ASSIGNMENT 1

Question 1
Define the following terms.
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14
1.15

Activation Energy of a reaction

Homogeneous Catalyst
Heterogeneous catalysts
Rate determining step
Homogeneous reactions
Elementary reactions
Heterogeneous reactions
Conversion of A
Space time
Space velocity
Molecularity
Order of reaction
Dimensions of the rate constant
Steady-state approximation
Net rate of change of a reaction
[30]

Question 2
The homogeneous decomposition of ozone proceeds with the rate equation:

rO3

O3
k
O2

A suggested mechanism is :
O3 O2 O *
Step 1:
Step 2:

O3 O * 2O2

Determine the rate equation

[15]
Question 3
Derive a design equation in terms of conversion for three steady state plug flow reactors
with volume V1, V2, and V3 in series.
[10]
Total [ 55 ]
ASSIGNMENT 2

Question 1
Ethylene is combusted with air to produce carbon dioxide and water. Set up a
stoichiometric table for the reaction. Include any inerts. Show the values for the initial
molar ratios for all components. Air is added with an excess of 20 % of amount moles
required for Ethylene.
[9]
Question 2
Find the overall order for the irreversible gas reaction performed in a batch reactor
2 H 2 2 NO N 2 2 H 2O

from the following constant volume data obtained using equilmolar amounts of hydrogen
and nitric oxide. The reactor is operated isothermally at 320 K.
Total Pressure
[ mm Hg ]
Half Life
[s]

200

240

280

360

265

186

115

67

Show calculations for 115 s. Summaries the rest in table form.

[ 20 ]
Question 3
An elementary homogenous first order reaction can be represented by the following
equation:
A k1 R

From experimental results it were established that catalyse C increase the rate of
conversion of A. The homogeneous reaction can be represented by the following
equation:
A C k2 R C

Explain and show all relevant figures and derivations how you would apply the integral
method to solve the relationship between the catalyse concentration and the rate constants

[7]
Question 4
The herbicide atrozine is found in the Des Plaines River, USA. It is treated by passing
the river through a gently sloping rectangular marsh. In the marsh, the atrozine degrades
according to first order kinetcs:
Atrozine

products

4.1 What type of reactor would you model the marsh as? Why?
(3)
4.2 Set up the equations necessary to solve for the conversion of atrozine.
(10)
4.3 What will the conversion of atrozine be once the river has passed through the marsh?
(7)
Additional Information
k = 16 x 10 -5 hr-1
Marsh details
Width
Length
Average depth

80 m
1200 m
0.25 m

Entering volumetric flow rate:

Entering concentration of atrozine:

2 m3.hr-1
10-5 mol.L-1
[ 20 ]
Total [ 56 ]

ASSIGNMENT 3
Question 1

Component A is converted into product R in a plug flow reactor according to the

following stoichiometry:
A R

This elementary liquid reaction was investigated at 2 temperatures with the results
tabulated below. The initial concentration of R was zero.
Temperature

Conversion of
A

Time
[minutes]

45 oC
85 oC

60 %
58.1 %

10
1

(i)

Calculate the equilibrium conversion for the temperatures: 25,35, 45, 55,65,75 and
85 oC. Draw a diagram XAe vs temperature. Determine the temperature at which 80
% conversion is obtained.
(16)
(ii)
Determine the rate constants for the forward and reverse reactions for the
temperature determined in (i). Obtain a relationship between the rate constant
and temperature using Arrhenius law.
(22)
Additional information
Go,298 K = -12000 J.mol-1
R,o , 298 K = -65 000 J.mol-1
CP,A = CP,R = 25 J.mol.-1K-1 = constant
[38]
Question 2
For the parallel reactions:
A + BR

desired

A + BS

undesired

2.1

dCR/dt = k1CACB0.6
dCS/dt = k2CA0.6CB1.7

Give the expression for the overall fractional yield for:

2.1.1) A plug flow reactor

2.1.2) A mixed flow reactor.
(6)
2.2

Explain the concentration combinations needed to achieve the best possible

conversion of R. You need to find the ratio rs/rR
(9)
[15]

