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1.
(a)
(i)
(ii)
(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)
(ii)
(iii)
Kp = p(NO2)2
p(N2O4)
There must be some symbolism for pressure, and no [ ]
(iv)
3
[16]
PMT
2.
(a)
(i)
(ii)
HCl: pH = 1.13
[H+] = 0.074 mol dm3
[HCl] = 0.074 mol dm3 [0.074 to 0.07413]
HOCl: pH = 4.23
[H+] = 5.89 105 mol dm3 (1)
Ka = [H+] [OCl] (1)
[HOCl]
[H+] = [OCl] (1) or implied later in calculation
[HOCl] = [H+]2/ Ka = 0.0932 mol dm3 (1)
(b)
(i)
(ii)
H2SO4 H+ + HSO4(1)
or
+
H2SO4 + H2O
(c)
(d)
(iii)
(i)
Kc =
(ii)
(i)
(ii)
[Cl 2 ] 2 [H 2 O] 2
[HCl]4 [O 2 ]
4HCl
+
O2
2Cl2
equilibrium mols 0.20
[ ] eq 10 (1)
0.020
+
2H2O
0.050 (1) 0.30 and 0.30 (1)
0.0050
0.030
0.030
As more (gas) molecules on the left (1), equilibrium is driven from left to right (1)
2
(iii)
PMT
3.
(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)
Temp
(Increases)
Press
Increases/faster (1)
(c)
(i)
(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)
(d)
(e)
[13]
4.
(a)
(b)
[H 3 O + ][A ]
Ka =
(1)
[HA]
(c)
(i)
PMT
(ii)
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
(iii)
(d)
(i)
(ii)
(e)
(f)
(g)
(i)
(ii)
[H + ] 2
(1)
1
[H+] = 1.8 105 = 4.24 103 (1)
pH = log (4.24 103)
= 2.37/2.4 (1) 2 to 4 sig. figs.
1.8 105 =
[21]
PSO2 PO2
2
5.
(a)
(i)
Kp =
PSO3
[ ] no mark
( ) OK
(1)
PMT
(ii)
Mols at start
mols at equ
2SO3
2
0.5
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
10 = 5.46
2.75
0.7
10 = 2.73
PO2 =
2.75
0.5
10 = 1.83
PSO3=
2.75
PSO2 =
n.b. could show mole fraction for all 3 and then 10 later to
give partial pressure.
(b)
(i)
No effect (1)
(ii)
No effect (1)
1
[8]
6.
(a)
(i)
(ii)
(iii)
(b)
(i)
Kp =
p(CO) p(H 2 ) 3
(1)
p(CH 4 ) p(H 2 O)
not [ ]
No change (1)
PMT
(c)
(ii)
KP increase (1)
(iii)
No change (1)
(i)
Kp =
(ii)
(iii)
(iv)
1
p(CH 4 ) (1)
1
[12]
7.
(a)
(b)
PMT
14
12
pH 10
8
6
4
(c)
2
0
(d)
(e)
10
20
30
40
50
Volume of alkali added / cm 3
(i)
Ka =
or
Ka =
(ii)
2
[11]
PMT
8.
(a)
(b)
(i)
12.25 100%
(1) = 95% (1)
(12.25 + 0.1 + 0.5)
(ii)
(c)
(i)
(ii)
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)
PMT
(d)
(i)
(ii)
1
[18]
9.
(a)
(i)
(ii)
(b)
(c)
(i)
(ii)
(d)
(i)
Ka =
[H + ][A ]
(1)
[HA]
allow [H3+O]
(ii)
PMT
(e)
[H+] =
K a [HA]
(1)
[A ]
10.
(a)
(i)
(ii)
(b)
(c)
(d)
0.2
30
= 3.33 103
0.1
1.8
60
60
3
1.67 10
0.03 (1)
(0.03) 2
= 4860or 4.86 104 (1)
Kc =
(3.33 10 3 ) 2 1.67 10 3
mol1 dm3 (1)
(i)
Kc decreases (1)
(ii)
(i)
no effect (1)
(ii)
no effect (1)
(i)
(ii)
(iii)
10
PMT
(iv)
2
[14]
11.
