The university of Dodoma

College of Natural and Mathematical Sciences

Chemistry Department

CH 223: Chemical Kinetics and Catalysis

Instructor: Omari Sufiani

Tutorial solution
 Question 1
The following data were obtained in a second series of
experiments on the rate of reaction between
compounds M and N at a constant temperature.
Experiment Initial concentration Initial concentration Initial rate/mol dm-3s-
of M/mol dm-3 of N/mol dm-3 1
4 0.25 0.50 3.10 x 10-6
5 0.40 0.20 To be calculated

The rate equation for this reaction is rate=k[M]2[N]

i. Use the data from experiment 4 to calculate a vale for
the rate constant, kr at this temperature. State the
units of k.
Value for k………………………………………
Units of k……………………………………………..
ii. Calculate the value of initial rate in Experiment 5.
 Question 1
i. rate=k[M]2[N]
• 3.1 x 10-6 mol dm-3s-1=k[0.25]2[0.5]

3.1 x 10−6 mol dm−3s−1

• k= *0.25+2*0.5+
• 9.92 x 10 -5 mol-2 dm-6s-1
ii. Rate= 9.92 x 10 -5 x [0.4]2[0.2]
= 3.17 x 10-6 mol dm-3 s-1
 Question 2
(a) Explain how each of the following factors
affect the rate of reaction: Concentration of
reactants, Temperature, Nature of reactants,
Presence of a catalyst
(b) Explain the difference between the average
and instantaneous rate of a chemical
reaction.
 Question 2
• Rate= k[N2O5]
𝑅𝑎𝑡𝑒
• K=
*N2O5+
4.84 𝑥 10 ;4
• = = 5.2 x 10-3 s-1
0.093
9.67 𝑥 10;4
• = = 5.12 x 10-3 s-1
0.186
38.67 𝑥 10;4
• = = 5.2 x 10-3 s-1
0.745
 Question 3
(a)Suppose a reaction is of the nth order and
involves a single reactant of initial concentration
A0. A → Product
• Write the rate equation and deduce the
expression for rate constant.
• Solution
k
A → Product
 Question 3
;𝑑[𝐴]
• Rate = = k[A]n Rate equation
𝑑𝑡
𝐴𝑡 𝑑[𝐴]
• 𝐴0 𝐴 𝑛
= −𝑘 𝑑𝑡
1 1 1
• 𝑛 1 − 𝑛 1 = -kt
;𝑛:1 𝐴𝑡 ; 𝐴0 ;
1 1 1
k = 𝑛 1 −
𝑡(𝑛;1) 𝐴𝑡 ; 𝐴0𝑛;1
 Question 3
(b)A substance decomposes at 600 K with a rate
constant of 3.72 x 10-5 s-1
(i) Calculate the half life of the reaction (ii)
What fraction will remain undecomposed if
the substance is heated for 3 h at 600 K?
Solution
Rate= k[A]
Conc/s=k conc
K=s-1
 Question 3
𝑙𝑛2
• t1/2=
𝑘
• K= 3.72 x 10-5 s-1
𝑙𝑛2
• K=
3.72 x 10−5 s−1
• = 18629.03 s or 5.17 h
ii. A = A0e-kt
𝐴
• A0 = e-kt
• =exp(-3.72 x 10-5 x 3x60x60)
• =0.669
 Question 4
The variation in the partial pressure of
azomethane with time was followed at 600 K,
with the results given below. Confirm that the
decomposition is first-order in azomethane, and
find the rate constant at 600 K.
• CH3N2CH3(g) →CH3CH3(g) + N2(g)
t/s 0 1000 2000 3000 4000

