1.

C
[1]

2. B
[1]

3. (a) replacement/substitution of atom/group by another (atom/group);

by species with lone pair of electrons/attracted to electron
+
deficient part of molecule/positive centre/δ carbon atom; 2
(b) 1; 1
(c) 0;
–
rate not affected by change in [OH ]/OWTTE; 2

(d) rate = k[C4H9Br] (ECF from (b) and (c)); 1

 
k   rate 
 [C H Br]  = 0.2;
(e) 4 9

–1
min ; 2
Allow ECF from (d).

+ –
(f) C4H9Br  C4H9 + Br /in equation with curly arrows;
+ –
C4H9 + OH  C4H9OH/in equation with curly arrows; 2
No penalty if primary structure is shown. No credit for SN2
mechanism, except by ECF
from (d).

(g) the slowest step in the reaction;

the first step (however described); 2
(h) the number of reactant molecules/species in the rate-determining step;
1 (ECF from SN2 mechanism in (f)); 2
[14]

4. C
[1]

5. D
[1]

1
6. (i)

N um ber
of
m o le c u le s /
fre q u e n c y T 1

T 2

E a E n e rg y
both axes correctly labelled;
T2 peak/lower;
and to right of T1; 3
Area under graph is not important.

(ii) rate increased/changes;

as more molecules with ≥ Ea; 2
No explicit reference to graph required.
[5]

7. (i) the power of a reactant’s concentration in the rate equation/sum of

n
powers of concentration/rate = k[X] , where n = order of reaction; 1
Must be in terms of powers of concentration.

(ii) experiment 1—2 : [X] doubles and rate×4;

2nd order for X;
experiment 2—3 : [Y] doubles and rate×2;
1st order for Y; 4

2
(iii) rate = k[X] [Y](ECF from (ii))
–2 2
for experiment 1, 1.0×10 = k (0.25) (0.25);
k = 0.64;
–2 6 –1
mol dm s ; 4
Allow ECF from rate expression.

2
 2
(iv) rate = 0.64[0.40] [0.60];
= 0.061; 2
Final answer to 2 sig figs only.
Allow ECF from (iii).
[11]

8. B
[1]

9. C
[1]

+ 2+
10. (i) CaCO3(s) + 2H (aq)  Ca (aq) + H2O(l) + CO2(g) 1
States not required, accept molecular equation.
(ii) rate decreases with time;
as concentration decreases so fewer (successful) collisions;
draw tangent to the curve at time t;
rate = slope or gradient; 4

(iii)
V o lu m e o f
C O 2 p ro d u c e d

in a l
o rig
II

T im e
I. (less CO2 because) amount of HCl is limiting and half the
orginal/OWTTE;
II. (same amount of CO2 because) amount of HCl is the same;
curve less steep because less frequent (accept fewer) collisions 5
Awarded last mark if in either I or II.
[10]

3
11. (i) the increase in the concentration of a product/decrease in the
concentration of a reactant per unit time 1
–1 –1
(ii) s /min etc. 1
–
(iii) no effect (as [OH ] does not appear in the rate expression) 1
(iv) first order/one 1
(v) 8.0 seconds (since four half-lives elapse) 1
[5]

12. D
[1]

13. B
[1]

14. D
[1]

15. C
[1]

16. (a) (i) it is decreasing;

less frequent collisions/fewer collisions per second or (unit) time; 2
(ii) reactant(s) used up/reaction is complete; 1
Do not accept reaction reaches equilibrium.

(b) (i) it would increase; 1

Accept a quantitative answer such as “doubles”.
(ii) more frequent collisions;
collisions or molecules have more
energy (OWTTE); more molecules with energy  Ea; 3
(iii) rate would be lower;
smaller surface area; 2
[9]

4
17. D
[1]

18. (a) (order with respect to) NO = 2;

(order with respect to) H2 = 1;
rate increases×4 when [NO] doubles/OWTTE; 3
2
(b) rate = k[NO] [H2]; 1
ECF from (a).

–6 –3 –1 –3 2 –3
(c) (2.53×10 mol dm s = k (0.100 mol dm ) (0.100 mol dm ))
–3
k = 2.53×10 ; 1
–2 6 –1
mol dm s ; 1
ECF from (b).

(d) agrees/yes;
slow step depends on X and NO;
X depends on H2 and NO;
(so) NO is involved twice and H2 once;
Overall equation matches the stoichiometric equation;
Award [1] each for any three of the four above.
OWTTE
ECF for “no”, depending on answer for (b).
4 max
Or agrees/yes;
 X
  
and H 2 NO = constant;
rate of slow step = k [X][NO]
2
= k [H2][NO] ; 4
ECF for “no”, depending on answer for (b).

