GAZI UNIVERSITY

CHEMICAL ENGINEERING
ChE341 CHEMICAL REACTION ENGINEERING

EXAMPLES

1) The first order reaction A B is carried out in a constant-volume batch reactor (k=0.31 min-1).
Derive an equation for time as a function of reactant concentration and calculate the time
necessary to reduce the number of moles of A to 1% of its initial value.

CA = 0.01CA0 k=0.31 min-1 t= 15 min

2) Find the first-order rate constant for the disappearance of A in the gas reaction 2A  R if, on
holding the pressure constant, the volume of the reaction mixture, starting with 80% A,
decreases by 20% in 3 min.

3 min

V V= 0.8 V

2A R
0.8 A 0.4 R
0.2 inert 0.2 inert

1 0.6
When 𝑥 =0 𝑥 =1

.
𝜀 = = - 0.4
∆𝑉 = 0.8 V − V = -0.2 V

.
-ln (1- .
) = k (3 min)

k= 0.231 min-1
3) The following reaction takes place in the gas phase at 400oC.

A+ B → C

The initial composition is as follows (mole percents).

A : 0.40 B: 0.40 C: 0.11 Inerts: 0.09

The reaction takes place in an isothermal reactor that is maintained at a constant pressure of 1 atm.

If the reaction is first-order in A and first-order in B, and if the value of k is 2 liters/mole min, how

long will it take for the mole fraction C to reach 0.15?

NC = NC0 + NA0 XA NA = NA0- NA0 XA NB = NB0 - NB0XB

NA0 XA = NB0XB also NA0 = NB0 that’s why NA = NB

Suppose initially 100 moles mixture

Mole fraction of C yC = 0.15 =

0.15 = XA = 0.086
( )

-rA = - = = k CA C B

CA = CB so

- = = k CA 2

CA0 2 (1−𝑋𝐴) 2
=k( )

( )
= k𝐶 ∫ 𝑑𝑡= k𝐶 𝑡
( )

.
.
 𝑋𝐴
𝜀 ln (1 − 𝑋 ) + (1+ 𝜀 ) k𝐶 𝑡
(1−𝑋𝐴 ) =

A + B → C

40 A
40 B
11 C (11+40) = 51 C
9 inert 9 inert

100 60

( . )
𝜀 = = -0.4 = = 7.248x 10-3 mol/L
. ( )

0.086
−0.4ln (1 − 0.086 ) + (1- 0.4) (2) (7.248x 10 )𝑡
(1−0.086) =

t = 6.33 min
4) Pure gaseous A is prepared under refrigeration and is introduced into a thin-walled capillary
which acts as reaction vessel as shown in Figure. No appreciable reaction occurs during
handling. The reaction vessel is rapidly plunged into a bath of boiling point water, reactant A
decomposes to completion according to the reaction A→R+S, and the following data are
obtained:
Time, min 0.5 1 1.5 2 3 4 6 10 ∞
Length of capillary occupied by reaction 6.1 6.8 7.2 7.5 7.85 8.1 8.4 8.7 9.4
mixture, cm
Find the rate equation in units of moles, liters and minutes.

V= V0(1 + 𝜀𝐴 𝑋𝐴 )
L : Length of capillary occupied by reaction mixture
S : Cross sectional area of capillary tube

L . S = L0 S (1 + 𝜀𝐴 𝑋𝐴 )

L / L0 = ( 1 + 𝜀 𝑋 )

A→R+S
1A 1R,1S

1 2

2−1
𝜀 = =1
1

At any t L / L0 = ( 1 + 𝑋 ) 𝑋 = ( L / L0) -1

𝑋 = ( L / L0) -1

At t =∞ 𝑋 = 1 𝑠𝑜 2 = L∞ / L0 L0 = L∞ / 2 , L0 = 9.4 / 2 =4.7 cm
- = = k CA 2

CA0 2 (1−𝑋𝐴) 2
=k( )
.
.

𝑋𝐴
𝜀 ln (1 − 𝑋 ) + (1+ 𝜀 ) k𝐶 𝑡
(1−𝑋𝐴 ) =

𝜀 = 1,

ln(1 − 𝑋 ) + 2 = k𝐶 𝑡
( )

.
Time, min 0.5 1 1.5 2 3 4 6 10 ∞
L, cm 6.1 6.8 7.2 7.5 7.85 8.1 8.4 8.7 9.4
𝑋 = ( L / 4.7) -1 0.297 0.446 0.53 0.6 0.67 0.72 0.79 0.85 1

ln(1 − 𝑋 ) + 2 0.5 1.04 1.5 2.08 2.9 3.88 5.94 9.47

( )

Slope = 0.79 = k𝐶
5) The data in table is about the reaction of sulfuric acid with diethylsulfate in aqueous solution
at 22.9OC.
H2S04 + (C2H5)2SO4  2C2H5SO4H
Initial concentrations of H2S04 and (C2H5)2SO4 are each 5.5 mol/liter. Find a rate equation for this
reaction.

A+B ↔ 2R

Assume second order reversible reaction

(Since CR at ∞ time < 2 𝐶 it is reversible )

− = k1 CACB – k2 CR2

since 𝐶 = 𝐶 = 5.5 and 𝐶 𝑥 =𝐶 𝑥 CA = CB

𝑎𝑛𝑑 − = k 1 CA 2 – k 2 CR 2

CA= CA0 − 𝐶 𝑥 CR = 2 𝐶 𝑥

At equilibrium since − =0, k2 CRe 2 = k1 CAe2

k2 (2𝐶 𝑥 e)2 = k1 (CA0 --- 𝐶 𝑥 e)2

( )
k2 =

Inserting k2 to the main equation,

 ( )
− = CA0 =k1 CA02(1 − 𝑥 )2– ( ) (2 𝐶 𝑥 )2

integration of rate equation gives

CR= CR0 + 2 𝐶 𝑥 and 𝑥 =

t(min) CR XA
mol/L

0 0 0 0
48 1.38 0.125 0.259
75 2.24 0.2036 0.466
96 2.75 0.25 0.616
127 3.31 0.3 0.813
162 3.81 0.346 1.033
180 4.11 0.37 1.193
267 4.86 0.442 1.77
410 5.42 0.49 2.67
∞ 5.80 0.527

CRe 𝑥 e
Slope =0.00675 =2 k1 ( -1) 5.5
.

k1, k2 can be calculated seperately

( )
k2 =

k1=1.3 x 10-4
k2=2.6 x 10-5

r=1.3 x 10-4 CACB – 2.6 x 10-5 CC2