Kinetics Solution PDF

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)
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 = 135.5 46 = 89.5 mg/L

XB3 = 135.5 36 = 99.5 mg/L

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 = 131 72 = 59 mg/L

XB2 = 131 46 = 85 mg/L

XB3 = 131 36 = 95 mg/L

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
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

Kinetics Solution PDF

Uploaded by

Copyright:

Available Formats

Kinetics Solution PDF

Uploaded by

Document Information

Original Description:

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

Kinetics Solution PDF

Uploaded by

Copyright:

Available Formats

ENV 6015

Solutions to Kinetics Problem Set

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

From the equation:

At half-life of the reaction: C A =

To invert 95% of a pound of sugar:

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

for zero-order reaction

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

Using the Arrhenius equation:

BODBay1 = 135.5 mg/L

XB2 = BODBay1 C2, then

XB3 = BODBay1 C3, then

XB4 = BODBay1 C4, then

2.42 *10 6 gallons

Time Bay 4 = 1.77hr

BODBay1 = 131 mg/L

XB2 = BODBay1 C2, then

XB3 = BODBay1 C3, then

XB4 = BODBay1 C4, then

Retardant Kinetic Model Regression

Actual vs Predicted BOD

Predicted BOD, mg/L

Actual BOD, mg/L

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

Standard Error of Estimate

K-S Statistic = 0.1537

Significance Level = 0.9843

Constant Variance Test

Power of performed test with alpha = 0.0500: 0.9994

Stud. Del. Res.

Reactant concentration (mg/L)

Reactant concentration-1 (L/mg)

The rate constants are:

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

You might also like