(e) reaction involves four molecules;

statistically/geometrically unlikely; 2
(f) the rate of formation of H2O(g) = 2×rate for N2(g);
because 2 moles H2O formed with 1 mole N2/OWTTE; 2
[14]

19. C
[1]

5
20. (a) energy for the conversion of a gaseous molecule into (gaseous) atoms;
(average values) obtained from a number of similar bonds/compounds/OWTTE;
CH4(g) → C(g) + 4H(g); 3
State symbols needed.
(b) (bond breaking) = 1890/654;
(bond formation) = 2005/769;
–1
enthalpy = –115(kJ mol ) 3
Allow ECF from bond breaking and forming.
Award [3] for correct final answer.
Penalize [1] for correct answer with wrong sign.

(c) molecules have insufficient energy to react (at room temperature)/

wrong collision geometry/unsuccessful collisions;
extra energy needed to overcome the activation energy/Ea for the reaction; 2

(d)

E a

e n e rg y re a c ta n ts
p ro d u c ts

re a c tio n p a th
exothermic shown;
activation energy/Ea shown; 2
Allow ECF from (b).
[10]

21. (a) measure volume of carbon dioxide/CO2/gas produced/measure pH; 4

starts at origin and levels off

6
 measure mass of chemicals/apparatus;

starts high and decreases

Graph should show increase as reaction progresses
(as HCl is consumed).

(b) Method 1
use powdered MgCO3/OWTTE;
particles collide more frequently/increased surface area/OWTTE;
Method 2
increase (reaction) temperature/heat/warm;
more of the collisions are successful/more particles with E > Ea/OWTTE;
Method 3
increase acid concentration;
more frequent (reactant) collisions;
Method 4
add catalyst;
lowers activation energy/Ea/OWTTE; 6 max
Award [2] each for any three methods

(c) (i) stays the same;

MgCO3 was already in excess; 2
(ii) stays the same;
same quantities of reactants used; 2
[14]

22. (i) reversible reaction/reaction may proceed in either direction

(depending on reaction conditions) equilibrium/dynamic equilibrium; 1
(ii) no effect;
catalyst will speed up both forward and reverse reactions (equally)/
increase the rate at which equilibrium is achieved; 2
(iii) acidity: no effect;
equilibrium shifts to the right;
Kc: no change; 3
[6]

7
23. (a) 1/first order;
rate is (directly) proportional to concentration of oxygen/OWTTE; 2
(b)

ra te

[N O (g )]
correct axes;
correct shape curve; 2

(c) 3/third order; 1

Allow ECF from (a) and (b).
1
(d) overall effect on rate = 4× 2 /doubled/×2;
[NO(g)] doubled, rate =×4/quadrupled;
[O2(g)] halved, rate =×1/halved; 3
Allow ECF from (a) and (b).

2
(e) rate = k[NO(g)] [O2(g)];

k rate  6.3  104

[ NO( g )]2 [O2 ( g )] (3.0 10 2 ) 2 (1.0 10 2 ) ;

= 70;
–2 6 –1
mol dm s ; 4
Allow ECF.
State symbols not needed.
[12]

24. C
[1]

8
25. (a) molecules must have sufficient/minimum energy/energy ≥ activation energy;
appropriate collision geometry/correct orientation; 2
(b) increased frequency of collisions/collisions more likely;
Not just “more collisions”, there must be a reference to time.
increased proportion of molecules with sufficient energy to react/E ≥ Ea;
Not “activation energy is reduced”.
Proportion of molecules with E ≥ Ea is more important;
(dependent on correct second marking point); 3
[5]

26. B
[1]

27. C
[1]

28. C
[1]

29. D
[1]

30. (a) increase in product concentration per unit time/decrease in reactant concentration
per unit time; 1
Accept change instead of increase or decrease.

9
 (b) (i) high activation energy/not enough molecules have Ea/OWTTE;
incorrect collision geometry/OWTTE;
infrequent collisions; 2
Award [1] for any two reasons.

(ii) more energetic collisions/more molecules have (energy ) Ea;

more frequent collisions/collide more often; 2
(iii) add a catalyst;
increase the (total) pressure/decrease the volume of the container;
increase the concentration of C (or D); 2
Do not accept surface area.
Award [1] for any two.
[7]

31. (a) first order (with respect to O2); 1

(b) second order (with respect to NO); 1

2
(c) rate = k[NO] [O2]; 1
Allow ECF from parts (a) and (b).

