given as 0.8, Kp = 16 max (3)

42

(iii)

Same number of moles on each side


OR
(Total) pressure cancels
OR
(Pressure) units cancel
(May be shown by crossing out etc. in b(ii))

Accept Powers cancel


OR
They cancel
OR
Same number of molecules on each side
Reject Partial pressures cancel
OR
3
mol dm cancel
[11]

52.

(a)

(i)

One acid: CH3CH2COOH(aq)

Conjugate base: CH3CH2COO (aq) (1)


+

Other acid: H3O (aq)


Conjugate base: H2O(l) (1)
Ignore state symbols

Accept correct acids with conjugate bases in either order


(ii)

WEAK: dissociates/ionises to a small extent (1) OWTTE


Accept Few molecules dissociate
Accept Incomplete or partial dissociation
Accept Does not fully dissociate
Reject ions partially dissociate
ACID: proton donor (1)

2
+

Accept Produces H3O / hydrogen / H ions


+

Reject just contains H3O .

(b)

(i)

Ka

[CH 3 CH 2 COO ][ H 3 O ]
[CH 3 CH 2 COOH ]
+

1
+

Accept [H ] instead of [H3O ]


Reject any expression containing [H2O]

43

(ii)

([H ] =) 3.63 10 (mol dm ) (1)


3.44
Or 10
+

If Ka expression incorrect in (b)(i) or [H ] not squared, only 1


mark available

st

[H ] 2
5
[CH3CH2COOH] = 1.30 10

Or

(3.63 10 4 ) 2
[CH3CH2COOH] =

1.30 10 5

(1)
3

= 0.010 (1) (mol dm ) (1)


ASSUMPTIONS:
First assumption mark:
+

+
negligible [H ] from ionisation of water Or [CH3CH2COO ] = [H ] (1)
+

Accept No other source of H ions

Reject Just CH3CH2COO = H (ie no square brackets)


Second assumption mark:
Ionisation of the (weak) acid is negligible
+
Or x[H ] x where x is initial concentration of CH3CH2COOH
+

Or [H ]<<[HA] (1)

Accept Very slight ionisation


the initial [HA] = equilibrium [HA]
Reject any mention of non-standard conditions or temperature
not at 298 K
(c)

(i)

Ignore A solution of known pH which.


maintains nearly constant pH
OR
resists change in pH (1) OWTTE
on adding small amounts of acid or alkali (1)
Mark independently

44

(ii)

Working MUST be checked


First mark:
[acid]
+
[H ] = Ka [base] (1)

[ H ] [salt]
[acid]
Accept Ka =
Second mark:
Correct [acid] = 0.0025 and [salt] = 0.00375 (1)
Third mark:
Calculation of pH correct consequential on [acid] and [salt] used.

0.0025
[H ] = 1.30 10 0.00375
6
3
= 8.67 10 (mol dm )
pH = 5.06 (1)
+

Accept if [salt] and [acid] inverted, pH is 4.71 (2 marks)


Accept inverted with the original concentrations, pH = 5.19 (1
mark)
Ignore sig fig
OR
First mark:
pH = pKa

log10

[acid]
[salt] (1)

Reject in both cases, if [acid] = [0.0100] and [salt] =


[0.00500], pH = 4.59 (2 marks)
Second mark:
Correct [acid] = 0.0025 and [salt] = 0.00375 (1)
Third mark:
Calculation of pH correct consequential on [acid] and [salt] used.
[0.0025]
log 10
[0.00375] (1)
pH = 4.89
= 4.89 (0.18)
= 5.07 (1)
Accept 5.06
Ignore sig fig

3
[15]

45

53.

(i)

Lower temperature as reaction is exothermic/gives out heat /H is ve (1)


Higher/raise pressure as reaction moves towards fewer gaseous molecules (1)

Accept as reverse reaction is endothermic


Accept away from more gaseous molecules
Reject more gaseous products
(ii)

Lowering temperature decreases reaction rate (1)


Increasing pressure increases reaction rate (1)
Accept increasing pressure increases number of collisions
Consequential on either/both parts of (i)

Check they are consistent with (i)


(iii)

Energy of reactants above products hill in between (1)


Lower hill for catalysed reaction form same start to same finish (1)
Mark independently

U n c a ta ly s e d

E n e rg y

R e a c ta n ts
C a ta ly s e d
P ro d u c ts
R e a c tio n p a th

Accept labelled activation energies


Accept double hump acceptable
[6]

Kp
54.

(a)

(i)

( p NO ) 2
p N 2 p O2

Allow answer with brackets and/or x omitted


Ignore (g) and eq
Kp
Accept

p 2 NO
p N 2 p O2

Reject anything in [ ]
(ii)

Same number of moles on each side of the equation OR


The (partial pressure) units all cancel out (in the expression for K p)

46

(b)

(i)

(pNO) = 0.87 0.23 5.0 10


= 1.0 10

(1)

31

pNO = (1.0 10
= 3.2 10

31

16

31

(atm) (1)

Accept 3.16 10

16

(atm) (1)

Ignore sig fig


Mark consequentially only if based on reciprocal of
correct expression in (a)(i)

(ii)

0.87 + 0.23 (+ 3.2 10

16

) = 1.10 / 1.1 (atm)

Allow TE from (b)(i)

Reject answer based on adding 2 pNO

(iii)

pNO doubles/will become 6.4 10

16

Kp remains constant/is (still) 5.0 10

atm (1)
31

(1)

Ignore any neutral qualifications to these answers

Accept pNO will increase


Reject more than double
Reject answers with incorrect reasoning
(c)

(i)

Reaction will occur, but (very) little


NO is formed
OR
the equilibrium mixture is mainly
(unreacted) N2 and O2

Accept reaction occurs, but equilibrium lies (very much) to the


left
Reject Reaction is more likely to occur from right to left OR
Reverse reaction is favoured, unless included with
acceptable answer
(ii)

No change of state of any of the components is involved


(as the gases are heated up) OWTTE
OR
All components are gases (at these temperatures)
IGNORE Any reference to the number of particles involved

47

(iii)

(H is positive so)

H
T = Ssurroundings will be negative

No mark for negative alone

Accept negative, since for an endothermic reaction energy is


taken from the surroundings causing a decrease in disorder /
reduction in entropy
(iv)

(As T increases) Ssurroundings becomes greater/less negative/


more positive, so Stotal (also) becomes greater/less
negative/more positive/increases

Accept Ssurroundings becomes smaller, if qualified, e.g.


becomes closer to zero
(d)

Equilibrium might not have been reached (in the very short time the
gases are present in the engine)
Ignore references to the fact that the system is not closed

Accept other gases are present in the air (apart from N2 and
O2)
Accept temperature inside engine may be less than 1500K
Accept actual (total) pressure may be less than that assumed
[12]

48

55.

[C6H5CO2H] = (1/5 0.010 =) 0.002(0) mol dm

[C6H5CO2 ] = (4/5 0.020 =) 0.016 mol dm

Accept pKa = 4.20 (1)


Both correct (1)

0.002
Accept 0.016 (1)
+

[H ] (= Ka [C6H5CO2H] / [C6H5CO2 ]
5

= 6.3 10 0.0020 / 0.016)


6
= 7.875 10 (1)
Accept pH = (4.20 + 0.90) = 5.1 / 5.10 (1)
Do not penalise SF for the first two marks
+

pH = log[H ] = 5.1 / 5.10 (1)


Mark for final answer must be dependant on valid working
e.g. correct [acid]/[base] ratio.
Correct answer with no working (1)
Allow internal TE
[acid]
0.010
e.g. an
/[base] ratio of
/0.020 leads to a pH of 4.50 (2)
Reject 5.104 or 5
Reject 1 or >3 sig. fig.
[3]

56.

(i)

QWC
Stand alone marks
Lower yield / less hydrogen produced (1)
IGNORE any reference to rate
More (gaseous) molecules on rhs / fewer (gaseous)
molecules on lhs (1)

Reject equilibrium move left / reverse reaction favoured, if no


reference to yield
(ii)

QWC
Higher yield / more hydrogen produced (1) if this is
only explained in general terms of increasing rate of the
reaction, do not award the mark
(Forward) reaction is endothermic / absorbs heat (1)

If forward reaction is exothermic (0 out of 2)

49

(iii)

No effect (1)

1
[5]

57.

(a)
pH

14
12
10
8
B

4
2
1
0

10

20
V o lu m e 0 .1

30
40
N H 3 (a q ) a d d e d /c m

Do not worry about general shape of the curve, the scoring points are:
Starting pH ~ 1 and finishing pH between 9 and 11 (1)
3

Vertical at 25 cm (1)
Vertical range: at least three pH units in the range 3 to 8
e.g. pH range 3 to 6 OR 3 to 7 OR 3 to 8 OR 4 to 7
OR 4 to 8 OR 5 to 8 (1)
(do not need to start/finish on whole numbers)
Accept pH range 3 to 5

(b)

Middle of vertical pH range between 4 and 6 (1)

Bromocresol green
Indicator(s) CQ on graph [check table on question paper]

Accept more than one indicator for extended vertical regions

50

(c)

pH change around equivalence point too small


OR pH changes over too big a volume (1)
Accept too small a vertical (region)
OR no vertical (region)
OR no point of inflexion
OR no sudden change in pH
OR no straight section
for a sharp colour change of indicator (1)
Accept no sharp/clear/precise end point
OR very small range over which indicator changes colour
Reject no suitable indicator
OR No easy colour change
[If say ammonia is a strong base or ethanoic acid is a
strong acid, or both, (0 out of 2)]

2
[7]

58.

(a)

O
H

C
O

(b)

ester

(c)

(i)

1
Moles: C2H5OH: 3.75 (1)
Moles: HCOOC2H5 : 2.50 and moles H2O : 2.50 (1) for both

(ii)

Kc

[ HCOOC 2 H 5 ][H 2 O]
[HCOOH][C 2 H 5 OH]

Reject obviously round brackets ( )

51

2.50
Kc

(iii)

0.485

2.50

0.485

0.50

3.75
0.485
0.485 (1)
Must have clearly divided moles of each component by
st
0.485 for 1 mark e.g.
3
[HCOOC2H5] = [H2O] = 5.16 (mol dm )
3

and [HCOOH] = 1.03 (mol dm )


3
and [C2H5OH] = 7.73 (mol dm )
= 3.33 (1) stand alone mark
IGNORE sig.figs.

(2.50) 2
0.50 3.75 = 3.33 only scores (2) if it is stated
Accept
that V cancels either here or in (iv)
Kc

If [H2O] omitted in (ii), then answer


1

Kc = 0.647 mol dm
(2) but this will give
1
3
Kc = 1.33 mol dm with V omitted from calculation (1)
st

Reject 1 mark if 485 used as V in expression


(iv)

No, (as) equal numbers of moles on both sides


OR volumes cancel
3
OR mol dm cancel
OR units cancel
OR crossing out units to show they cancel

Accept equal powers/moles on both sides


OR powers cancel
Mark CQ on Kc expression in (ii)
Reject concentrations cancel
(d)

(i)

(as reaction) endothermic (1)


Accept exothermic in backward direction (or words to that
effect)
Kc decreases (1)
If state exothermic in forward direction, 1 mark only (out of 4)
for CQ increase in Kc
numerator in quotient (has to) decrease
OR denominator in quotient (has to) increase
OR fraction (has to) decrease (1)
yield of HCOOC2H5 decreases (1)

52

(ii)

no effect as catalysts do not affect (the value of) K


OR
no effect as catalysts do not affect the position of equilibrium
OR
no effect as catalysts do not affect the yield
OR
No effect as catalysts increase the rate of the forward and
backward reactions equally/to the same extent
OR
no effect as catalysts only increase the rate
OR
no effect as catalysts only alter the rate
no effect can be stated or implied
IGNORE any references to activation energy

Reject just catalysts increase rate


[13]

59.

(a)

(i)

uses E values to find Ereaction = (+) 1.57 (V) (1)


Reject 1.57

Zn + 2NO3 + 4H Zn

2+

+ 2NO2 + 2H2O (1)

Accept equation with equilibrium sign


Rejection equation with Zn on the right
(ii)

Ereaction for the production of hydrogen is (+) 0.76 (V) (1)


smaller than reaction in (i) so is less likely (1)
OR

NO3 being the oxidised form of a redox couple with a more

positive E than E H / H2 (1)


+

is a stronger oxidising agent than H (1)

53

(iii)

hexaaquacopper(II) (1)
2+
O H 2
H 2O C u O H 2
H 2O
O H 2
O H 2

O R
H 2O

O H

O H

H 2O

O H 2
O H 2
(1)
Both marks stand alone
[IGNORE charge]
[IGNORE how H2O ligand is bonded to central cation]

Accept hexaquacopper(II)
Reject formula
(iv)

ligand exchange/replacement/substitution (1)


2+

[Cu(H2O)6] + 4Cl
OR
2+
[Cu(H2O)6] + 4HCl

CuCl4 + 6H2O (1)


2

CuCl4 + 4H + 6H2O (1)

ALLOW
+

Accept H2CuCl4 + 2H for CuCl4 + 4H

(b)

(i)

E for the reaction is 0.39 (V) (so not feasible) [value is required].

2+

Accept Cu being the oxidised form of the redox couple with

the more negative E , will not oxidise I


(ii)

CuI is a solid (so conditions are not standard) (1)


Equilibrium is pulled over/moves to favour the r.h.s. (1)

Reject just conditions not standard

(iii)

[Cu(NH3)4]

OR [Cu(NH3)4(H2O)2]

Accept [Cu(NH3)2]
Reject [Cu(NH3)6]

Reject any 2+ complex

54

(iv)

(atmospheric) oxygen (1)


+

oxidises Cu to Cu

2+

(1)

Reject air for oxygen


(c)

(i)

starch (1)
blue-black/blue/black to colourless (1)

Reject clear for colourless


(ii)

(If added too early) insoluble complex/black solid formed, making


titre too low
OR (If added too early) insoluble complex/black solid formed,
removes iodine from solution
OR (If added too early) insoluble complex/black solid formed,
causes inaccurate titre.
OR (If added too early) insoluble complex/black solid formed, not
all the iodine is titrated.

(iii)

Amount thiosulphate = 0.01655 dm 0.1 mol dm (1)


= amount Cu

2+

amount of Cu

in 25.0 cm = 1.655 10 mol (1)

2+

in 250 cm = 1.655 10 10 (1)


2

mass of Cu (in sample) = 1.655 10 63.5 (1) = 1.051 g


% Cu in brass = 1.051 100/1.5 = 70 % (1)
[IGNORE sf]
[mass of 1.051g with working scores (4);
correct answer with no working scores (3).]
Mark consequentially

5
[22]

60.

(a)

The amount of a solid present is immaterial since Kc does not depend on


this
OR solids do not appear in expression for equilibrium constants
IGNORE any references to solid in excess.

(b)

Ag + I AgI
IGNORE state symbols

55

(c)

Correct answer with some working and correct units scores full marks.
Otherwise steps in calculation must make it reasonably clear to examiner
what is being calculated (QWC).

(initial amount) I = 0.100 mol dm 0.050 dm = 5 10 mol (1)


+

Amount Ag = 0.100 mol dm 0.031 dm = 3.1 10 mol (1)

equilibrium amount I = 3.1 10 mol (1)

I reacted = (5 3.1) 10 mol = 1.9 10 mol (1)


If this subtraction is not carried out then the next mark (for calculating
amount of sulphate) can not be awarded.
3
4
Thus amount of sulphate = 1.9 10 (= 9.5 10 mol) (1)

3.1 10 3 mol
conc iodide =

0.05 dm 3

(= 0.062 mol dm )
0.95 10 3 mol

3
0.05 dm 3
AND conc sulphate =
(= 0.019 mol dm ) (1)
3
The mark is for the process of dividing by 0.05 dm
2

Kc = 0.019/0.062 = 4.94 (1) Answer must be to 2 or more S.F.