Question 3
3.1 What assumptions are made in the shrinking core model?
(3)
3.2 Name the five consecutive steps may be distinguished in the shrinking core model.
(5)
[8]
[ 61 ]

ASIGNMENT 4
The second order saponification of ethyl acetate is carried out in a plug flow reactor
system. The reaction stoichiometry can be represented by the following equation:


C 2 H 5 CH 3 COO ( aq ) NaOH ( aq )

Na CH 3 COO ( aq ) C 2 H 5 OH ( aq )

The rate constant for the forward reaction is:

1
1
k 0.39175 exp 5472.7

273 T

m3

kmol.s

The equilibrium constant in terms of temperature is represented by the following

equation:
3885.44
T

K c 10
This reaction was investigated in under isothermal conditions

Tasks
(i)
(ii)

Setup an overall mass balance to predict the extent of conversion of ethyl

acetate.
Perform a sensitivity analysis on the developed model in terms of the
following parameters
a. Temperature
b. Initial reactant concentration
c. Ratio of initial components
d. Stirring speed. Use any method to solve the integral equation.

Additional information
Volume of single reactor = 10 L
The production rate of Sodium acetate is 25 kmol.hr-1.
Mark allocation:
Literature
Model Development
Calculations
Reactor Design
Discussion
Conclusion
Overall

5
10
20
15
40
5
5

Your assignment should include a computer model. Please supply the file on a CD.

MEMORANDUM
ASSIGNMENT 1
Question 1

1.1

The activation energy of a reaction is defined as the energy difference between the
reactants of the reaction and the activated complex
Homogeneous catalysts are catalysts that are in the same phase as the reactants.
Heterogeneous catalysts are not in the same phase as the reactants.
The slowest step in a sequence of reaction steps is known as the rate .;
determining step.
Homogeneous reactions are those in which the reactants, products ,and any
catalyst used forms one continuous phase: gaseous or liquid.
In an elementary reaction, the rate equation corresponds with the stoichiometric
equation.
Heterogeneous reactions require the presence of at least two phases to proceed at
the rate which they do.
Conversion XA as the number of moles of A that have reacted per mole of A fed to
the system.
The space time is the time necessary to process one reactor volume of fluid; based
on entrance conditions.
The space velocity is defined as the volume processed per unit time.
Molecularity is the number of molecules involved in reaction (only an elementary
reaction)
The order of reaction is the powers to which the concentrations are raised.
(time)-1 (concentration)1-n
Assume steady-state i.e. ignore all rates of change in the system that only exist for
a short time.
If component i takes part in more than one reaction its net rate of change is the
sum total of all the rates of change that a component undergoes.

1.2
1.3
1.4

1.5

1.6

1.7

1.8

1.9

1.10
1.11

1.12
1.13
1.14

1.15

Question 2

O3 k1 O2 O
*

O2 O k 2 O3
*

O3 O k3 2O2
*

2O2 k 4 O3 O

Let the k values refer to the components disappearing:

- rO3

The rate of appearance of

is :

*
*
2
k1 O3 k ' 2 O2 O k '3 O3 O k ' 4 O2

1.

 *
*
2
k1 O3 k2 O2 O k3 O3 O k 4 O2

r*

2.

from steady state approximation:

r*

k O k4 O2
1 3

k2 O2 k3 O3
2

3.

Substitute Equation 3 into 1

k O k4 O2
k O k4 O2
2
k1 O3 k2 O2 1 3
k3 O3 1 3
k4 O2
k2 O2 k3 O3
k2 O2 k3 O3
2

- rO3

Simplify

- rO3

- rO3

2 k1 k3 O3 2 k 2 k 4 O2

k 2 O2 k3 O3
2

For k4 very small, Equation 4 reduce to

- rO3

2 k1 k3 O3

k 2 O2 k3 O3
2

For k3 << k2, then

2 k1 k3 O3
k ' O3

O2
k 2 O2
2

- rO3

k1 O3 k 2 O2 k3 O3 k 2 O2 k1 O3 k 4 O2 k3 O3 k1 O3 k 4 O2 k 4 O2 k 2 O2 k3 O3
k 2 O2 k3 O3

The mechanism is correct.

