ENV 6015

Solutions to Kinetics Problem Set

1.

The inversion of sucrose proceeded as shown at 25oC: The initial concentration of

sucrose was 1.0022 moles/liter. Calculate the first order rate constant and the half-life of
the reaction. Why does this reaction follow a first order law despite the fact water enters
into the stoichiometric equation? How long would it take to invert 95% of a pound of
sugar?
C12H22O11 + H2O C6H12O6 + C6H12O6
Time, min.
Sucrose
inverted-M/L

30

60

90

130

180

0.1001

0.1946

0.2770

0.3726

0.4626

Solution:
The solution is diluted, [H2O] = 55.5 M/L vs [C12H12O11] = 1.0 M/L. The reaction is limited by
the concentration of C12H12O11 and follows first-order kinetics.
Sucrose + H2O Glucose
dC A
= k * C A
dt

after integration:
ln

CA
= k * t or ln CA = -k*t + ln CAi
C Ai

Thus, if we plot ln [CA] vs time, the resulting slope is equal to the rate constant k (min-1).
Time, min.
Sucrose invertedM/L
Sucrose
remaining M/L
Ln [CA]

30

60

90

130

180

0.1001

0.1946

0.2770

0.3726

0.4626

1.0022

0.9021

0.8076

0.7252

0.6296

0.5396

0.0022

-0.1030

-0.2137

-0.3213

-0.4627

-0.6169

Plot of ln C vs time
0.2

ln CA (sucrose remaining)

0
0

20

40

60

80

100

120

140

160

180

200

-0.2
ln CA = -0.0035*time - 0.0025
R2 = 1.0
-0.4

-0.6

-0.8
Time (min)

From the equation:

k = 0.0035 min-1

At half-life of the reaction: C A =

ln

C Ai
2

0.5 * C Ai
= 0.0035 * t 1
2
C Ai

t1 =
2

ln (0.5)
= 198 min
0.0035

To invert 95% of a pound of sugar:

ln

0.05 * C Ai
= 0.0035 * t 1
2
C Ai

t 95% =

ln(0.05)
= 856 min
0.0035

2.

Find the reaction order and rate constant for the decomposition of diazobenzenechloride
at 50oC if the initial diazobenzenechloride concentration is 10 grams/liter. The reaction
and nitrogen evolution are shown.
C6H5N2Cl C6H5Cl + N2
Time, min.
N2 cm3 evolved

6
19.3

9
26.0

12
32.6

14
36

18
41.3

22
45.0

24
46.5

26
48.4

39
50.4

58.3

Solution:
For t = , VN2 = 58.3 cm3; using the ideal gas law:

n N2 =

P * VN 2

= 0.0022 moles
atm * cm 3
o
82
323 K
o
mol * K
by stoichiometry, 0.0022 moles of C6H5N2Cl produce 0.0022 moles of N2. Assuming complete
reaction:
R *T

(1 atm )(58.3 cm 3 )

Initial mass of C6H5N2Cl = (0.0022moles)*(140 g/mole) = 0.309 grams

Volume of solution =

0.309 g
= 30.9 cm3
g
1
L

10 *
3
L 1000 cm

To determine the order of the reaction and the rate constant, we need to graph:
a) C vs time
b) Ln C vs time
c) 1/C vs time

for zero-order reaction

for first-order reaction
for second-order reaction

Note: the graphs can also be made by using mass or moles of C6H5N2Cl in lieu of concentration
Time (min)

N2 cm3
evolved

N2 moles
evolved

C (M/L of C6H5N2Cl
remaining)

ln C

1/C (L/M)

0
6
9
12
14
18
22
24
26
39

0.0
19.3
26.0
32.6
36.0
41.3
45.0
46.5
48.4
50.4
58.3

0.0000
0.0007
0.0010
0.0012
0.0014
0.0016
0.0017
0.0018
0.0018
0.0019
0.0022

0.071
0.048
0.039
0.031
0.027
0.021
0.016
0.014
0.012
0.010
0.000

-2.6
-3.0
-3.2
-3.5
-3.6
-3.9
-4.1
-4.2
-4.4
-4.6
--

14.0
21.0
25.3
31.8
36.7
48.1
61.5
69.4
82.7
103.6
--

a)
Plot of C vs time
0.08

Concentration (M/L)

0.07
0.06
0.05
C = -0.0015*time + 0.055
2
R = 0.81

0.04
0.03
0.02
0.01
0
0

10

15

20

25

30

35

40

45

30

35

40

45

Time (min)

b)
Plot of ln C vs time
0

10

15

20

25

0
-1

ln C

-2
ln C = -0.055*time - 2.79
R2 = 0.95

-3
-4
-5
-6
Time (min)

c)
Plot of 1/C vs time
120

1/Concentration (L/M)

100
80
1/C = 2.55*time + 6.1
R2 = 0.97

60
40
20
0
0

10

15

20

25

30

35

40

45

Time (min)

From the graphs we can see that the reaction follows first-order or second-order kinetics. Firstorder kinetic is chosen because the data points show a normal distribution around the trendline.
The second-order plot is not appropriate despite the higher R2 (0.97) because the data points
show a curvature.
From the trendline equation shown in the first-order graph (graph b), the rate constant K is:
K = 0.055 min-1

A certain reaction is 10 percent complete in 15 minutes at 40oC and in 3 minutes at 60oC.