Value consequential on dividing their moles by a volume.
1

mol dm (1) Stand alone

8
[10]

61.

(a)

(i)

Pairs: acid NH4 /ammonium ion and base NH3 /ammonia


+

acid H3O / hydronium ion and base H2O / water

Accept hydroxonium ion


[ NH 3 ][H 3 O ]
(ii)

Ka =

[ NH 4 ]

ignore lower case k

[NH 3 ][H ]
Accept Ka =

[NH 4 ]

Reject answers including [H2O]

56

(iii)

[H3O ] = 10 mol dm (1)


+

Assumption ionization of NH4 (negligibly) small (1)


+

Assumption [NH3] = [H3O ] (1)


+

Accept [NH4 ] = [NH4Cl] or NH4Cl totally ionized


5 2

thus [NH4Cl] = (1 10 ) / 5.62 10

10

= 0.178 mol dm (1)


Answer to 2 or more S.F.
(iv)

QWC
methyl red (1)
indicator constant or pKIn must be near the endpoint pH
OR indicator constant or pKIn must be near 5 (1)
nd

2 mark conditional on correct indicator

Accept pKIn in the steep part of the graph or it is a weak basestrong acid titration

(b)

CN + H2O
HCN + OH
IGNORE state symbols

Accept instead of
(c)

(i)

nucleophilic addition

57

(ii)

O (:)
C

(:)C N
(1) for both arrows

CN

(1) for intermediate

(1 )

O (:)
C

CN

O H
C

CN

CN

(:)C N

OR for second step

O (:)
C

C N

O H
C

C N

(1 )

Fish hook arrows (penalise once)


Ignore the groups attached to the carbonyl carbon throughout
The intermediate is not consequential on their first step
The minus of the cyanide ion can be on either the C or the N

The arrow can start from the minus of CN in step 1 (but not

from the minus of CN ) and can start from the minus of O in step 2
The arrow from the bond must not go past the O atom
Lone pairs not essential
+

Single step addition of HCN or initial attack by H /HCN scores zero


Autoionisation of C=O can only score the last two marks ie max 2
(iii)

QWC
if too acidic too small a concentration of cyanide ions (1)
Accept not enough / too little CN

if too alkaline too little HCN to donate the proton in the last step
+
OR H ion concentration too low (1)

58

(d)

(i)

rate = k[CH3CH2CH2Cl] [CN ]


Must be an equation
Must be [ ] NOT ( )
Ignore upper case K

Accept R or r for rate C3H7Cl] / [1-chloropropane]/


[chloropropane]
Accept [cyanide ion]/[cyanide]
Reject [KCN]
(ii)

N C

C 2H

C u rly a rro w
C u rly a rro w

N C

Cl

(1 )

H
C

C l

C 2H

N C

C
C 2H

H + C l

(1 )
T ra n s itio n s ta te

(1 )

Must have partial bonds in transition state


CN and Cl must be on opposite sides of central C in the
transition state
Accept negative charge on N of cyanide ion

Mechanism based on SN1 scores 0


Reject fish hook arrows (penalise once)
Reject arrow from N of CN
[19]

62.

(i)

higher pressure / temperature will increase rate of reaction


OR
higher pressure will increase production of methanol (as less
moles of gas on the RHS)

Accept higher pressure faster reaction


Accept higher temperature faster reaction
Accept higher pressure greater yield
Reject no catalyst used so cheaper

59

(ii)

Any three from:


lower temperature
increases yield / because reaction exothermic (1)
lower temperature costs less, (less energy used) (1)
Can gain 2 marks if both ideas of temperature and pressure put
together in same advantage
lower pressure costs less, (pipes thinner/less energy needed
to pressurise plant) (1)
catalyst speeds up reaction (1)
/allows a lower temperature to be used

Accept catalyst allows a lower pressure to be used


Reject lower temp/pressure easier to achieve
[4]

63.

(a)

(i)

[6 188.7 + 4 210.7] [4 192.3 + 5 205] (1)


1

+180.8 J mol K (1)


1

Accept +181 J mol K


Reject internal TE

(ii)

1 for missing + sign/missing or incorrect units but penalise only


once in part (a)
[IGNORE sig fig]

yes, as 9 molecules of gas are being changed to 10 molecules of


gas (therefore increase in disorder)

Accept TE from (i)


Not just 9 molecules going to 10 molecules
(iii)

905.6 1000 /1123 (1)


1

+ 806.4 J mol K / 0.8064 kJ mol K (1)


[IGNORE SF]
Accept + 806 J mol K

(iv)

+987.2 J mol K

1
1

Accept +987 J mol K


allow TE from (i) & (iii)
1

No TE if J mol K added to kJ mol K

60

(v)

All products/reaction goes to completion because Stot > 200 J


1

mol K /Stot is very large


[Needs to be consistent with (iv)]
(vi)

catalysed pathway should have lower Ea than uncatalysed pathway


and the peak of the curve should be above the energy level of the
reactants (1)
Energy of products should be lower than energy of reactants (1)

Kp
(b)

(i)

pNO 2 2
pNO 2 pO 2

p 2 NO 2
2
Accept p NO pO 2

Reject [ ]

(ii)

4.95
mole fraction NO2 = 5 or 0.99 (1)
0.025
mole fraction NO = 5 or 0.005
OR

0.025
mole fraction O2 = 5 or 0.005 (1)
(0.99) 2 (1.5) 2
3
3
6
Kp = (0.005) (1.15) = 5227200 / 5.2 10 (1)

atm (1) unit mark independent but consistent with


expression used in calculation.
IGNORE SF

Correct answer for Kp alone = 3 max


(iii)

Equilibrium lies to RHS/products side as Kp is large


OR reaction wont go to completion as Kp < 10
Must be consistent with (ii)

10

Allow TE from b(ii)

61

(iv)

Kp remains unchanged as pressure does not affect it / only


temperature affects Kp (1)
partial pressure of NO2 increases as eqm moves to side of
fewest (gas) molecules/RHS (1)
or
Partial pressure of NO2 increases as pp = mole fraction total
pressure

Accept justification in terms of entropy


[17]

64.

(a)

(i)

[CH 2 ClCO 2 ][H ]


Ka
[CH 2 ClCO 2 H]
+

1
+

Accept [H3O ] in place of [H ]


allow one set of sq brackets to be missing

(ii)

+ 2

[H ] = 1.3 10 0.001 (1)


= 1.3 10

[H ] = 1.3 10

1.14 10 (1)
3

pH = log 1.14 10 = 2.9(4) (1)


[IGNORE SF]
(iii)

Trichloroethanoic, as it has the largest Ka value (1)


and has (3 electron withdrawing) chlorine atoms to stabilise
the anion formed (on dissociation). (1)

(b)

(i)
H

Cl

H
O

ester group (1)


rest of molecule (1) dependent on first mark
(must be fully displayed)
methyl chloroethanoate (1)

No transferred error for name


(ii)

ester(s)

Reject ether

62

(iii)

nucleophile, (1)
as it has a lone pair (of electrons) on the (hydroxyl) oxygen (1)
which can attack the positive carbonyl carbon on the acid (1)
nd

rd

2 and 3 marks could be obtained by use of a diagram


Reject attack by CH3O
(iv)

(reflux) heat with NaOH(aq) (1)


(cool) and add HCl(aq) (1)
OR
reflux (1) [must be in context]
with HCl (1)

2
[15]

65.

(a)

Enthalpy/heat/energy change for one mole of a


compound/substance/ a product (1)
NOT solid/molecule/species/element
Reject heat released or heat required unless both mentioned
to be formed from its elements in their standard states (1)
ALLOW normal physical state if linked to standard conditions
Reject natural state / most stable state
standard conditions of 1 atm pressure and a stated temperature (298 K) (1)

Reject room temperature and pressure


Reject under standard conditions
(b)

(i)

Bonds broken
NN (+)945
and
()1308

Bonds made
6NH ()2346 (1)

3HH ()2253 (1)


H = 945 +1308 2346
= 93 sign and value (1)

1
H = 93 = 46.5 (kJ mol )
rd
sign and value q on 3 mark (1)
2

Accept 46.5 (kJ mol ) with working (4)


Accept + 46.5 with working max (3)
Accept +93 with working max (2)

63

(ii)
N

+ (3 )H

(E n th a lp y )

H
OR
93

(2 )N H

Accept 46.5
Correct labelled levels (1)
Reject Reactants and Products as labels
H labelled (1)
direction of arrow must agree with thermicity
Accept double headed arrow
Diagram marks cq on sign and value of H in (b)(i)
IGNORE activation energy humps
(iii)

350500 C (1)
Accept any temperature or range within this range
higher temperature gives higher rate (1)
but a lower yield because reaction is exothermic (1)
Accept favours endothermic reaction more than exothermic so
lower yield
OR
Lower temperature give higher yield because reaction is exothermic (1)
but rate is slower (1)

Accept cq on sign of Hf in (b)(i) or levels in (ii)


Reject lower temp favours exothermic reaction
(iv)

(v)

Iron / Fe (1) IGNORE any promoters


no effect on yield (1)

temp would have to be much higher for a reasonable rate then


yield would be too low
lower activation energy implies reasonable rate
OR
Allows reaction at a lower temp at a reasonable/fast rate giving
a reasonable yield.

Accept rate too slow without catalyst at a temp giving a


reasonable yield
Reject to lower activation energy of reaction

64

(c)

(i)

advantage
higher (equilibrium) yield/more NH3 in equilibrium
mixture/equilibrium shifts to right (1)
because smaller number of (gaseous) moles/molecules on rhs (1)
IGNORE any reference to change in rate

Reject just more ammonia


(ii)

disadvantage
(plant more) expensive because thicker pipes would be needed
OR
cost (of energy) for compressing the gases/cost of pump
OR
Cost of equipment/pressure not justified by higher yield

Accept stronger or withstand high pressure for thicker


Accept vessel/container/plant /equipment/reaction vessels for
pipes
Reject just more expensive
Reject just thicker pipes etc
Reject apparatus
[18]

66.

IGNORE s.f. throughout this question


(a)

Acid
+
Proton or H donor
+
+
Or forms H or H3O (1)
Weak
dissociates to a small extent
Or ionises to a small extent (1)

Accept few molecules dissociate


Or incomplete dissociation
Or partial dissociation
Reject not fully dissociated
Or not dissociated fully

65

(b)

2HCOOH(aq) + Na2CO3(aq) 2HCOONa(aq) + CO2(g) + H2O(l)


Or
HCOOH(aq) + Na2CO3(aq) HCOONa(aq) + NaHCO3(aq)
Species + balancing (1)
State symbols (1) Consequential on correct species

Accept 2HCOONa(aq) + H2CO3(aq)


Accept HCO2H for the acid

Accept HCO2Na or HCOO Na for salt


(c)

(i)

one acid: HCOOH


Conjugate base: HCOO
1 mark for both
Accept correct acids and conjugate bases in either order
ACCEPT

HCO2H and HCO2


OR
O
H C
O H
O
H C

other acid: H3O


Conjugate base: H2O
1 mark for both
+

Reject H for H3O

(ii)

2
+

[HCOO ][H 3 O ]
[HCOOH]
(Ka) =
+

Accept [H ] instead of [H3O ]


Must use square brackets

[HCO2 ] and [HCO2H]

66

(iii)

+ 2

[H ] = Ka [HCOOH]
OR
[H ] 2
K = [ HCOOH]
a

OR
+ 2
4
[H ] = 1.60 10 0.100 (1)
4
+
[H ] = 1.60 10 0.100
3
3
= 4.0 10 (mol dm ) (1)

pH = 4.8 scores (2) as square root has not been taken


IGNORE sig figs
+ 2
Max 1 if [H ] expression incorrect
+

pH = log10[H ]
pH = 2.40 (1)
+

Accept any pH value consequential on ] [H ], provided pH < 7


Reject pH = 2.39 (is a rounding error) so no third mark
Alternative method
pKa = 3.80 (1)
1
1
pK a log[acid]
2
pH = 2
(1)
pH = 1.90 (0.50)
pH = 2.40 (1)

Reject pH = 2.39 (is a rounding error) so no third mark

67

(d)

(i)

[acid]
+
[H ] = Ka [salt]
OR

0.0500
[H ] = 1.60 10 0.200 (1)
5
3
= 4.00 10 (mol dm ) (1)
+

0.100
Reject 0.400
pH = 4.40 (1) IGNORE sig figs
Reject 4.39 (rounding error) so no third mark
OR
[HCOOH]


pH = pKa log10 [HCOO ] (1)
4

pH = log10(1.60 10 ) log10

0.0500

0.200 (1)

0.100
Reject 0.400
pH = 3.80 (0.60)
pH = 4.40 (1) IGNORE sig figs

Reject 4.39 (rounding error) so no third mark

68

(ii)

Addition of H ions:

+
HCOO + H HCOOH (1)
Accept if described in terms of HA

H + A shifting to left

Addition of OH ions:

HCOOH + OH HCOO + H2O (1)


If the ionisation of sodium methanoate shown with
then max (1) out of 2 for above equations

Addition of OH ions:
+

H + OH H2O must be followed by more dissociation of


+

HCOOH (to restore [H ])


Accept molecular equations or equations described in words
+

or notation involving HA, H and A .


(buffer solution has) high concentrations

Or a large reservoir of both HCOOH and HCOO


+

relative to added H / OH (1)


+
(hence virtually no change in [H ])

Accept just large reservoir of both HCOOH and HCOO


[16]

67.

(a)

IGNORE s.f. throughout this question


(i)

moles SO2 (10.0 9.00) = 1.00 (mol)


moles O2 (5.00 4.50) = 0.500 (mol)
moles SO3 9.00 (mol)
all 3 correct (2)
2 correct (1)

Reject multiples of the stated moles


(ii)

All three total number of moles (1)


i.e.

1.00
( 0.0952) or 2 21
10.5
0.500
X O2
( 0.0476) or 1 21
10.5
9.00
X SO3
( 0.857) or 18 21 or 6 7
10.5
X SO2

Reject rounding to 1 sig fig


Mark consequential on (a)(i)

69

(iii)

All three total pressure (1)


i.e.

1.00
2.00 or 4 21
10
.
5
pSO2 =
= 0.190 (atm)
0.500
2.00 or 2 21
pO2 = 10.5
= 0.0952 (atm)
9.00
2.00 or 36 21 or 12 7
10
.
5
pSO3 =
= 1.71 (atm)
Mark consequential on (a)(ii)

Kp
(iv)

(1.71) 2
(0.190) 2 (0.0952)
1

Kp = 851 (1) atm (1)


Mark consequential on (a)(iii) and (a)(iv)

Accept answer with units and no working (2)


Accept correct answers between 845 and 855 as this covers
rounding up etc
1

Reject wrong units e.g. mol dm


(b)

(i)

(Kp) decreases

(ii)

(Kp decreases so)

Reject any Le Chatelier argument (this prevents access to 1


mark)

st

p 2 SO3
2
fraction/quotient p SO 2 pO 2
has to decrease (to equal new kp) (1)

so shifts to left hand side (1) this mark only


available if (b)(i) answer was kp decreases.
Reject shifts to right, even if answer to (b)(i) was kp increases
(as
(c)

(i)

p SO 3

decreases whereas

No effect/none/zero (effect)

p SO 2

and

p O2

increase)

2
1

70

(ii)

(d)

Increases
OR
more SO3/more sulphur trioxide
OR
increases amount of SO3/sulphur trioxide

(i)

No effect/none/zero (effect)

(ii)

No effect/none/zero (effect)

1
[13]

68.

(a)

1
Accept H3O

(b)

HCOOH/HCO2H (1)
HNO3 (1)
1 for each extra incorrect answer

Accept C and E
[3]

69.

