Reaction Kinetics Answers PDF

149 For
2
Examiner’s
Use
REACTION KINETICS WS 1
Answer all the questions in the spaces provided.
11 The oxidation of nitrogen monoxide occurs readily according to the following equation.
NO(g) + !" O2(g) ⎯→ NO2(g)
The following table shows how the initial rate of this reaction depends on the concentrations
of the two reactants.
[NO] [O2] initial rate

/ mol dm–3 / mol dm–3 / mol dm–3 s–1
:(
Yi 0.03 )x
0.0050 0.0050 0.02
's
0.0050 0.0075
"
( 0.010 0.0075 0.12
(a) (i) Use the data to determine the order of reaction with respect to each of the
reagents.
order with respect to NO 2nd Order

…………………………
order with respect to O2 1st Order

…………………………
(ii) Write the rate equation for the reaction, and use it to calculate a value for the rate
constant, k, stating its units. '
rate -
KENO ] COD
rate equation .............................................................................................................
.
0.005/[0-005]
0.02 -_k[
2 I
dm 's
-
1<=1.6×105
-
mot
1.6×105
°
numerical value of k = …………………………

-
2 6 - I
Mol dm s
units of k …………………………
(iii) Use your rate equation in (ii) to calculate the rate of reaction when
[NO] = [O2] = 0.0025 mol dm–3.
rate = (2.6×1096.0025)-[0-0025]
-
3
=
2.5×10 moldm -351
3mo1dm35 ?
-
2.5×20
rate of reaction =…………………………
[6]
[J’06 P4 Q1]
© UCLES 2006 9701/04/M/J/06
CEDAR COLLEGE REACTION KINETICS WS 1

150 4
22 Acetals are compounds formed when aldehydes are reacted with an alcohol and an acid For
catalyst. The reaction between ethanal and methanol was studied in the inert solvent Examiner’s
dioxan. Use
H+
CH3CHO + 2CH3OH CH3CH(OCH3)2 + H2O
ethanal methanol acetal A
(a) When the initial rate of this reaction was measured at various starting concentrations of
the three reactants, the following results were obtained.
experiment [CH3CHO] [CH3OH] [H+]

relative rate
number / mol dm–3 / mol dm–3 / mol dm–3
"
f x. !:I
"
1 0.20 0.10 0.05 1.00
0.25 I
"
( (
2 0.10 0.05 1.25
3 0.25 0.16 0.05 2.00 ,

4 0.20 0.16 0.10 3.20
(i) Use the data in the table to determine the order with respect to each reactant.
1st Order
order with respect to [CH3CHO] ............................................................
order with respect to [CH3OH]

1st Order
............................................................
order with respect to [H+]

1st Order
............................................................
(ii) Use your results from part (i) to write the rate equation for the reaction.
rate =k[CH3CHO][CH3OH][ H 'T
..................................................................................................................................
(iii) mot -2dm

State the units of the rate constant in the rate equation ........................................... 651
(iv) Calculate the relative rate of reaction for a mixture in which the starting
concentrations of all three reactants are 0.20 mol dm–3.
K= =
1000
1.00
T.gg ,
rate -
- 100010.233 8 moldm -35 ?
relative rate = ......................................................
[6]
© UCLES 2011 9701/42/O/N/11

151 5
(b) The concentration of the acetal product was measured when experiment number 1 was For
allowed to reach equilibrium. The result is included in the following table. Examiner’s
Use
[CH3CHO] [CH3OH] [H+] [acetal A] [H2O]

/ mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3
at start 0.20 0.10 0.05 0.00 0.00
at equilibrium (0.20–x) GIO -
2n ) 0.05 x N
at equilibrium 0.275 0.05 0.05 0.025 0.025
(i) Complete the second row of the table in terms of x, the concentration of acetal A at
equilibrium. You may wish to consult the chemical equation opposite.
(ii) Using the [acetal A] as given, 0.025 mol dm–3, calculate the equilibrium
concentrations of the other reactants and products and write them in the third row
of the table.
(iii) Write the expression for the equilibrium constant for this reaction, Kc, stating its
units. [
acetal AHHH
'
[ CHEO ][ CHSOH) mot -1dm

'
Kc = ................................................................. units = ........................................
(iv) Use your values in the third row of the table to calculate the value of Kc.
Kc -
[ 0025110.025 ]
[0175/10.05]
-
'
Kc = 1.43mA -1dm
......................................................
[9]
[N’11 P41 Q2]
[Total: 15]
© UCLES 2011
CEDAR COLLEGE
9701/42/O/N/11
[Turn over
152 For
2
Examiner’s
Use
3 1 The reaction between iodine and propanone is catalysed by hydrogen ions.
H+
CH3COCH3 + I2 ⎯⎯⎯→ CH3COCH2I + HI
The reaction is found to be first order with respect to [CH3COCH3] and with respect to [H+],
and zero order with respect to [I2].
(a) What do you understand by the term order of reaction?

Order of reaction is the power to which the concentration
..........................................................................................................................................
reagent is raised in a rate equation

of ......................................................................................................................................[1]
a
.
(b) Construct a rate equation for the reaction.
rate = KCC COCH 33 H Has l 'T

......................................................................................................................................[1]
The following sketches show three ways in which the concentration of reagents might vary
during the reaction.
[reactant] [reactant] [reactant]
time time time
A B C
(c) Which of the above graphs correctly describes how the concentration of reactant
changes with time for
(i) the propanone concentration,

A
_____________________
(ii) the iodine concentration? B

_____________________
[2]
9701/4/O/N/03

153
(d) When carried out in 0.1 mol dm–3 HCl solution, the rate was found to be
0.002 mol dm–3 s–1. Predict the rate of reaction in 0.2 mol dm–3 HCl and in
0.3 mol dm–3 HCl solution. Plot your figures on the following graph, and draw a line
through the points.
0.010
0.008
rate / mol dm–3 s–1
0.006 •
0.004 •
0.002
0 •
0 0.1 0.2 0.3

[HCl] / mol dm–3
[2]
(e) Only one of the following outline reaction mechanisms is consistent with the observed
kinetics.
I2 + H+ ⎯⎯→ intermediate ×
A
! intermediate + CH3COCH3 ⎯⎯→ products
[slow]
[fast]
CH3COCH3 + H+ ⎯⎯→ intermediate ✓

B
! intermediate + I2 ⎯⎯→ products
[slow]
[fast]
CH3COCH3 + H+ ⎯⎯→
C
! intermediate + I2 ⎯⎯→
intermediate
products x
[fast]
[slow]
CH3COCH3 + I2 ⎯⎯→
D
! intermediate + H+ ⎯⎯→
intermediate x
products
[slow]
[fast]
Decide which mechanism is consistent, explaining the reasons for your choice.
B
Mechanism letter (A, B, C or D) _____________________
Reasons
The rate is the slowest the
determining step step in
..........................................................................................................................................
chemical reaction CH , COOH and Ht are both first
..........................................................................................................................................
.
will be
order ,
so
they part of the slow step Is is
..........................................................................................................................................
.
zero order therefore it is not

part of the slow step
......................................................................................................................................[3]
,
.

154 4 For
Examiner’s
Use
(f) When the starting concentrations of propanone, iodine and H+ were 0.20 mol dm–3,
0.01 mol dm–3 and 0.5 mol dm–3 respectively, the rate of decrease of [I2] was found to
be 3.3 x 10–6 mol dm–3 s–1.
(i) Suggest a method you could use to measure [I2].

Titrate iodine solution with standardised Na 2503 C sodium thiosulfate) solution
...................................................................................................................................
.
of known concentration starch indicator is added close to the end point

. - .
(ii) Use these figures and your rate equation in part (b) to calculate a value for the rate
constant k.
3. 3 × 10-5
...................................................................................................................................
(iii) What are the units of k?
dm mot 15 ?
'
-
...................................................................................................................................
[3]
rate 3) l Ht ]
[N’03 P4 Q1]
=
k CCH 3 COCH [Total : 12]
2 3.3×10-6
(a) Methanoic K is [a weak
acid, HCO2H, [ 0.5
0.2 ]acid,=
with] Ka = 1.77 x 10–4 mol dm–3.
(i) Ka of methanoic acid.

Write an expression for the10-5
K 3.3 ×=
...................................................................................................................................
–3
(ii) Use your expression to calculate the [H+] in a 0.0500 mol dm solution of
methanoic acid.
...................................................................................................................................
(iii) Calculate the percentage of HCO2H molecules that are ionised in this solution.
(iv) Calculate the pH of this solution.
...................................................................................................................................
[4]
9701/4/O/N/03

For
Section A Examiner’s
Use
Answer all the questions
155 in the spaces provided.
41 A bromoalkane, R–Br, is hydrolysed by aqueous sodium hydroxide.
(a) (i) Write a balanced equation for this reaction.

R Brt NaOH R -
OH -iNaBr
....................................................................................................................................
-
(ii) What type of reaction is this?

It is a substitution reaction
nucleophilic
.
....................................................................................................................................
[2]
(b) The concentration of bromoalkane was determined at regular time intervals as the
reaction progressed.
Two separate experiments were carried out, with different NaOH concentrations.
The graph below shows the results of an experiment using [NaOH] = 0.10 mol dm–3.
0.010
.€
•
NaOH oss
0.009
.
-01 0.008
NaOH
0.007 A
0.006
[R–Br]
0.005
/ mol dm–3
0.004
0.003
0.002
•
half-life data .
\
0.001
.
0
0 50 100 118 15 0 2 00 236 2 5 0
time / min
When the experiment was repeated using [NaOH] = 0.15 mol dm–3, the following results
were obtained.
time / min [R–Br] / mol dm–3

0 0.0100
40 0.0070
80 0.0049
120 0.0034
160 0.0024
200 0.0017
240 0.0012
(i) Plot these data on the axes above, and draw a line of best fit.
© UCLES 2013 9701/42/M/J/13

156
3
For
(ii) Use one of the graphs to confirm that the reaction is first order with respect to R–Br. Examiner’s
Show all your working, and show clearly any construction lines you draw. Use
1st half life 128mi -

-
.
2nd half life

ns.gsuggsesnfeishaatffiisesgaeercorneatffith
236 mins -_
-
Wrt I RBD
.
[ 236-118=118 mins ) Ra [ RBD

'
(iii) Use the graphs to calculate the order of reaction with respect to NaOH. Show all
your working, and show clearly any construction lines you draw on the graphs.
185
1-5
0×10
×
When [ OH
0*2=5
] ?
When I OH -1=0.25
-3 -3
= 0.1 moldm moldm
rate rate Rx COH ]
01=5.4×10
= . =
5 121
0.0-1=8.26×10-5
First Order
5.40×-10-5=0.054
(iv) Write the rate equation for this reaction, and calculate the value of the rate constant.
rate = KLRBRILOH ] initial rate .