(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)
(b)
As printed
Ssurroundings =
OR =
H
T
(+464.5 10 3 )
(1)
298
Amended
Ssurroundings =
OR =
H
T
(+71.0 10 3 )
(1)
298
= 238(.3) J mol1 K1
ONLY accept 3 or 4 SF
IF correct answer, sign and units with no working (1)
(c)
(i)
Stotal = +174.8 1558.7
= 1384 / 1380 J mol1 K
IF + 174.8 1560
= 1385(.2)
= 1385 / 1390 J mol1 K1
IF + 174.8 1559
= 1384 J mol1 K1
ONLY penalise incorrect units OR no units in (a)(ii), (b) and (c)(i) once
(ii)
PMT
(i)
(ii)
[11]
12.
(a)
(i)
(ii)
[H+] is acceptable.
(iii)
(iv)
(b)
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)
12
PMT
(ii)
[H ] = Ka[acid]
(1)
[salt]
+
1.30 10 -5 0.025
(1)
0.050
13.
(a)
(b)
pH = Ig [H+(aq)]
OR [H+(aq)] = 10pH / 109.6 = 109.6 (method) (1)
= 2.5(1) 1010 mol dm 3 (2)
(i)
Kw = [H+(aq)][OH(aq)]
(ii)
[OH (aq)] =
[H
Kw
+
(aq )]
1.0 10
2.51 10 10
= 3.98 / 4(.0) 105 mol dm3
14
(iii)
(iv)
(v)
13
PMT
(c)
(i)
(ii)
Amount of Ca(OH)2 =
100 1.99 10 5
1000
= 1.99 106 mol (1)
2 100 1.99 10 5
1000
= 3.98 106 mol (1)
Amount of HCl =
Volume of HCl =
(iii)
(iv)
1
[15]
14.
(a)
(i)
14
PMT
(ii)
(iii)
[H O ] [NO
+
(b)
(i)
(ii)
(iii)
(iv)
Ka =
[HNO 2 ]
2
[18]
15
PMT
15.
(a)
(b)
(c)
(d)
(e)
(f)
)
) Any one
)
Kc = [NO2(g)]2 / [N2O4(g)]
State symbols required
(i)
(ii)
No effect
H
T
H 1000
T
(g)
Ssurroundings =
(h)
OR
2
[13]
16.
(a)
(i)
(ii)
16
PMT
(b)
(i)
(ii)
(iii)
Ka. =
[H 3 O + ][A ]
(1)
[HA]
pH = pKa
1
[10]
17.
(a)
(b)
(c)
(d)
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 )
(i)
Kp =
(ii)
p ( NO) 2
Kp increases (1)
Equilibrium moves to r.h.s. (1)
which is the exothermic direction (1)
1
1
(i)
Kp = p (Ni(CO)4) / p(CO)4
(ii)
2
[12]
17
PMT
18.
(a)
(iii)
(iv)
Stotal = 219.1 + 433 = +213.9 / +213.8 J mol1 K1/ +214 J mol1 K1/
+0.214 kJ mol 1K1 (1)
Positive so possible (1)
(i)
(ii)
(v)
(b)
(c)
(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)
(iii)
Kp = p(CH3OH)/p(CO)p(H2)2
(iv)
(i)
(ii)
[17]
19.
(i)
18
PMT
[H + ][C 4 H 9 COO ]
OR [H3O+] for [H+]
[C 4 H 9 COOH]
(ii)
Ka =
(iii)
(iv)
(v)
2
[11]
20.
(b)
(c)
(i)
(ii)
19
PMT
(d)
(i)
(ii)
(iii)
[9]
21.