(a)

(i)

pH = 3.5 (1)
+
log10[H ] = 3.5
+

[H ] = 3.16 10 (mol dm ) (1)


4

2.5(1) 10 (mol dm ) based on pH = 3.6 (2 marks)

Accept T.E. from wrong pH providing < 7


4

Accept 3.2 10 (mol dm )


4

3 10 (mol dm ) allowed if evidence of rounding being


applied

(ii)

[H ][CH 3 CH 2 CH 2 CO 2 ]
Ka = [CH 3 CH 2 CH 2 CO 2 H] (1)

Accept version with [H3O ]


Accept molecular formulae

[ H ][C 4 H 7 O 2 ]
[C 4 H 8 O 2 ]
Accept

71

(iii)

[H ] 2
Ka = [CH 3 CH 2 CH 2 COOH] (1)
(3.16 10 4 ) 2
st
0.00660
=
(1 mark can be scored here)
5

= 1.5 10 (mol dm ) (1)


Ignore units
Only 2 sig. fig. allowed

Accept TE from (i)


Allow any number of s.f. provided consistent with calculation
Reject TE from (ii)
(b)

(i)

CH3CH2CH2CO2H ((aq)) + NH3 ((aq))

CH3CH2CH2CO2( )NH4( ) ((aq))


Molecular formulae acceptable

Accept eqn via NH4OH CH3CH2CH2CO2 +NH4


Reject any amide product
(ii)

Ammonium butanoate (1)


(Excess) butanoic acid (1)
no TE from (b)(i)

Accept ammonium ions and butanoate ions (1)


Reject butanoate ions alone
Reject formulae
(iii)

A buffer (mixture) (1)


There is a relatively small rise /change in pH (as
aqueous ammonia is added) OWTTE (1)
Mark independently

Reject sharp neutralisation point/no change in pH


(iv)

There is no large increase in pH / vertical shape to the


graph (at the end-point) OWTTE

Accept no sudden change in pH


Reject no indicator has the required pH range

72

(v)

EITHER
3
End-point = 30 cm (1)
3
[NH3] = (10/30) 0.00660 = 0.00220 (mol dm ) (1)
OR
3
5
10 cm of butanoic acid contain 6.60 10 mol
5
From equation this requires 6.60 10 mol NH3
3

From graph, end-point = 30 cm (1)


5
[NH3] = 6.60 10 (1000/30)
3

= 2.20 10 / 0.00220 (mol dm )(1)


nd
Allow internal TE for 2 mark based on an incorrect
3
equivalence point i.e. 0.0660 (mol dm )

Allow T.E. from (b)(i)


[13]

70.

(a)

Heat/enthalpy/energy change per mole of substance/compound/product


OR
heat/enthalpy/energy change for the formation of 1 mol of substance/
compound/product (1)
heat released and heat required not allowed unless both mentioned
NOT molecule
from its elements in their standard states (1)
at 1 atm pressure and a stated temperature/298 K (1)
NOT room temperature and pressure
NOT under standard conditions

(b)

(i)

3
1

(H = 306 (399)) = (+) 93 (kJ mol )

ALLOW kJ
Incorrect units lose mark otherwise
(ii)

The equilibrium moves to right hand side


OR amount of dissociation increases (1)
Because the (forward) reaction is endothermic (1)
Needs to be consistent with (i)
If (i) has a negative answer (exothermic)
equilibrium moves to left hand side (1)
Because (forward) reaction is exothermic (1)
If answer to (i) is +93 or 93 but state that this is exothermic
If reaction moves to left hand side (1)
If reaction moves to right hand side (0)

73

(iii)

add chlorine (1)


which drives equilibrium to the left (1)
OR
increase the (total) pressure (1)
because there are fewer (gas) molecules on left hand side (1)
OR
add PCl3 (1)
Which drives equilibrium to the left (1)

2
[8]

71.

(a)

(i)

- lg (0.05) = 1.3(0)

IGNORE sig figs from this point on in this question

(ii)

[OH ] = 1 10

14

/ 0.05 = 2 10

13

(mol dm )

OR via pOH
Correct answer with no working (1)

(b)

(i)

Ka = [H2PO4 ][H3O ]/[H3PO4]


+

NOT using H instead of H3O

(ii)

[H3O ] = 10

1.20
3

= 0.063 (mol dm ) (1)


0.063 2
Ka = 0.500 0.063 (1)
3

NOT consequential on (b)(i)


3

= 9.08 10 (1) mol dm (1)


3
+
= 9.11 10 if [H3O ] not rounded
ALLOW
0.063 2
Ka = 0.500 (1)
3

= 7.94 10 (1) mol dm (1)


3
+
= 7.96 10 if [H3O ] not rounded

ALLOW consequential marking on numerical errors


Correct answer with units and some working (4)
(c)

(i)

Assign the terms acid/base (1)


link the pairs (1)

74

(ii)

(d)

presence of H from the first dissociation keeps equilibrium to left


/suppresses ionisation

Bromocresol green (1)


pKin/range/colour change (of indicator) lies in vertical section
OR
For alternative indicators pKin/range/colour change (of indicator) lie
outside vertical section (1)

2
[12]

72.

(a)

(i)

EITHER

2+

E = (+) 0.15 (V) OR E (MnO4 / Mn ) more positive or

greater than E

(Cl2 / Cl ); accept reverse argument (1)

(so) MnO4 reacts with Cl OR Cl ions form Cl2


OR KMnO4 reacts with HCl (1)
OR

2+
2MnO4 + 16H + 10Cl 2Mn + 8H2O + 5Cl2 (1)

(ii)

(b)

(i)

E = (+) 0.15(V) (1)

stated colour change of colourless to (pale) pink NOT purple OR


stays (pale) pink
OR pink to colourless
OR first excess of (coloured) manganate((VII))
IGNORE self-indicating
2+
IGNORE references to Mn

(Multiply iron half-equation by five to) cancel out electrons


OR balance electrons

75

(ii)

Moles MnO4

0.0200 20.10
1000
=

= 0.000402 mol MnO4 (1)


Moles Fe

2+

per 25.0 cm

= 0.00201 mol Fe
Moles Fe

2+

= 5 0.000402
2+

(1)

200
2+
per 200 cm = 0.00201 25 mol Fe
2+
= 0.01608 mol Fe (1)
3

Mass of FeSO4 . 7H2O = 0.01608 278


= 4.47g or via concentrations (1)

4.47
= 6.00 100%
= 74.5% (1) ALLOW 74.7% / 75%

Percentage purity

Correct answer + working (5)


ALLOW 2 or more sig figs
6.00
If start by dividing 278 , and final answer is incorrect, candidate can
access first three marks only.
If third step omitted, answer 9.3% OR 9.33% OR 9.4%

(c)

(i)

E = + 1.46 ( 0.13) = ( + ) 1.59 (V)


Correct answer alone (1)

PbSO 4 precipitated (1)


[H

( aq) ] not 1 mol dm


2

(ii)

(1)

any of these

[ Pb ( aq) ] not 1 mol dm (1)

the conditions (in the car battery) are not standard (1)

temperature non-standard alone or not 1 atm pressure


alone does not score

1
[11]

73.

(a)

(i)

Fe2O3 + 3CO 2Fe + 3CO2 (1)


H = (3 394) - (3 110) (822)
1
= 30 (kJ mol ) (2)
Multiply by 3 twice (1)
Correct answer with sign (1)
ALLOW consequential calculation if wrong stoichiometry
If O2 given as product 1 max on consequential calculation

76

(ii)

(i) is more likely because the rate of a reaction between a solid


and a gas will be faster than that between two solids
ALLOW
(i) is more likely because it is exothermic (and (ii) is endothermic)
OR
products in (i) are more thermodynamically stable relative
to reactants than in (ii)

Consequential on (a)(i)
pH 2 4
(b)

(i)

Kp =

pH 2 O 4

(1) ps are essential NO [ ]

1. 6 4
4
= 1.2 = 3.16 / 3.2 and no units (1)

Consequential on Kp expression provided no Fe or Fe3O4 included


(ii)
QWC

KP decreases (1)
Because forward reaction release heat / exothermic
OR reverse reaction absorbs heat / endothermic (1)
Dependent on Kp decreases

nd

Do not allow 2 mark if decrease is explained in terms of position


moving to the left, UNLESS moving is a consequence of Kp decreasing.
(c)

IGNORE state symbols


X: 2H2O + O2 + 4e
2+

( )

4OH (1)

( )

( )

OR this OR multiples (1)

Y: Fe Fe + 2e / Fe 2e Fe
IF and Y not identified 1 (out of 2)

2+

(1)

iron(II) hydroxide
(1)
ALLOW Fe(OH)2 / [Fe(OH)2(H2O)4]
(d)

covalent bonds labelled (1)


dative bonds labelled OR shown as arrows (1)
ALLOW dot and cross diagram (2)
Structure with Fe-Fe bond does not score first two marks
Tetrahedral (around Fe) (1)
ALLOW good 3-D diagram dependent on 4 covalent/dative bonds around Fe
If Al2Cl6 ALLOW max 2 (out of 3)
Any mention of ionic 0 (out of 3)

77

(e)

(i)

add (aqueous) sodium hydroxide / ammonia (1) ALLOW OH (aq)


red/brown/foxy red/red-brown/rust ppt/solid (1)
OR
add (aqueous) potassium hexacyanoferrate(II)/hexacyanoferrate(II)
ions (1)
(Prussian) blue ppt/solid (1) - ALLOW result for near miss spelling
of reagent
OR
add (aqueous) potassium thiocyanate (1)
blood red (solution) (1) NOT ppt

(ii)

Fe

3+

polarises the (OH bond in water) ligands (1)


3+

2+

[Fe(H2O)6] + H2O [Fe(OH)(H2O)5] + H3O


OR in words
eg deprotonation (of the ligand) by the (solvent) water (1)
+

the H3O / H (aq) ions make the solution acidic (1) - stand alone

3
[19]

74.

(a)

(i)

H(g) +

O(g)

Cl(g)

in top RH box

H2(g) + O2(g) + Cl2(g) in lower box


Brackets around the state symbols are not required

(ii)

(iii)

(b)

589 667 = 78 (kJ mol )


ALLOW final answer on its own

667 464 = (+)203 (kJmol )


ALLOW final answer on its own

(i)

(1 )

(1 )

(1 )

+ +

C l
+ +

(1 )

+ +
+
+

ALLO W

C l

+
+

+ +

ALLOW all dots/crosses


ALLOW 1 max if electrons are correct but atoms are not identified
If ionic dot and cross diagram (0)

78

(ii)

100 106 (1)


as lone / non-bonding pairs take up more space/
repel more strongly than bonded pairs (1)
NOT bonds being repelled/H and Cl being repelled

(c)

No change (1)
as number of gaseous reactant molecules = number of gaseous product
molecules (1)
ALLOW 1 max if candidates state or imply a very small change with correct
justification
eg hardly changes
doesnt change much
very little effect/change

2
[9]

75.

(a)

pentyl dichloroethanoate (1)


ALLOW 1,1 OR 2,2ALLOW pent-1-yl /all one word
NOT penten
NOT pentan
NOT pentanyl
ester (1)
ALLOW esther

(b)

(i)

2
3

using a pipette remove a known volume (say 20 cm ) (1)


remove some solution either with a pipette
3
OR a known volume / 20 cm
titrate with an alkali (such as sodium hydroxide) (1)
of known concentration (1)
dependent on previous mark ie must have mentioned alkali
IGNORE quenching
using a named indicator eg. phenolphthalein/methyl orange (1)
NOT litmus / universal indicator
Measure pH on its own 1 (out of 4)
But if calculation fully explained from pH can get full marks

Kc
(ii)

CHCl 2 COOC 5 H11 (l)


CHCl 2 COOH(l) C 5 H10 (l)

State symbols not required

79

(iii)

C5H10

1.7
1.7 (1) 0.3 = 5.67(5.7) NOT 5.66

CHCl2COOC5H11

0 .6
0.6 (1) 0.3 = 2

(1) for moles at eq by 0.3 in both cases

(iv)

0.6 / 0.3
2Kc = 1.33 1.7 / 0.3
3

2
(1) = 1.33 5.67
1

= 0.265 (1) dm mol / mol dm (1)


3

NOT dm
ALLOW 0.27 / 0.26 / 0.264
Penalise 1 SF or 4SF or more SF but only take off 1 mark maximum in
(iii) and (iv) for significant figure errors
ALLOW TE from expression in (ii)
TE using numbers for (iii) full marks possible

3
[13]

76.

(a)

Dynamic reaction continuing (all the time) (1)


ALLOW rate forward = rate back
Equilibrium concentrations (of the substances) do not change /
remain the same (1)
NOT concentrations all equal
NOT amounts do not change

(b)

(i)

350 450 C OR 620-720 K (1)


>1 5 atm (1)
2
Values can be given in kPa or kNm

(ii)

High yield favoured by low temperature (1)


High rate favoured by high temperature (1)
So, temperature used is a compromise (1) conditional on first two marks
ACCEPT correct inverse argument

80

(iii)

(c)

(i)

Too costly for extra yield


OR Position of equilibrium is well to right under these conditions
OR Corrosion problems at high pressure
OR Only need elevated pressure in practice to push gases through system
OR Capital cost high
OR Maintenance cost high
OR High energy cost
OR Sulphur dioxide liquefies.
NOT too costly without explanation
NOT too dangerous

H = 2Hf(SO3) 2 Hf(SO2) = (395 2) ( 297 2) (1)


1

= 196 (kJ mol ) (1) IGNORE units


1

196 (kJ mol ) with some working (2)


No consequential mark other than failing to multiply by two to get
1
98 kJ mol max (1)
Any positive answer (0)

QWC

(d)

(ii)

(i)

Hf is defined as formation from elements


OR Hf of an element is defined as 0 (in its standard state)
OR all elements are given the value zero
It is an element on its own (0)

V2O5 OR V205
NOT name
2 5
NOT V O .
If name and formula given, ignore name.

81

(ii)

R e a c ta n ts /R
(E n th a lp y /
/S O 2 + O 2
h e a t / e n e rg y )

P ro d u c ts /P /S O

U n c a ta ly s e d

(1 )

C a ta ly s e d

(1 )

E u th a lp y le v e ls

(1 )

U n c a ta ly s e d

(1 )

C a ta ly s e d

(1 )

E u th a lp y le v e ls

(1 )

A LLO W

(E n th a lp y /
h e a t / e n e rg y )

R e a c ta n ts /R
/S O 2 + O 2

P ro d u c ts /P /S O

ALLOW endothermic intermediates


ALLOW single hump for catalysed pathway: (energy)
If the diagram shows H endothermic, then can score the first two marks.
rd

If y-axis label is wrong 3 mark can not be awarded


rd
Catalysed and uncatalysed labels missing scores 3 mark only
If two diagrams drawn, full credit can be given if the catalysed
Ea is clearly less than the uncatalysed.
If H and Ea confused, then max 2

QWC

(iii)

Changes mechanism to one of lower Ea


OR to a different route with lower Ea (1)
NOT Lowers Ea alone.
Reactants (chemically) adsorb on catalyst surface
OR (at given T) more collisions have E > Ea
so more successful collisions (1)

(e)

Forms (a difficult to condense) mist / fog / smoke / too violent /


too exothermic
NOT extremely reactive

1
[18]

82

77.