-
s
-
moldm
-
3
min ?
K =
mot -2dm 3mm -
I
.
[7]
(0.1×0.01)
(c) Nitric oxide, NO, and bromine vapour react together according to the following equation.
2NO(g) + Br2(g) 2NOBr(g) H = –23 kJ mol–1
The reaction has an activation energy of +5.4 kJ mol–1.
Use the following axes to sketch a fully-labelled reaction pathway diagram for this
reaction.
Include all numerical data on your diagram.
" " " no " ?
2NO + Br2
energy
/ kJ mol–1
* .→⇒ . .
.
.
ZNOBR
extent of the reaction

[2]
[J’13 P42 Q1]
[Total: 11]
© UCLES 2013 9701/42/M/J/13 [Turn over

157
4
4
52 For
Ethyl ethanoate is hydrolysed slowly by water in the following acid-catalysed reaction. For
Examiner’s
2 Ethyl ethanoate is hydrolysed slowly by water in the following acid-catalysed reaction. Examiner’s
Use
Use
H+ +
H
CH3CO2CH2CH3 + H2O CH3CO2H + CH3CH2OH
CH3CO2CH2CH3 + H2O CH3CO2H + CH3CH2OH
TheThe
concentration of ethyl ethanoate was determined at regular time intervals as the reaction
concentration of ethyl ethanoate was determined at regular time intervals as the reaction
progressed.
progressed.
TwoTwo
separate experiments
separate experimentswere carried
were out,
carried with
out, different
with differentHCl
HClconcentrations.
concentrations.
TheThe
following
following graph shows the results of an experiment using[HCl
graph shows the results of an experiment using [HCl] ]==0.1
0.1mol
moldm
dm–3..
–3
0.200.20
-
0.180.18
0.160.16
0.140.14
0.120.12
[CH3[CH
CO32CO
CH22CH
CH23CH
] 3]
mol–3dm–3
/ mol/dm 0.100.10
0.080.08
0.060.06
0.04
0.04
0.02
0.02
0
0 0 20 40 60 62.5 80 100 120 125
0 20 40 60 80 100 120
time / min
time / min
(a) When the experiment was carried out using [HCl ] = 0.2 mol dm–3, the following results
(a) When theobtained.
were experiment was carried out using [HCl ] = 0.2 mol dm–3, the following results
were obtained.
[CH3CO2CH2CH3]
time / min
[CH3CO 2CH
/ mol 2CH3]
dm –3
time / min
/ mol dm –3
0 0.200
0 0.200
10 0.160
1025 0.160
0.115
2550 0.115
0.067
5075 0.067
0.038
75
100 0.038
0.022
100
125 0.022
0.013
125 0.013
© UCLES 2013 9701/41/M/J/13
© UCLES 2013 9701/41/M/J/13

158
5
For
(ii) Use one of the graphs to show that the reaction is first order with respect to Examiner’s
CH3CO2CH2CH3. Use
Show all your working, and show clearly any construction lines you draw on the
graphs.
szsminfsn :s:haY÷'
Ent half-life !
:c
::
:::t%t
.ae
:c
is
[125-62.5--62.5]
half life 125 min -
wrt CCH3C0zCHzCH3 ] .
Ra [ CHsC0zCHzCH3 ] ?
(iii) Use the graphs to calculate the order of reaction with respect to HCl.
Show all your working, and show clearly any construction lines you draw on the
graphs.
2
[ HCl ]
3
( HCl ]
-3
0.2 mold
-
O I moldm
-
m
-
- -
.
Rate is doubled
rate =
0.2
-
rate =
OL
-
1st Order
47=21×10-3
95
moldm -3mi 4.3×10-3 n
'
= moldm
-3
mini ? Rx CHU ]
(iv) Write the rate equation for this reaction, and calculate the value of the rate constant.
rate = K[CH3C0zCHzCH3][ HCl ]

rate 2.1×10-3 moldmtdmin ?
Og
= =
K mot 1dm
's
?
-
min [7]
2.1×10-32=0.21
-
-
(02×0.1)
(b) (i) Why is it not possible to determine the order of reaction with respect to water in this
experiment?
It
Wrt water
is not
possible to determine the order of reaction
....................................................................................................................................
as it is a solvent and its concentration cannot be changed .
....................................................................................................................................
(ii) Although [CH3CO2CH2CH3] decreases during each experiment, [HCl ] remains the
same as its initial value.
Why is this?
HCl is a
catalyst therefore its concentration remains
....................................................................................................................................
,
the the reaction

same
throughout .
....................................................................................................................................
[2]
[J’13 P41 Q2]
[Total: 9]

..........................................................................................................................................
159
.................................................................................................................................... [4]
6 (b) The reaction rate was studied using two solutions of different hydroxide ion
concentrations.
run A: [OH–] = 0.20 mol dm–3
run B: [OH–] = 0.40 mol dm–3
The following graphs show how the concentration of the ester, 4-nitrophenyl ethanoate,
varied over time in the two runs.
0.001
0.0009
0.0008
0.0007
[ester] / mol dm–3
0.0006
0.0005
0.0004
run A
0.0003
0.0002
run B
0.0001
0 "
0 10 12 20 24 30 40 50 60
time / min
9701/4/S02

160
5 For
Examiner's
Use
(i) By drawing tangents on the graphs, measure and calculate the initial rates of
reaction during the two runs. Give the units in each case.
mold m 3mi 2- ?
-
s -
5.0×10
jf1_
=
initial rate of run A ....................................................................................................

?
O.gg#--I.OxI0-4moldm-3min-
initial rate of run B ....................................................................................................
[3]
(ii) By using your results, calculate the overall order of reaction with respect to [OH–].
1st Order This is because when I OHI is doubled rate -
............................................................................................................................
.
, [1]
also doubles .
(iii) From the curve of run B, determine the order of reaction with respect to [ester].
1st Order
............................................................................................................................
.
[1]
(iv) Explain how you arrived at you answer in (iii).
constant at 1st
Half -
life is 12 min half life min

..................................................................................................................................
.
. =
12
;
2nd half life 24 min [ 24-12=12 min ]
............................................................................................................................ [1]
-
= .
.
(v) Write a rate equation for the reaction.

k Lester ] [ OH I
-
rate
............................................................................................................................
=
[1]
(vi) Use your rate equation and the initial rates to calculate a value for the rate
constant, including units.
5.0×10-5 K [0.001310-2]
..................................................................................................................................
=
K 3 I I
0.25 dm mot
-
-
=
min
............................................................................................................................
.
[2]
[Total:
[J’04 P413]
Q2]
9701/4/S02 [Turn over

161 3 For
Examine
Use
72 (a) What do you understand by the term order of reaction?
Order of reaction is
the to which the concentration [1]
of
power
....................................................................................................................................
a
reagent is raised in a rate equation .
(b) Cyanohydrins can be made by reacting ketones with an acidified solution of sodium
cyanide.
(CH3)2C=O + H+ + CN– → (CH3)2C(OH)CN
In a series of experiments, the reaction was carried out with different concentrations of
the three reagents, and the following relative initial rates were obtained.
experiment [(CH3)2CO] [H+] [CN–] relative initial rate /

number / mol dm–3 / mol dm–3 / mol dm–3 mol dm–3 sec–1
1 0.020 0.060 0.060 1.00
of
II
xazsf !:
2 0.020 0.050 0.050 0.833
x.
3 0.020 0.050 0.060 1.00
4 0.025 0.050 0.050 1.042
(i) Use the data in the table to deduce the order of the reaction with respect to
1st Order
propanone ....................................................
O Order
hydrogen ions ..............................................
1st Order
cyanide ions .................................................
(ii) Hence write a rate equation for this reaction.
rate = KLCC Hs ) 2 CO ] [ CNT
..................................................................................................................................
Two different mechanisms have been suggested for this reaction
Mechanism A: (CH3)2C=O + H+ → (CH3)2COH+

(CH3)2COH+ + CN– → (CH3)2C(OH)CN
Mechanism B: (CH3)2C=O + CN– → (CH3)2C(O–)CN

(CH3)2C(O–)CN + H+ → (CH3)2C(OH)CN
(iii) Which mechanism is consistent with the rate equation you deduced in (ii), and
which step in this mechanism is the slower (rate determining) step? Explain your
answer.
Rate of is
reaction
determined by the slow step Mechanism B .
..................................................................................................................................
-
consistent the
with
is rate
because equation the reaction
..................................................................................................................................
is 1st Order wit [ LCH 3) CO ] and [ CN ] it must be the
determining
rate
-
..................................................................................................................................
;
.
Ht step .
0 Order , sois it must come

after
..................................................................................................................................
the
slow step It
does .
not
appear in the rate equation .
[7]
[J’05[Total:
P4 Q2]8]

162
8 2 In the late 19th century the two pioneers of the study of reaction kinetics, Vernon Harcourt
and William Esson, studied the rate of the reaction between hydrogen peroxide and iodide
ions in acidic solution.
H2O2 + 2I– + 2H+ 2H2O + I2
This reaction is considered to go by the following steps.
step 1 H2O2 + I– IO– + H2O
step 2 IO– + H+ HOI
step 3 HOI + H+ + I– I2 + H2O
The general form of the rate equation is as follows.
rate = k[H2O2]a[I–]b[H+]c
(a) Suggest how the appearance of the solution might change as the reaction takes place.
The colourless to red brown [1]
appearance changes from
.
....................................................................................................................................
-
(b) Suggest values for the orders a, b and c in the rate equation for each of the following
cases.
numerical value
case
a b c
step 1 is the slowest overall 1 I 0
step 2 is the slowest overall I I 1
2.
step 3 is the slowest overall 2
[3]
A study was carried out in which both [H2O2] and [H+] were kept constant at 0.05 mol dm–3,
and [I–] was plotted against time. The following curve was obtained.
0.001
0.0009
0.0008 CH 202 ] and [ Ht ] are
significantly
larger than [ IT Hence
0.0007 any change
.
in their concentration will be

negligible
0.0006 be considered
and
they effectively
can
[I– ion] / mol dm–3 0.0005 constant . Hence , only change

in rate is
0.0004 due to the

change of LIT
.
0.0003
0.0002
0.0001
0
0 30 60 90 120 150 180 210 240 270 300
time / s