(a)
(i)
KP = p (CO2)
(ii)
1.48 (atm)
1
must have atm1
1.48
(b)
(i)
(ii)
Kp =
p(Cl 2 ) p(NO) 2
(p(NOCl)) 2
2NOCl
2NO
Cl2
Start
1
0
0
0.22
+0.22
+0.11
eq moles
0.78
0.22
0.11
(1)
total moles of gas 1.11
mole fractions above values 1.11 (1)
0.7027
0.1982
0.09910
partial pressure / atm above values 5.00 (1)
3.51
0.991
0.495
2
0.495 atm (0.991 atm)
(1)
Kp =
(3.51 atm) 2
= 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
20
PMT
(iii)
(iv)
2
[12]
22.
(a)
(b)
QWC*(ii)
(iii)
PMT
(iv)
1.74 105 =
[ H + ][ salt ]
(1)
[acid ]
3
[14]
23.
(a)
(i)
(ii)
(iii)
(iv)
(b)
(i)
Kp =
pNi (CO) 4
if square brackets [ ] are used (0)
pco 4
22
PMT
(ii)
0.25
99
1 = (0.00252) PCO =
= (0.9975) (1)
99.25
99.25
(c)
2
[16]
24.
(a)
23
PMT
(b)
(i)
(ii)
OR
pH = pKa lg
[acid]
[salt]
(1)
0.25
(1)
0.125
pH = 3.4(5) (1)
IGNORE no. of decimal places but penalise pH = 3
(iii)
4
[13]
25.
(a)
(i)
(ii)
H
T
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)
24
PMT
(b)
(i)
(Kp) =
PNO 2
(1)
PNO 2 PO 2
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
(c)
(i)
(ii)
2
(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)
PMT
rate = k[NO]2[O2]
rate = k[NO][O2]
(iv)
third / 3
second / 2
(v)
8000 (1)
1
[20]
26.
(a)
(i)
- lg (0.05) = 1.3(0)
(ii)
OR via pOH
Correct answer with no working (1)
(b)
(i)
(ii)
Ka = [H2PO4][H3O+]/[H3PO4]
NOT using H+ instead of H3O+
[H3O+] = 101.20
= 0.063 (mol dm3) (1)
Ka =
0.063 2
(1)
0.500 0.063
(i)
26
PMT
(ii)
(d)
2
[12]
27.
(a)
(b)
(i)
(ii)
Kc =
27
PMT
(iii)
C5H10
CHCl2COOC5H11
1.7
= 5.67(5.7) NOT 5.66
0.3
0.6
=2
0.6 (1)
0.3
1.7 (1)
(iv)
2Kc =
0.6 / 0.3
1.7 / 0.3
1.33
(1) =
2
1.33 5.67
3
[13]
28.
(a)
28
PMT
(b)
(i)
Bonds broken
Bonds made
NN (+)945
6NH ()2346 (1)
and
(+)1308
(1)
3HH
(+)2253
H = 945 +1308 2346
= 93 sign and value (1)
H = 93 = 46.5 (kJ mol1)
sign and value q on 3rd mark (1)
2
N2 + (3)H 2
(Enthalpy)
H
OR
93
(2)NH 3
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)
29
PMT
(iv)
(v)
(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
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
30
PMT
29.
Acid
Proton or H+ donor
Or forms H+ or H3O+ (1)
Weak
dissociates to a small extent
Or ionises to a small extent (1)
(c)
(i)
2
+
31
PMT
(ii)
(Ka) =
[HCOO ][H 3 O + ]
[HCOOH]
Accept [H+] instead of [H3O+]
(iii)
[H+]2 = Ka [HCOOH]
OR
[H + ] 2
Ka =
[HCOOH]
OR
[H+]2 = 1.60 104 0.100 (1)
[H+] = 1.60 10 4 0.100
= 4.0 103 (mol dm3) (1)
pH = 4.8 scores (2) as square root has not been taken
IGNORE sig figs
Max 1 if [H+]2 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
pH = pK a log[acid] (1)
2
2
pH = 1.90 (0.50)
pH = 2.40 (1)
32
PMT
(d)
(i)
[H+] = Ka
[acid]
[salt]
OR
0.0500
(1)
0.200
= 4.00 105 (mol dm3) (1)
[H+] = 1.60 104
Reject
0.100
0.400
[HCOOH]
pH = pKa log10
(1)
[HCOO ]
0.0500
pH = log10(1.60 104) log10
(1)
0.200
Reject
0.100
0.400
pH = 3.80 (0.60)
pH = 4.40 (1) IGNORE sig figs
33
PMT
(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+])
30.