(a)

starts at 2.2 (1)


3
vertical section at 40cm of sodium hydroxide (1)
vertical section centred between pH 8-9 and between 2 to 3 squares high (1)
shape to include initial jump and finish between pH = 12 13 (1)
nd

rd

If curve drawn back to front, only 2 and 3 marks available


(b)

(i)

maintains nearly constant pH / resists change in pH (1)


on adding small amounts of acid or alkali (1)

acid

[ acid ]
H Ka[salt
]

(ii)

pH = pKa lg [salt]

OR

(1)

0.25
0
[H ] = 1.78 10 .125 (1)
+

[H ] = 3.56 10 (mol dm )

pH = 3.4(5) (1)
IGNORE no. of decimal places but penalise pH = 3
(iii)

acid partially ionised and salt fully ionised


OR equations (1)

HA + OH A + H2O (1)
+

ALLOW H + OH H2O followed by more dissociation of HA

A + H HA (1)

[HA] and [A ] are large (relative to H and OH added) / large reserves of

undissociated acid and salt (and so the values of [HA] and [A ] do not
change significantly) (1)

NOTE: If no equations given for effect of adding OH and H , correct


explanation can score (1) out of these two marks.

4
[13]

78.

(a)

The emf of a half-cell measured relative to the standard hydrogen electrode (1)
3

(b)

all solutions at 1 mol dm concentration and gases at 1 atm pressure / 101 kPa
and at a stated temperature / 298K (1)
Standalone mark
ALLOW pressure of 100 kPa

Introducing another metal wire would set up its own p.d. / can
only measure a potential difference / need source and sink for
electrons / voltmeter requires two connections

83

(c)

(i)

2Fe(s) + O2(g) + 2H2O(l) 2Fe

2+

(aq) + 4OH (aq) or multiples

OR
2Fe(s) + O2(g) + 2H2O(l) 2Fe(OH)2 (s)
Species (1)
balancing (1)

(ii)

QWC

(iii)

Do not allow species mark if electrons still in equation, but allow


balancing mark if 4e on both sides

E react = (+) 0.84 (V) (1)


Greater than zero therefore feasible (1)

Zn oxidises preferentially to Fe / Zinc acts as sacrificial (anode) (1)


If Sn used (and damaged), Fe oxidises; preferentially (1)
Disallow oxidises more readily
2+
E Zn / Zn more negative than for Fe
OR

2+
E Zn / Zn more positive than for Fe
OR

E cell for Zn being oxidised by O2 is more positive than for Fe


being oxidised by O2
OR

similar E arguments related to preferential oxidation with Sn (1)


disallow higher or bigger for more negative or more positive

3
[10]

79.

(a)

(b)

(i)

Forms ions which have partially filled d-orbitals


OR
Forms ions which have a partially filled d-subshell

(ii)

Scandiurn / Sc and Zinc / Zn

(i)

Fe

2+

Mn
(ii)

Fe

2+

3+

Mn

[Ar] 3d

6
5

[Ar] 3d (1) for both correct

is 3d / half filled d-subshell which is more stable than 3d (1)

2+

is (already) 3d (which is more stable than 3d ) (1)

84

(c)

Shape (1)
Bonding to correct atoms (1)
(4)

(4)
CN

CN
N C

CN
Fe

Fe

O R

N C

C N

N C

CN

N C

CN

CN
CN

2
(d)

Two As atoms oxidised from +3 to +5 per mole of As2O3

(loss of 4e ) (1)

if 5 moles oxidised, total 20e Lost / change in oxidation no. = 20 (1)

4 moles MnO4 reduced, total 20e gained / change in oxidation no. 20

each Mn(VII) gains 5e / change in oxidation no. 5 (1)


Mn(ll) / Mn

(e)

2+

(1) NOT standalone mark


+

(i)

VO3 + 2H / 2H3O VO2 + H2O / 3H2O

(ii)

No because oxidation no. of V is +5 in VO2 / Oxidation no. of V


unchanged (at +5)

(iii)

First green colour : VO2 and VO


3+

Second green colour : V


Violet colour : V

2+

2+

(1)

/ [V(H2O)6 ]

3+

(1)

2+

/ [V(H2O)6 ] , (1)

3
[16]

80.

(a)

3OCl 2Cl + ClO3 (1)

(b)

chlorine (in OCl ) is (simultaneously) oxidised from +1 to +5 (1)


and reduced from +1 to 1 (1)
If only oxidation numbers given max 1 (out of 2)
If oxidation numbers omitted max 1 (out of 2)

(i)

blue / black to colourless

85

2
3
no. moles S 2 O 3 used = 12.5 0. 1 / 1000 = 1. 25 10 (1)

(ii)

no. moles I2 = 1.25 10 / 2 = 6.25 10

(1)

no. moles ClO = no. moles 12 (1)

no. moles ClO in original 10 cm = 10 6.25 10


= 6.25 10

(iii)

(c)

QWC

(d)

(1)
3

no. moles ClO in 1 dm = 100 6.25 10 (1) = 0.625

mass Cl2 = 0.625 71


= 44.4 (g)
mark consequentially on (ii)
must be 3s.f. in final answer

Cl2 is the stronger oxidising agent because Cl2 oxidises S from


(+)2 to (+)6 (1)
but l2 oxidises S from (+)2 to (+)2.50 (1)

O2 oxidises KI / iodide to l2. or balanced equation (1)


ll2 reacts with starch / paper to give blue / black (1)

2
[14]

81.

(i)
H

(ii)

ALLOW all dots or crosses


ALLOW TE for a butene/pentene in (a)(i)
IGNORE circle

1
[2]

82.

(a)

(i)

Negative with some sensible explanation eg fewer moles of product (1)


3 moles of gases going to 2 moles of gases (1)
MUST mention gases or no changes in state

86

(ii)

Positive with some explanation eg exothermic so surroundings


gain entropy (1)

H
Ssurroundings = T

[OR given in words]

OR
Stotal = Ssystem + Ssurroundings [OR given in words]
as reaction goes, Stotal must be positive therefore Ssurroundings
must be positive
OR
Surroundings gain energy so more ways of arranging energy (1)

(Kp)

(b)

(i)

PNO 2

PNO 2 PO 2

(1)

Check that it is not a + on denominator.


(P ) 2 2
ALLOW ( ) but NOT [ ] eg ALLOW ( NO 2 ) etc
2
ALLOW (pNO2)
1

nd

Atm / Pa / kPa / m N
(1) 2 mark dependent on 1
1
1
ALLOW atms / atmospheres

NOT atm etc


1
NOT Kpa
(ii)

st

Temperature
A lower temperature is needed to get a better yield (and would
cost less) because the reaction is exothermic (1)
but the lower temperature may slow the reaction down too much
OR reverse argument (1)
Pressure
A high pressure will increase yield as only two moles on the right
compared to three on the left/less moles on the right hand side (1)
It will also increase the rate of the reaction (1)
Low pressure because of cost only gets mark if higher yield
at higher pressure identified
To award any of the yield marks must say why

87

(c)

(i)

Must be a quantity that can be measured


Eg
The pressure could be measured (1)
as it will decrease as the reaction proceeds because there are only
two/fewer moles on the right compared to three on the left (1)
OR colour (1)
as the nitrogen(IV) oxide is brown whereas the other gases
are colourless (1)
OR total volume (1)
which will decrease by one third/because there are fewer moles (1)
ALLOW acidity because NO2 acidic and others not (1 max)
NOT dilatometry
NOT temperature

(ii)

[NO] second order

(1)

because when conc of NO is doubled, the rate goes up four times (1)
[O2] first order

(1)

Then (iii), (iv) and (v) must follow consistently from (ii)
(iii)

ALLOW TE from (ii) e.g.


2

rate = k[NO] [O2]

rate = k[NO][O2]

(iv)

third / 3

second / 2

(v)

8000 (1)

2 1

dm mol s (1)

1 1

8 (1) dm mol s (1)

Units can be given in any order


(d)

The activation energy must be low


OR bond energies low
NOT more successful collisions
NOT large rate constant

1
[20]

83.

(a)

(i)

KP = p (CO2)

(ii)

1.48 (atm)

allow without brackets, IGNORE p [ ]

Penalise wrong unit

1
1
Answer is consequential on (a) (i) e.g. 1.48 must have atm

88

p(Cl 2 ) p(NO) 2

(b)

(i)

Kp =

(ii)

(p(NOCl)) 2

allow without brackets, penalise [ ]

2NOCl

2NO

Start
1
0

0.22
+0.22
eq moles
0.78
0.22
total moles of gas 1.11
mole fractions above values 1.11 (1)
0.7027
0.1982
partial pressure / atm above values 5.00 (1)
3.51
0.991
2
0.495 atm (0.991 atm)
(3.51 atm) 2
K =
(1)

Cl2
0
+0.11
0.11

(1)

0.09910
0.495

= 0.0395/ 0.0394 atm (1)


range of answers 0.0408 / 0.041 0.039 / 0.0392 NOT 0.04
ACCEPT 2 S. F
Correct answer plus some recognisable working (5)
Marks are for processes

Equilibrium moles
Dividing by total moles
Multiplying by total pressure
Substituting equilibrium values into expression for KP

Calculating the value of KP with correct consequential unit.


(iii)

As the reaction is endothermic stand alone (1)


the value of KP will increase (as the temperature is increased) - (1)
st

consequential on 1 answer (if exothermic (0) then KP decreases (1))


For effect on KP mark, must have addressed whether reaction is
endothermic or exothermic
(iv)

Because (as the value of KP goes up), the value of


2

pCl2 (pNO) / (pNOCl) (the quotient) must also go up (1)


and so the position of equilibrium moves to the right stand alone (1)
But mark consequentially on change in K in (iii)
If position of equilibrium moves to right so Kp increases (max 1)
IGNORE references to Le Chateliers Principle

2
[12]

89

84.

(a)

(b)

CH3COOH labelled as base and linked to CH3COOH2 labelled


(conjugate) acid (1)

H2SO4 labelled acid and linked to HSO4 labelled (conjugate) base (1)
If acids and bases correct but not clearly or correctly linked 1 (out of 2)
Just link but no identification of acids and bases (0)
(i)

QWC*(ii)

(pH) more than 7 / 8-9 (1)


Indicator: phenolphthalein ALLOW thymolphthalein OR thymol blue
(mark consequentially on pH) (1)
Mark consequentially on pH but if pH7 do not allow either methyl
orange or phenolphthalein

As OH / base removes H ions / Hneut is per mole of H2O produced / (1)


+

H + OH = H2O
the equilibrium shifts to the right (1)
and so all the ethanoic acid reacts (not just 1% of it) (1)
OR
Endothermic (OH) bond breaking (1)
is compensated for (1)
by exothermic hydration of ions (1)
OR

+
1
H for CH3COOH + H2O CH3COO + H3O = +2kJ mol / almost zero /
very small (1)
Hneut [CH3COOH] = +2 + Hneut [HCl] (1)
the same (for both acids) (1)
OR
Hneut is per mole of H2O produced (1)
(heat) energy required for full dissociation (of weak acid) (1)
so Hneut slightly less exothermic (for weak acid) (1)
3

(iii)

+ 2

[H ] = Ka [CH3COOH] = 1.74 10 0.140 = 2.44 10


+

[H ] = 0.00156 (mol dm ) (1)


+
pH = 2.81 consequential on [H ] but not pH7 (1)
ACCEPT 2.80/2.8 (answers to 1 or 2 dp)
The assumptions are two from:
+

[H ] = [CH3COO ] this mark can be earned from working /


+

negligible [H ] from ionisation of water (1)


+

[CH3COOH] = 0.140 [H ] 0.140 (mol dm ) / ionisation of acid


negligible (1)
solution at 25C (1) max 2

90

(iv)

[ H ][ salt ]
5
1.74 10 = [acid ] (1)
+
5
5
[H ] = 1.74 10 0.070 = 1.22 10 (1)
0.100
pH = 4.91 / 4.9 / 4.92 NOT 5
Max 2 if 0.140 / 0.200 is used (1)

3
[14]

85.

(a)

(i)

Fe [Ar]
6 2
3d 4s
or 3d64s2
or 3d64s2
2 6
or 4s 3d (1)
2+

Fe
[Ar]
6
3d
or 3d6
6

or 3d 4s (1)
Letter d must be lower case
Any additional letters of numbers (0)

91

(ii)

The mark is for the shape

ALLOW bond to H of H2O (except on left side if OH2 is given)


IGNORE charge unless incorrect

(iii)

[Fe(H2O)6]

2+

+ 2OH [Fe(OH)2(H2O)4] + 2H2O

OR
2+

[Fe(H2O)6] + 2OH Fe(OH)2 + 6H2O


+

(iv)

(v)

OR equations with 2NaOH as reactant and 2Na as product


IGNORE state symbols

Green precipitate / solid foxy-red / red-brown / brown / orange


Both colours and precipitate / solid needed
NOT darkens

N2 + 3H2 /

2NH3

OR equation with Cl2

92

(b)

2+

(i)

Emf of cell / potential difference of cell containing Fe and Fe (1)


and standard hydrogen electrode / half cell NOT SHE
3 +
OR hydrogen electrode and 1 mol dm H and 1 atm H2 (1)
3

2+

1 mol dm Fe
IGNORE temperature
QWC*(ii)

Emf of hydrogen electrode is zero stated or implied (e.g. if


calculate Ecell = +0.44(V)) (1)
+

2+

Fe + 2H Fe + H2 (1) equation stand alone


Potential for the reaction is positive so reaction is feasible (1)
OR
+
2+
H and ()H2 has a more +ve electrode potential than Fe and Fe (1)
+

(iii)

(c)

2Fe

3+

H will oxidise Fe / H is an oxidising agent / Fe is a reducing


+
agent for H / other correct redox statement (1)
+
2+
Fe + 2H Fe + H2 (1) stand alone

High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions

+ 2I 2Fe

2+

+ I2 or words E = (+) 0.23V (1)


3+

3+

So I would reduce Fe / Fe would oxidise I / E positive so reaction


L R (1)
OR reverse argument (2)
OR
3+
2+

Fe and Fe has a more positive electrode potential than I2 and I (1)

I will reduce Fe

3+

/ Fe

3+

will oxidise I (1)

2
[15]

86.

(a)

(i)

Step 1
hydrogen bromide / HBr / concentrated hydrobromic acid / KBr +
concentrated H2SO4 (1)
Step 2
sodium / potassium hydroxide / NaOH / KOH (1)
+
then any acid OR its formula OR H (1)
Step 3
(potassium) (di)chromate((VI)) and sulphuric acid / acidified
OR their formulae / Tollens / Fehlings / Benedicts / acidified
(potassium) manganate(VII) (1)

93

(ii)

(1)
Not enough energy / heat to break (and cause rotation) the ( / double)
bond (1)

(b)

(i)

(ii)

(c)

CH3CH(OH)CH(OH)COO
OR structural formula drawn.
ALLOW acid

CH3C(OH)(CN)CH2COOH
OR structural formula drawn.

(i)

(ii)

The acid is partially ionised


+
+

OR equation HX (+H2O) H (H3O ) + X (1)

QWC
+

The salt is totally ionised OR equation NaX Na + X (1)

When OH ions are added they react with the large reservoir of HX (1)
molecules

OH + HX H2O + X (or words), thus removing the added OH ions (1)


rd

th

Alternative 3 and 4 marks:

+
OH reacts with H from ionisation of acid (1)
Causing further ionisation of large reservoir of HX (1)

94

H salt

(ii)

Ka = weak acid
+

pH

K a weak acid
+
salt
or [H ] =
3.80

H X

or Ka =

HX

(1)

[H ] = 10
= 10
= 1.58 10 (mol dm ) (1)
+
4
4
[salt] = Ka [weak acid] [H ] = 2.63 10 0.500 1.58 10
3

= 0.832 / 0.830 (mol dm ) (1)


3

mass of salt in 1000 cm = 0.832 (or 0.830) mol dm 124 g mol


= 103 (g) (1)
3
mass of salt needed to be added to 100 cm = 10.3 (g) (1)
OR
salt
weak acid

weak
acid

salt (1)
pH = pK + log
or pH = pK log
a

pKa = log 2.63 10 = 3.58 (1)


log [salt] / [weak acid] = pH pKa = 3.80 3.58 = 0.22
0.22

[salt] / [weak acid] = 10


= 1.66
3
[salt] = 1.66 0.500 = 0.830 (mol dm ) (1)
3
3
1
mass of salt in 1 dm = 0.830 mol dm 124 g mol = 103 (g) (1)
3
mass of salt in 100 cm = 10.3 (g) (1)

5
[18]

87.