163 For
5
Examiner’s
Use
To gain full marks for the following answers you will need to draw relevant construction lines
on the graph opposite to show your working. Draw them using a pencil and ruler.
(c) Calculate the initial rate of this reaction and state its units.
3
rate mold m
-
001
351
6
Or 741×10
-
-
=
=
mold m
135 s
741×10-6 mold miss

'
rate = ........................ units ....................... [2]
(d) Use half-life data calculated from the graph to show that the reaction is first order with
respect to [I–].
}
1sthalf life
feisty
:D
't:!
an
Innes
trait
that
:
-
"
-
-1988
2nd half life - -
aos .
.
go ,
.................................................................................................................................... [2]
(e) Use the following data to deduce the orders with respect to [H2O2] and [H+], explaining
your reasoning.
[H2O2] / mol dm–3 [H+] / mol dm–3 relative rate
:-[
"
0.05 0.05 1.0
:s
-
l I
:f: (
" '
%
"
0.07 0.05 1.4

x. .
.
0.09 0.07 1.8
Lines 142 :
LH 2021 increases
-
1.4
by so does rate
.
.......................................................................................................................................... .
Lines H2O a ] increases rate

143
!g
by 1.8 so does
.......................................................................................................................................... .
Rate is independent of Ht 1st Order

.
* order with respect to [H O ] = .....................................................

2 2
O Order
order with respect to [H+] = .....................................................
[2]
(f) From your results, deduce which of the three steps is the slowest (rate determining)
step.
Step I is the slowest step

....................................................................................................................................
.
[1]
[Total:
[N’08 P411]
Q2]
© UCLES 2008 9701/04/O/N/08 [Turn over

(ii) Describe the type of bonding that occurs between a ligand and a transition element.
..................................................................................................................................
164 [2]
9 (b) Chromium hexacarbonyl undergoes the following ligand replacement reaction.
Cr(CO)6 + PR3 Cr(CO)5 PR3 + CO
Two separate experiments were carried out to study the rate of this reaction.
In the first experiment, the ligand PR3 was in a large excess and [Cr(CO)6] was measured
with time. The results are shown on the graph below.
0.01000
0.00800
concentration / mol dm–3
0.00600
0.00400
0.00200
0.00000
0 200 400 600 700 800 1000 1200 1400 1600
time/s
In the second experiment, Cr(CO)6 was in a large excess, and [PR3] was measured with
time. The following results were obtained.
time / s [PR3] / mol dm–3
0 0.0100
120 0.0076
200 0.0060
360 0.0028
(i) Plot the data in the table on the graph above, using the same axis scales, and draw
the best-fit line through your points.
© UCLES 2011 9701/43/O/N/11

165
5
(ii) Use the graphs to determine the order of reaction with respect to Cr(CO)6 and PR3. For
In each case explain how you arrived at your answer. Examiner’s
Use
Cr(CO)6
half life s
-700
2nd half life 1400 s 700=700 s
1st..................................................................................................................................
- -
=
dy
-
Constant half lives 1st Order Reaction Ra [ Cr CCO ) 6 ] .
..................................................................................................................................
= .
PR3
rate of reaction is constant as the
The ..................................................................................................................................
is a
graph
°
straight
line Therefore , 0 Order Reaction Ra CPR , ]
.
..................................................................................................................................
. .
(iii) Write the rate equation for the reaction, and calculate a value for the rate constant,
using the method of initial rates, or any other method you prefer.
6
I
-
rate K C Cr CCO ) s ] g. 0.01 9.8×10 mots

-
0.01
= .
=
..................................................................................................................................
1020
..................................................................................................................................
K =
9.8×10-6 9.8×10-4 s
-
L
..................................................................................................................................
= .
..................................................................................................................................
(iv) State the units of the rate constant.

-1
he units of K are see .
..................................................................................................................................
(v) Four possible mechanisms for this reaction are given below. Draw a circle around
the letter next to the one mechanism which is consistent with the rate equation you
have written in (iii).
A Cr(CO)6 Cr(CO)5 + CO fast

Cr(CO)5 + PR3 Cr(CO)5 PR3 slow
B Cr(CO)6 Cr(CO)5 + CO slow

Cr(CO)5 + PR3 Cr(CO)5 PR3 fast
C Cr(CO)6 + PR3 [OC- - -Cr(CO)4- - -PR3] Cr(CO)5 PR3 + CO

(transition state)
D Cr(CO)6 + PR3 Cr(CO)6 PR3 slow

Cr(CO)6 PR3 Cr(CO)5 PR3 + CO fast
Explain your answer.

Mechanism B is consistent This is because
it
. is the
..................................................................................................................................
one that does not involve PR rate
in its
only ,
determining
-
..................................................................................................................................
[9]
C slow ) step
.
[N’11 P43 Q2]

[Total: 11]
© UCLES COLLEGE
CEDAR 2011 9701/43/O/N/11 [Turn
REACTION KINETICS WS over
1
166
4
10 For
2 Nitrogen monoxide, NO, is formed in a reversible reaction when air is heated to the temperature Examiner’s
of a car engine. Use
(a) (i) Suggest a ‘dot-and-cross’ electronic structure for nitrogen monoxide.
* NEO
(ii) The enthalpy change of formation of nitrogen monoxide is +90 kJ mol–1. What is the
enthalpy change for the following reaction?
2NO(g) N2(g) + O2(g) 180

Hr = .....................
-
kJ mol–1
(iii) Explain why nitrogen monoxide is formed in the car engine.

is needed to break the bond
High temperature strong triple
....................................................................................................................................
in Nz
C NIN ) . .
(iv) Using bond enthalpy values from the Data Booklet and your answer in (ii) above,
calculate a value for the bond energy of nitrogen monoxide.
180=24 HCNO ) -
994-496
I
AH C NO ) -1655 KJ mot
-
bond energy = .......................... kJ mol–1

[5]
(b) At 800 K, nitrogen monoxide reacts with hydrogen according to the following equation.
+655×2
equation I 2H2(g) + 2NO(g) 2H2O(g) + N2(g)
The following table shows how the initial rate of this reaction depends on the partial
pressures of the reagents.
experiment p(H2) / atm p(NO) / atm initial rate / atm s–1
1×41×2×2
1 0.64 1.60 1.50 10–7
2
3
( 0.64
0.32
0.80
1.60
( 3.75
7.50
10–8
10–8
(i) Find the order of the reaction with respect to each reactant, explaining how you
arrive at your answer.
Experiments I and 2 : as
pc NO ) doubles , rate quadruples
.
-
....................................................................................................................................
Thus ,
it is 2nd Order .
....................................................................................................................................
I and 3 C Hz )
doubles , rate also
Experiments as
:
p
-
....................................................................................................................................
doubles Thus , it is 1st Order
....................................................................................................................................
. .
....................................................................................................................................
© UCLES 2012 9701/41/M/J/12

167
(ii) Write down the rate equation and the units of the rate constant.
rate KCPNO )4pHz ) units atm -25 ?
;
-
-
....................................................................................................................................
.
The following mechanism has been put forward for this reaction.
step 1 NO + NO N2O + O
step 2 H2 + O H 2O
step 3 H2 + N2O N2 + H2O
(iii) Show how the overall stoichiometric equation I can be derived from the three
equations for the individual steps given above.
2N0t2Hz s Nz -12420
(iv) Suggest which of the three reactions in the mechanism is the rate determining step.
2 is the rate This
determining step
is
Step
.
-
....................................................................................................................................
Hz .Nz0 is NO
because it involves formed from
.
....................................................................................................................................
[8]
(c) The following information on half-reactions relates to the reaction between HNO3 and an
excess of FeSO4.
Fe3+ + e– Fe2+ E = +0.77 V

3H + NO
+
3
–
+ 2e –
HNO2 + H2O E = +0.94 V
HNO2 + H + e + –
NO + H2O E = +0.99 V
(i) Suggest the formula of the nitrogen-containing final product of this reaction.
NO
....................................................................................................................................
(ii) Write an equation for the formation of this nitrogen-containing product.

HN0zt Htt e- NO t H2O
Felt Fest -1 e-
HNOztHttFe4 Not Fe3ttHz0

(iii) Nitrogen monoxide forms a dark brown complex with an excess of FeSO4(aq).
What kind of bonding is involved in the complex formation?
Dative Bonding C
Ligand Complex
)
....................................................................................................................................
(iv) Suggest a formula for this complex. 't
[ FeCHz0)4 ( NO ) , ]
....................................................................................................................................
[4]
[J’12 P41 Q2]

168
4
11 For
2 Carbon monoxide, CO, occurs in the exhaust gases of internal combustion engines. Examiner’s
Use
(a) (i) Suggest a dot-and-cross diagram for CO.
CO
(ii) Suggest one reason why CO is produced in addition to CO2 in some internal
combustion engines.
Combustion of hydrocarbons takes in
Incomplete place
....................................................................................................................................
the internal combustion engine due to limited
supply of oxygen
.................................................................................................................................... .
(iii) Carbon monoxide can be removed from the exhaust gases by a catalytic converter.
Write an equation for a reaction that occurs in a catalytic converter that removes CO.
NO -1 CO
1Nzt CO2
....................................................................................................................................
2 [3]
(b) The standard enthalpy change of formation, , of CO is –111 kJ mol–1, and that of CO2 is
–394 kJ mol .
–1
Calculate the standard enthalpy change of the following reaction.

