CHEN 305: Chemical Reaction Engineering

I
TUTORIALS

Chemical Engineering Department

Ahmadu Bello University, Zaria
Course Outline
• Interpretation of batch
• Introduction reaction kinetic data from
• Classification of reactions constant volume batch
• Definition of reaction rate reactor
• Variables affecting reaction • Reversible and Irreversible
rates
• Series, Parallel and Autocatalytic
• Kinetics of homogenous reactions
reactions • Variable volume batch
• Elementary and non-
elementary reactions
reactor
• Molecularity and reaction order • Reversible and Irreversible
• Rate constant • Series, Parallel and Autocatalytic
reactions
• Temperature dependency
theories • Analysis of total pressure data
• Activation energy • Single ideal reactors
• Rate expressions from • Batch, mixed and plug-flow reactors
postulated mechanisms
• Design equations
Chemical Reaction Engineering I 2
 Problem 1 Expressing Rate in Terms of Changes in Concentration with Time

PROBLEM: Hydrogen gas has a nonpolluting combustion product (water vapor). It is used as a
fuel aboard the space shuttle and in earthbound cars with prototype engines:
2H2(g) + O2(g) → 2H2O(g)

(a) Express the rate in terms of changes in [H2], [O2], and [H2O] with time.

(b) When [O2] is decreasing at 0.23 mol/L·s, at what rate is [H2O] increasing?

PLAN: We choose O2 as the reference because its coefficient is 1. For every molecule of O 2 that
disappears, two molecules of H2 disappear, so the rate of [O2] decrease is ½ the rate of
[H2] decrease. Similarly, the rate at which [O2] decreases is ½ the rate at which [H2O]
increases.
SOLUTION:
D[O2] 1 D[H2] 1 D[H2O]
(a) Rate = - =- =
Dt 2 Dt 2 Dt

(b) Calculating the rate of change of [H2O]:

1 D[H2O] D[O2]
=- = -(-0.23 mol/L·s)
2 Dt Dt

D[H2O]
= 2(0.23 mol/L·s)
Dt

= 0.46 mol/L·s
 Problem 2 Determining Reaction Orders from Rate Laws

PROBLEM: For each of the following reactions, use the give rate law to determine the
reaction order with respect to each reactant and the overall order.

(a) 2NO(g) + O2(g) → 2NO2(g); rate = k[NO]2[O2]

(b) CH3CHO(g) → CH4(g) + CO(g); rate = k[CH3CHO]3/2
(c) H2O2(aq) + 3I-(aq) + 2H+(aq) →I3-(aq) + 2H2O(l); rate = k[H2O2][I-]

PLAN: We inspect the exponents in the rate law, not the coefficients of the balanced equation,
to find the individual orders. We add the individual orders to get the overall reaction
order.

SOLUTION:
(a) The exponent of [NO] is 2 and the exponent of [O2] is 1, so the reaction is second order with
respect to NO, first order with respect to O2 and third order overall.
 3 3
(b) The reaction is 2 order in CH3CHO and 2 order overall.

(c) The reaction is first order in H2O2, first order in I-, and second
order overall. The reactant H+ does not appear in the rate law, so
the reaction is zero order with respect to H+.
Problem 3 Determining Reaction Orders from Rate Data

Table 1: Initial Rates for the Reaction between A and B

Initial Rate Initial [A] Initial [B]
Experiment (mol/L·s) (mol/L) (mol/L)
1 1.75x10-3 2.50x10-2 3.00x10-2

2 3.50x10-3 5.00x10-2 3.00x10-2

3 3.50x10-3 2.50x10-2 6.00x10-2

4 7.00x10-3 5.00x10-2 6.00x10-2

[B] is kept constant for experiments 1 and 2, while [A] is doubled. Then [A] is kept constant
while [B] is doubled.
 Finding m, the order with respect to A:
We compare experiments 1 and 2, where [B] is kept constant but [A] doubles:
Rate 2 k[A] m [B] n
2 2
=
Rate 1 k[A] m [B] n
1 1
m
[A] 2 [A]2 m
= m =
[A]1 [A]1
m
3.50x10-3 mol/L·s 5.00x10-2 mol/L
=
1.75x10 mol/L·s
-3
2.50x10-2 mol/L

Dividing, we get 2.00 = (2.00)m

so m = 1
 Finding n, the order with respect to B:

We compare experiments 3 and 1, where [A] is kept constant but [B] doubles:

Rate 3 k[A] m [B] n

3 3
=
Rate 1 k[A] m [B] n
1 1
n
[B] 3 [B]3 n
= n =
[B]1 [B]1

m
3.50x10-3 mol/L·s 6.00x10-2 mol/L
=
1.75x10 mol/L·s
-3
3.00x10-2 mol/L

Dividing, we get 2.00 = (2.00)n

So, n = 1
 CLASS WORK Determining Reaction Orders from Rate Data

PROBLEM: Many gaseous reactions occur in a car engine and exhaust system.
One of these is

NO2(g) + CO(g) → NO(g) + CO2(g) rate = k[NO2]m[CO]n

Use the following data to determine the individual and overall reaction
orders:
Initial Rate Initial [NO2] Initial [CO]
Experiment (mol/L·s) (mol/L) (mol/L)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20
PLAN: We need to solve the general rate law for m and for n and then add those
orders to get the overall order. We proceed by taking the ratio of the rate
laws for two experiments in which only the reactant in question changes
concentration.
SOLUTION:

To calculate m, the order with respect to NO2, we compare experiments 1 and 2:

m m
rate 2 k [NO2]m2[CO]n2 [NO2] 2 0.080 0.40
= = =
rate 1 k [NO ] [CO]
m
2 1
n
1 [NO2] 1 0.0050 0.10

16 = (4.0)m
So, m = 2
The reaction is second order in NO2.
To calculate n, the order with respect to CO, we compare experiments 1 and 3:

n
rate 3 k [NO2]m3[CO]n3 [CO] 3
= =
rate 1 k [NO2]m1 [CO]n1 [CO] 1

n
0.0050 0.20
=
0.0050 0.10

1.0 = (2.0)n

so n = 0
The reaction is zero order in CO.
rate = k[NO2]2[CO]0 or rate = k[NO2]2
Problem 4 Determining the Energy of Activation

PROBLEM: The decomposition of hydrogen iodide,

2HI(g) → H2(g) + I2(g), has rate constants of 9.51x10-9
L/mol·s at 500. K and 1.10x10-5 L/mol·s at 600. K.
Find Ea.
PLAN: We are given two rate constants and two temperatures, so we
can use the Arrhenius equation to solve for Ea.
SOLUTION:
-1
k E 1 1 k 1 1
ln 2 = - a − so Ea = -R ln 2 −
k1 R T2 T1 k1 T2 T1
-1
ln 1.10x10-5 L/mol·s 1 1
Ea = -(8.314 J/mol·K) −
9.51x10-9 L/mol·s 600.K 500. K

= 1.76x105 J/mol = 1.76x102 kJ/mol