(a)
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 =
34
PMT
(iii)
1.00
2.00 or 4 21
10.5
= 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
pSO3 =
10.5
= 1.71 (atm)
pSO2 =
(iv)
Kp =
(1.71) 2
(0.190) 2 (0.0952)
(i)
(Kp) decreases
(ii)
p 2 SO3
p 2 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
(c)
(i)
No effect/none/zero (effect)
35
PMT
(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]
31.
(a)
H+
1
Accept H3O+
(b)
HCOOH/HCO2H (1)
HNO3 (1)
1 for each extra incorrect answer
Accept C and E
[3]
32.
(a)
(i)
pH = 3.5 (1)
log10[H+] = 3.5
[H+] = 3.16 104 (mol dm3) (1)
2.5(1) 104 (mol dm3) based on pH = 3.6 (2 marks)
(ii)
[H + ][CH 3 CH 2 CH 2 CO 2 ]
(1)
Ka =
[CH 3 CH 2 CH 2 CO 2 H]
Accept
(iii)
Ka =
[H + ][C 4 H 7 O 2 ]
[C 4 H 8 O 2 ]
[H + ] 2
(1)
[CH 3 CH 2 CH 2 COOH]
36
PMT
(3.16 10 4 ) 2
(1st mark can be scored here)
0.00660
= 1.5 105 (mol dm3) (1)
Ignore units
Only 2 sig. fig. allowed
(i)
37
PMT
(v)
EITHER
End-point = 30 cm3 (1)
[NH3] = (10/30) 0.00660 = 0.00220 (mol dm3) (1)
OR
10 cm3 of butanoic acid contain 6.60 105 mol
From equation this requires 6.60 105 mol NH3
From graph, end-point = 30 cm3 (1)
[NH3] = 6.60 105 (1000/30)
= 2.20 103 / 0.00220 (mol dm3)(1)
Allow internal TE for 2nd mark based on an incorrect
equivalence point i.e. 0.0660 (mol dm3)
33.
(a)
14
pH
12
10
8
B
4
2
1
0
0
10
20
30
40
Volume 0.1 M NH3 (aq) added/cm3
Do not worry about general shape of the curve, the scoring points are:
Starting pH ~ 1 and finishing pH between 9 and 11 (1)
Vertical at 25 cm3 (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)
Bromocresol green
Indicator(s) CQ on graph [check table on question paper]
38
PMT
(c)
2
[7]
34.
(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]
39
PMT
2.50
(iii)
Kc =
0.485
0.50
2.50
3.75
0.485 (1)
0.485
0.485
Must have clearly divided moles of each component by
0.485 for 1st mark e.g.
[HCOOC2H5] = [H2O] = 5.16 (mol dm3)
and [HCOOH] = 1.03 (mol dm3)
and [C2H5OH] = 7.73 (mol dm3)
(2.50) 2
= 3.33 only scores (2) if it is stated
0.50 3.75
that V cancels either here or in (iv)
Accept K c =
(i)
40
PMT
(ii)
35.
(a)
(b)
Ag+ + I AgI
IGNORE state symbols
41
PMT
(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 dm3 0.050 dm3 = 5 103 mol (1)
Amount Ag+ = 0.100 mol dm3 0.031 dm3 = 3.1 103 mol (1)
equilibrium amount I = 3.1 103 mol (1)
I reacted = (5 3.1) 103 mol = 1.9 103 mol (1)
If this subtraction is not carried out then the next mark (for calculating
amount of sulphate) can not be awarded.
Thus amount of sulphate = 1.9 103 (= 9.5 104 mol) (1)
3.1 10 3 mol
8
[10]
36.