-
111×2=-222 N
C(s) + CO2(g) 2CO(g)
-394 -1 n= -222 -394
21-111 )
Elements
z=t172kJmot ? +172
H o = ....................................... kJ mol–1
[2]
(c) Carbon monoxide reacts with a ruthenium(II) chloride complex according to the equation
[Ru(H2O)2Cl 4]2– + CO [Ru(H2O)(CO)Cl 4]2– + H2O.
(i) Describe the type of reaction that is occurring here.
....................................................................................................................................
(ii) During the reaction, the colour of the solution changes from deep blue to green.
Explain the origin of colour in transition element complexes, and why different
complexes often have different colours.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
© UCLES 2012 9701/42/M/J/12

169
The following table shows how the initial rate of this reaction varies with different
concentrations of reactants.
[[Ru(H2O)2Cl 4]2–] / mol dm–3 [CO] / mol dm–3 rate / mol dm–3 s–1
1×2
1.1 10–2 1.7 10–3 1.6 10–7
X 2
( 1.6
2.2
10–2
10–2
3.6
2.7
10–3
10–3
2.3
3.2
10–7
10–7
(iii) Use these data to determine the order of reaction with respect to each reagent, and
write the rate equation for the reaction.
and 3 : As the concentration
Comparing Experiments I of the
....................................................................................................................................
-
I l Ru C H2O ) Cl 4) ] doubles , the rate also doubles

2-
complex z
....................................................................................................................................
.
Hence First Order

wit the
complex , the reaction
is
....................................................................................................................................
.
However the change of concentration of CO has no

....................................................................................................................................
,
effect on rate Therefore , worst CO

.
it is Zero Order
....................................................................................................................................
,
.
KURUC H2O ) z Cla ] ]

"
R -
....................................................................................................................................
-
There are three possible mechanisms for this reaction, which are described below.
X
slow
mechanism 1 [Ru(H2O)2Cl 4] + CO
2–
[Ru(H2O)(CO)Cl 4]2– + H2O
slow
mechanism 2 [Ru(H2O)2Cl 4]2– [Ru(H2O)Cl 4]2– + H2O
fast
[Ru(H2O)Cl 4]2– + CO [Ru(H2O)(CO)Cl 4]2–
x
slow
mechanism 3 [Ru(H2O)2Cl 4] + CO
2–
[Ru(H2O)2(CO)Cl 4]2–
fast
[Ru(H2O)2(CO)Cl 4]2– [Ru(H2O)(CO)Cl 4]2– + H2O
(iv) Deduce which of these three mechanisms is consistent with the rate equation you
suggested in part (iii). Explain your answer.
Mechanism 2 is consistent This is because CO is not .
....................................................................................................................................
part of the slow step , which is the rate determining

....................................................................................................................................
-
step ; since CO is 0 Order

....................................................................................................................................
.
[10]
[J’12 P42 Q2]

Section A

170
12
1 (a) The oxidation of nitrogen(II) oxide is shown in the equation.
2NO(g) + O2(g) 2NO2(g)
The initial rate of this reaction was measured, starting with different concentrations of the two
reactants. The following results were obtained.
experiment [NO] [O2] initial rate

number / mol dm–3 / mol dm–3 / mol dm–3 s–1
1×3×4
1 0.032 0.012 4.08 10–3
( 7×2×4 0.024 )xg

2 0.032 8.15 10–3
3 xz 0.064 0.024 3.28 10–2
4 0.096 0.036
(i) Use the data in the table to determine the order with respect to each reactant. Show your
reasoning.
Experiments 142 concentration
of
of Oz doubles ,
:
as
Comparing
-
.............................................................................................................................................
rate also doubles Thus , wont Oz , it is a 1st Order Reaction

.
.............................................................................................................................................
.
Comparing Experiments 243 as : concentration

-
NO doubles ,
.............................................................................................................................................
Order Reaction
rate quadruples Thus , wit NO it is a 2nd
.............................................................................................................................................
.
,
.
(ii) Calculate the initial rate in experiment 4. Give your answer to two significant figures.
Land 4 :-[ NO ] triples and CO2 ] triples

Comparing Experiments
Rate =
(32×3) (4.08×10-3)
=
0.11016 mold m
-
351 0.11
initial rate = ............................. mol dm–3 s–1
(iii) Write the rate equation for this reaction.

]
'
R KENO
-
] Oz [
.............................................................................................................................................
-
(iv) Use the results of experiment 1 to calculate the rate constant, k, for this reaction.
Include the units of k.
4.08×10-3 = K [0.032510-022]
k= 4.08×10-3 =
332
123×10-5
332
rate constant, k = .......................................... mot Zdmb
-
units ..........................................
51
[6]
© UCLES 2014 9701/41/O/N/14

171
3
(b) (i) On the following axes
● draw two Boltzmann distribution curves, at two different temperatures, T1 and T2 (T2 > T1),
● label the curves and the axes.
ng
:*:
YI Ea
.
C KE )
Energy
(ii) State and explain, using your diagram, the effect of increasing temperature on the rate of
reaction.
temperature increases , the rate also increases This is

As .............................................................................................................................................
.
because more particles have energy greater than the

.............................................................................................................................................
activation the
energy This increases frequency of successful
.............................................................................................................................................
.
[5]
collisions .
(c) The compound nitrosyl fluoride, NOF, can be formed by the following reaction.
2NO(g) + F2(g) 2NOF(g)
The rate is first order with respect to NO and F2.

The reaction mechanism has two steps.
Suggest equations for the two steps of this mechanism, stating which is the rate determining °
slower step.
steel ; institutes
....................................................................................................................................................
as
....................................................................................................................................................
I is the rate
Step determining step
-
.............................................................................................................................................. [2]
[N’14 P41 Q1]
[Total: 13]

172
4
13
2 (a) Bromate(V) ions, BrO3–, react with bromide ions in the presence of acid to produce bromine.
Write an ionic equation for this reaction.
05+5 Br 6 Ht 3h20
-
Br t 3 Brat
....................................................................................................................................................
.............................................................................................................................................. [2]
(b) The initial rate of this reaction was measured, starting with different concentrations of the three
reactants.
The following results were obtained.
experiment [BrO3–] [Br –] [H+] initial rate

number / mol dm–3 / mol dm–3 / mol dm–3 / mol dm–3 s–1
1 0.040 0.020 0.50 2.64 10–4

2
3
4
0.040
0.040
0.080
:4
I( I
0.020
0.080
0.020
. 1.00
0.50
0.50
1.06
1.06
5.21
10–3
10
10
–3
–4
BY
.
(i) Use the data in the table to determine the order with respect to each reactant. Show your
reasoning.
Experiments I and 4 :as [ Br 05 ] doubles , rate also doubles .
.............................................................................................................................................
-
Thus it is a 1st Order Reaction Experiments Land 3 .
.............................................................................................................................................
: -
[ Br ] quadruples does Thus rate it is a Order 1st

-
so
as .............................................................................................................................................
.
, ,
Reaction Experiments I and 2 as [ Ht ) doubles rate quadruples

:
.............................................................................................................................................
. -
,
.
Thus , reaction is 2nd Order .
(ii) Write the rate equation for this reaction. '
] L Br HH 'T
-
rate -
k C Br 05
.............................................................................................................................................
.
(iii) Use the results of experiment 1 to calculate the rate constant, k, for this reaction.
Include the units of k.
5)
2
2.64 × 10-4 -
-
K [ 0.04 ] [ 0.02 ] CO .
1. 32 mot 3dm 951

-
rate constant, k = .......................................... units ..........................................

[6]
[N’14 P43 Q2]
[Total: 8]
© UCLES 2014 9701/43/O/N/14

6
173
6
4 In aqueous solution, 2-chloro-2-methylpropane, (CH3)3CCl, reacts with sodium hydroxide, NaOH.
4 This
14 is a nucleophilic
In aqueous solution, substitution reaction.
2-chloro-2-methylpropane, (CH3)3CCl, reacts with sodium hydroxide, NaOH.
This is a nucleophilic substitution reaction.
(CH3)3CCl (aq) + NaOH(aq) (CH3)3COH(aq) + NaCl (aq)
(CH3)3CCl (aq) + NaOH(aq) (CH3)3COH(aq) + NaCl (aq)
(a) Show the mechanism for this reaction. Include all necessary curly arrows, lone pairs and
(a) relevant
Show thedipoles.
mechanism for this reaction. Include all necessary curly arrows, lone pairs and
relevant dipoles.
H3C•BBB
C Hs
Sts
¢
8
Hsc
-
Hsc :CI
-
-
- -
C Cl tzc -
-
OH +
[ CHS
:-O,
[3]
[3]
The rate of this reaction was investigated using a large excess of sodium hydroxide.
The rate of this reaction was investigated using a large excess of sodium hydroxide.
(b) The graph below shows the results of the experiment.
(b) The graph below shows the results of the experiment.
0.60
0.60
0.50
0.50
0.40
0.40
[(CH3)33)CCl
[(CH ]
3CCl ] 0.30
/ mo 0.30
/ mol dm
–3
l dm–3
0.20
0.20 •
0.10
0.10
00
00 20
20 40 50 60
60 88 00 100
100 120
120 140
140 160
160
time //ss
time
©©UCLES
UCLES2015
2015 9701/41/O/N/15
9701/41/O/N/15

174
7
) CCl
3 3
using half-lives.
(i) What is meant by the half-life of a reaction?

It is the time taken the concentration
for of a
.............................................................................................................................................
reactant to fall to half
of its original value
.......................................................................................................................................
.
[1]
(ii) Calculate the half-life for this reaction. Show all your working and show clearly any
construction lines on the graph.
1st Half life -
= 505
100
2nd Half life s
-
-
-
Half life - -
-
LOOS -
505=50 [1]
(iii) What would be the effect on the half-life of this reaction if the initial concentration of
[(CH3)3CCl ] was doubled?
There would the half life

be no
effecton
-
....................................................................................................................................... [1]
.
(c) (i) Use the graph in (b) to determine the rate of reaction at 80 s.
Show all your working.
rate mold m-351

0.41=2.73×10-3
=
150
'
2.73×10-3 mi 35
rate = ............................. units mold
............................. [2]
The rate equation for this reaction is shown.
rate = k [(CH3)3CCl ]
(ii) Calculate the value of the rate constant, k, for this reaction and give its units.
2. 73×10-3 = k [ 0.19 ]
K = 0.0143
I
0.0143 S
-
k = ............................. units ............................. [1]

[N’15 P41 Q4]
[Total: 9]

175
8
4
15 (a) Ethanal, CH3CHO, dimerises in alkaline solution according to the following equation.
2CH3CHO CH3CH(OH)CH2CHO
The initial rate of this reaction was measured, starting with different concentrations of CH3CHO
and OH–. The following results were obtained.
initial rate of reaction

[CH3CHO] / mol dm–3 [OH–] / mol dm–3
(relative values)
×2 0.10 0.015 XZ 1
( 0.20 (
1×4
0.015 2
0.40 yxz
0.030yxz 8
(i) Deduce the order of the reaction with respect to CH3CHO.
1st Order
....................................................................................................................................... [1]
(ii) Deduce the order of the reaction with respect to OH–.