Question 3
IN = OUT + DISAPPEARANCE + ACCUMULATION

4.
5.

FA= FA+dFA - rAdV

dFA = + rAdV
but FA = FAo (1 - XA)

V
C Ao
vo

XA

dX A

rA

For multiple reactors in series

total

A3
A2
dX A
dX A
dX A
1 2 3 C Ao


C Ao
X Ao rA X A1 rA X A 2 rA

X A1

XA

dX A

rA

ASSIGNMENT 2
Question 1
C2H4 + 3 O2 2 CO2 + 2 H2O
Let the initial concentration of Ethylene be CAo.
From the Stoichiometry, the initial oxygen concentration is determined as follows:
FBo = 1.2 x ( 3 FAo)
B

FBo 1.2 3

3.6
FAo
1

N2 initial molar ratio

I B

0.79
0.79
3.6
13.5
0.21
0.21

Compound
C2H4
O2

Symbol
A
B

CO2
H2O
N2

C
D
I

Entering
FAo
FBo = B FAo
= 3.6 FAo
0
0
FI = I FAo =
13.5 FAo

Change
- FAo XA
- 3 FAo XA

Leaving
FA = FAo (1- XA)
FB = FAo (3.6 - 3 XA )

2 FAo XA
2 FAo XA
-

FC =2 FAo XA
FD =2 FAo XA
FI = 13.5 FAo

Question 2
2 H 2 2 NO N 2 2 H 2O

From Reaction - rA

k C H 2 C NO

For equimolar addition of reactants, it follows:

rA k C H 2 C NO kC H 2 kC n H 2
For nth order method:

CA1-n - CAo 1-n = (n-1) kt ( n 1)

Applying the half life method:

at half life CA = CAo

t1
2

F n1 1 C 1n
A
k ' n 1
o

where F = 0.5

plot log t vs log CAo give a straight line with slope (1-n)
For the data supplied : For 115 s
PTot = 280 / 760 = 0.368 kPa
From Daltonss Law
PTot = PH2 +PNO +PN2 +PH2O ( Let H2 = A )
From Stoichiometry PN2 = 0.5 ( PAo PA)

From Stoichiometry PH2O = ( PAo PA)

Also PH2 = PNO (stoichiometric amounts added)
Thus PTot = PA + PA + 0.5 ( PAo PA) + ( PAo PA)
1.5 PA = 1.5 PAo PTot

Also at half life, PAo = 2 PA

1.5 PA = 1.5 (2 PA ) PTot

PA = (PTot ) / 1.5

PA = CA RT CA = PA / RT = (PTot / 1.5 ) / RT = (368.42 / 1.5) / (8.314 * 320 )

= 0.092 mol.m-3
From Half life definition: CAo = CA x 2 = 0.184 mol.m-3

Summary of Results
Total
Pressure

200

240

280

320

360

133.333333

160

186.6667 213.3333

240

266.666667

320

373.3333 426.6667

480

265

186

[ mm Hg ]
Partial
Pressure
Of A
[ mm Hg ]
Initial
Partial
Pressure
Of A
[ mm Hg ]
Half Life
[s]

115

104

67

Pressure
kPa

0.351

0.421

0.491

0.561

0.632

CAo
mol/m3

0.132

0.158

0.185

0.211

0.237

log CAo

2.120

2.199

2.266

2.324

2.375

log t1/2

2.423

2.270

2.061

2.017

1.826

1- n = slope from curve = -2.271

Therefore the reaction order is 3.27

Question 3
Homogeneous catalysed reactions can be represented by the following equations:
A k1 R

A C k2 R C

The reaction rates are:

d CA

dt

d CA

dt

k1C A
1

k 2 C ACC
2

The overall rate of disappearance of reactant A is then:

d CA

dt

k1C A k 2 C ACC

d CA

dt

k1 k 2CC C A

On integration the following equation is obtained:

C
ln A ln1 X A k1 k 2 CC t k observed t
C Ao
The values of k1 and k2 is obtained by performing a number of runs at different catalysed
concentrations. A plot of kobserved vs CC is then used to determine k1 and k2 from the
intercept and slope respectively.

k observed

0.05

0
0

0.05
CC

Question 4
4.1 What type of reactor would you model the marsh as? Why?

