PACY2000

Tutorial 6: Kinetics

Using the method of initial velocities

1.

a) What is the order with respect to: P4

H2

Rate  [P 4 ]  n Rate  [[H 2 ]  n

2
   2
  
 [P ]   [[H ] 
Rate
1  4 1 Rate
1  2 1
6.39  10  4  [P ]  n 6.40  10  4  [[H ]  n
  4    2 
6.40  10  4  [P 4 ]1  3.20  10  4  [[H 2 ]1 
 [P ]  n  [[H 2 ]  n
1   4   n  0 2   
 [[H ]   n  1
 [P 4 ]1   2 1

b) Write the rate law for this reaction.

Rate  k[H ]
2

c) Determine the value and units of the rate constant, k. [0.0427 s-1]

Rate  k[[H ]
2
4 1 1
6.39  10 molL s  k [ 0.0150 mol / L ]

6.39  10 4 molL 1s  1 1

k   0.0427 s
0.0150 mol / L
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2. The initial rate of a reaction depended on the concentration of a substance J as follows:

[J]0/(10-3 mol l-1) 5.0 8.2 17 30

-7 -1 -1
V0/(10 mol l s ) 3.6 9.6 41 130

Determine the order of the reaction with respect to J and calculate the rate constant.
[2; k = 1.4 x 10-2 L mol-1 s-1]
The rate law expression is, v0 = k[J]0x

Answer
The rate law expression is, v0 = k[J]0x
logv0 = log k + xlog[J] 0

[J]0 log [J]0 v0 log v0

5.00E-03 -2.30 3.60E-07 -6.44
8.20E-03 -2.09 9.60E-07 -6.02
1.70E-02 -1.77 4.10E-06 -5.39
3.00E-02 -1.52 1.30E-05 -4.89

log [J]0
0.00
-1.00-2.50 -2.00 -1.50 -1.00 -0.50 0.00
-2.00
-3.00
log v0

-4.00
-5.00
y = 2.0005x - 1.8429
-6.00
-7.00

The slope of the graph is 2 = x

Thus, the order of the reaction with respect to J and the overall order of the reaction = 2.
The rate constant can be calculated by using the y-intercept.
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Zero order reactions

3. A pharmacist dissolved a few milligrams of a new antibiotic drug into exactly 100 ml of distilled
water and placed the solution in a refrigerator (5 C°). At various time intervals, the pharmacist
removed a 10 ml aliquot from the solution and measured the amount of drug contained in each
aliquot.
Time (hr) 0.5 1 2 4 6 8 12
AB.(mol/L) 84 81 74 61 48 35 8.7

a) What is the rate of decomposition of this antibiotic ? [-K= 6.6 mol.L-1 hr-1, 0.0018 mol.L-1 s-1 ]
b) What was the concentration of antibiotic in the original solution prepared by the pharmacist?
[A0 (intercept) = 87.3 mol/L]
c) Give the equation for the line fits the experimental data.[Y= mX+ b A= - 6.6 t + 87.3]

a) Zero- order
-K= slope
-1 -1
= 6.6 mol.L-1hr-1 = 0.0018 mol.L s

100 Zero order reaction

80
y = -6.5489x + 87.298
AB.(mol/L)

60
40
20
0
0 5 10 15
Time (hr)

b) A0 (intercept) = 87.3 mg/ml

c) Y= mX+ b
A= - 6.6 t + 87.5
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First order reactions

4. The concentrations of lactate at various times t during its enzymatic oxidation to pyruvate are
given below:

t/s 0 100 250 350 500 650

[lactate]/(mmol l-1) 32.00 27.24 21.38 18.21 14.29 11.22

Confirm that the reaction is first order and determine the rate constant k.
Calculate the half-life of the reaction.
[k = 1.61 x 10-3 s-1; t½ = 430 s]

Answer [A]
  kt
ln
[A] slope   k
0
 1.61 10 3 s 1  k
y  mx
 k  1.61 103 s 1
t/s [lactate]/(mmol l-1) [Lactate]\[L]0 ln [lactate]
0 32 1 0.00 0.693
t1 
100 27.24 0.85125 -0.16 2 k
250 21.38 0.668125 -0.40
0.693
350 18.21 0.5690625 -0.56 
500 14.29 0.4465625 -0.81 1.61  10 3 s 1
650 11.22 0.350625 -1.05  430 s

0.20 First order plot ln[L]/[L]o vs Time

0.00
0 100 200 300 400 500 600 700
-0.20
ln [L]/[L]O

-0.40

-0.60

-0.80

-1.00
y = -1.61E-03x + 9.81E-05
-1.20
time [s]
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5. The rate of a reaction was followed by measuring the absorbance of a solution at various times:
Time/min 0 18 57 130 240 337 398
Absorbance 1.39 1.26 1.03 0.706 0.398 0.251 0.180