(a)

ester or its formula H 2 O 2


HOCH 2 CH 2 OH CH 3 COOH 2

KC =
both molar masses (1)
HOCH2CH2OH

Moles at start
24.8 / 62 = 0.400
Moles at equilibrium
0.400 0.320 = 0.080

(1)

+ 2CH3COOH

Ester

+2H2O

66.0 / 60 = 1.10 (1)


1.10 0.640 = 0.460

0.320

0.640 (1)

Concentration at equilibrium divide above by 0.0900 dm (1)


0.080 / 0.0900 = 0.889
5.11
3.56
OR explain why volume cancels in this case

7.11

3.56 7.11 2
0.889 5.11 2

180
KC =
= 23.2
= 7.76 / 7.8 / 7.74 etc. (1)
There are no units for K (1)

95

(b)

(c)

Amount of ethan-1, 2-diol = 1054 / 62 = 17 mol


560
1054
Amount of ethene = 28 = 20 mol
or 1240 100 (1)
Yield = 17 100 20 = 85% (1)
(i)

(ii)

(d)

Any acid with two COOH groups or its acid dichloride or its dimethyl
ester (1)
Accept HOOCCOOH

(Where R = the hydrocarbon part of their diacid).


for correct ester linkage drawn out (1)
for remainder with continuation (1)

No, because the acid would hydrolyse / is a catalyst for the hydrolysis
of the ester.
OR
Yes, not hydrolysed at low temperature / only hydrolysed at high
temperature

The ester cannot form (intermolecular) hydrogen bonds but the acid can (1)
The ester does not have a +hydrogen atom
OR
the acid has +hydrogen / polar OH / O and H have a large difference in
electronegativities (1)
thus less energy / heat is required to separate molecules of the ester (1)
but as ethanoic acid has fewer electrons than propanoic acid, (1)
it has weaker intermolecular instantaneous induced dipole / induced
dipole forces / van der Waals / dispersion / London forces (1)
Allow vdW

5
[18]

96

88.

(a)

(i)

(1)
cycle with state symbols or as energy level diagram. (1)
labels (in symbols, words or numbers) (1)
2+

Hsoln = Hlat + Hhyd Ca + 2 Hhyd OH OR values


Hlat = 1650 + 2 (460) (16.2) (1)
= 2553.8
(ii)

Solubility increases down the group (1)


(if this is wrong, no marks available in this part)
QWC

(b)

(i)

(ii)

(c)

Hhyd of cation decreases / less exothermic (1)


but Hlatt decreases more (1)
therefore Hsol gets more exothermic / increases (1)

Calcium hydroxide will be less soluble at the higher temperature, (1)


(if this is wrong, no marks available in this part)
because the reaction is exothermic (left to right) (1)
(an increase in temperature will cause a) decrease in the value of K
(and (1) hence drive the equilibrium to the left).

The solubility will decrease,


(if this is wrong, no marks available in this part)

because the addition of OH ions will increase [OH ] /

concentration of OH (1) driving the equilibrium to the left. (1)

The three gases are:


hydrogen bromide
bromine
sulphur dioxide

) (1)
) OR formulae (1)
) (1)

The hydrogen chloride / CaCl2 / chloride evolved is not a strong enough


reducing agent to reduce / cannot reduce the concentrated sulphuric acid (or
sulphuric not a strong enough oxidising agent to ) (1)

4
[18]

97

89.

(a)

(i)

+313.4 4 197.6 29.9 (1) Absence of 4 (0)


1 1

1 1

= 506.9 J mol K OR 507 J mol K OR answer in kJ (1)


NOT 510 ie 2 SF
Missing or wrong units ie answer does not match units 1 max
(ii)

Negative as expected because only 1 mole of gas on the RHS but 4


moles of gas on the LHS
Mark can be awarded if answer based on moles only rather than
states [5 moles 1 mole]

(iii)

surroundings

= H/T (1) For equation or use of equation


= 191 000 / 323
1 1
= (+) 591 J mol K (1) OR answer in kJ
1

ALLOW (+) 591.3 J mol K / (+) 590 J mol K


ALLOW 2, 3 or 4 SF
+ sign not needed provided there is evidence in calculation to
show positive
In (i) and (ii) missing units is penalised once UNLESS a
different unit error is made hence penalise twice)

(iv)

(b)

(i)
(ii)

1 1

S total is positive/(+84 J mol K ) so reaction should go forwards


ALLOW TE from (a)(i)

pNi(CO ) 4
pco 4
Kp =
if square brackets [ ] are used (0)

Ni(CO)4 moles at eq 0.25 (1)


total number of moles = 99.25

0.25
99
PNi(CO)4 = 99.25 1 = (0.00252) PCO = 99.25 = (0.9975) (1)
nd

2 mark must be to at least 3 SF or working must be shown ie


some evidence that their total number of moles
Kp = 0.25 / 99.25 / (99/99.25)
3

= 2.54 10 (1) atm (1)


Units marked independently
3
ALLOW 2.5 10
Many have total number of moles as 100 even when it is not
rd
ALLOW TE for 2nd and 3 mark if it should be 100 or just TE
for third mark if it shouldnt be 100 from their working
3
[Kp = 2.6 or 2.60 10 ]
4

98

(iii)

Increasing the pressure/ concentration of CO would force the


reaction to the RHS with the smallest number of gaseous molecules
(1)
NOT pressure with rate
Reduce the temperature so that the reaction goes in the exothermic
direction / increase the temperature to increase rate (1)
Do not allow equilibrium to be reached by passing the CO over the
nickel/recovering the product formed (1)
Use a catalyst to increase rate / increase the surface area of the nickel
to increase number of collisions (1)

(c)

The reaction can be reversed by increasing the temperature (1)

as S surroundings will become less positive/more negative as the temperature


is increased (and Ssystem will remain almost unchanged) so Stotal becomes
negative for the forward reaction (1)

2
[16]

90.

(a)

(b)

(i)

rate forward = rate back (1)


no change in concentration/partial pressure/amount (1)

(ii)

(%) increases (1)

(iii)

None (1)

If temperature too low, rate too slow/high temperature gives fast rate(1),
but if too high, yield too small/high yield needs low temperature (1)
therefore a compromise temperature (of 450 C) (1)
and catalyst for quick rate (at temperature 450 C)/catalyst not effective
if temperature below 400 C (1)

4
[8]

91.

(i)

Weak acid is dissociated to a small extent/slightly dissociated/


ionised/few molecules dissociate
ALLOW partial dissociation
NOT not fully dissociated.

99

(ii)

[H ][C 4 H 9 COO ]
+
+
Ka = [C 4 H 9 COOH] OR [H3O ] for [H ]

(iii)

Ka = [H3O ] / [acid] OR [H3O ] = Ka [acid] (1)

+ 2

st

[H3O ] = 1.23 10 (1) dependent on 1 mark


pH = 2.91/2.92 (1) ACCEPT 2.9 1 or 2 d.p.
Correct answer with working (3)
Correct answer with no working (1)
ALLOW TE only if pH below 7

(iv)

(v)

nd

rd

starting pH 2.9 ALLOW starting in 2 or 3 boxes above pH 2 (1)


consequential on (iii)
pH range vertical max 6 to 12 min 710 (1)
3
Equivalence point at 25cm (1)
General shape of curve and finish at pH between 1213 (1)
st
3
and end in 1 three boxes above 12, extending to 4050 cm
If drawn wrong way round 2 max ie equivalence point (1) and
vertical drop (1) marks can be awarded

Thymol blue (1) Consequential on (iv)


(Completely) changes colour within vertical portion/the working
range of the indicator is within the vertical portion / pK ind 1 in
vertical position / pKind in centre of vertical position (1)

2
[11]

92.

(a)

(i)
(ii)

(iii)

[CH 3 CH(NH 2 )COOC 2 H 5 ][H 2 O]


Kc = [CH 3 CH(NH 2 )COOH][C 2 H 5 OH] IGNORE minor slip in formulae 1
Bonds broken: OH and CO
Bonds made: CO and OH (1)
Notes that there is no change (and therefore H is zero) (1)
OR
Bonds broken + (464 + 358) = (+) 822
And bonds made (358 + 464) = () 822 (1)
therefore H = 0 OR correct signs (1)

No effect (1)
Increases (1)

100

(b)

(i)

O
C
+

D o n o t a c c e p t + v e c h a rg e o n c o v a le n tly b o n d e d H in
N H 3+ b u t O K i f d a t i v e c o v a l e n t b o n d t o H +

O R
O

C
O

(ii)

ALLOW CH3CH(NH3 )COO / CH3CH(NH3 )CO2 brackets can be


omitted

Attraction between (ionic) charges on different ions/zwitterions (is


strong)

(iii)
+

N H
H 3C

N H

CO O

+ H

H 3C

H 3C

CO O H

N H

(H 3C C H (N H 3)C O O H )+
H 3 C C H (N H 3)C O O H +

N H

CO O

+ O H

H 3C

H
A C C E P T v a r ia tio n s s ta r tin g w ith

CO O

+ H 2O

H
H 3C

N H 2
C C O O H
H

(c)

(i)

MUST be balanced equations


Can use NaOH or HCl etc

Nonsuperimposable on its mirror image


OR has no plane of symmetry / it has an asymmetric carbon atom
NOT 4 different groups on a C atom on its own

(ii)

One diagram correct and 3D (1)


st
Mirror image (1) can be awarded if 1 mark not given because of a nearly
correct structure eg ester
2

(iii)

Rotation of the plane of (plane)polarised light in opposite directions

1
[13]

101

93.

Penalise units only once in this question


(a)

(b)

(2192.3)[191.6 + (130.6 3)] (1)


1
1
= 198.8/199 J mol K (1)

92.2 1000 / 92.2 /


298
298
H / T (1)
1

1 1

= + 309(.4) J mol K / + 0.309(4) kJ mol K (1)

(c)

(d)

(i)

198.8 + 309 = + 110 J mol K (3 SF)


OR
1 1
198.8 + 309.4 = + 111 J mol K (3 SF)
[Do not penalise missing + sign if penalised already in (b)]
NOT 4SF. Penatise SF only once on paper

(ii)

Yes, as Stotal is positive / total entropy change

(i)

Higher T makes Ssurroundings decrease (so Stotal is less positive)

(ii)

Cost (of energy) to provide compression/ cost of equipment


to withstand high P/ maintenance costs.
NOT safety considerations alone

Different phase/state (to the reactants)

(iii)

[9]

94.

(a)

(i)

pH = log(10) [H3O ] (1)


+

OR [H ] instead of [H3O ] applied throughout

(b)

(ii)

[H3O ] greater than 1 (mol dm )

(i)

[H 3 O ][A ]
[HA]
Ka. =
(1)
+

[H3O ] = 1.14 10 mol dm


pH = 2.9(4) (1)
(ii)

(iii)

1
1

(1)
3

Start at the same pH as in (i) (1)


3
Graph showing vertical at 25 cm (1)
vertical section 35 units in length with midpoint around pH 8 (1)
general shape correct including buffer zone and final pH not > 13 (1)

pH = pKa

1
++++++++++++++++++++++++++++++++++++

102

[10]

103

95.

(a)

Pressure exerted by the gas if it alone occupied the same volume at the
same temperature/mole fraction total pressure

p ( N 2 ) p (O 2 )
(b)

(c)

(d)

p ( NO) 2

(i)

Kp =

(ii)

Correct number of moles (1)


Correct mole fractions (1)
Correct partial pressures (1)
3
2.45 10 (1) ACCEPT 24 SF

Kp increases (1)
Equilibrium moves to r.h.s. (1)
which is the exothermic direction (1)

(i)

Kp = p (Ni(CO)4) / p(CO)

(ii)

High partial pressure with some reason (1)


so the pressure Ni(CO)4 increases to keep Kp constant. (1)

2
[12]

96.

(a)

(i)

(ii)

(b)

(i)

(ii)

(iii)

The potential (difference) / e.m.f. (of a halfcell) relative to the


standard hydrogen electrode (1)
3
Concentrations (of all ions) 1 mol dm and
(any gases at) pressure 1 atm (1)
Ignore any references to temperature

One from:
Can only measure a potential difference
Or
So that comparisons can be made between any half cells

2+

5H2O2 + 2MnO4 + 6H 5O2 + 2Mn + 8H2O (2)


(1) for species
(1) for balancing the correct species

E reaction = + 0.84 (V) (1)


or if just states 0.84, must mention that this is a positive value

Fizzing/bubbles (1)
(pink) colour lost / stays colourless (1)
(end point) solution remains pink / pale purple (1)

2H2O2 2H2O + O2 (1)


O (in H2O2) oxidised from 1 to 0 (in O2) (1)
O (in H2O2) reduced from 1 to 2 (in H2O) (1)

3
[12]

104

97.

(a)

(i)

(ii)

(b)

C2H6(g)/(I) C2H4(g) + H2(g)


If a state symbol is missing (0)
If (aq) (0)

At high pressure reaction goes in direction to reduce


pressure/to oppose change by Le Chateliers principle (1)
towards side with fewer molecules/moles (1)

Shapes of orbitals between and above carbon

If p orbitals drawn msut show overlapping


Shapes (1) ACCEPT crescents for bonds NOT lines for bond
Labels (1)
(c)

(d)

Addition of bromine water/solution (1)


from yellow/brown/orange to colourless (1)
OR
acidified potassium manganate(VII) (1)
from pink/purple to colourless (1)

Addition (1)
Elecrophilic/electrophile OR appropriate explanation (1)

2
[9]

98.

(a)

(i)
(ii)

Methanol is the biggest/ most complex molecule / greatest M R /most


atoms/most electrons

Ssystem = 239.7 197.6 2(130.6)


l 1

= 219.1/ 219 J mol K


Method (1)
answer + units (1)

(iii)

yes as 3 molecules 1 OR yes as (2) gases a liquid

(iv)

Ssurr = H/T (stated or used) (1)


1

= (129/ 298) = +0.433 kJ mol K / +433 J mol K /+ 432.9 (1)


1 for wrong units/ no units / more than 4 SF
1 for wrong sign/ no sign
(v)

2
1

Stotal = 219.1 + 433 = +213.9 / +213.8 J mol K / +214 J mol K /


1 1

+0.214 kJ mol K (1)


Positive so possible (1)

105

(b)

(i)

Temperature
Faster at 400C (1)
even though yield is lower (1)
Pressure
Higher pressure improves yield of methanol (1)
Higher pressure increases rate (1)
Maximum 3

(ii)

Not in same phase as reactants. ALLOW state instead of phase

(iii)

Kp = p(CH3OH)/p(CO)p(H2)

(iv)

Partial pressure of methanol = 200 55 20 = 125 atm (1)


2
Kp = (125)/5520

(c)

(i)
(ii)

= 5.68 10 / 5.7 10 atm (1)

Number of molecules / fraction of molecules with energy EA /number


of molecules which have enough energy to react.

Vertical line / mark on axis to show value to the left of line EA

1
[17]

99.