p/Pa 10.9 7.63 5.32 3.71 2.59

 Question 3
• Plot ln(p/p0) against t
• The plot is straight, confirming a first-order
reaction, and its slope is −3.6 × 10−4.
• Therefore, kr = 3.6 × 10−4 s−1.
 Question 5
• The rate of formation of C in the reaction 2A +
3B → C + 4D is 2.7 mol dm-3 s -1. State the
rates of formation and consumption of the
participants
• Solution
𝑑[𝐶]
The rate of formation of C= = 2.7 𝑚𝑜𝑙𝑑𝑚 −
𝑑𝑡
3𝑠 − 1
;1 𝑑[𝐴] ;1 𝑑[𝐵] 𝑑[𝐶] 1 𝑑[𝐷]
Rate= = = =
2 𝑑𝑡 3 𝑑𝑡 𝑑𝑡 4 𝑑𝑡
 Question 5
• The rate of consumption of A
;𝑑[𝐴]
=2(2.7 𝑚𝑜𝑙𝑑𝑚 − 3𝑠 − 1)=5.4 moldm-3s-1
𝑑𝑡
𝑑[𝐵]
=3(2.7 𝑚𝑜𝑙𝑑𝑚 − 3𝑠 − 1)=8.1moldm-3s-1
𝑑𝑡
𝑑[𝐷]
=4 2.7 𝑚𝑜𝑙𝑑𝑚 − 3𝑠 − 1 = 10.8 𝑚𝑜𝑙𝑑𝑚 −
𝑑𝑡
3𝑠 − 1
 Question 6
• The stoichiometry equation for the oxidation
of bromine ions by hydrogen peroxide in
acidic solution is
• 2Br- + H2O2 + 2H+ →Br2 + 2H2O
• Since the reaction does not occur in one stage,
the rate equation does correspond to this
stoichiometric equation
v = k[H2O2][H+][Br- ]
 Question 6
(a) If the concentration of H2O2 is increased by a
factor of 3, by what factor is the rate of
consumption of Br- ions increased?
;1 𝑑[𝐵𝑟;] ;𝑑[H2O2] ;1 𝑑[H+] 𝑑[𝐵𝑟2]
Rate= = = = =
2 𝑑𝑡 𝑑𝑡 2 𝑑𝑡 𝑑𝑡
1 𝑑[H2O ]
2 𝑑𝑡
𝑑[𝐵𝑟;] ;𝑑[H2O2]
= 2( )
𝑑𝑡 𝑑𝑡
;[3]
=2
𝑑𝑡
The rate of consumption of Br- ions will increase six
times.
 Question 6
(b) If the rate of decomposition of Br- is 7.2 x 10-
3 mol dm-3 s-1, what is the rate of consumption

of hydrogen peroxide?
;𝑑[H2O2] ;1 𝑑[𝐵𝑟;]
=
𝑑𝑡 2 𝑑𝑡
;7.2 x 10−3 mol dm−3 s−11
=
2
=3.6 x 10-3 mol dm−3 s−1
 Question 6
( c) What is the effect on the rate constant k, of
increasing the concentration of Bromide ion?
Solution
There will be no effect on rate constant, k,
because k, does not depend on the
concentration of reactants.
 Question 6
(d) If by the addition of water to the reaction
mixture the total volume were doubled, what
would be the effect on the rate of change of
concentration of Br-? What would be the effect on
the rate constant k?
Solution
The addition of water will reduce the concentration
of Br- and the rate of change in its concentration
will be lowered.
There will be no effect on rate constant k because k
does not depend on the concentration of reactants.
 Question 7
A second-order reaction of the type A + B P was
carried out in a solution that was initially 0.075 mol
dm-3 in A and 0.060 mol dm-3 in B. After 1.0 h the
concentration of A had fallen to 0.020 mol dm-3. (a)
Calculate the rate constant (b) What is the half life
of the reactants?
Solution
[𝐴] 𝐴 0;𝑥
• Integrated rate: ln = 𝑙𝑛 = 𝐴 0−
[𝐵] 𝐵 0;𝑥
𝐴
𝐵 0𝑘𝑡 + 𝑙𝑛 0
𝐵 0
 Question 7
x= [A]0-[A]=[B]0-[B]=0.075-0.020=0.055
0.075;0.055 0.075
ln =(0.075-0.060)k(1x60x60)+ln
0.06;0.055 0.060
1.3863 = 66326k+ 0.0 2231
1.3863;0.02231
k=
66326
=1.754 x 10-5 dm3mol-1s-1
 Question 7
(b) Half life of reactants
1
t1/2=
𝐴 0𝑘
1
= = 760167.24 s 211.2 h
0.075𝑥1.754 x 10 −5
1
= = 712656.78 s or 197.96 h
0.08𝑥1.754 x 10−5
 Question 8
• The reaction between bromate ions and
bromide ions in acidic aqueous solution is
given by the following equation BrO3-(aq) +
5Br-(aq) + 6H+→3Br2 (g) + 3H2O (l)
• A kinetic study involving this reaction gave the
following results
 Question 8
Exp. [BrO3- ]0/M [Br-]0/M [H+]0/ M Initial rate/M s-1