Assuming that absorbance is proportional to concentration, show graphically that the reaction is
first order and determine the rate constant. [k = 8.5 x 10-5 s-1]

t/min [A] [A]/[A]O ln [A]/[A]O slope   k

 5.11 10 3 min1  k
0 1.39 1 0
18 1.26 0.906 -0.098
k  5.11 103
1 1
57 1.03 0.741 -0.300 
min 60s
130 0.706 0.508 -0.677
240 0.398 0.286 -1.251  8.52  10 5 s 1
337 0.251 0.181 -1.712
398 0.18 0.129 -2.044

First order plot ln[L]/[L]o vs Time

0
0 100 200 300 400 500
-0.5
y = -5.11E-03x - 7.47E-03
ln [L]/[L]O

-1

-1.5

-2

-2.5
time [s]

131
6. I, which is used in treating thyroid cancer, has a half-life of 8.07 days. Calculate the decay
constant for 131I (in s-1 first order). [9.93 x 10-7 s-1]

Answer
t1/2 = 0.693
k
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Pseudo-first order reaction

7. The acid-catalysed hydrolysis of sucrose, in aqueous solution, to give a mixture of glucose and
fructose,
H+
sucrose + H2O  glucose + fructose
was followed at 27C. The following results were obtained:
Time/min 0 60 130 180
Sucrose concentration/(mol l-1) 1.000 0.807 0.630 0.531
Show graphically that the reaction is first order and determine the rate constant.
[k = 5.87 x 10-5 s-1]

t/min [Sucrose] M [S]/[S]O ln[S]/[S]O

0 1 1 0
60 0.807 0.807 -0.21
130 0.63 0.63 -0.46
180 0.531 0.531 -0.63

First order plot ln[S]/[S]o vs Time

0
0 50 100 150 200
-0.1

-0.2
ln [S]/[S]O

-0.3

-0.4

-0.5
y = -3.52E-03x - 1.72E-03
-0.6

-0.7
time [s]

slope   k
 3.52  10 3 min1  k

k  3.52  10 3
1 1

min 60s
 5.87  10 5 s 1
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Second order reactions

8. The kinetics of the reaction between methyl p-toluenesulphonate and sodium iodide in acetone
solution at 26.5C were followed by a titration method. Equal initial concentrations of each
reactant were used and the concentration of each reactant at the following times is given below:

Time/h 0 0.5 1 2 3 4 5 6 7 8
Concentration 5.00 4.85 4.72 4.48 4.26 4.03 3.86 3.70 3.55 3.40
-1 -2
/(mol l x 10 )

Show graphically that the reaction is second order and determine the rate constant.
[k = 3.25 x 10-4 l mol-1 s-1]

t/hr [A], M 1/[A] M-1

0 0.05 20.00
0.5 0.0485 20.62
1 0.0472 21.19 y  mx  c
2 0.0448 22.32
1 1
3 0.0426 23.47  kt 
[A] [A] 0
4 0.0403 24.81
5 0.0386 25.91
6 0.037 27.03
7 0.0355 28.17
8 0.034 29.41

35.00 First order graph of 1/[A] vs t

30.00
25.00
20.00
1/[A]

15.00
10.00
5.00 y = 1.17x + 20.01
0.00
0 5 10
time, hr

slope  k
1.17Lmol 1hr 1  k
1.17 1 1
k  
hr 60 min 60 s
 3.25  10 4 Lmol 1s 1
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9. A reaction in solution between Compounds A and B was followed over a period of 60 min at 310
K by assaying the concentrations of A and B that remained at various times. The following results
were obtained:
Time/min Concentration of A/(mol l-1) Concentration of B/(mol l-1)
0 0.100 0.200
10 0.066 0.166
20 0.046 0.146
30 0.034 0.134
60 0.014 0.114
Determine the order of the reaction and calculate the value of its rate constant.
[k = 3.8 x 10-3 l mol-1 s-1]

( [B]/[B]0
t/ min [A], M [A]/[A]0 [B], M [B]/[B]0 /[A]/[A]0) ln( [B]/[B]0/[A]/[A]0)
0 0.1 1 0.2 1 1 0  [B] 
 [B] 
10 0.066 0.66 0.166 0.83 1.26 0.23 ln 0
  ([B] 0 [A] 0 ) kt
 [A] 
 [A] 
20 0.046 0.46 0.146 0.73 1.59 0.46  0 
30 0.034 0.34 0.134 0.67 1.97 0.68 y  mx  c
60 0.014 0.14 0.114 0.57 4.07 1.40

1.6 Second order reaction

1.4
1.2
ln( [B]/[B]0/[A]/[A]0)

1 y = 0.0234x - 0.0064
0.8
0.6
0.4
0.2
0
-0.2 0 10 20 30 40 50 60 70
time,min

slope  k
0.023 min 1  k [B] 0 [A] 0 
0.023 min 1 0.023min 1
k   0.23 L mol 1 min 1
[B] 0 [A] 0 (0.2  0.1)M
1 1
k  0.23L mol 1   3.8  10 3 L mol 1 s 1
min 60s
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Arrhenius parameters
10. The rate constants, k, for the first order decomposition of an acid in aqueous solution were
measured at various temperatures:
T (°C) k/(s-1)
0 2.46 x 10-5
10 1.08 x 10-4
20 4.78 x 10-4
30 1.63 x 10-3
40 5.76 x 10-3
50 1.85 x 10-2
60 5.48 x 10-2

