Kinetics

TUTORIAL 2
1. At 25 C, the half-life period for the decomposition of N205 is 5.7 hours and
is independent of the initial pressure of N205, calculate:
a- The time for the reaction.
b- The specific rate constant for the reaction.
Answer:
a. The t1/2 is independent on the initial conc. So, it is
1st order reaction, hence the reaction never goes to
an end and the life time is infinity.
b. t1/2 =
k=

0.693
k

0.693 0.693
=
= 0.1215 hr-1
t half
5 .7

2. A drug product is known to be ineffective after it has decomposed 30%.The original

concentration of one sample was 50 mg/ml. When assayed 20 months later the
concentration was found to be 40 mg/ml, assuming that the decomposition is first order,
what should be the expiration time on the label? What is the half-life of this product?

Answer:
-log Ct = log Co (kt / 2.303)
log 40 = log 50 (k.20 / 2.303)
20k/2.303 = log 50 -log 40 = log50/40
k= log50/40 . 2.303/20 = 0.01116 m-1
-log Ct = log Co (kt / 2.303)
log (50*70/100) = log 50 (0.01116t / 2.303)
log (35) = log 50 (0.01116t / 2.303)
tshelf = log 50/35 . 2.303/0.01116
tshelf =31.97 month

0.693
0.693
=
= 62.1 month
K
0.01116
3. An ophthalmic solution dispensed at 5 mg/ml conc. exhibits a first order reaction, with
a rate constant of 0.0005 day-1. How much drug is remaining after 120 days? & how long
will it take for the drug to degrade to 90% of its initial concentration?
Answer:

- thalf =

-log Ct = log Co (kt / 2.303)

log Ct = log 5 (0.0005*120 / 2.303)
log Ct =0.6729
Ct = 4.71 mg/ml
-T90% =0.105/K
= 0.105/0.0005
= 210 days
4. The initial concentration of both ethyl acetate and sodium hydroxide in a reaction
mixture was 0.01 M each. The change in the concentration "x" of alkali during 20
minutes was 0.00566 mole/liter. Compute a: the second order rate constant, b: the half
life of the reaction.

Answer:
When a = b
x
= kt
a (a x)
K=

x
0.00566
=
=
at (a x) 0.01 * 20(0.01 0.00566)

t1/2 =

1
1
=
=
ak
0.01 * 6.52

6.52

L.mole-1min-1

15.34 min

5. Tetracycline undergo epimerization. At the equilibrium point the distribution consisted

of 32% of tetracycline and 68% of epi-tetracycline. Measuring the concentration of
tetracycline at different time interval and plotting the data according to the following
equation lead to a straight line the slope of which equals 0.01 min-1, calculate both
Kf and kr

5. Answer:

slope = (Kf + Kr)/2.303

Also: at equilibrium
Kf *Aeq = Kr *Beq
So, now you have 2 equations and 2 unknowns, the 2 equations can be solved
simultaneously.
Kf
Kr
Kf
Kr

=
=

Beq
Aeq

68%
32%

0.68
= 2.125
0.32

Kf = 2.125 Kr
slope = (Kf + Kr)/2.303
Slope * 2.303 = Kf + Kr
0.01 * 2.303 = Kf + Kr
Kf = 0.02303 - Kr
2.125 Kr = 0.02303 - Kr
3.125 Kr = 0.02303
Kr = 0.0073696 min-1
Kf = 2.125 Kr
Kf = 2.125 * 0.0073696 = 0.01566 min -1

6. The rate of decomposition of 0.056 molar glucose at 140 c in an aqueous solution

containing 0.35 HCI was found to be:
Time (hr)
Glucose
Remaining
(mole/102)

0.5

12

5.52

5.42

5.32

5.02

4.80

4.52

4.10

What is the order of glucose decomposition and the specific reaction rate constant?
Determine the half-life period. Does the available data allow an accurate calculation
of the kinetic parameters?

Answer:
We cannot determine the order or t1/2 because the readings are incomplete.
To determine the order of a reaction, you must be given data until
Ct = 1/2Co.( i.e the initial concentration reaches half.)
Using the graphical method:
No.6
time
(h)
0.5
2
3
4
6
8
12

glucose remaining
mole
5.52
5.42
5.32
5.02
4.8
4.52
4.1

log (glucose remaining

mole)
0.741939078
0.733999287
0.725911632
0.700703717
0.681241237
0.655138435
0.612783857

remaining glucose (mole)

No.6 Tut 2
6

y = -0.1307x + 5.6197
R2 = 0.9839

5
4

Series1

Linear (Series1)

2
1
0
0

10

15

time (h)

No.6 Tut. 2
y = -0.0118x + 0.7531
R2 = 0.9881

Log remaining glucose

(mole)

0.8
0.7
0.6
0.5

Series1

0.4

Linear (Series1)

0.3
0.2
0.1
0
0

10
time (h)

15

By equation:
zero order
t (h)
0.5
2
3
4
6
8
12

C0 or a
5.6
5.6
5.6
5.6
5.6
5.6
5.6

ct
5.52
5.42
5.32
5.02
4.8
4.52
4.1

C0-ct
0.08
0.18
0.28
0.58
0.8
1.08
1.5

0.16
0.09
0.093333
0.145
0.133333
0.135
0.125

First order
t

0.5
2
3
4
6
8
12

C0 or a ct
c0/c
log c0/c 2.303/t
k
5.6
5.52 1.014493 0.006249
4.606 0.028783
5.6
5.42 1.03321 0.014189
1.1515 0.016338
5.6
5.32 1.052632 0.022276 0.767667 0.017101
5.6
5.02 1.115538 0.047484 0.57575 0.027339
5.6
4.8 1.166667 0.066947 0.383833 0.025696
5.6
4.52 1.238938 0.09305 0.287875 0.026787
5.6
4.1 1.365854 0.135404 0.191917 0.025986
average
k=

0.024004

t1/2 = 0.693/k= 28.86979 h

7.