3.75103
k  1.75102 ;
(d) (3.5010 2 ) 2 (1.7510 2 )
6 –2 –1
dm mol s ; 2
Award [1] mark for the answer and [1] mark for units.
Allow ECF from part (c).

(e) NO + NO N2O2;
N2O2 + O2  2NO2;
second step is rate determining step;
Allow ECF from part (c).
OR
NO + O2 NO3;

NO3 + NO  2NO2;
second step is rate determining step; 3
Allow ECF from part (c).
[8]

32. B

10
 [1]

33. (a) time for reactant concentration to halve/OWTTE; 1

Accept “time for mass to halve”.

(b) 1000 s;
1000 s; 2
Accept 900-1100 s.

(c) first order;

constant half-life;
rate = k[A]; 3
Allow ECF for rate expression from stated order.

rate 3.75 105

k / ;
(d) [D]2 [E] (1.35 102 ) 3

= 15.2;
Accept answer in range 15.2 to 15.3.
2 6 1
mol dm min ; 3
[9]

34. A
[1]

35. C
[1]

36. ([A] against time) - straight line with negative gradient;

Accept any decreasing curve
([B] against time) - decreasing curve;
Award [1] unless half - lives clearly not constant
(rate against [A]) - any horizontal straight line;
(rate against [B]) - straight line through origin;
Award [3] for all four correct, award [2] for any three correct
and [1] for any two correct.
[3]

37. C
[1]

11
38. A
[1]

39. D
[1]

40. (a) first order;

constant half-life; 2

(b) rate = k[HI][H2O2]; 1

ECF from(a).

(c) 47 sec;
Accept answer in range 45 to 49.

 
 t 1  0.693   0.015;
 k 
 2 2
Accept answer in range 0.014-0.015.
ECF from half-life.
[5]

41. C
[1]

12
42. (i) 2ICl + H2  I2 + 2HCl; 1
(ii) ICl order
1;
because doubling [ICl] doubles rate (when [H2] constant);
H2 order
2;
because halving [H2] quarters rate (when [ICl] constant);
or doubling [H2] quadruples rate (when [ICl] constant); 4
2
(iii) rate = k [ICl][H2] ; 1
ECF from (ii).
3 2
(iv) k = 5.00×10 ÷0.100×0.0500 = 20;
2 6 1
mol dm s ; 2
ECF from (iii).
2 2 3 1
(v) rate = 20×0.200×0.100 = 4.00×10 (mol dm s ); 1
ECF from (iii).
[9]

43. (a) (i) it relates to the geometric requirements of the reaction/orientation

of reactants on collision/OWTTE; 1
(ii) minimum energy needed for reactants to react (on collision)/OWTTE; 1
(iii) k measured at different values of temperature;
graph plotted of ln k against 1/T;
intercept on y-axis is ln A;
intercept
A=e ;
measured slope of graph =  Ea/R;
Ea = – R×gradient; 5
Award [1] each for any five.

13
 (b) (i) homogeneous catalyst is in same phase as reactants and heterogeneous
catalyst is in different phase from reactants; 1
(ii) 4

E a

E cat

C H 2C H 2  C l2

H

C H 2 C lC H 2C l

OR

E a
H
E cat
C H 2 C H 2  C l2

H
C H 2C lC H 2 C l

reactants line higher than product line (labels not needed);

ΔH label;
Ea label;
Ecat label;
[12]

44. B
[1]

45. A
[1]

14
46. (a) change of concentration/mass/amount/volume/of a reactant/product with time; 1
Do not accept “substance”.

(b) all the CaCO3(s) has been consumed/no further CO2(g) is produced/reaction
is complete; 1
Do not accept reaction has stopped or all reactants used up.

(c) line on graph should be initially less steep/a smaller gradient and should
plateau at the same mass loss; 1

M a ss lo ss / g

T im e / m in u te s

(d) there are more particles with KE greater than or equal to Ea;
collisions more frequent/more collisions per unit time/more
successful/forceful collisions per unit time;
the rate increases; 3

3 3 1
(e) 1.00×10 (mol cm s ) 1
Ignore units even if wrong.
Apply 1(sf).
[7]

15
47. (a) (i) (C) first order;
doubling [C] doubles rate/OWTTE;
(D) zero order;
changing [D] has no effect on rate/OWTTE; 4
1 0
(ii) rate = k[C]/rate = k[C] [D] ; 1
Apply ECF from (a)(i).

rate 1.0 10 6

/ 3
;
(iii) k = [C ] 2.0 10
4
= 5.0×10 ;
1
min ; 3
Apply ECF from (a)(ii).