1st Order
....................................................................................................................................... [1]
(iii) State the overall rate equation for this reaction.

kCCH3CHO][ OH ]
rate = ............................................................................................................................ [1]
(iv) State the units for the rate constant, k.

-2
MOI -1dm 's
....................................................................................................................................... [1]
(v) Calculate the initial rate of reaction (relative value) for a reaction where the [CH3CHO] is
0.30 mol dm–3 and [OH–] is 0.030 mol dm–3.
rate -_kCCH3CHO][
OH ]
rate -_ 666.610.30 ][ 0.030 ]

[1]
= Gmoldm -35 ?
© UCLES 2016 9701/42/F/M/16

176
9
(b) (i) A three-step mechanism has been proposed for the reaction in (a).
O O
step 1 CH3 C + –
OH –
CH2 C + H 2O
H H
O O O
–
O
step 2 CH3 C + –
CH2 C CH3 C CH2 C
H H H H
–
O O OH O
step 3 CH3 C CH2 C + H 2O CH3 C CH2 C + –
OH
H H H H
Using your rate equation in (iii), predict which is the rate-determining step.
1
rate-determining step ...........................
reactant in the
Both the species are present
explanation .........................................................................................................................
1st Step which is the rate

determining step
.............................................................................................................................................
-
.
,
[2]
(ii) Describe the chemical behaviour of CH3CHO in step 1.
It behaves as a Brons ted

Lowry Acid , as it is
-
an
Ht [1] donor
....................................................................................................................................... .
(c) Name the mechanism occurring in steps 2 and 3.

It is Addition
Nucleophilic
..............................................................................................................................................
.
[1]
(d) Using the diagram below, show the mechanism for step 2 showing the relevant curly arrows
and dipoles.
g -
O
ra
CH3 C '
f
H
O
–
CH2 C
H
[2]
[M’16 P42 Q4]
[Total: 11]
© UCLES 2016 9701/42/F/M/16 [Turn over

177
4
16
3
methane.
2H2S(g) + CH4(g) CS2(g) + 4H2(g)
(a) Write the expression for Kp for this reaction, and state its units.
Kp =
units .............................
[2]
(b) The initial partial pressures of the two gases in a mixture at 1000 K are recorded.
H2S(g) 200 atm CH4(g) 100 atm
The mixture is left to reach equilibrium.
It is found that the equilibrium partial pressure of CS2(g) is 2 atm and that of the remaining
CH4(g) is 98 atm.
(i) Calculate the equilibrium partial pressures of H2S(g) and H2(g).
p(H2S) = ............................. atm
p(H2) = ............................. atm

[2]
(ii) Calculate the value of Kp at this temperature.
Kp = ............................. [1]
© UCLES 2016 9701/41/M/J/16

178
5
(c) (i) Predict the sign of S o for this reaction. Explain your answer.
2H2S(g) + CH4(g) CS2(g) + 4H2(g) H o = +241 kJ mol–1
.............................................................................................................................................
....................................................................................................................................... [1]
The free energy change, G o, for this reaction at 1000 K is +51 kJ mol–1.
(ii) Calculate the value of S o for this reaction, stating its units.
S o = ............................. units ............................. [2]
(d) How would the value of G o, and hence the spontaneity (feasibility) of this reaction change as
the temperature increases? Explain your answer.
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [2]
[J’16 P43 Q3]
[Total: 10]

179
14
17
6 The reaction between 1-chloro-1-phenylethane and hydroxide ions to produce 1-phenylethanol is:
C6H5CHCl CH3 + OH– C6H5CH(OH)CH3 + Cl –

1-chloro-1-phenylethane 1-phenylethanol
The rate of this reaction can be studied by measuring the amount of hydroxide ions that remain in
solution at a given time. The reaction can effectively be stopped if the solution is diluted with an
ice-cold solvent.
(a) Describe a suitable method for studying the rate of this reaction at a temperature of 40 C,
given the following.
–3
1-chloro-1-phenylethane, labelled A
–3
sodium hydroxide, labelled B
–3
HCl
Method :3 e fore ensure that both solutions

mixing ,
....................................................................................................................................................
,
A and B are at 40°C Mix known volumes
of solutions
....................................................................................................................................................
.
A and B , then start the clock and add

a pH meter .
....................................................................................................................................................
Then at a known time , remove a
sample of mixture
....................................................................................................................................................
,
and add it to the ice cold solvent Titrate it

against
- .
....................................................................................................................................................
HCl and then record the pH Repeat this
by titrating
.
....................................................................................................................................................
samples at regular intervals and record the

pH readings
....................................................................................................................................................
at the known time intervals
..............................................................................................................................................
.
[4]
(b) The rate of this reaction was measured at different initial concentrations of the two reagents.
The table shows the results obtained.
[C6H5CHCl CH3] [OH–]

experiment relative rate
/ mol dm–3 / mol dm–3
( 0.10 ( 0.20 ( 1.0

1 112 0.05 x 2 0.10 X 2 0.5
2
3 0.15 0.10 1.5
4 0.20 0.15 to be calculated
(i) Deduce the order of reaction with respect to each of [C6H5CHCl CH3] and [OH–].
Explain your reasoning.
Experiments 2dg 3 : as
order with respect to [C6H5CHCl CH3] ................................................................................. -
]
[ Cs Hs CHU CH 3 is trebled , so is rate Hence 1st Order
.............................................................................................................................................
. .
,
Experiments I :
42
as both the
order with respect to [OH–] .................................................................................................
-
concentrations are doubled so is rate Hence 0 Order

.............................................................................................................................................
.
, , [2]
as C OH I has effect rate
-
no on .
© UCLES 2017 9701/41/M/J/17

180
15
(ii) Write the rate equation for this reaction, stating the units of the rate constant, k.
KCCGHSCHCICH 's ]
rate = ............................................................................................................... mol dm–3 s–1
I
g-
units of k = ..........................................................................................................................
[1]
(iii) Calculate the relative rate for experiment 4. 1<=10
rate -_
1010.203=2.0
2.0
relative rate for experiment 4 = .............................. [1]
(c) (i) Use your answers in (b)(i) to help you to draw the mechanism for the reaction of
1-chloro-1-phenylethane with hydroxide ions, including the following.
SNI
Ctµ
Cst
8-
p
Cl OH
µ
( H cats H
C
CH
Colts CH 's '
c CHZ
-
,
a. OH
-
CGHS
[3]
(ii) This reaction was carried out using a single optical isomer of 1-chloro-1-phenylethane.
Use your mechanism in (i) to predict whether the product will be a single optical isomer or
a mixture of two optical isomers. Explain your answer.
Being SNI , the mixture of two optical isomers is formed , because

.............................................................................................................................................
the.......................................................................................................................................
intermediate is planar and the nucleophile COAT can [1]
approach from topor bottom or direction
any
.
[J’17 P43 Q5]

181
4
182 (a) Complete the table to show how both AgNO3(aq) and NH3(aq) could be used to distinguish
between solutions of NaCl (aq) and NaI(aq).
test performed observation with NaCl observation with NaI
Add AGN 03 Cag ) Cl forms white

-
-
a
ppt . I forms a
yellow ppt
.
Add NH 3
cap ppt .
dissolves ppt .
is insoluble
[2]
Important information for this question
+
(pr) and I–(pr).
The reaction between 2-chlorobutane and sodium iodide in propanone is shown.
CH3CH2CHCl CH3(pr) + Na+(pr) + I–(pr) CH3CH2CHICH3(pr) + NaCl (s)
The rate of this reaction can be investigated by measuring the electrical conductivity of the reaction
mixture. The electrical conductivity changes as the reaction progresses due to the precipitation of
the NaCl produced.
(b) (i) Suggest how the electrical conductivity will change as the reaction proceeds. Explain your
answer.
This because the
The
conductivity will decrease number
is
.............................................................................................................................................
.
of Natl
-
I ions will decrease as being used up[1]

they
are
.......................................................................................................................................
,
.
(ii) Describe a suitable method for studying the rate of this reaction at a temperature of 40 C,
using the following.
in propanone
Method :
Ensure that both solutions are at 40°C This
.............................................................................................................................................
.
be done a water bath Mix known volumes

using
.............................................................................................................................................
can .
of known solutions and start the clock Measure

.............................................................................................................................................
.
conductance at
regular intervals Prepare a curve
.............................................................................................................................................
.
conductance
against time this
experiment
for Repeat
.............................................................................................................................................
.
at different concentrations
.............................................................................................................................................
.
.............................................................................................................................................
....................................................................................................................................... [3]
© UCLES 2017 9701/42/M/J/17

182
5
(c) The rate of this reaction was measured at different initial concentrations of the two reagents.
[CH3CH2CHCl CH3]
experiment [I–] / mol dm–3 relative rate
/ mol dm–3
1 0.06 0.03 3
( 0.10 tf
" " " "
2
3 0.06
0.03
0.05
)×w , 5
5
) xs.si .
(i) Deduce the order of reaction with respect to each of [CH3CH2CHCl CH3] and [I–].
Explain your reasoning.
Experiments I and 2 : as
order with respect to [CH3CH2CHCl CH3] ............................................................................
-
concentration increases by 167 , so does rate so 1st Order