The following are the concentrations of Salphadiazien remaining at various times

during the thermal decomposition at 40 oC.
Time
(months)

12

16

20

24

Conc.
(mg/5ml)

100

81.4

68.8

56.4

44.6

36.2

31.2

Using the above data determine:

a. The order of the decomposition reaction using two different methods.
b. The rate constant of the reaction.
c. The shelf life of the product.
Answer:
No7 graphical method:

0
4
8
12
16
20
24

Co or a

100
100
100
100
100
100
100

ct

100
81.4
68.8
56.4
44.6
36.2
31.2

No.7 Tut 2

Log ct

2
1.910624
1.837588
1.751279
1.649335
1.558709
1.494155

y = -2.8661x + 94.193
R2 = 0.9733

120
100
conc mg/5ml

80

Series1

60

Linear (Series1)

40
20
0
0

10

15
time months

20

25

30

No.7 Tut 2
y = -0.0215x + 2.0013
R2 = 0.9978

Log conc. mg/5ml

2.5
2
1.5

Series1
Linear (Series1)

1
0.5
0
0

10

15

20

25

30

time months

By equation:
zero order
t

0
4
8
12
16
20
24

Co or a

100
100
100
100
100
100
100

ct

100
81.4
68.8
56.4
44.6
36.2
31.2

Co-Ct

k=Coct/t

c0/c

log c0/c

0
18.6
4.65
31.2
3.9
43.6 3.633333
55.4
3.4625
63.8
3.19
68.8 2.866667

first order
t

0
4
8
12
16

Co or a

20
24
t1/2 method:

100
100
100
100
100
100
100

ct

2.303/t

100
1
0
81.4 1.228501 0.089376 0.57575 0.051458
68.8 1.453488 0.162412 0.287875 0.046754
56.4 1.77305 0.248721 0.191917 0.047734
44.6 2.242152 0.350665 0.143938 0.050474
36.2 2.762431 0.441291 0.11515 0.050815
31.2 3.205128 0.505845 0.095958 0.04854

n = [log (15/15)/log (100/80)]+1 =1

B) slope= -k/2.303= -0.0215
therefore
k= 0.0495145month-1
C) t 90% : 0.105/k =
0.105/0.0495145 = 2.12 m

8. A fast reaction in solution between compounds A and B was followed over a period of
60 s at 3I0 K by assaying the concentrations of A and B that remained at various time
intervals. The following results were obtained:

Time (s)

Concentration of A (mol /dm3)

Concentration of B (mol /dm3)

0.2

0.1

10

0.166

0.066

20

0.146

0.046

30

0.134

0.034

60

0.114

0.014

a. Determine the order of the reaction and

b. Calculate the value of its rate constant.
c. Calculate the half life of the product.

Answer:
No.8
A)
Graphical method:
time (s)

0
10
20
30
60

remaining conc of A

0.2
0.166
0.146
0.134
0.114

Log remaining conc of A

-0.698970004
-0.779891912
-0.835647144
-0.872895202
-0.943095149

Try second order plot when the initial concentrations are not equal.
remaining
remaining
time (s)
conc of A
conc of B
b
a
0
0.2
0.1
0.1
10
0.166
0.066
0.1
20
0.146
0.046
0.1
30
0.134
0.034
0.1
60
0.114
0.014
0.1
x=aab-x(
remaining x(remaining) remaining)
b(a-x)
0
0.2
0.1
0.034
0.166
0.066
0.054
0.146
0.046
0.066
0.134
0.034
0.086
0.114
0.014

0.02
0.0166
0.0146
0.0134
0.0114

0.2
0.2
0.2
0.2
0.2

x= b remaining
0
0.034
0.054
0.066
0.086

b(aa(b-x) x)/a(b-x)
0.02
1
0.0132 1.257576
0.0092 1.586957
0.0068 1.970588
0.0028 4.071429

Log

0
0.099534157
0.200565028
0.294595886
0.60974682

No.8 tut 2
0.7

y = 0.0101x
2
R = 0.9996

Log b(a-x)/a(b-x)

0.6
0.5
0.4

Series1

0.3

Linear (Series1)

0.2

Linear (Series1)

0.1
0
-0.1 0

20

40

60

80

time (s)

B) k= slope * 2.303/(a-b)
k=0.0101*2.303/(0.2-0.1)
k=
0.232603 dm3/mol.s
C) Half life: The half-life or shelf life of a secondorder reaction can
Only be calculated when the initial concentration of both
Reactants are equal (a = b).
T1/2= 1/ak