Estimate its activation energy.

3.

Solution:
Assuming first-order kinetics:
C
ln t = k * t
C0
at 40oC
ln

0.9 * C 0
ln(0.9)
= k 40 k40 = 0.007 min-1
= k 40 * 15min
15
C0

at 60oC
ln

0.9 * C 0
ln(0.9)
= k 60 * 3min
= k 60 k60 = 0.035 min-1
3
C0

Using the Arrhenius equation:

k = A*e

EA
RT

ln (k ) = ln (A ) -

EA
E
ln (A ) = ln (k ) + A
RT
RT

at 40oC:

at 60oC

ln (A ) = ln (k 40 ) +

EA
RT40

ln (A ) = ln (k 60 ) +

EA
RT60

then,
ln (k 40 ) +

EA
E
= ln (k 60 ) + A
RT40
RT60

k
R * ln 40
k E 1
1
k 60
E A =

ln 40 = A *
1
1
k 60 R T60 T40

T60 T40
J
0.007
* ln

O
mol * K
0.035 E = 69,800 J/mol
A
1
1

O
O
333 K 313 K

8.314

EA =

In English units:
Cal
0.007
* ln

O
mol * K
0.035
1
1

O
O
333 K 313 K

1.987

EA =

EA = 16,680 Cal/mol

4.

The following data were obtained through a treatment plant treating a pulp and paper mill
waste. The volume of the aeration tanks is 2,420,000 gallons divided into four bays.
Determine the first order rate constant using a retardant kinetic model.
3

Flow, MGD (m )
Recycle, MGD (m3)
BOD Influent, mg/L
BOD Recycle, mg/L
BOD, Bay 1, mg/L
BOD, Bay 2, mg/L
BOD, Bay 3, mg/L
BOD, Bay 4, mg/L
VLSS, mg/L

Test 1
25.0 (94,500)
7.85 (29,700)
157
67
75
47
39
34
1850

Test 2
20.5 (77,500)
7.90 (29,900)
165
42
69
45
32
26
2000

Solution:
The retardant reaction equation is
k

X = C 0 1 (1 + r * t ) r

The BOD concentration entering Bay 1 during test 1 was calculated as follows

mg
gallons
mg
gallons
25 * 10 6
+ 7.85 * 10 6

* 67
*157
L
day
L
day

BOD Bay1 =

gallons
gallons
25 *10 6

+ 7.85 * 10 6
day
day

BODBay1 = 135.5 mg/L

XB1 = BODBay1 C1, then
XB1 = 135.5 72 = 63.5 mg/L

XB2 = BODBay1 C2, then

XB2 = 135.5 46 = 89.5 mg/L

XB3 = BODBay1 C3, then

XB3 = 135.5 36 = 99.5 mg/L

XB4 = BODBay1 C4, then

XB4 = 135.5 30 = 105.5 mg/L

2.42 *10 6 gallons

Volume
Total time =
(Q Recycle + Q IN ) = 25 *10 6 gallons + 7.85 *10 6 gallons = 0.074 days = 1.77 hr

day
day

1.77hr
= 0.44hr
4
1.77hr
= 3*
= 1.33hr
4

1.77hr
= 0.88hr
4

Time Bay 1 =

Time Bay 2 = 2 *

Time Bay 3

Time Bay 4 = 1.77hr

The BOD concentration entering Bay 1 during test 2 was calculated as follows

gallons
mg
gallons
mg
20.5 * 10 6
+ 7.9 * 10 6

* 165
* 42
day
L
day
L

BOD Bay1 =

gallons
gallons
20.5 * 10 6

+ 7.9 * 10 6
day
day

BODBay1 = 131 mg/L

XB1 = BODBay1 C1, then
XB1 = 131 72 = 59 mg/L

XB2 = BODBay1 C2, then

XB2 = 131 46 = 85 mg/L

XB3 = BODBay1 C3, then

XB3 = 131 36 = 95 mg/L

XB4 = BODBay1 C4, then

XB4 = 131 30 = 101 mg/L

2.42 * 10 6 gallons
Volume
Total time =
(Q Recycle + Q IN ) = 20.5 *10 6 gallons + 7.9 *10 6 gallons = 0.085 days = 2.05 hr

day
day

2.05 hr
2.05 hr
Time Bay 1 =
= 0.51 hr
Time Bay 2 = 2 *
= 1.02 hr
4
4
2.05 hr
Time Bay 4 = 2.05 hr
Time Bay 3 = 3 *
= 1.53 hr
4
Using non-linear regression with the equation for retardant reaction and the data for XBi and
TimeBay i for test 1 and test 2 (shown in next table) we can obtain the values for r and k.