(a)
(i)
(ii)
Ka =
[ NH 3 ][H 3 O + ]
+
[ NH 4 ]
Accept Ka =
[NH 3 ][H + ]
+
[NH 4 ]
42
PMT
(iii)
(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)
2nd mark conditional on correct indicator
Accept pKIn in the steep part of the graph or it is a weak basestrong acid titration
(b)
HCN + OH
CN + H2O
IGNORE state symbols
Accept instead of
(c)
(i)
nucleophilic addition
43
PMT
(ii)
O(:)
C
C O
(:)CN
(1) for both arrows
CN
(1)
O(:)
H CN
OH
C
C CN
CN
(:)CN
O(:)
C CN
OH
C
CN
(1)
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)
44
PMT
(d)
(i)
H
H
NC
H H
Cl
NC C
Cl
NC
C2 H 5
C2 H 5
H + Cl
C2 H 5
37.
(a)
(i)
45
PMT
(ii)
(iv)
+987.2 J mol1 K1
(vi)
(b)
(i)
Kp =
pNO 2
pNO 2 pO 2
Accept
p 2 NO 2
p 2 NO pO 2
Reject [ ]
46
PMT
(ii)
4.95
or 0.99 (1)
5
0.025
or 0.005
5
mole fraction NO =
OR
mole fraction O2 =
Kp =
0.025
or 0.005 (1)
5
(0.99) 2 (1.5) 2
3
(0.005) (1.15)
38.
(a)
(i)
Ka =
47
PMT
(ii)
(iii)
(b)
(i)
H
O
Cl
ester(s)
Reject ether
(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)
(iv)
2
[15]
48
PMT
39.
(a)
(i)
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].
49
PMT
(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 Ecat/
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)
QWC
Decrease temperature (1)
because (forward) reaction exothermic (1)
increase pressure (1)
because more moles (of gas) on left (1)
50
PMT
40.
(a)
(i)
First mark:
[ H 2( g ) ] = [ I 2( g ) ]
OR
Use of (5.0 104)2 (1)
If [HI] not squared, first mark only.
Second mark:
[ HI ( g ) ] 2 =
(5.0 10 4 ) 2
0.019
OR
0.019 =
(5.0 10 4 ) 2
[HI (g) ] 2
OR
[HI(g)] =
(5.0 10 4 ) 2
0.019
(1)
Third mark:
[HI(g)] = 3.6 103 (mol dm3) (1)
Correct answer scores 3 marks.
Ignore state symbols.
Ignore units unless wrong.
Ignore s.f.
(b)
(i)
Kp =
2
p HI
p H2 p I2
[ ] scores (0)
51
PMT
(ii)
Ignore s.f.
Correct answer with no working scores (1)
52
PMT
(iii)
41.
(a)
(i)
(b)
(i)
Ka =
[CH 3 CH 2 COO ][ H 3 O + ]
[CH 3 CH 2 COOH ]
53
PMT
(ii)
[H + ] 2
1.30 10 5
Or
[CH3CH2COOH] =
(3.63 10 4 ) 2
(1)
1.30 10 5
= 0.010 (1) (mol dm3) (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)
(i)
54
PMT
(ii)
[acid]
(1)
[base]
Accept Ka =
[H + ] [salt]
[acid]
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
0.00375
6
= 8.67 10 (mol dm3)
pH = 5.06 (1)
[H+] = 1.30 105
[acid]
(1)
[salt]
3
[15]
55
PMT
42.
(a)
(i)
Kp =
( p NO ) 2
p N 2 p O2
p 2 NO
p N 2 p O2
Reject anything in [ ]
(ii)
(b)
(i)
(ii)
(iii)
56
PMT
(c)
(i)
(iii)
(H is positive so)
H
= Ssurroundings will be negative
T
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]
57
PMT
43.
0.002
(1)
0.016
44.
(a)
Kp =
2
p NO
2
p N 2 O4
Reject [ ]
(b)
(i)
First mark:
X N 2O4 = 0.10
58
PMT
( X NO2 PT ) 2
3.52 =
X N 2O4 PT
0.81
PT
0.10
PT = 0.435 (atm) (1)
3.52 =
(c)
(i)
Reject more
(ii)
First mark:
Fraction/quotient/
2
p NO
2
p N 2 O4
45.