(a)

(i)

NH3 base and NH4 acid (1)

(ii)

(iii)

H2O acid and OH base (1)


OR
linking (1)
acid and base correctly identified (1)

Starting pH of (just above) 11 (1)


Graph showing vertical line between pH 4 and 6
With vertical section 35 units in length (1)
3
at a volume of HCl of 20 cm (1)
Final pH of between 1 and 2 (1)

Named indicator consequential on vertical part of their graph (1)


Because all of its range is within the vertical part of the graph /
pKind 1 is within vertical part of graph / it changes colour
completely/ stated colour change (MO: yellow red; BB: blue
yellow; PP: pink colourless) within the pH of the vertical part of
the graph (1)

H O NO
3

(b)

(i)

HNO 2
Ka =
square brackets essential

106

(ii)

+ 2

[H ] = [NO2 ] or [H ] = Ka [HNO2] (1)


+

[H ] = (Ka 0.12) = 0.00751 mol dm (1)


+

pH = log [H ] = 2.12/2.1 (1)


+
ALLOW any correct conversion of [H l into pH provided the
answer is less than 7
(iii)

Moles NaNO2 = 1.38/69 = 0.020 (1)

[NO2 ] = 0.020 / 0.10 = 0.20 (mol dm )


K a [acid]
4.70 10 4 0.120
+
4
0.20
[H ] = [salt] =
= 2.82 10 (1)
pH = log 2.82 10
(iv)

= 3.55 /3.6 /3.5 (1)

In a buffer both [acid] and [salt] must be large compared to the


+
added H or OH ions (1)
but in NaNO2 alone [ HNO2] is very small (1)
OR
+

to remove both H and OH there must be a large reservoir of

both NO2 ions and HNO2 molecules (1)


which there are a solution of NaNO2 and HNO2 but not in NaNO
alone (1)

2
[18]

100. (a)

(i)

Use E values for reduction of Fe


and Fe

2+

to Fe by

Zn (E cell

3+

to Fe

2+

by Zn (E

cell

= + 1.53V) (1)

= +0.32V)(1)

They have positive E so are feasible (1) NOT will happen


OR
2+
3+
2+
2+
ALLOW Zn /Zn is more negative than both Fe /Fe and Fe /Fe (1)
so zinc is a stronger reducing agent (1)
so zinc reducing both is feasible (1)

(b)

2+

(ii)

Reduction of Fe

(i)

Mn O4 + 5Fe + 8H Mn
Species (1)
Balance (1)
Any state symbols ignored.

(ii)

2+

has high activation energy / kinetically stable


+

2+

+ 5Fe

3+

+ 4H2O
2

purple colour of MnO4 lost (1)


end point when yellow / colourless solution (1)
becomes (permanently) pink (1)

107

(c)

st

Amount MnO4 in 1 titration = 0.0182 dm 0.0200 mol dm


4

= 3.64 10 mol (1)


Amount Fe

2+

in original solution = 5 above value = 1.82 10

Amount Fe

2+

in 2 titration = amount of Fe

nd

2+

and Fe

3+

mol (1)

original solution (1)

= 0.0253 dm 0.0200 mol dm 5 = 2.53 10 mol


Amount of Fe

3+

in original solution = 0.00253 0.00182 = 7.10 10 mol (1)


3+

Amount zinc needed to reduce Fe = 0.000710 = 0.000355 mol


1
Mass of zinc = 0.000355 mol 65.4 g mol = 0.0232 g (1) 2,3 or 4 SF
Consequential on their moles iron
The marks are for the following processes:

Either volume of MnO4 to moles of MnO4 (1)


Convert to moles of Fe

2+

by multiplying either moles of MnO4 by 5 (1)

nd

Realising that 2 titration measures total number of moles of iron (1))


Subtracting to get original moles Fe

3+

(1)

Going to moles Zn then mass Zn (1)


OR

3+
rd
Volume MnO4 for Fe , which has been reduced by zinc (1) 3 point
3

= 25.3 cm 18.2 cm = 0.0253 dm 0.0182 dm = 0.0071 dm (1) 4


point

th

st

Amount of MnO4 = 0.0071 dm 0.0200 mol dm = 1.42 10 mol (1) 1


point
Amount Fe
point

3+

reduced by zinc = 5 above value = 7.10 10


4

nd

mol (1) 2

Amount zinc needed = 7.10 10 = 3.55 10 mol


4
1
th
mass of zinc needed = 3.55 10 mol 65.4 g mol = 0.00232 g (1) 5
point

(d)

(i)

[Fe(H2O)6]

2+

+ H2O [Fe(H2O)5OH] + H3O

H3O in equation (1)


other ion in equation (1)
2+
(Fe ) polarises the OH bond in ligand (1)

(ii)

[Fe(H2O)6]
3+

3+

more acidic than [Fe(H2O)6]

Fe higher charge density than Fe


3+
Fe ion if more polarising (1)

2+

2+

(1)

(1)
3
[20]

108

109

101. (a)

(b)

(c)

Pressure NOT partial pressure


intensity or change of colour
volume

)
) Any one
)

Kc = [NO2(g)] / [N2O4(g)]
State symbols required

1
2

Mol NO2 at equilibrium = 0.0120 / 1.20 10 (1)


2

Kc = (0.0120) (0.0310)
3

(d)

(e)

(f)

(g)
(h)

= 4.6 / 4.65 10 (1) mol dm (1)

(i)

Amount of NO2 reduced

(ii)

No effect

As Kc is bigger, more NO2 is produced so heat helps forward reaction /


by Le Chateliers principle reaction goes forward to use up heat /
as temperature increases Stotal must be more positive so Ssurroundings
(= H/T must be less negative

Positive / + with some attempt at explanation (1)


1 mol / molecule gas 2 mol / molecule gas / products more disordered
than reactants (1)

H
Ssurroundings = T

OR

H 1000
T

Stotal is positive as reaction occurs (1)


So Ssystem must be more positive than Ssurroundings is negative (1)

2
[13]

102. (a)

A series of compounds with the same functional group /


same or similar chemical properties (1)
NOT same (physical) properties (0)
NOT same physical and chemical properties (0)
with the same general formula (1)
where one member differs from the next by CH2 (1)

110

(b)

(i)

It will move to the right (1)

Which is the exothermic direction (1)

2nd mark conditional upon first statement


(ii)

The rate of reaction would be too slow if cooled (1)


yield too small / too little reactants converted
OR converse arguments (1)

NOT equilibrium yield


(c)

(i)

H
H

H
C

H
(ii)

No, as both the end carbons have two H atoms

O H O H O H O H

(iii)

Penalise C-HO once


Or CH2(OH)CH(OH)CH(OH)CH2OH (1) for adding two OH groups across
one double bond, and (1) for adding it across both.
Consequential on structure in (c)(i)
2
1 mark per double bond max 2
[11]

103. (a)

(i)

Pairs up CH3CH2COOH and CH3CH2COO

and H2O/H3O (1); correct identification of which is acid and


which base (1)
(ii)

Ka = [CH3CH2COO ] [H3O ] / [CH3CH2COOH] (1)

2
1

[H ] is acceptable.

(iii)

[H ] = (Ka[HA]) or Ka[HA] (1) = (1. 3 10 0.10)


3
3
= 1.14 10 mol dm (1) pH = 2.9 or 2.94, i.e. to 1 or 2 d.p. (1)
Consequential on the value of [H+] provided the pH resulting is
between 0 and 7.

111

(iv)

(b)

14

[H ][OH ] = 10 (1) = 1.14 10 [OH ]

14
3
Thus [OH ] =10 10 (1)
12
3
= 8.77 (8.8) 10 mol dm (1) units needed (2 or 3 sf)
+
Consequential on the answer to (iii) for [H ]
12
Allow 8.71 10 if solved using pH + pOH and pH = 2.94;
12
7.9 10 if solved using pH + pOH and pH = 2.9.

CH3CH2COO + H2O
CH3CH2COOH + OH (1)
Hydroxide ions make the solution alkaline (1) or propanoate
ion deprotonates the water
or CH3CH2COONa + H2O CH3CH2COOH + NaOH (1)
Explanation then must comment that acid is weak/not fully
ionised

(c)

(i)

(ii)

Solution that maintains almost constant pH (1)


for small addition of acid or alkali (1)

pH = pKa + lg [salt]/[acid] (1)


= 4.9 + Ig (0.05)/(0.025) (1) for dividing by 2
= 5.19 or 5.2 (1).

If the Henderson equation is wrong but concs are divided by 2


then 1/3 max.
Or

H Ka[acid]
(1)
[salt]

1.30 10 -5 0.025
(1)
0.050

pH = 5.19 or 5.2 (1)


If the concns are twice what they should be, ie. candidate does
not spot the volume increase, then max (2). The pH is still 5.2,
so care is needed.
[16]

112

104. (a)

(i)

P 24.6 / 31} (1) 0.794 / 0.794 = 1 } EF is PF5 (1)


F 75.4 /19}
3.97 / 0.794 = 5 }
Mr of EF = 126 (1)
Therefore MF = EF = PF5 (1)

4
1

There must be some use of the data of 126 g mol


OR
Mass of phosphorus in I mole = 126 24.6/100 = 31 (1)
Mass of fluorine in 1 mole = 126 75.4/100 = 95 (1)
Moles of phosphorus in 1 mole compound = 31/31 = 1
Mole of fluorine in 1 mole compound = 95/19 = 5 (1)
MF = PF5 (1)

F
F

90
F
F

F
F

O R

120

(ii)

F
(1)

note: there must be an attempt at a 3-D drawing (i.e. one wedge


and one dotted line)
Angles drawn on diagram of 90 (1) and 120 (1)

(iii)
( )

( )

F
F
F

F
F
F

F
90

O R

F
(1 )

note: again it must be 3-D (again wedges and dotted lines)


Name stated as octahedral (1)
Angle marked / stated as 90 (1)
(b)

HF has intermolecular hydrogen bonding (but others do not) (1)


Because F atom is very small / other halogen atoms / chlorine etc. radii are too
large (1)
Hydrogen bonding is stronger than IMF/vdW/dipole-dipole/induced dipoledipole/dispersion forces and so more energy required (to boil) (1)

Do not give any marks if the candidate answers in terms of


strength of covalent bonds.
Do not give all 3 marks unless the candidate has expressed
their ideas clearly.

113

(c)

[H ][F ]
Ka = [HF]

allow H or H 3 O

(1)

-2.04

[H ] = 10

-3

(1) = 0.009120 mol dm


+ 2

[H ] = [F ] or Ka = [H ] / [HF]
(0.009120) 2
(0.009120) 2
or
(1)
0.0150
= (0.150 0.009120)
-4

-3

= 5.90 10 (1) mol dm (1) or = 5.55 (or 5.54) 10

-4

the unit mark can be given in the expression for K.


[18]

[CO 2 ][H 2 ] 4

105. (a)

Kc =

CH 4 H 2 O 2

(1)
Starting amounts:

CH 4 10g / 16 g mol

0.625 mol

H 2 O 54 g / 18g mol 1 3.0 mol

(1)

Equilibrium amounts:
CH4 = 0.625 2.0 = 0. 1 25 mol (1)
H2O = 3.0 2.0 = 2.0 mol (1)
CO2 = 0.0 + 2.0 = 0.500 mol (1)
H2 = 2.0 mol (given)
Equilibrium concentrations:
3

above values 4 dm (1)

Kc
2

-6

= 1.0 (or 1 or 1.00) (1) mol dm (1)


(b)

(mark consequently)
[CH4] = 0.03125 mol dm

-3

[H2O] = 0.500 mol dm

-3

[CO2] = 0.125 mol dm

-3

[H2] = 0.50 mol dm

-3

[CO 2 ] eq [H 2 ] eq

[CH 4 ] eq [ H 2 O] eq

0.125 0.50 4
0.03125 0.500 2

H = (-394) [(-76) + (2 242)] (2) 1 mark for 2, 1 mark for signs and values
= + 166 (1) kJ mol

166 scores zero

114

(c)

A catalyst (of nickel) is used because the reaction, even at 750C, is too slow /
to speed up the reaction (1)
Then any six of the following eight points:
a temperature of 750C is used:

as the reaction is endothermic (1)

a high temperature increases the value of the equilibrium constant (1)

and so increases the equilibrium yield (1)

a high temperature also favours a fast rate (1)

but a temperature > 750 would be too expensive / cause engineering


problems (1)
Temperature could score up to 5 but max 6 for T and P combined.
If their calculation in (b) gives an exothermic answer, mark consequentially
[exothermic (1), decreases Kp (1), decreases yield (1) but faster rate(1), so 750 is
compromise of fast rate and lower yield (1)]
A pressure of 30 atm is used

even though the reaction goes from 3 to 5 gas moles / more gas moles of
right of equation (1)

causing a decrease in equilibrium yield (1)

but a moderately high pressure is needed to push the gases through the
plant (1)

Ignore any reference to rate


Pressure could score up to 3 but max 6 for T and P combined.
Do not give all 7 marks unless the candidate has expressed their ideas clearly
[18]

106. (a)

(i)

Two reactants form one product

(ii)

Substitution reactions occur under these conditions

(iii)

The electrons of the double / bond polarise the Br Br molecule (1)


and Br

is the electrophile (1)

OR show Br
(b)

Br

attacking in the correct orientation

(i)

Br

H
C

Br
H

Br
H

H
C

H
(1 )

(ii)

No rotation about a C =C double bond


OR only single bonds can rotate

H
C

C
C

H
(1 )

H
Br
2

115

(c)

(i)
H

H
H
H

C
C

H
(ii)

Low temperature because exothermic reaction (1)


High pressure because fewer molecules of product than of
reactants gases are being converted into liquids (1)

2
[10]

107. (a)

(b)

pH = Ig [H (aq)]
+
pH
9.6
9.6
OR [H (aq)] = 10
/ 10
= 10
(method) (1)
10
3
= 2.5(1) 10 mol dm (2)

(i)

(ii)

Kw = [H (aq)][OH (aq)]

Kw

[OH (aq)] = H aq
1.0 10 14

10
= 2.51 10
5
3
= 3.98 / 4(.0) 10 mol dm

(iii)

1
5

[Ca(OH)2(aq)] = 0.5 3.98 10 )


5

= 1.99 / 2(.0) 10 mol dm


(iv)
(v)

=1.99 / 2(.03) 10 74
3
=0.00147 (g dm ) MUST be to 3 SF

Due to reaction with carbon dioxide in the air / temperature differences

116

(c)

(i)

pH = 3(.0) Penalise if more than 2 SF

(ii)

100 1.99 10 5
1000
Amount of Ca(OH)2 =
6

= 1.99 10 mol (1)


2 100 1.99 10 5
1000
Amount of HCl =
6

= 3.98 10 mol (1)


1000 2 100 1.99 10 5
1000
Volume of HCl =

= 4(.0) / 3.98 cm

OR 4(.0) / 3.98 10 dm (1)

(iii)

(iv)

Vertical portion of the graph (between pH 7 and 4) at about 4 cm (1)


Correct initial and finishing pH (910 and 3) and general shape (1)

Phenolphthalein changes colour outside pH range of end point/ pH range


of phenolphthalein is too high.

1
[15]

108. (a)

(i)

Rates of forward and back reactions the same (1).

(ii)

Moves equilibrium to left hand side (1)

being the side with the smaller number of molecules/moles (1)

117

(b)

(i)

2NO + O2 2NO2(1) or N2O4

(ii)

4NO2 + 2H2O + O2 4HNO3 (2)


(1) species (1) balance.
Answer could be in terms of a reactions that give HNO2 and HNO3
as the first stage.
i.e. 2NO2+ H2O HNO2 + HNO3
(2HNO2 + O2 2HNO3)
or 3NO2+ H2O 2HNO3 + NO

F r a c tio n
of
m o le c u le s

E acat

E auncat

(c)

E n e rg y

(i)

Axis labels (1)

Starts at or near origin (not on y or x axis) skewed distribution


that is reasonably asymptotic to the x-axis (1)
(ii)

Ea for the uncatalysed reaction shown well to the right of the


peak and Ea for catalysed reaction to the left of this, still to the
right of the peak (1)

Some comment concerning the areas under the curve to right of


Ea lines or labelled shading (1)

Greater number of collisions (or particles) have energy greater


than the activation energy / enough energy to react (1)

Therefore greater number of successful collisions (1).