Determine the energy of activation and the Arrhenius Z factor for the reaction by constructing a graph.
[97.1 kJ mol-1; 9.3 x 1013 s-1]
Answer

T (C) T (K) 1/T (K-1) k ln k

0 273 3.66E-03 2.46E-05 -10.61
10 283 3.53E-03 1.08E-04 -9.13
20 293 3.41E-03 4.78E-04 -7.65
30 303 3.30E-03 1.63E-03 -6.42
40 313 3.19E-03 5.76E-03 -5.16
50 323 3.10E-03 1.85E-02 -3.99
60 333 3.00E-03 5.48E-02 -2.90

38.00 Arrhenius plot of ln k vs 1/T

28.00
y = -11681x + 32.17
18.00
ln k

8.00

-2.00
0.00E+00 1.00E-03 2.00E-03 3.00E-03 4.00E-03
-12.00
1/T (K-1)

Ea E
lnk  lnZ   a  slope  11681 K
RT R
y  mx  c lnk  lnZ 
Ea
Ea  11681 K  8.314  10 3 KJ mol 1K 1
RT
 97.1 kJ/mol
lnZ  c  32.17
 Z  e32.17  9.3  1013 s 1
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11. If a first-order reaction has an activation energy of 104.6 kJ mol-1 and, in the equation
k = Ze-Ea/RT Z has a value of 5x1013s-1, at what temperature will the reaction have a half-life of 60 s.
[76 C]
Answer
0.693
t1 
2 k

 0.0116s1
0.693
k 
60 s

Ea

k  Ze RT
E
ln k  ln Z  a
RT
(ln k  ln Z ) RT  Ea
Ea
T 
(ln k  ln Z ) R
 104.6 kJ/mol

[ln(0.0116s )  ln (5  1013 s 1 )] 8.314  10 3 kJ mol 1K 1
 349 K
 76 C

Michaelis-Menten kinetics

12. The enzyme-catalysed conversion of a substrate at 25 C has a Michaelis constant of 0.035 mol
L-1. The rate of the reaction is 1.15 x 10-3 molL-1s-1 when the substrate concentration is 0.110
molL-1 [1.52 x 10-3 molL-1s-1]

Vk m  [S] (1.15  103 molL1s 1  0.035molL1)  0.110 molL1

V max  
[S] 0.110 molL1
 1.52  103 molL1s 1
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13. The kinetics of an enzyme is measured as a function of substrate concentration vs initial rate (v0)
at each of these concentrations. Note M = mol/L

[S] (M) V0 [M / min]

3 10.40
5 14.50
10 22.50
30 33.80
90 40.50

Calculate the Vmax and Km for this enzyme?

[S] M 1/S VM/min 1/V
3.00 0.33 10.40 0.10
5.00 0.20 14.50 0.07
10.00 0.10 22.50 0.04
30.00 0.03 33.80 0.03
90.00 0.01 40.50 0.02

0.12 Michaelis-Menten plot

1/V [1/uMmin-1]

0.10
0.08
0.06
0.04 y = 0.2245x + 0.0223
0.02
0.00
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
1/[S] [1/uM]

1 1
 c  0.022
V max μM /min
V max  45.5 μM/min

Km
 slope  0.224 min
V max
 Km  V max  slope
 45.5 μM/min  0.224 min  10 μ M
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Mechanism
14. a) The experimentally determined rate law for the reaction of ethyl bromide with OH- is:

-d[CH3CH2Br] = k[CH3CH2Br][OH-]
dt
I. Determine the overall order of the reaction.
Rate= k[CH3CH2Br][OH-] second order

II. Write the reaction mechanism consistent with the experimentally determined rate orders
for the reaction.

III. Draw a qualitative enthalpy profile for this mechanism, showing intermediates, activated
complexes and activation enthalpy. The process is exothermic.
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b) In contrast, the experimentally determined rate law for the reaction of tert-butyl bromide with
OH- is:
-d[(CH3)3CBr] = k[(CH3)3CBr]
dt
I. Determine the overall order of the reaction.
Rate= k[H3C)3CBr] first order

II. Write the reaction mechanism consistent with the experimentally determined rate orders
for the reaction. Indicate the slow and fast step.

III. Draw a qualitative enthalpy profile for this mechanism, showing intermediates, activated
complexes and activation enthalpy. The process is exothermic.

(c) Why do the two reactions in a and b proceed by two completely different mechanisms?
In the SN2 mechanism the nucleophile attacks the carbon from the back, and this step can be
hindered by this carbon being attached o bulky methyl groups. Therefore in (a) SN2 is favoured
over SN1 because the primary carbon in CH3CH2Br is in a less sterically hindered environment
compared to the carbon in (H3C)3CBr
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