.............................................................................................................................................
;
.
Experiments I and 3 as : concentration

order with respect to [I–] .....................................................................................................
-
increases
by 2.67 so does rate so 1st Order
.............................................................................................................................................
.
, ;
[2]
(ii) Write the rate equation for this reaction, stating the units of the rate constant, k.
K C CH 3GHz CH Cl CH 3) IT [
rate = ............................................................................................................... mol dm–3 s–1
I
MOI 1dm 3g
-
-
units of k = ..........................................................................................................................
[1]
(iii) Calculate the relative rate for experiment 4.
K =
3 1666.7
0.06 XO .
03
5. 3
relative rate for experiment 4 = .............................. [1]
rate =
16667-[0-08] [ 0.04 ]
= 5.3

183
6
(d) (i) Suggest the mechanism for the reaction of 2-chlorobutane with iodide ions. Draw out the
steps involved, including the following.
A Either sN1orSNz can be shown .
SNL
Cst
④Ct
g-
I
H H
Hsc .
C
H
X.
[ CH tho
,
CH
Hscz
's
Hscz CH , -
: I [3]
(ii) This reaction was carried out using a single optical isomer of 2-chlorobutane.
Use your mechanism in (i) to predict whether the product will be a single optical isomer or
a mixture of two optical isomers. Explain your answer.
SNI , a
Being mixture
of two optical isomers will be
.............................................................................................................................................
and the intermediate
formed can be formed
by the [1]
.......................................................................................................................................
the topor
nucleophile II approaching from
-
[J’17 P42 Q2]

(e) (i) State the number of peaks that would be seen in the carbon-13 NMR spectrum of
bottom plane
CH3CH2CHCl CH3.
.
....................................................................................................................................... [1]
(ii) There are two isomers of CH3CH2CHCl CH3 that have fewer peaks in their carbon-13
NMR spectra than CH3CH2CHCl CH3.
Draw the structures of the isomers and state the number of peaks for each isomer.
isomer 1 isomer 2
number of peaks = .............................. number of peaks = ..............................

[3]
[Total: 18]
© UCLES 2017 9701/42/M/J/17

2

184
19
1 The compound nitrosyl bromide, NOBr, can be formed by the reaction shown.
2NO + Br2 2NOBr
(a) Using oxidation numbers, explain why this reaction is a redox reaction.
This is a redox reaction because N is oxidised as its
....................................................................................................................................................
oxidation number
changes from +2 to -13 ; and Bra
....................................................................................................................................................
reduced as its oxidation 0 to -1 [2]
changes from
number
is...............................................................................................................................................
(b) Nitrosyl bromide contains a trivalent nitrogen atom.
Draw the ‘dot-and-cross’ diagram for NOBr. Show outer electrons only.
Be A
O .
.
N .
Br
[2]
(c) The rate of the reaction was measured at various concentrations of the two reactants, NO and
Br2, and the following results were obtained.
initial rate
experiment [NO] / mol dm–3 [Br2] / mol dm–3
20-3×3
/ mol dm–3 s–1 K =3 4 .
1 0.03 0.02 3.4 10 –3
( 0.04 (00372×6.02)
"
2 0.03 6.8 10–3 1×2
3 ( 0.09 0.04 xgg 6.1 10–2
K -
-
188.9
The general form of the rate equation for this reaction is as follows.
rate = k [NO]a[Br2]b
(i) What is meant by the term order of reaction with respect to a particular reagent?
It is the power to which the concentration of a

.............................................................................................................................................
raised in a rate
is
reactant equation
.......................................................................................................................................
.
[1]
© UCLES 2017 9701/41/O/N/17

185
3
(ii) Use the data in the table to deduce the values of a and b in the rate equation.
Show your reasoning.
Concentration doubles and so does
Experiments 142 :
.............................................................................................................................................
-
rate Hence , b I as Brz -

1st Order =
.............................................................................................................................................
.
- .
Experiments 243
As
:
concentration changes by x3 ,
.............................................................................................................................................
-
rate changes by X 9 Hence , a 2 as [ NO ] .

-
- 2nd Order=
....................................................................................................................................... [2] .
(iii) Use the data in the table to calculate the initial rate for experiment 4.
' '
rate = k [ NO ] [ Bra ]
=
188.9 (0.22340-06) o.gg
initial rate = .............................. mol dm–3 s–1 [1]
(iv) Use the results of experiment 1 to calculate the rate constant, k, for this reaction.
Include the units of k. ' '
rate = k [ NO ] [ Bra ]
0.0034CO K 0334002 ]
's
-1
.
=
288.9 mot 2dm

-
rate constant, k = ............................. units ............................. [2]
(v) By considering the rate equation, explain why the rate decreases with decreasing
temperature.
As the temperature decreases , k also decreases

.............................................................................................................................................
.
Hence the rate decreases

.......................................................................................................................................
.
[1]
(d) The reaction between X and Y was studied.
2X + Y Z
The following sequence of steps is a proposed mechanism for the reaction.
step 1 2X V
step 2 V + Y Z
The general form of the rate equation for this reaction is as follows.
rate = k [X]m[Y]n
Step 1 is the slower step in the mechanism.
Deduce the values of m and n in the rate equation.

2
m = ..................................................................
O
n = .................................................................
[1]
[N’17 P41 Q1]
[Total: 12]

2

186
20
1 The compound chlorine dioxide, Cl O2, can be prepared by the reaction shown.
1
NaCl O2 + 2 Cl 2 Cl O2 + NaCl
(a) Using oxidation numbers, explain why this reaction is a redox reaction.
is a redox reaction because Cl is oxidised
This....................................................................................................................................................
as
,
its oxidation number

changes from -13 to -14 Ck is .
....................................................................................................................................................
reduced its oxidation number 0 to I
changes from
as
..............................................................................................................................................
, [2]
- .
(b) The central atom in the molecule of Cl O2 is chlorine.
Draw the ‘dot-and-cross’ diagram for Cl O2. Show outer electrons only.
• •
O Cl O
a. •
Be
as
Op
[2]
(c) The reaction between Cl O2 and F2 is shown.
2Cl O2 + F2 2Cl O2F
The rate of the reaction was measured at various concentrations of the two reactants and the
following results were obtained.
experiment [Cl O2] / mol dm–3 [F2] / mol dm–3

initial rate K = 2.20×10-3
/ mol dm–3 s–1
1 0.010 0.060 2.20 10–3 ( 0.01 ) C 0.06 )

3 to be calculated 0.040 7.04 10–3 K =3 .
66
The rate equation is rate = k [Cl O2][F2].
(i) What is meant by the term order of reaction with respect to a particular reagent?
It is the concentration to which the

power of a
.............................................................................................................................................
is raised in a rate equations

reagent
.......................................................................................................................................
.
[1]
© UCLES 2017 9701/42/O/N/17

187
3
(ii) Use the results of experiment 1 to calculate the rate constant, k, for this reaction.
Include the units of k. 1027 C Fz rate = KCC ]
K C 0.01 ) C 0.06 ) )
( 0.0022 = x
3. 7 mot 1dm 351 [2]

-
rate constant, k = ............................. units .............................
(iii) Use the data in the table to calculate
rate = KCC 1027 C Fz ]

=3 .
66×0.025×0.06
=
5.5×10-3 5.50×10-3
initial rate = ............................. mol dm–3 s–1
l O2] in experiment 3.
704×20-3=3.66 (a) ( Or 04 )
= Or 048
0.048
[Cl O2] = ............................. mol dm–3
[2]
(d) (i) What is meant by the term rate-determining step?

The rate
determining step is the slowest step in a
.............................................................................................................................................
-
multi step reaction

.......................................................................................................................................
- .
[1]
(ii) The equation for the reaction between Cl O2 and F2 is shown.
2Cl O2 + F2 2Cl O2F
rate = k [Cl O2][F2]
The mechanism for this reaction has two steps.
Suggest equations for the two steps of this mechanism, stating which of the two steps is
the rate-determining step.
CIO z t Fz CIO z → Fz
step 1 ..................................................................................................................................
CIO 2 t Cl Oz Fz → 2002 F
step 2 ..................................................................................................................................
.
I
rate-determining step = ............................. step
[2]
'
(e) By considering the rate equation, explain why the rate increases with increasing temperature.
As increases K also increases Thus , the
temperature
....................................................................................................................................................
,
.
rate increases
..............................................................................................................................................
.
[1]
[N’17 P42 Q1]
[Total: 13]

188
4
212 Nitrogen monoxide, NO(g), reacts with hydrogen, H2(g), under certain conditions.
2NO(g) + 2H2(g) N2(g) + 2H2O(g)
(a) rate of reaction.

It is the concentration
of
in
change a
....................................................................................................................................................
time
per unit
reactant
..............................................................................................................................................
.
[1]
(b) Identify a change in the reaction mixture that would enable the rate of this reaction to be
studied.
The decrease in
pressure
.............................................................................................................................................. [1]
.
The rate equation for this reaction is given.
rate = k [NO]2[H2]
The result of an experiment in which NO reacted with H2 is shown in the table.
initial [NO] / mol dm–3 initial [H2] / mol dm–3 initial rate of reaction / mol dm–3 s–1
2.50 10–3 2.50 10–3 1.27 10–3
(c) Use the data and the rate equation to calculate a value for the rate constant k.
Give the units of k.
c Hz ]
'
rate -
- K C NO ]
1.27×10 K 3) 2x (2.5×10-3)
-
x C 2.5×10
8. 13×104
k = ..............................
' I
2dm
-
mot
-
s
units = ..............................
[2]
(d) A second experiment is performed at the same temperature. The initial concentration of H2(g)
is 4.60 10–3 mol dm–3. The initial rate of the reaction is 2.31 10–3 mol dm–3 s–1.
Calculate the initial concentration of NO(g).
c Hz ]
'
rate -
- K C NO ] -
2. 31×10-3=(8.13×104) ( 4.6×10-3 ) x ( n )
×
2. 49×20-3
initial concentration of NO(g) = .............................. mol dm–3 [1]
© UCLES 2018 9701/41/M/J/18

189
5
(e) State the order of the reaction with respect to NO(g) and with respect to H2(g), and the overall
order of the reaction.
[NO] 2
[H2] I
overall order 3
[1]
(f) The reaction is believed to proceed in three steps.
1 2NO N2O2
2 N2O2 + H2 N2O + H2O
3 N2O + H2 N2 + H2O
(i) Deduce which of the three steps is the rate-determining step.
2
....................................................................................................................................... [1]
(ii) Explain your answer to (i).