4
[12]

109. (a)

(b)

(i)

pH = log10 [H ] / pH = lg [H ] (1)

(ii)

KW = [H ] [OH ] or KW = [H3 O] [OH ] (1)

fully ionised / fully dissociated / almost completely ionised (1)

1
1

118

(c)

(i)

0.70 (or 0.699) (1)

119

(ii)

(d)

[H ] = KW / [OH ] = 1.25 10
pH = 13.9 or 13.90 (1)

14

(1)
2

[H ][A ]
Ka = [HA] (1)

(i)

allow [H3 O]

(ii)

(e)

[H ] = (Ka [HA]) (1) = 0.00474 (1)


pH = 2.32 / 2.33 (1)

K a [HA]

+
[H ] = [A ] (1)
5

[H ] = (5.62 10 0.3) / 0.6 = 0.0000281 / 2.81 10


pH = 4.55 (1)
Or
[A ]
pH = pK + log [HA]

(1)
3

[0.600]
= log10 (5.62 10 ) + log10 [0.300] = 4.55
5

If initial error in statement of [H ] or Henderson equation max 1


[13]

110. (a)

(i)

Kc = [SO3] / [SO2] [O2] (1)

0 .2
30

(ii)

0 .1
60

= 3.33 10

1. 8
60
3

1.67 10
0.03 (1)
2
(0.03)
3 2
3
4
Kc = (3.33 10 ) 1.67 10 = 4860or 4.86 10 (1)
mol
(b)

(c)

dm (1)

(i)

Kc decreases (1)

(ii)

shifts to left / in reverse (1)

(i)

no effect (1)

120

(d)

(ii)

no effect (1)

(i)

Kp = pSO3 / pSO2 pO2 (1) penalise square brackets

(ii)

Total number of moles (1) consequential on a (ii)


SO2 = 0.0952(4); O2 = 0.0476 (2); SO3 = 0.857 (1) (1)

(iii)

Partial pressures: SO2 = 0. 190 (5) atm; O2 = 0.0952 (4) atm;


SO3 = 1.71(4) atm (1) i.e. multiply answer in (ii) by 2

(iv)

1.714 / 0.1905 0.09524 = 850 (1)

atm

(1)

2
[14]

111. (a)

(i)

[Ar]3d (1)
2
allow 1s etc

(b)

(i)

Zn / Iron (1) not the zinc ion or iron ion

more negative potential than -0.28V (1)


NB this mark must show evidence of use of the data

gives +E for reduction reaction (1)


consequential on second mark
(ii)

rate too slow / activation energy too high / kinetically stable /


allow oxide layer if metal electrode specified (1)

non-standard conditions (1)

(c)

2+

(i)

Co(H2O)6

(ii)

Example:
2+

(1)

Co(H2O)6 + 4Cl CoCl4 + 6 H2O


Any valid equation that shows a ligand exchange but begins with
2+
Co(H2O)6 (1)
ligand exchange correctly balanced (1)

2
[9]

121

112. (a)

(i)
(ii)

(iii)

Forward and reverse reactions occur at the same rate (1)


so there is no change in the proportions of reactants and products (1)

Proportion of HI expected to become smaller (1)


because reaction will respond to temperature increase by shifting in the
endothermic direction (1)

No change expected because catalysts affect only the rate at


which equilibrium is attained.

(b)
E n e rg y

E a
(u n c a ta ly s e d )
H 2 (g ) + l 2 (g )
(p ro d u c ts )

E a
(c a ta ly s e d )

2 H l(g )
(re a c ta n ts )

P ro g re s s o f re a c tio n
Products at higher energy level than reactants (1)
Line going up from reactants to peak (corresponding to transition state),
then down to products (1)
Second line with lower peak representing the catalysed reaction (1)
Activation energies of uncatalysed and catalysed reactions correctly marked (1)

4
[9]

113. (a)

(i)

Gases have much higher entropies than solids as there are many more
ways of arranging the entities / less ordered / more random(ness)
OR reverse argument (1)
ZnCO3 has more atoms/is more complex than ZnO (1)

(ii)

system

= (+43.6) + (+213.6) (+82.4)


1

=+174.8/175 J mol K

method (1)
answer, sign and units (1)
Correct answer, sign and units with no working (2)

122

(b)
As printed

Amended

H
S surroundings = T

H
S surroundings = T

( 464.5 10 3 )
298
OR =
(1)

( 71.0 10 3 )
298
OR =
(1)

= 1560 / 1559 J mol K


answer, sign and units (1)

= 238(.3) J mol K
answer, sign and units (1)

ONLY accept 3 or 4 SF

IF correct answer, sign and units with no working (1)


(c)

(i)

total

= +174.8 1558.7
1

= 63.5 / 64 / 63 / 63.2 / 63.4 J mol K

= 1384 / 1380 J mol K


IF + 174.8 1560
= 1385(.2)
1 1
= 1385 / 1390 J mol K
IF + 174.8 1559
1 1
= 1384 J mol K

ONLY penalise incorrect units OR no units in (a)(ii), (b) and (c)(i) once

(ii)

Natural direction is right to left /reverse as S


is negative / less than zero.

total

/total entropy change


1

MUST be consistent with (i)


(d)

(i)

Kp = p co2 ((g) eqm)

(ii)

Increase temperature / reduce pressure (1)

Decreases S surroundings (negative) and hence increases S total / Le Chateliers


principle applied (i.e increasing temperature, reducing pressure) (1)
2
[11]

123

114. (a)

(b)

(i)

Dynamic:
reaction occurring in both directions / rate of forward reaction
and reverse reactions equal (1)
Equilibrium:
constant concentrations / no change in macroscopic properties (1)

(ii)

all substances in same phase / are all in the gaseous state (1)

(i)

Higher yield of ammonia / (equilibrium position) moves to. r.h.s (1)


Fewer product molecules (1)

Lower yield of ammonia / (equilibrium position) moves to 1.h.s. (1)


since this absorbs heat/ shift in endothermic direction / the
reaction is exothermic (1)

(ii)

[7]

115. (a)

(i)

(ii)
(iii)

(b)

(c)

fraction of the total pressure generated by a gas or


or
pressure gas would generate if it alone occupied the
volume
or
Ptotal mol fraction (1)

Kp

p(CO) p(H 2 ) 3
p(CH 4 ) p(H 2 O) (1)

not [ ]

Increase in total pressure will result in less product


molecules in the equilibrium mixture / equilibrium
moves to left (1)
because more molecules on product side of the equilibrium
than on left (1)

(i)

No change (1)

(ii)

KP increase (1)

(iii)

No change (1)

(i)

Kp

1
p(CH 4 ) (1)

124

9.87 10 kPa / 9.87 10


Allow 3 5 sig fig

(iii)

equilibrium has moved left in favour of gas (1)


exothermic going left to right/in the forward direction / as
written (1) Stand alone

Answer yes or no with some sensible justification (1)


e.g. No the costs would not justify the amount produced

(iv)

Pa

(ii)

consequential on (i) (1)

[12]

116. (a)

(b)

Few molecules dissociate (into protons) / partially dissociated / ionised (1)


Not fully dissociated scores zero
Maintains an almost constant pH / resists change in pH (1)
with the addition of small amounts of acid or alkali (1)

14
12
pH 10
8
6
4
2
0
(c)

(d)

10

20

30
40
50
V o lu m e o f a lk a li a d d e d / c m 3

starting pH (1) at 2.8


endpoint (1) vertical between 6 and 11 including 7-10
3
vertical (1) at 25 cm
general shape (1) finish above 12

Almost horizontal area marked on graph (1)

125

(e)

(i)

Ka

[CH 3 COO ][H ]


[CH 3 COOH] (1)

or
Ka

(ii)

[CH 3 COO ][H 3 O ]


[CH 3 COOH]
(1)

1
3

pH = pKa at half way to neutralisation point = 12.5 cm (1)


This could be shown on the graph

because pH = pKa when [CH3COO ] = [CH3COOH] (1)

2
[11]

117. (a)

(i)

Equation (1)

O H

O
+

O H

H 2O

(1 )

2 H 2O

There are several ways of answering the rest of this section


Alternative 1
E = + 2.47V (1)
This is positive, therefore reaction feasible (1)
Alternative 2
Both E values are positive, so sum of E is positive (1)
Therefore reaction is feasible (1)

126

N um ber /
f r a c tio n o f
m o le c u le s
( w ith
e n e rg y E )

E a cat

(ii)

(E )

Maxwell-Boltzmann graph - 1 mark for shape of graph


1 mark for correct axes
plotted and labelled
1 mark for Ea and Eacat
Do not award third mark if either of the E values is on left hand
side of max on hump
Explanation
area under graph to right of Ecat> area to right of Ea (1)
greater number/ fraction of molecules or particles have enough
energy to react on collision or greater number of effective /
successful collisions (1)
If draw two graphs showing different temperature ignore
(iii)

(b)

The reactant/ 1,4-dihydroxybenzene (and the product/ quinone both)


have delocalised ring (or resonance) systems/ or described
delocalisation (or resonance) (1)
these average bond energies are for localised bonds / do not
apply to benzene ring compounds / compounds with delocalised
or resonance systems. (1)

20 dm oxygen is 20/24 = 0.833 mol (1)


3
amount peroxide in 1 dm = 0.833 mol 2 (1) = 1.67 mol
mass 1.67 mol 34 g mol

(c)

= 57 / 56.6 / 56.7 / 56.8 g (dm ) (1)

(i)

H2O2 O2+ 2H + 2e (1)

(ii)

2MnO4 + 6H + 5 H2O2 2Mn + 8H2O + 5O2


species on correct side of equation (1) balance (1)

2+
MnO4 + 8H + 5e Mn + 4H2O If the overall equation, is
not correct allow 1 mark for this equation if correct
ignore

2+

127

(iii)

Higher concentration increases collision frequency / more collisions


per unit of time (1)
therefore causes increase in reaction rate (1)
More successful collisions therefore faster gets 1 mark
(no reference to higher concentration)

2
[18]

118. (a)

The marks are for:


writing the expression for K
substituting correctly
calculating p(SO3)
correct generation of the ratio
calculation of the ratio to give answer which rounds to 95 t
2

Kp = pSO3 / pSO2 pO2 (= 3.00 10 ) (1)


4

3.00 10 = pSO3 / 0.1 0.1 0.5 (1) if no expression for Kp is


given this correct substitution can score 2 marks
2

pSO3 = 150
pSO3 = 12.25 (1)
12.25 100%
(12.25
0.1 0.5) (1) = 95% (1)
Ratio of SO3 =

(b)

(i)

The marks are for


Recognizing the existence of hydrogen bonds ( between molecules) (1)
That each molecule can form more than one hydrogen bond
because of the two OH (and two S=O groups) / or a description of
hydrogen bonds in this case / or a diagram showing the
hydrogen bonds (1)

(ii)

(c)

(i)

That hydrogen bonds make for strong intermolecular forces


(and hence high boiling temperature) which requires higher
energy to break / separate molecules (1)

If water is added to acid heat generated boils and liquid spits out (1)
if acid added to water the large volume of water absorbs the heat
generated (and the mixture does not boil) (1)

pH = log10 (0.200) = 0.70 (1)


allow 0.7 or 0.699

128

(ii)

realising that the first ionisation / dissociation of sulphuric


and that of HCl are both complete (1)
that the second ionisation of sulphuric is suppressed by the
+
H from the first (1)
little contribution from 2nd ionisation so reduces the pH
+
very little / increases the [H ] very little (1)

(d)

(i)

Lead equations 1 mark


+

Pb + H2SO4 PbSO4 + 2H + 2e (1)


or
2

Pb + SO4

PbSO4 + 2e

Lead(IV) oxide equations 2 marks


+

PbO2 + H2SO4+ 2H + 2e PbSO4 + 2H2O


or
2

(ii)

PbO2 +SO4 + 4H + 2e PbSO4 + 2H2O+


Species (1) balancing (1)

PbO2 + Pb + 2H2SO4 2PbSO4 + 2H2O (1)

1
[18]

119. (a)

(i)

(ii)

(i)

(ii)

Equilibrium shifts to left / lower yield (1) must be clear not


implied
more (gas) molecules on right (1)

Equilibrium shifts to left / lower yield (1) must be clear not


implied
forward reaction exothermic / shift to endothermic direction /
moves to absorb heat / rate of reverse reaction increases more
than rate of forward reaction (1)

increased rate (1)


Molecules closer together / less space between molecules /
higher concentration / same number of molecules in less space
(1)
more collisions/ collide more frequently (1)

Increased rate (1)


More molecules /collisions have (at least) the activation energy
(1)
More of the collisions successful / more of the collisions lead to
reaction (1)

129

(c)

(i)

Platinum (plus rhodium) / Pt (Rh) (1)

(ii)

Alternative route (1)


With lower activation energy (1) this mark is consequential on
previous mark
Increase in rate because there are more successful collisions (1)

Increased surface area / more active sites (1)

(iii)

[15]

120. (a)

only partially dissociated / ionised / not fully dissociated (1)


+
+
into H ions / H3 O / proton donor (1)

(b)

[H 3 O ][A ]
[HA]
Ka =
(1)

(c)

(i)

9.0 to 9.4 (1)

(ii)

9.0 to 9.4 (1)


or same answer as (c)(ii)

(iii)

pKa = 5.6 (1)


6

(d)

Ka = 2.5 10 (1) consequential

(a solution that) resists change in pH / retains an almost


constant pH (1)
on addition of small quantities of acid or alkali (1)

5.2 to 5.8 (1)


5.5 or 5.6 (1) or answer from (c) (iii) based on misreading scale
of graph, eg. 4.8

Phenolphthalein (1)
indictor changes colour between pH 7 and 10 this is vertical part of graph (1)
methyl orange would change in acid / give pH between pH4 and pH6 (1)
n. b. must be +ve statement about methyl orange

(i)

(ii)

(e)

130

(f)

(g)

exothermic reaction / heat (energy) released during reaction (1)


HCl is strong acid fully ionised (1)
this is weak acid so some energy used for dissociation (1)

(i)

pH = log(10) [H ] or in words

(ii)

[H ] 2
5
1.8 10 = 1
(1)
+

[H ] = 1.8 10

= 4.24 10

(1)

pH = log (4.24 10 )
= 2.37/2.4 (1) 2 to 4 sig. figs.

3
[21]

PSO2 2 PO2
121. (a)

(i)

Kp =

PSO3 2

(1)

[ ] no mark
( ) OK

(ii)

2SO3
2
0.5

Mols at start
mols at equ

2SO2
0
1.5

+ O2
0
0.75

(1)

Mark by process
1 mark for working out mole fraction
1 mark for 10
1 mark for correct substitution in Kp and answer
1 mark for unit

i.e.

