The University of Western Ontario

Faculty of Engineering
DEPARTMENT OF CHEMICAL AND BIOCHEMICAL ENGINEERING
CBE 9110A Chemical Kinetics and Equilibria

Assignment # 4
Due Date: Wednesday, November 9, 2016 by 6 p.m.
Problem 4.1
A catalytic gas phase reaction is taking place in an isothermal ideal plug flow reactor, filled
with catalyst particles.
A

Some data on the performance of the reactor are shown in the following table.
Space time (h-kg -cat/l)

Fractional conversion of A
(xA)

0.32

0.55

20

0.9

30

0.96

Are the above data consistent with the hypothesis that the reaction is first order and
irreversible? Show your analysis and explain your reasoning.
(20)

Problem 4.2
The kinetics of saponification of saponification of methyl acetate have been studied
O

||

||

CH3-C-O-CH3 + NaOH

CH3-C-O-Na+ + CH3OH

In an isothermal plug flow reactor at 25oC. An acetone-water mixture was used, and the initial
concentration of methyl acetate and sodium hydroxide were both 0.05 g.mol/l. The
experimental data are given in the following table.

Kinetics of methyl acetate saponification

#

Space time (s)

Fractional conversion of NaOH

34.4

0.208

69.0

0.321

139

0.498

69.5

0.342

130

0.466

281

0.670

94.8

0.415

189

0.58

a) Find a rate equation that accurately describes the data in the above table. Specify
numerical values for the unknown constants in the rate equation.
(30)
Problem 4.3
Rate constants fro a liquid phase, second order reaction determined at several temperatures
are presented below.
Temp. (C)

20

25

30

35

40

105k(dm3mol-1s-1)

2.7

4.0

5.8

8.6

13.0

Calculate the Arrhenius parameters A and E for this reaction and show the units. (15)
Problem 4.4
Hexamethylene tetramine-bromine [(CH2)6N4Br4], abbreviated as HABR, can
oxidizethioglycollic acid TGA) to the corresponding disulfide, abbreviated as RSSR. The
overall reaction can be represented as
HABR + 4TGA

2RSSR + 4HBr + (CH2)6N4

This kinetics of this reaction were studied at 298 oC by Gangwani et al. 2002) using glacial
acetic acid as a solvent. Experiments were run in an ideal batch reactor using a large excess
of TGA relative to HABR. The initial reaction rate was measured at various combinations of
initial concentrations. The results are tabulated below.

HABR (mol/l)

TGA (mol/l)

0.1

0.001

-rHABRx106
(mol/l.s)
2.33

0.2

0.001

3.76

0.4

0.001

5.41

0.8

0.001

6.92

1.5

0.001

7.97

3.0

0.001

8.72

0.2

0.002

6.66

0.2

0.004

15.6

0.2

0.006

21.4

10

0.2

0.008

24.0

How well does the rate equation below fit the data?

(20)

Determine values of k and K via a graphical analysis.

(15)

References
Roberts, G.W., Chemical Reactions and Chemical Reactors, Wiley,2009.
Fogler, H.S., Elements of Chemical Reaction Engineering, 4th ed., Prentice Hall, 2006.
Gangwani, H., P.K. Sharma, and K.K. Banerji, Kinetics and mechanism of the oxidation of
some thioacids by hexamethylene tetramine-bromine, React. Kinet. Catal. Lett., 69(2),
369-374 (2002).