(a)
(i)
H2O(l)
H+(aq) + OH(aq)
OR
2H2O(l)
H3O+(aq) + OH (aq)
59
PMT
(ii)
KW = [H+(aq)][OH(aq)]
OR
KW = [H3O+(aq)][OH(aq)]
IGNORE STATE SYMBOLS
(iii)
pH = log10[H+]
OR
pH = log10[H3O+]
OR
in words
Accept pH = lg 1/[H+]
(iv)
KW = [H+][OH]
5.48 1014 = [H+]2 (1)
[H+] = 5.48 10 14
[H+] = 2.34 107 (mol dm3)
pH = 6.6(3) (1)
correct answer with no working (2)
(b)
(i)
12.5
60
PMT
(ii)
4.8 / 4.9
[no consequential marking from (i)]
Reject 5 or 5.0
(iii)
Ka =
[CH 3 COO ][ H + ]
[CH 3 COOH ]
OR
[CH 3 COO ][ H 3 O + ]
Ka =
[CH 3 COOH ]
61
PMT
(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]
46.
(a)
(i)
(ii)
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)
62
PMT
(b)
Ssurroundings =
H
T
OR
123800
(1)
298
= 415 J mol1 K1 (1)
(i)
(d)
(i)
Kp =
p PCl3 p CL2
p PCl5
(1)
Accept capital P
Accept use of ( )
If expression the wrong way up allow second mark if units given
as atm1
Reject use of [ ]
63
PMT
(ii)
Substance
Moles at
start
PCl5(g)
Moles at
equilibrium
Peq /atm
0.15
4.32
0.25
= 2.592
0.20
(1)
PCl3(g)
0.05
0.05
4.32
0.25
= 0.864
Cl2(g)
0.05
0.864
0.25
All three(1)
All three(1)
If moles at eqm are given as 0.025 for PCl3(g) and for Cl2(g)
then 4th column should be 3.24, 0.54 and 0.54
and gets 2 (out of 3)
(iii)
0.864 0.864
)
(2.592)
= 0.288 (atm)
(Kp =
64
PMT
47.
(a)
(i)
Ka =
[H + ][HCO 3 ]
(1)
[CO 2 ]
(ii)
Accept Ka = 10pKa
(b)
(c)
(d)
(i)
[acid]
[base]
[acid]
= 0.9 (1)
[base]
[acid]
= 0.126 (1)
[base]
Accept 0.13
Reject 0.12
(ii)
Before race
[CO2] = 0.126 0.0224 = 2.82 103
OR
2.52 102 2.24 102 = 2.8 103
65
PMT
(iii)
2
[11]
48.
C
[1]
49.
C
[1]
50.
A
[1]
51.
C
[1]
52.
(a)
(b)
(c)
1
[3]
53.
(a)
(b)
66
PMT
(c)
1
[3]
54.
(a)
methyl butanoate
Accept Methyl butaneoate
Reject an missing
(b)
Hydrolysis
(d)
QWC
may not taste the same as natural product which may contain
other impurities
or alternative ideas
67
PMT
(e)
[C 3 H 7 COOH(l)][CH 3 OH(l)]
(1)
[C 3 H 7 COOCH 3 (l)][H 2 O(l)]
Accept eq subscripts
Kc =
Moles at
equilibrium
Concentration /
mol dm3
0.05
0.05
0.05
0.95
1.67
1.67
1.67
31.7
1.67 1.67
(1) = 0.053 (1)
1.67 31.7
ignore significant figures unless value given to 1 s.f.
Kc =
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)
55.
(a)
(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]
56.
(a)
(b)
(ii)
(iii)
(c)
(i)
1
68
PMT
(ii)
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)
Increase the volume of acid to (at least) 50 cm3 (1)
Or measure the time to produce less than the full amount of gas
Or use a smaller piece of magnesium. (1)
(iii)
(iv)
(v)
QWC
Rate of reaction reduced because less surface area in contact
with the acid. (1)
69
PMT
(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]
57.
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)
70