1 .5
PSO2 = 2.75 10 = 5.46
0 .7
PO2 = 2.75 10 = 2.73
0 .5
PSO3= 2.75 10 = 1.83

n.b. could show mole fraction for all 3 and then 10 later to
give partial pressure.
2

Kp = (5.46) (2.73) / (1.83) = 24.5 (1) atm (1)

131

(b)

(i)

No effect (1)

(ii)

No effect (1)

1
[8]

122. (a)

(i)

CH3COOH + H2O

CH3COO + H3O (1)

If no water present (0)

(ii)

[H 3 O ][CH 3 COO ]
[CH 3 COOH]
Ka =
(1)
+

allow [H ] instead of [H3O ]

(iii)

+ 2

[H ] = Ka [acid] / some recognition that [H ] = [anion] (1)


+

[H ] = 1.8 10 2.00 (1)


3
pH = log10 (6 10 ) = 2.2(2) (1)
or
pH = pKa log10 [acid] (1)
= 4.74 - 0.3 (1) = 2.2(2) (1)

O
C

(1 )

O
(2 )

or
O
(b)

(c)

C H

(i)

CH

C H

CH

(ii)

propyl ethanoate (1)

(iii)

catalyst (1)

(i)

0.001 1000 (1) 2 (1) = 2 cm

1cm scores 1 mark

(ii)

33 or (35 ans on (i)) (1)

(iii)

33 cm = 3.3 10 mol NaOH = 3.3 10 mol remaining ethanoic acid (1)


1

132

(iv)

3.3 10

mol propanol (1)

6.7 10 mol ester (1)


2

6.7 10 mol water (1)

(v)

0.67 0.67
Keq = 0.33 0.33 = 4.1(1) scores (2 marks)
or
6.7 10 2 6.7 10 2
3.3 10 2 3.3 10 2 = 4.12 (1)
3

+ Some reference to volume or 100 cm used


e.g volumes cancel (1)

(d)

st

st

(i)

1 (1) and 1 (1)

(ii)

6 10 = k 1 0.1 (1)
3
1
3
1
k = 6 10 (1) mol dm sec (1)

Consequential on (i)

3
[23]

123. (a)

(b)

(i)

The potential difference between a standard hydrogen electrode


and the (half-) cell (1)
3
all concentrations measured at 1 mol dm and any gases are at 1 atm pressure (1)
2

(ii)

Fluorine or F2 (1)

(i)

all/listed (1)

(ii)

iodine and bromine (1)

(iii)

This answer is consequential on part (ii)


Mix solution of Cr(II) - blue with the oxidising agent given in (ii) (1)
goes green and stays green / but does not go orange (1)

2
[7]

133

124. (a)

(i)

NaNO3 + H2SO4
Base2
Acid1

HNO3 + NaHSO4
Acid2
Base1 (2)

There must be some attempt to link the acid/base pairs for second mark
If candidate writes the actual ions they must link the pairs
e.g

HNO3 and NO3 (1) H2SO4 and HSO4 (1)


(ii)

Nitric acid escapes / leaves the system (1)


Moves to the right / completion / the system never reaches equilibrium (1) 2

H O

O
N

(iii)

(1 )

O
an unclear diagram can be rescued by a correct label
Three centres of negative charge / three separate groups of bonding electrons / 3
sigma bond pairs / one double bond electrons repel more than the single bond
electrons leading to angles not all at 120 / localised double bond pairs same as
single bond pairs (1)
Some argument or reasoning based on electron pair repulsion / electron pairs
or bond pairs repel as far apart as possible / equally (1)
NOT bonds repel / atoms repel

(b)

The candidate must explain that weak refers to dissociation


and that dilute refers to concentration.
e.g weak - does not fully dissociate (into ions) (1)
dilute - low concentration (of moles per unit volume) (1)

(c)

(i)

2NaNO3 2NaNO2 + O2 (1)

(ii)

The (cat)ion size decreases from Na to Mg and the charge increases or the
charge density increases (1)
+
2+
The polarising power of the ion increases from Na to Mg or a description of
what is happening during polarisation (1)
The more polarised/distorted the anion the easier it is to decompose the nitrate (1)

1
+

2+

The final mark may be gained by mention of the magnesium ion distorts the
electron cloud more / weakens the N-O bond more
Or
Trend in charge and size (1)
Comparison of lattice energies of the nitrate and the product (1)
Balance in favour of one with sodium and other with magnesium (1)

3
[13]

134

125. (a)

Still reacting / rate of forward reaction and backward reaction equal / implication that
forward and backward reactions are still taking place (1)
But concentrations constant / no macroscopic changes (1)

(b)

(c)

Temp

(Increases)

Left / to SO2 / to endothermic / lower yield (1)

Press

Increases/faster (1)

Right to SO3 / to smaller number of molecules (1)


3

(i)

Increases rate / or suitable comment on rate (1)


Moves position of equilibrium to endothermic side / or suitable comment on
equilibrium such as reasonable yield / less SO3 (1)
Either compromise in which the rate is more important than the position of
equilibrium
or
optimum temperature for catalyst to operate
or
valid economic argument (1)
3

(ii)

Increases rate / more SO3 / only needs small pressure to ensure gas passes through
plant / high or reasonable yield obtained at 1 atms or at low pressure anyway (1)
and
references to economic cost against yield benefit
e.g increase in pressure would increase yield of product but the increase in yield
would not offset the cost of increasing the pressure (1)
2

(iii)

Catalyst speeds up reaction (1)

(d)

Vanadium (V) oxide / vanadium pentoxide / V2O5 (1)

(e)

Any one use


production of fertilizers, detergents, dyes, paints, pharmaceuticals (in) car batteries,
pickling metal
1
[13]

126. (a)

(i)

(ii)

HCl: pH = 1.13
+
3
[H ] = 0.074 mol dm
3
[HCl] = 0.074 mol dm [0.074 to 0.07413]

HOCl: pH = 4.23
+
5
3
[H ] = 5.89 10 mol dm (1)
+

Ka = [H ] [OCl ] (1)
[HOCl]
+

[H ] = [OCl ] (1) or implied later in calculation


+ 2
3
[HOCl] = [H ] / Ka = 0.0932 mol dm (1)

135

(b)

(i)

[H ] = 0.10 / 0.1047 / 0.105 (1)

(ii)

H2SO4 H + HSO4 (1)

or

H2SO4 + H2O H3 O + HSO4 ignore state symbols

HSO4

H + SO4 (1) Must be


+

H2SO4 + H2O
(iii)

(i)
(ii)

[HCl] 4 [O 2 ]

4HCl
+
O2
2Cl2 + 2H2O
equilibrium mols 0.20
0.050 (1) 0.30 and 0.30 (1)
[ ] eq 10 (1)
0.020
0.0050 0.030
0.030
2

= 1010 or 1012 or 1013 or 1012.5

[0.020] x [0.005]
(i)

[Cl 2 ] 2 [H 2 O] 2

Kc = [0.030] x [0.030]

(d)

ignore state symbols

second ionisation suppressed by the first ionisation (1)

Kc
(c)

H3O + SO4

(mol dm ) (1)

As reaction (left to right) is exothermic (1)


Decrease in temperature drives equilibrium to from left to right (1)

(ii)

As more (gas) molecules on the left (1), equilibrium is driven from left to right (1)
2

(iii)

A catalyst has no effect (1)


As it only alters the rate of the reaction not the position of equilibrium / it alters the
rate of the forward and reverse reactions equally (1)
2
[20]

H
127. (a)

(i)

Nx H ( 1 )
H

Shape for NH3


Shape for BF3

Bx x F

(1 )

Can be all or all x

pyramidal (1)
planer triangular (1)
o

(ii)

Both bond angles NH3 104 to 180 and BF3 120 (1)

NH3 has H bonding (between (+ H and N) (1)


which is stronger than van der Waals (1)
others have van der Waals (1)
van der Waals get larger as molecules have more electrons / get larger (1)
intermolecular forces stronger PH3 SbH3 (1)

136

(b)

(i)

Dative covalent bond / donation of lone pair ammonia

BF3(1)

(ii)

HNH becomes 109 (1)


o
FBF also becomes 109 (1)
Or both become 109 (2)
both become tetrahedral / HNH increases FBF / both become same (1)

(c)

Amount hydrazine = 1000g/32g mol = 31.25 mol (1)

4
1
Hc = 1.83 10 / 31.25 = 585.6 kJ mol (1)
Break NN
Make NN
944
4 NH + 388 4
4 OH 463 4
O=O + 496
(Bond energy NN + 2048)
2796 (1)
(Bond energy NN + 2048) 2796 = 586
1
Bond energy NN = + 162 kJ mol (1)
4
[17]

H 2N
128. (a)

(i)

C O 2C 2H

Benzocaine is

or H2N C6H4 CO2C2H5


(1)

(1)

(NH2 group in any position on ring) (1 for each group);


Either:
+
+
RNH2 + H RNH3 (1)
RNH2 + CH3COCl RNHCOCH3 + HCl (1)
RCO2C2H5 + NaOH RCO2Na + C2H5OH (1)
RCOONa + HCl RCO2H + NaCl (1)
Or:
amines are bases and react with acids (1)
Amines react with acid chlorides to form amides (1)
Esters are hydrolysed by alkali to salt and alcohol (1) The carboxylic acid is
formed on acidification. (1)
6
(ii)

N H

RCOOH + NaHCO3 RCOONa + H2O + CO2 (1)

C O 2H + H N O 2+ H

C O 2 H + 2 H 2O

(1)
H O 2C

O H

H O 2C

Coupling in any position on phenol ring

O H

(1)

137

(iii)

(b)

(i)

Substance X forms a zwitterion / dipolar molecule/ compound of formula


+

H3N COO (1)


Ionic substances tend to be soluble in water and have high melting
temperatures (1)
Quality of language (1)
1

[HA] = 21.37g / 137g mol (1) = 0.156 mol dm


5
3
Ka = 1.20 10 mol dm (1)
+

[H ] = [A ] = (Ka [HA]) (1) = 1.37 10 mol dm


pH = 2.86 (1)
(ii)

[A ] = 0.0500mol dm (1)
3
[acid] = (moles of original acid moles NaOH)/0.100 (1) = 0.0280 mol dm
+
[H ] = Ka [HA]

[A ]
5
6
= 1.20 10 (0.0280/0.0500) (1) = 6.72 10
6
pH = lg[6.72 10 ] (1) = 5.17
Alternative answer route via Henderson Equation acceptable

(c)

(i)

Strong acid/strong base:

H3O + OH 2H2O

H = 57.2 kJ mol

HA + OH A + H2O
(ii)

H + OH H2O or H3O + OH 2H2O (1)

HA + H2O H3O + A H = + 8.3 kJ mol


+

H = + 8.3 57.2 = 48.9 kJ mol

(2)

Answer alone scores 1 mark only

Ionisation is endothermic (1) Ka increases and pH falls (1)

2
[25]

129. (a)

(i)

Reagent: potassium dichromate (VI)/potassium manganate (VII) (1) or


formulae sulphuric acid or hydrochloric acid (1) or formulae
If potassium manganate(VII) chosen not HCl or conc H2SO4 for second mark
+

Acidfied dichromate or H / Cr2O7 (1)


(ii)

amount of propanol = 5.67/60 = 0.0945 mol (1)


amount of propanoic acid produced = 0.64 0.0945
= 0.06048 mol (1)
yield of propanoic acid = 74 0.06048 = 4.5 / 4.48 / 4.476 g (1)

OR

by mass ratio: ratio acid/alcohol = 74/60 = 1.23 (1)


100% yield = 1.23 5.67g = 6.99 g (1)
64% yield = 6.99 g 0.64 = 4.5 / 4.48 / 4.476 g (1)

138

(b)

(i)

(ii)

increase in temperature:
(position of ) equilibrium goes to the right (1)
as endothermic left to right (1)
on the addition of sodium propanaoate
the position of equilibrium goes to left (1)
higher concentration of / more propanoate ions
or
sodium propanoate produces propanoate ions (1)

pH rises (consequential on above) (1)

14
s ta rt p H 2 to 4 (1 )

12

c o rre c t g e n e ra l sh a p e (1 )

v e r tic a l 6 /7 .6 to 1 0 / 1 2 ( 1 )
6

a t 2 5 c m 3 (1 )

(c)

(i)
(ii)

10

20

30

40

50

indicator : thymol blue (1) consequential on vertical part of graph


reason: pH change sharp around pKin value / its colour changes around end point
pH / band pH8 to 10 shown on graph (1)
2

(d)

(i)

(ii)

fully dissociated and reactions identical


OR
+

H + OH H2O (1)

HCN weak acid / partially dissociated (1)


Hionisation of HCN endothermic (1)

2
[19]

139

130. (a)

(i)

2Ca(NO3)2 2CaO + 4NO2 + O2


formulae correct (1) balance (1). Ignore any state symbols.
The balance mark is not standalone.

(ii)

steam / fizzing sound / crumbles (1)


solid swells up / milky liquid produced / comment about sparingly soluble
substance (1)
CaO + H2O Ca(OH)2 (1) ignore any state symbols

(iii)

less (1)

(iv)

(Cat)ion size increases down the Group / charge density decreases (1)
(not atom size)
The polarizing power of the cation decreases down the Group (1).
The less polarized the anion is by the cation the more difficult the nitrate is to
decompose (1).
Polarisation mark could come from the less the electron cloud is distorted
or
trend in cation size (1)
comparison of the lattice energies of the nitrate and the oxide (1)
balance in favour of oxide at top of group
and the nitrate at the bottom (1)
3

(b)

(i)

same number of particles in a smaller volume / gas density increased (1) 1

(ii)

comment related to the number of molecules on each side to explain a shift to


l.h.s. (1) (not just due to Le Chatelier)
so at higher pressure equilibrium moves to favour N 2O4 (1)
2

(iii)

Kp = p(NO2)
p(N2O4)

There must be some symbolism for pressure, and no [ ]


(iv)

(Kp = p(NO2) = 48)


p(N2O4)
2

p(NO2) = 48 0.15 = 7.2 (1)


p(NO2) = 2.7 (1) atm (1) accept 2.683 / 2.68 / 2.7
Answer and units conditional on (iii).

3
[16]

140

131. (a)

(i)

Restricted / no rotation about the C=C bond (1)


a
d
C

(ii)

(b)

(i)
(ii)

in th e c a s e o f s o rb ic a c id a = b a n d d = e ( 1 )
e

The four groups do not need to be different

Four (1)
two for each double bond (1)

A system that resists changes of pH (1)


+

on the addition of small amounts of H or OH

RCOOH

RCOO

(1)

+ H (1)

This equation must show

RCOOK RCOO + K (1) or high concentration of sorbate ion from the


complete ionisation of the salt
This equation, if given, must not show
first equilibrium suppressed (1)
+

When H added : RCOO

+ H RCOOH (1)

When OH added : RCOOH + OH RCOO + H2O reducing the effect of the

addition of the OH (1)


Judge quality of language at this point but show it at the end of the question
as a whole (1)
4max
+
Q of L
(c)

(i)

C H 3C H

C H

C H

C H C O O H

+ 2 B r2

C H 3CH

CH

CH

CH C O O H

B r

B r

Br

Br

product can be shown as CH3(CHBr)4COOH

(ii)

Molar mass of sorbic acid = (6 12) + 8 + (2 16) = 112 g mol

(1 )

1
1

(1)

amount of sorbic acid = 7.00/112 = 0.0625 mol (1)


amount of bromine

= 0.0625 2 = 0.125 mol (1)

concentration of bromine solution = 0.125/0.125


3
= 1.00 mol dm (1)

141

(d)

(i)

Aqueous ethanol favours substitution whereas pure ethanol


favours elimination (1)

C H 3CH

CH

CH

CH C O O H

O H

O H

O H

O H

(ii)

c a n a ls o s h o w --- -C O O

(1 )

This is consequential on (c)(i)


(iii)

Large number of OH groups on product will hydrogen bond with water so


soluble (1)
Nonpolar chain in bromo compound inhibits solubility/ cannot hydrogen bond
extensively with solvent /only one OH group / intermolecular bonds stronger than
bonds formed with water (1)
2

(e)

(i)

Long hydrophobic chain with polar end (1)

17

35

CO O C H

17

35

CO O C H

17

35

CO O C H
(1 )

3N aO H

C H 2O H
3 C

(ii)

17

35

CO O N a + CH O H
(1 )

C H 2O H

Any plausible fat will do but it must be an ester of glycerol for full marks. If ester
is not of glycerol but has at least two acid groups max 2
Use of R in place of Cl7H35 is acceptable

3
[25]

142