Bay 1, Test 1
Bay 2, Test 1
Bay 3, Test 1
Bay 4, Test 1
Bay 1, Test 2
Bay 2, Test 2
Bay 3, Test 2
Bay 4, Test 2

Time
0.44
0.88
1.33
1.77
0.51
1.02
1.53
2.05

X
63.5
89.5
99.5
105.5
59
85
95
101

From the print out of the nonlinear regression presented on the next page:
r = 1.93 hr-1

and
k = 1.90 hr-1

The following plots show the predicting capabilities of the model obtained:

Retardant Kinetic Model Regression

110
100

X, mg/L

90
80
70
60
50
1.8

136
135

1.6

Tim 1.4
e, h 1.2
our 1.0
s
0.8

134
133
132
0.6
130

131

D
BO

60

70

tial
I ni

g/L
,m

Actual vs Predicted BOD

80

70

Predicted BOD, mg/L

60

50

40

30

20

10

0
0

10

20

30

40

50

80

Actual BOD, mg/L

10

Print out of the non-linear regression (Sigmaplot 9.0)

Retardant Kinetic Model Regression
Equation
X = C0*(1-(1+ar*time)-k/ar)
Number of Iterations Performed = 13
R

Rsqr

0.9807

0.9618

ar
k

Adj Rsqr

Standard Error of Estimate

0.9554

3.6618

Coefficient

Std. Error

1.9288
1.9019

0.6495
0.2578

2.9698
7.3773

P
0.0250
0.0003

VIF
23.5717<
23.5717<

Analysis of Variance:
Uncorrected for the mean of the observations:
DF
SS
MS
Regression 2
62924.5454
31462.2727
Residual
6
80.4546
13.4091
Total
8
63005.0000
7875.6250
Corrected for the mean of the observations:
DF
SS
MS
Regression 1
2024.0454
2024.0454
Total
7
2104.5000
300.6429

F
150.9457

P
<0.0001

Statistical Tests:
PRESS

155.4762

Durbin-Watson Statistic

0.9845 Failed

Normality Test

Passed (P = 0.9843)

K-S Statistic = 0.1537

Significance Level = 0.9843

Constant Variance Test

Passed (P = 0.4979)

Power of performed test with alpha = 0.0500: 0.9994

Regression Diagnostics:
Row
Predicted
Residual
1
61.5737
1.9263
2
84.5659
4.9341
3
96.8156
2.6844
4
104.1603
1.3397
5
64.3279
-5.3279
6
86.1790
-1.1790
7
97.2035
-2.2035
8
103.9607
-2.9607

Std. Res.
0.5260
1.3474
0.7331
0.3658
-1.4550
-0.3220
-0.6017
-0.8085

Stud. Res.
0.7119
1.4710
0.8040
0.4229
-1.8134
-0.3461
-0.6690
-0.9549

Stud. Del. Res.

0.6792
1.6794
0.7770
0.3919
-2.4623<
-0.3191
-0.6349
-0.9466

11

5.

The data presented in the table below were obtained from a batch reactor experiment with
an initial reactant concentration of 100 mg/L. Determine the order of reaction. The value
of activation energy and the rate of coefficients for each temperature.
Reactant Concentrations (mg/L)
10oC
20oC
94
90
74
61
54
37
40
22
30
14
16
5
9
2

Time (days)
0.1
0.5
1.0
1.5
2.0
3.0
4.0

30oC
85
44
20
9
4
1
-

Solution:
The order of reaction is determined using plots of C vs time, ln C vs time, and 1/C vs time.
a) C vs time

Plot of C vs time
10oC

20oC

30oC

Reactant concentration (mg/L)

100

80

60

40

20

0
0

Time (days)

12

b) ln C vs time
Plot of ln C vs time
10oC

20oC

30oC

3
ln C

ln C = -0.60*time + 4.6

2
ln C = -0.98*time + 4.59
1
ln C = -1.54*time + 4.55
0
0

Time (days)

c) 1/C vs time
Plot of 1/C vs time
10oC

20oC

30oC

Reactant concentration-1 (L/mg)

1.2
1.0
0.8
0.6
0.4
0.2
0.0
0

Time (days)

From the plots we can observe that the reaction follows first-order kinetics.

13

The rate constants are:

10oC K10 = 0.60 day-1
20oC K20 = 0.98 day-1
30oC K30 = 1.54 day-1
The activation energy:
K
J
0.98
ln 20 * R * T20 * T10
* 293o K * 283o K
ln
* 8.314
o
K
0.60
mol
*
K

Ea = 10
=
T20 T10
293o K 283o K

Ea = 33,600 J/mole
In English units:
K
Cal
0.98
ln 20 * R * T20 * T10
ln
* 293o K * 283o K
* 1.987
o
K
0.60
mol * K
Ea = 10
=
T20 T10
293o K 283o K

Ea = 8,030 Cal/mole

14

6.

Temperature-rate relationships are often represented by an expression shown below:

Using temperature in degrees Celsius, determine the value of using the data of Problem
5.
K T = K 20 * (T 20 )

Solution:
For 30oC:

K 30 = K 20 * (30 20 )

= 10

K 30
K 20

= 10

= 10

K 20
K 10

= 10

1.54
0.98

= 1.05

0.98
0.60

= 1.05

For 10oC:
K 20 = K 10 * (2010 )
Then:
= 1.05

15