It is the slowest
step or the rate
determining
-
.............................................................................................................................................
because it is the total both I
step of steps and
.............................................................................................................................................
it contains two NO Hz
2.......................................................................................................................................
i.e and one
; [1]
.

190
6
(g) A third experiment is performed under different conditions. A small amount of H2(g) of
concentration 0.0200 mol dm–3 is mixed with a large excess of NO(g). The concentration of
H2(g) is found to have a constant half-life of 2.00 seconds under the conditions used.
(i) half-life.
It is the time taken for the concentration to

.............................................................................................................................................
become its original

half of value
.......................................................................................................................................
.
[1]
(ii) Use the axes below to construct a graph of the variation in the concentration of H2(g)
0.02
-
[H2] / mo l dm–3
0.01
0
0 1 2 3 4 5 6
time / s
[2]
[J’18 P41 Q2]
(h) NO(g) acts as a catalyst in the oxidation of atmospheric sulfur dioxide.
(i) Give two equations to describe how NO(g) acts as a catalyst in this process.
equation 1 ...........................................................................................................................
equation 2 ...........................................................................................................................
[1]
(ii) Explain why NO(g) can be described as a catalyst in this reaction.
.............................................................................................................................................
....................................................................................................................................... [1]
(iii) Describe, with the aid of an equation, an environmental consequence of the oxidation of
atmospheric sulfur dioxide.
.............................................................................................................................................
....................................................................................................................................... [1]
[Total: 14]
© UCLES 2018 9701/41/M/J/18

191
4
222 Iodine monochloride, ICl, is a yellow-brown gas. It reacts with hydrogen gas under certain conditions
as shown.
2ICl (g) + H2(g) 2HCl (g) + I2(g)
Experiments are performed using different starting concentrations of ICl and H2. The initial rate of
each reaction is measured. The following results are obtained.
relative rate
experiment [ICl ] / mol dm–3 [H2] / mol dm–3
of reaction
1×1751.75 )
1 4.00 10–3 4.00 10–3 1.00 175
X
2 4.00 10 –3
7.00 10 –3
3 4.00 10–3 1.00 10–2 2.50
ay (
4 x 5.00 10–3 8.00 10–3 x 14 2.50
5 7.00 10–3 8.00 10–3 3.50
(a) Identify a change, taking place in the reaction mixture, that would enable measurements of the
rate of this reaction to be made.
colour be observed
Change in can
.............................................................................................................................................. [1]
.
(b) 2 (g).
Experiments 1dg 2 :
....................................................................................................................................................
When rate of reaction increases

by 1.75 ,
the
....................................................................................................................................................
concentration
of Hz increases 275 also
by
....................................................................................................................................................
increases and that ICI

of stays unchanged
.............................................................................................................................................. [1]
.
(c) ICl (g).
Experiments 445 :
....................................................................................................................................................
When rate increases

by 1.4 , the concentration
....................................................................................................................................................
ICI also 1.4 ; and that H2
of increases
by of
....................................................................................................................................................
stays unchanged
.............................................................................................................................................. [1]
.
(d) Complete the rate equation for the reaction between ICl (g) and H2(g).
KCI CDC H2 ]
rate = ................................................................................................................................... [1]
© UCLES 2018 9701/42/M/J/18

192
5
(e) Use experiment 3 to calculate a numerical value for the rate constant, k.
rate KCI CDC H2 ]
6.25×104
-
K 4.00×10 3) (1.00×10-2) k = .............................. [1]

-
2.5 = C
K = 6.25×104
(f) The reaction 2ICl (g) + H2(g) 2HCl (g) + I2 ICl
order with respect to H2(g).
Suggest a mechanism for this reaction. You should assume
ICI t Hz HCl t HI
........................................................................
HI t ICI
second step ................................................ HCl t I 2
........................................................................
[2]
(g) 2(g). This

method uses a large excess of ICl (g) and measures how the concentration of H2(g) varies with
time.
(i)
H2(g) concentration.
Plot concentration of Hz vs time A
a
graph of
.............................................................................................................................................
.
.
constant
life
shows that the reaction is 1st Order
half
determine
gradient
tangent
graph
Draw
time
a.
.............................................................................................................................................
.
concentration
concentration
theon and
.............................................................................................................................................
its gradient The .
concentration 1 at I
/ 2
.............................................................................................................................................
at 2
radiant
11g 2. Plot a graph of rate
.............................................................................................................................................
=
Hz It must be a
vs
of line
straight
. .
....................................................................................................................................... [3]
through the origin of the graph .
(ii) Explain the reason for using a large excess of ICl (g).
Excess is used so that CICD remains
unchanged
.............................................................................................................................................
.
....................................................................................................................................... [1]
(h) A chemical reaction may be speeded up by the presence of a catalyst.
Explain why a catalyst increases the rate of a chemical reaction.
reaction
It provides an alternative route thefor
....................................................................................................................................................
with a lower Ea C activation ) Since more

.............................................................................................................................................. [1]
energy
.
number
of molecules have
energy greater than [J’18[Total:
P42 Q2]
12]
the Ea , the rate of reaction increases .

193
6
41 (a) The reaction between iodide ions and persulfate ions, S2O 82−, is slow. For
Examiner’s
2I− + S2O 82− I2 + 2SO 42− 1 Use
The reaction can be speeded up by adding a small amount of Fe2+ or Fe3+ ions. The
following two reactions then take place.
2I− + 2Fe3+ I2 + 2Fe2+ 2
2Fe2+ + S2O 82− 2Fe3+ + 2SO 42− 3
(i) What type of catalysis is occurring here?
Homogeneous
..................................................................................................................................
(ii) The rates of reactions 2 and 3 are both faster than that of reaction 1. By considering
the species involved in these reactions, suggest a reason for this.
In reactions 2 and 3 the ions are
oppositely charged and so attract
..................................................................................................................................
,
other In
reaction
similarly
ions
each..................................................................................................................................
the
I are charged and so
.
,
repel each other .
(iii) The following reaction pathway diagram shows the enthalpy profile of reaction 1.
T
enthalpy ^
progress of reaction
Use the same axes to draw the enthalpy profiles of reaction 2 followed by reaction
3, starting reaction 2 at the same enthalpy level as reaction 1.
[4]
© UCLES 2009 9701/04/M/J/09

194 7
(b) The oxidation of SO2 to SO3 in the atmosphere is speeded up by the presence of For
nitrogen oxides. Examiner’s
Use
(i) Describe the environmental significance of this reaction.
503 produces acid rain which lowers the pH of lakes

.................................................................................................................................. .
(ii) Describe a major source of SO2 in the atmosphere.

The combustion of fossil fuels is a major source of 502
.................................................................................................................................. .
(iii) By means of suitable equations, show how nitrogen oxides speed up this reaction.
502 t NO 2 503 t NO
..................................................................................................................................
NO + NO 2
2102
..................................................................................................................................
[4]
[J’17 P42 Q2]
[Total: 8]
3
(c)
2 When aqueous solutions of KI and K2S2O8 are mixed almost no reaction occurs, but when a
few drops of Fe2+(aq) or Fe3+(aq) are added, iodine, I2(aq), is produced at a steady rate.
(i) Write an equation for the overall reaction.
Iraq
"
25042
-
2 I 5208 )
-
) t ) t
Cag Cag
.............................................................................................................................................
(ii) State the precise role of the iron ions during this reaction.
C Fest ) act as
Iron ions homogeneous catalysts
.............................................................................................................................................
.
(iii) By means of equations or otherwise, explain why the presence of either Fe2+ or Fe3+ is able
to speed up the reaction.
"
2 Fest + 2 I 2 Fe Iz
-
+ .
.............................................................................................................................................
2 Fe 3++25047
"
2 Fe 52082
-
t
.............................................................................................................................................
The reactants are both negative ions , so would also

they
.............................................................................................................................................
[3]
repel each other .
[Total: 14]

195
4
For
23 Nitrogen oxides in the atmosphere are homogeneous catalysts in the formation of acid rain. Examiner’
Use
(a) What is meant by the following terms?
catalyst
the rate reaction the Ea

It ...........................................................................................................................................
speeds up of by lowering
( activation ) of the reaction and remains
energy unchanged
...........................................................................................................................................
at the end of the reaction .
homogeneous
and reagents are in the same

phase
Catalysts
...........................................................................................................................................
.
...........................................................................................................................................
[2]
(b) (i) State a major source of nitrogen oxides in the atmosphere, explaining how they are
formed.
Lightning
is a
major source of nitrogen oxides
....................................................................................................................................
.
They are formed

when
nitrogen reacts with
....................................................................................................................................
ire Nz t Oz
oxygen
....................................................................................................................................
.
;
(ii) Use equations to describe the chemical role played by nitrogen oxides in the
formation of acid rain.
502 t NO 2 503 t NO
....................................................................................................................................
NO t
I 02 NO 2
....................................................................................................................................
503 t H2O H 2504

....................................................................................................................................
....................................................................................................................................
[5]
© UCLES 2012 9701/43/O/N/12

196
5
For
(c) Use the following axes to draw a fully labelled reaction pathway diagram showing the Examiner’s
effect of a catalyst on an exothermic reaction. Label the H and Ea values. Use
says
•
Ea ( un catalysed )
Be
energy reactants
ed )
extent of reaction
[3]
[J’12 P43 Q2]
[Total: 10]

197
6
For
34 (a) Catalysts can be described as homogeneous or heterogeneous. Examiner
Use
(i) What is meant by the terms homogeneous and heterogeneous?
: Reactant and
the same
Catalyst are in
:!
....................................................................................................................................
pphhads
: Reactant and Catalyst are in different
....................................................................................................................................
(ii) By using iron and its compounds as examples, outline the different modes of action
of homogeneous and heterogeneous catalysis.
Choose one example of each type, and for each example you should
state what the catalyst is, and whether it is acting as a homogeneous or a

heterogeneous catalyst,
write a balanced equation for the reaction,
outline how the catalyst you have chosen works to decrease the activation
Homogeneous
Heterogeneous
energy.
Heterogeneous
.
Catalyst : Fe in the Haber Process