1 0.1 0.1 0.1 8.0 x 110-4

2 0.2 0.1 0.1 16.0 x 10-4

3 0.2 0.2 0.1 32.0 x 10-4

4 0.1 0.1 0.2 32. x 10-4

Deduce the rate law for this reaction and determine

the value of the rate constant, k for the reaction.
 Question 8
• Solution
• Initial rate = k[BrO3- ]a [Br-]b [H+]c
• To determine order of reaction with respect to
BrO3- consider Exp. 1 and 2
• From Exp. 1
• 8.0 x 10-4 = k [0.1]a[0.1]b[0.1]c
• From Exp. 2
• 16.0 x 10-4 = k [0.2]a[0.1]b[0.1]c
 Question 8
• Take Exp. 1/Exp.2
8.0 x 10−4 k*0.1+a*0.1+b*0.1+c
• =
16.0 x 10−4 k*0.2+a*0.1+b*0.1+c
• a= 1
• Use Exp. 2 and 3 to determine order of Br-
16.0 x 10−4 k*0.2+a*0.1+b*0.1+c
• =
32.0 x 10−4 k*0.2+a*0.2+b*0.1+c
• b= 1
 Question 8
• Use Exp. 1 and 4 to determine order with
respect to H+
8.0 x 10−4 k*0.1+a*0.1+b*0.1+c
• =
32.0 x 10−4 k*0.1+a*0.1+b*0.2+c
• c=2
• Rate law
• Rate = k[BrO3- ][Br-][H+]2
 Question 8
• Exp. 1,2, 3 and 4 gives
8.0 x 10−4
• k= 2
*0.1+*0.1+*0.1+
• K= 8.0 M-3s-1
 Question 9
Given that the first-order rate constant for the
overall decomposition of N2O5 is k = (4.3 x 1013 s-
1)exp(-103000/RT), [The activation energy is in J

mol-1] calculate
(a) The half-life at -10 ˚C
(b) The time required for 90% reaction at 50 ˚C.
 Question 9
(a) k=4.3 x 1013 s-1exp(-103000/Rx 263)
ln 2
t1/2=
𝑘;10
𝑙𝑛2
=
4.3 x 1013 s−1exp(−103000/8.314x 263)
=1280 h.
(b) The time required for 90% reaction at 50 ˚C.
• A=A0e-kt
𝐴
• =e-kt
𝐴0
• 10=e-kt
 Question 9
𝑙𝑛10
• t=
𝑘
𝑙𝑛10
• =
4.3 x 1013 s−1exp(−103000/8.314x 323)
• 2428 s or 40.47 mins
 Question 10
The following table gives kinetic data for the
following reaction at 25 C:
• OCl¯ + I¯ → OI¯ + Cl¯
[OCl¯]/mol L-1 [I¯]/ mol L-1 [OH¯]/mol L-1 D[OI¯]/dt
10 − 4 mol L − 1 s − 1

0.0017 0.0017 1.0 1.75

0.0034 0.0017 1.0 3.50
0.0017 0.0034 1.0 3.50
0.0017 0.0017 0.5 3.50

What is the rate law of the reaction? What is

the value of the rate constant?
Same solution as in problem 6
 Question 11
• The rate of the second-order
decomposition of acetaldehyde (ethanal,
CH3CHO) was measured over the
temperature range 700 –1000 K, and the
rate constants are reported below. Find
the Arrhenius parameters Ea and A.
T/K 700 730 760 790 810 840 910 1000

K(dm3mo 0.011 0.035 0.105 0.343 0.789 2.17 20.0 145

l−1s−1)
 Question 11
• Plot ln K against 1/T
• From the graph intercept (pre-exponential
factor A) = 6.01
• Slope=5.696
𝐸𝑎
• slope=
𝑅
• Ea= slope x R
• =5.696 x 8.314
• =47.36 J
 Question 12
• The rate constant for the decomposition of
a certain substance is 2.80 × 10−3 dm3
mol−1 s−1 at 30°C and 1.38 × 10−2 dm3
mol−1 s−1 at 50°C. Evaluate the Arrhenius
parameters of the reaction.
• Solution
;𝐸𝑎 ;𝐸𝑎
lnk30= + ln 𝐴 and lnk50 = + ln 𝐴
𝑅𝑇30 𝑅𝑇50
 Question 12
;𝐸𝑎 ;𝐸𝑎
• Lnk30-ln50= + ln 𝐴 − + ln 𝐴
𝑅𝑇30 𝑅𝑇50
𝑙𝑛𝑘30 𝐸𝑎 1 1
• = −
𝑙𝑛𝑘50 𝑅 𝑇50 𝑇30
ln 2.80
× 10−3 𝐸𝑎 1 1
• = −
ln 1.38 × 10−2 8.314 323 303
• Ea=-5.582 J
;𝐸𝑎
• From lnk30= + ln 𝐴
𝑅𝑇30
;5.582
• ln2.8 x 10-3=- 𝑙𝑛𝐴 +
8.313𝑥303
• -5.878=-2.18 x 10-3 +lnA
• A=2.806 x 10-3
 Question 13
Define the terms in and limit the generality
of the expression lnk = lnA−Ea/RT.
Solution
k=rate constant
A=pre exponential factor
Ea=Activation energy
R=gas constant
T=kelvin (absolute) temperature
 Question 13
• The assumption that activation energy E and
pre-exponential factor A change with
temperature is approximate. If A and E don't
change seriously during the experimental
temperature range, Arrhenius equation can
be used. But it should be corrected if it's
used for extrapolation purpose. Moreover,
corrected Arrhenius equation has different
activation energy E and pre-exponential
factor A at different temperature range.
 Question 14
• At 518 oC, the rate of decomposition of a
sample of gaseous acetaldehyde, initially
at a pressure of 363 Torr, was 1.07 Torr s-1
when 5.0 percent had reacted and 0.76
Torr s-1 when 20.0 per cent had reacted.
Determine the order of the reaction.
• Solution
• Rate ∝[A]n∝(Pressure A)n rate= k(P0-x)n
 Question 14
𝑟𝑎𝑡𝑒 1 1.07 𝑇𝑜𝑟𝑟 𝑠;1
= =
𝑟𝑎𝑡𝑒 2 0.76 𝑇𝑜𝑟𝑟 𝑠;1
k(P0−5%)n k(P0−0.05)n
=
k(P0−20%) k(P0−0.20)n
n