(b) time for half of (amount/concentration of) reactant to react/disappear;

1
t 2 ( = 0.693÷0.033) = 21 min; 2
Units needed for second mark.
[10]

48. A
[1]

49. A
[1]

50. C
[1]

51. (a) order of NO: second/2 - [NO] doubled, rate×4/OWTTE;

order of Br2: first/1 - as [Br2] doubled, rate of reaction doubled/OWTTE; 2
Reason needed for each mark.

2
(b) rate = k [NO] [Br2]; 1
Allow ECF from (a).

16
 3 2 2 3
(c) 3.20×10 = k(2.00×10 ) ×5.00×10
3
k = 1.60×10 ;
6 2 1
dm mol s ; 2
Allow ECF from (b).

(d) (i) no effect/K changes only with temperature/OWTTE; 1

(ii) decrease (by a factor of 2); 1

(e)

E a

E a (c a t)

E a w ith o u t c a ta ly s t

H R /E R
E n th a lp y o f E a w ith c a ta ly s t
re a c ta n ts
H P/E P
E n th a lp y o f
p ro d u c ts

T im e

curve clearly showing Ea without catalyst (Ea);

curve clearly showing Ea with catalyst (Ea(cat));
labelling for x axis; 3
Accept time/progress of reaction/course of reaction/OWTTE.
Award [2 max] if an enthalpy level diagram for an endothermic
reaction has been correctly drawn.
[10]

17
52. D
[1]

53. B
[1]

54. (i)

T1
N u m b e r/F ra c tio n o f M o le c u le s

T2 > T 1

T 2

E n e rg y /s p e e d
T2 peak lower/T1 higher;
T2 peak at higher energies/T1 curve at lower energies; 2
Maximum [1] if axes not labeled correctly
(ii) minimum energy required to react/energy difference between
reactants and transition state; 1
(iii) makes the reaction go faster;
because it lowers the activation energy/Ea; 2
[5]

18
55. (i) a curve showing concentration decreases with time; 1
i.e .

[a c id ]

T im e
No penalty if curve reaches x axis
Do not accept a straight line
(ii) slope decreases; 1
(iii) rate decreases;
fewer collisions per unit time; 2
[4]

56. B
[1]

57. D
[1]

+
58. (i) rate = k[CH3COCH3][H ];
2
rate = k[CH3COCH3] ;
+ 2
rate = k[H ] ; 3
+
(ii) [CH3COCH3] doubles, rate doubles and [H ] doubles, rate doubles;
[Br2] double, no effect on rate;
OR
[CH3COCH3] doubles, rate quadruples;
+
[Br2] doubles/[H ] doubles, no effect on rate;
OR
+
[H ] doubles, rate quadruples;
[Br2] doubles/[CH3COCH3] doubles, no effect on rate; 2
The answer given must correspond to the selected expression in (i).

19
 (iii) constant half-life;
at least two sets of data to justify statement; 2
3
e.g. [ ] from 1.6 to 0.8 mol dm , 10s; 0.8 to 0.4, 10s; 0.4 to 0.2,
10s.

(iv) decrease in the colour of the bromine/OWTTE;

catalyst;
increases rate/speeds up reaction;
by lowering Ea/activation energy (by providing an alternate pathway); 4
[11]

59. B
[1]

60. A
[1]

61. C
[1]

62. (a) (order with respect to) H2 = 1;

(order with respect to) NO = 2; 2

2
(b) rate = k[H2][NO] ; 1
ECF from (a).

−6 –3 –1 −3 –3 2
(c) (2.53×10 mol dm s = k(0.100 mol dm )(0.100 mol dm ) )
–3
k = 2.53×10 ;
−2 6 –1
mol dm s ; 2
ECF from (b).

20
(d) agrees/yes;
slow step depends on X and NO;
(so) NO is involved twice and H2 once;
overall equation matches the stoichiometric equation/OWTTE;
ECF for “no”, depending on answer for (b).
OR
agrees/yes;
[X]
and [H 2 ][ NO] = constant;
rate of slow step = k[X][NO];
but X depends on H2 and NO;
2
rate of slow step = k[H2][NO] ; 4 max
Award [1] each for any three of the four above.
ECF for “no”, depending on answer for (b).

(e) reaction involves four molecules;

statistically/geometrically unlikely; 2

(f) the rate of formation of H2O = 2×rate for N2;

because 2 moles H2O formed with 1 mole N2/OWTTE; 2
[13]

21