....................................................................................................................................
.
Homogeneous
Nz and Hz adsorb onto the surface of Fe
....................................................................................................................................
and this the bonds are weakened
during process ,
.
....................................................................................................................................
This makes them easier to break .
....................................................................................................................................
Nz
cop
t 3 Hz
cop
2 NH 3
Cop
....................................................................................................................................
.
Fees )
....................................................................................................................................
Once NHS is formed , it des orbs from the
....................................................................................................................................
surface .
....................................................................................................................................
"
Fe the reaction between
Catalyst : in
•
....................................................................................................................................
I and 52087 The catalysed reaction is
-
un
....................................................................................................................................
slow because the reactants
negatively charged
....................................................................................................................................
repel each other .
....................................................................................................................................
ZITA
opt
2
2504 Taq
-
5208 Iz
caq , , t ca
op
a
....................................................................................................................................
Reaction
Catalysed ,
Feisatopt
zcaopFe
-
Taff
Iiaq II
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
[8]
© UCLES
CEDAR 2012
COLLEGE 9701/41/O/N/12 REACTION KINETICS WS 2
1987
For
(b) The reaction between SO2, NO2 and O2 occurs in two steps. Examiner’s
Use
NO2 + SO2 NO + SO3 H 1o = –88 kJ mol –1
1
NO + 2 O2 NO2 H 2o = –57 kJ mol–1
The activation energy of the first reaction, Ea , is higher than that of the second reaction,
1
Ea .
2
Use the axes below to construct a fully-labelled reaction pathway diagram for this
reaction, labelling Ea , Ea , H 1o and H o2.
1 2
Dodd
÷¥¥
Tea
Ea I
NO2 + SO2
energy
BE dH2
-
I
-
57 KJ mot Noztsoz
fog
extent of reaction
[2]
[J’04 P4 Q3]
[Total: 10]
( W' 121013 )

199
8
45 (a) Chlorine dioxide undergoes the following reaction in aqueous solution.
2Cl O2 + 2OH– Cl O2– + Cl O3– + H2O
The initial rate of the reaction was measured at different initial concentrations of Cl O2 and OH–.
[Cl O2] [OH–] initial rate

experiment
/ mol dm–3 / mol dm–3 / mol dm–3 s–1
1 1.25 10–2 1.30 10–3 2.33 10–4

2
X 2
( 2.50 10–2 1.30
x
10–3
4 ( 9.34 10–4
3 2.50 10–2 2.60 10–3 1×2
1.87 10 ) –3 Xz
(i)
each reactant. Show your reasoning.
Experiments I and 2 : when CCI Oz ] doubles , the

.............................................................................................................................................
-
rate Hence , the reaction is 2nd Order

quadruples
.............................................................................................................................................
.
.
Experiments 2 and 3 when [ OH ] doubles the

.............................................................................................................................................
: -
rate also doubles Hence the reaction is 1st Order

.............................................................................................................................................
.
,
.
.............................................................................................................................................
.............................................................................................................................................
k C CIOs ] [ OH ]
'
rate equation = ............................................................

[3]
(ii) k State its

units.
k [ CIOs ] YOH I
-
rate =
'
9.34×10-4 = k [2.5×10-2] [2.30×10-3]

K -
-
1.15×103
1. 15×103
k = .............................. mot -2dm 51 [2]
'
units ..............................
(b) (i) Explain the difference between heterogeneous and homogeneous catalysts.
Homogeneous catalysts are in the same physical state

.............................................................................................................................................
reactants However , are in a
as the
heterogeneous catalysts
.............................................................................................................................................
.
different state from the reactants

physical
....................................................................................................................................... [1]
.
© UCLES 2017 9701/42/F/M/17

200
9
(ii) Complete the table using ticks ( ) to indicate whether the catalyst used in the reaction is
heterogeneous or homogeneous.
catalysed reaction heterogeneous homogeneous
manufacture of ammonia in the Haber process
removal of nitrogen oxides from car exhausts
oxidation of sulfur dioxide in the atmosphere

[2]
(c) Some reactions are catalysed by one of the products of the reaction. This is called autocatalysis.
VII 4
–
2 H)2. Mn 2+
ions catalyse this reaction. The reaction is slow in the
absence of a catalyst.
(i) Balance the equation for this reaction.
2
......MnO 6 + + ......(CO
+ ......H 5 2 20 8
2H)2 ......Mn + ......CO2 + ......H2O
– 2+
4
[2]
(ii) The graph shown is a concentration-time graph for a typical reaction.
concentration
of reactant
time
(i).
~
concentration
of MnO4–
time
[2]
© UCLES 2017 9701/42/F/M/17 [Turn over

201
10
(d) (i)
reaction. Suggest why catalysts are used in industrial processes.
Ea
¥¥uots
Reaction
uncatalysed
Energy Catalysed Reaction
activation Progress of Reaction

>
Catalyst lowers the C ) both

energy for
.............................................................................................................................................
forward and reverse reactions Hence the process

.............................................................................................................................................
.
less and occurs atalower temperature

requires energy
............................................................................................................................................. .
[3]
(ii) The reaction for the Haber process to produce ammonia is shown.
N2(g) + 3H2(g) 2NH3(g) H o = –92 kJ mol–1
At 500 Kp for this

equilibrium is 1.45 10–5.
Kp for this equilibrium.
"
( pNHs5 units = atm

Kp =
20×16013
3 at equilibrium at 500
of N2 is 20 atm and that of H2 is 60 atm.
At 500°C :
"
1.45×10 5=CpNH3 )
-
20×16033 7.91
pNH = .............................. atm
3
[2]
[M’17 P42 Q4]
PNH 3=7.91
[Total: 17]
© UCLES 2017 9701/42/F/M/17

tetrahedral [CuBr2Cl 2]2– .............................................................................................................
[3]
202
Cf )
(f)
6 Many enzymes contain transition metal complexes.
Describe, with the aid of a suitably labelled diagram, how an enzyme catalyses the breakdown
of a substrate molecule.
enzyme
substrate
Product
active site substrate enzyme
enzyme
-
complex
The shape of the substrate is to the

complementary
....................................................................................................................................................
active site The substrate binds to the
shape of the
....................................................................................................................................................
.
active site When the reaction is

completed , the products
....................................................................................................................................................
.
released The activation is lowered the [3]

are
energy by
..............................................................................................................................................
.
enzyme
.
[N’17 P42 Q6]

[Total: 13]
© UCLES 2017 9701/42/O/N/17

0 1 2 3 4 5 6
time / s
[2]
203
7 (h) NO(g) acts as a catalyst in the oxidation of atmospheric sulfur dioxide.
(i) Give two equations to describe how NO(g) acts as a catalyst in this process.
NO NOZ
-11202
equation 1 ...........................................................................................................................
NO 2+502 NO -1503
equation 2 ...........................................................................................................................
[1]
(ii) Explain why NO(g) can be described as a catalyst in this reaction.
Nags is regenerated ire it remains unchanged at

.............................................................................................................................................
,
the end of the reaction

.......................................................................................................................................
.
[1]
(iii) Describe, with the aid of an equation, an environmental consequence of the oxidation of
atmospheric sulfur dioxide.
503 t H2O Hzsoy

.............................................................................................................................................
Acid rain is formed which lowers the pH in lakes
.......................................................................................................................................
.
[1]
,
[J’18 P41 Q2]
[Total: 14]
© UCLES 2018 9701/41/M/J/18

Reaction Kinetics Answers PDF

Uploaded by

Copyright:

Available Formats

Reaction Kinetics Answers PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Reaction Kinetics Answers PDF

Uploaded by

Copyright:

Available Formats

149 For

NO(g) + !" O2(g) ⎯→ NO2(g)

[NO] [O2] initial rate

order with respect to NO 2nd Order

order with respect to O2 1st Order

numerical value of k = …………………………

© UCLES 2006 9701/04/M/J/06

CEDAR COLLEGE REACTION KINETICS WS 1

experiment [CH3CHO] [CH3OH] [H+]

3 0.25 0.16 0.05 2.00 ,

order with respect to [CH3OH]

order with respect to [H+]

(iii) mot -2dm

© UCLES 2011 9701/42/O/N/11

[CH3CHO] [CH3OH] [H+] [acetal A] [H2O]

at start 0.20 0.10 0.05 0.00 0.00

at equilibrium (0.20–x) GIO -

at equilibrium 0.275 0.05 0.05 0.025 0.025

[ CHEO ][ CHSOH) mot -1dm

Kc = ................................................................. units = ........................................

(a) What do you understand by the term order of reaction?

reagent is raised in a rate equation

(b) Construct a rate equation for the reaction.

rate = KCC COCH 33 H Has l 'T

[reactant] [reactant] [reactant]

time time time

(i) the propanone concentration,

(ii) the iodine concentration? B

CEDAR COLLEGE REACTION KINETICS WS 1

0 0.1 0.2 0.3

CH3COCH3 + H+ ⎯⎯→ intermediate ✓

zero order therefore it is not

CEDAR COLLEGE REACTION KINETICS WS 1

(i) Suggest a method you could use to measure [I2].

of known concentration starch indicator is added close to the end point

(iii) What are the units of k?

(i) Ka of methanoic acid.

(iv) Calculate the pH of this solution.

CEDAR COLLEGE REACTION KINETICS WS 1

41 A bromoalkane, R–Br, is hydrolysed by aqueous sodium hydroxide.

(a) (i) Write a balanced equation for this reaction.

(ii) What type of reaction is this?

time / min [R–Br] / mol dm–3

© UCLES 2013 9701/42/M/J/13

CEDAR COLLEGE REACTION KINETICS WS 1

1st half life 128mi -

2nd half life

[ 236-118=118 mins ) Ra [ RBD

rate rate Rx COH ]

rate = KLRBRILOH ] initial rate .

2NO(g) + Br2(g) 2NOBr(g) H = –23 kJ mol–1

The reaction has an activation energy of +5.4 kJ mol–1.

" " " no " ?

extent of the reaction

© UCLES 2013 9701/42/M/J/13 [Turn over

© UCLES 2013 9701/41/M/J/13

© UCLES 2013 9701/41/M/J/13

CEDAR COLLEGE REACTION KINETICS WS 1

rate = K[CH3C0zCHzCH3][ HCl ]