0.95 n
1.4079= =(1.1875)n
0.80
log1.4079=nlog1.1875
𝑙𝑜𝑔1.4079
n= 1.99 ≈ 2 second order reaction
𝑙𝑜𝑔1.1875
 Question 15
• At 518 oC, the half-life for the
decomposition of a sample of gaseous
acetaldehyde, initially at 363 Torr was 410
s. When the pressure was 169 Torr, the
half-life was 880 s. Determine the order of
the reaction.
• Solution
1 1
• Half life, t1/2∝ 𝑛 1 ∝ ∝ P01-n
𝐴0 ; 𝑃0𝑛;1
 Question 15
1
𝑡 (1) 410 𝑠 3631;𝑛
• 2
1 = =0.4659 = = (2.1479)1-
𝑡 (2) 880 𝑠 169 1;𝑛
2
n

• Log0.4659=(1-n)log2.1479
𝑙𝑜𝑔0.4659
• (1-n)= =-0.999
𝑙𝑜𝑔2.1479
• n=1+0.999=1.999 ≈2.000 second order
reaction
 Question 16
A second order reaction of type A + B → P
was carried out in a solution that was
initially 0.075 mol L-1 in A and 0.080 mol L-1
in B. After 1 hour the concentration of A had
fallen to 0.045 mol L-1. (a) Calculate the rate
constant
Solution
As in question 7
 Question 17
A reaction 2B →P has a second–order rate
law with k = 4.30×10-4 dm3 mol-1 s-1.
Calculate the time required for the
concentration of B to change from 0.210
mol dm-3 to 0.010 mol dm-3.
Solution
• For a second order reaction type: 2B→ P,
𝑑[𝐵]
The rate law: - = 2𝑘 𝐵 2
𝑑𝑡
 Question 17
𝐵 𝑡 𝑑[𝐵] 𝑡
• 𝐵0 𝐵 2 = 0
2𝑘𝑑𝑡
1 1
• − = 2𝑘𝑡
𝐵𝑡 𝐵0
1 1
• − = 2𝑥4.30×10−4 dm3 mol−1 s−1 t
0.01 0.21
• t=110742 s or 1.11 x 105 s
 Question 18
Hydrogen peroxide reacts with thiosulfate ion in
slightly acidic solution as follows: H2O2 +
2S2O32- +2H+ →2H2O + S4O62-
This reaction is second order, independent of
the hydrogen ion concentration in the pH range
4 to 6. The rate constant, k = 9.1×10-2 mol-1L
min-1 were obtained at 25 oC and pH 5.0, and
initial concentrations: [H2O2] = 0.036 mol L-1,
[S2O32-] =0.024 mol L-1. How long will it take
for 50% of the thiosulfate ion, 2S2O32- to react?
 Question 18
Solution
• For second order reaction of type:
aA+bB→P,
𝑑[𝐴]
• The rate law: - = 𝑘 𝐴 [𝐵]
𝑑𝑡
• The integrated equation:
( 𝐴 0;𝑎𝑥) 𝐴
• ln = (𝑏 𝐴 0 − 𝑎 𝐵 0𝑘𝑡 + 𝑙𝑛 0
( 𝐵 0;𝑏𝑥) 𝐵 0

• [A]=[H2O2], [B]=[S2O32-], a=1, b=2

 Question 18
• bx=2x=50%[B]0, x=0.25x0.024= 6.0 x
10-3
(0.036;6.0 x 10−3)
• ln =(2(0.036)-
(0.024;2(6.0 x 10−3)
0.036
1(0.024))(9.1 x 10 )t + ln
-2
0.024
• 0.9163=4.68 x 10-3t + 0.405
• t = 117.06 s