(3)

As a plug flow reactor. The reasons are as follows:

(i)
(ii)

it has a gentle slope, resulting that the water will flow slowly from the
entrance to the exit, with minimal mixing
the inlet flow rate is much smaller than the total volume of the marsh, an
indication that the degree of mixing is very small;

4.2 Set up the equations necessary to solve for the conversion of atrozine.

MARSH

(10)

FA
CA

FAo
CAo

Mass Balance
In = Out

Disappearance of
+
reactant by reaction

For Steady state : Accumulation = 0

Consider the abovementioned mass balance in terms of rates

Input of A
(moles/time)

FA

Output of A
(moles/time)

FA + d FA

Disappearance =

(-rA) d V

units

moles A reacting

volume of differential element

time volume of fluid

of A
(moles/time)
For Steady state the rate of Accumulation of A in the reactor is:
d NA / dt = 0
FA

But FA =

(FA + d FA
FAo

)+

(-rA) d V

(1- XA)

Therefore
-dFA =
-d[FAo (1- XA)]
FAo dXA

(-rA) d V
=

(-rA) d V
=

(-rA) d V

Group terms that are dependent

1/ (-rA) dXA

1/ FAo d V

Accumulation of
reactant

Integrate over the whole reactor

X Af

FAo

C Ao

V
o

C Ao

X Af

dX A
(-rA )

dX A
(-rA )

0
X Af
0

dX A
(-rA )

dV

FAo
0

17.

4.3 What will the conversion of atrozine be once the river has passed through the
marsh? (7)
DESIGN EQUATION

V
o

C Ao

X Af

dX A
(-rA )

24000
1

2
16 x 10 5

X Af

24000
1

2
16 x 10 5

X Af

dX A
(1 - X A )

dX A
(1 - X A )

Integration Yields

24000 16 x 10 5
2

0.15 1 - X A

XA = 0.85

ln 1 - X A

ASSIGNMENT 3
Question 1
The performance / design equation of a plug flow reactor is

p C Ao

Integration Yields

XA

A
dX A
dX A
1

C
o rA Ao o k1C A k 2 C R k1

k1 p
X Ae

XA

dX A
o X A
1
X Ae

1.

2.

ln 1 X A

X
Ae

The equilibrium conversion is a function of the equilibrium constant which is a function

of temperature. The equilibrium constant at different temperatures needs to be
determined. Then the equilibrium conversion can then be determined:
The specific heats are the same, thus Cp = 0, thus the heat of reaction is independent of
temperature:
RR,o , 298 K = -65 000 J.mol-1

The equilibrium constant at 25 oC is determined as follows:

12000
o
126.9
K 298o C exp G298
RT exp
8.314 298

The equilibrium constant at other temperatures is determined as follows:

ln

K o
298 C

o
G298 1 1

8.314 T 298

o
G298
1
1
K T K 298o C exp

8.314 T 298
The equilibrium conversion is determined as follows:

X Ae

K
K 1

The values are summarised in the table below:

Temperature
[K]
298
308
318
328
338
343.3
358

, at T
126.91
54.14
24.37
11.52
5.69
3.98
1.56

Xae
0.992
0.982
0.961
0.920
0.851
0.799
0.610

From the table is determined that the temperature should remain below 343.3 K to ensure
that 80 % conversion is achieved.
(ii) The rate constants for the forward reaction is determined from the design equation.

k1 p
X Ae

ln 1 X A

X
Ae

The equilibrium conversion is determined using the supplied temperature, determine the
corresponding equilibrium constant and then the equilibrium conversion
XAe = 0.958 at 45 oC
Substitute this value in the design equation with corresponding data results in the rate
constant, k1:
For t = 45 oC XA = 0.6, and = 10 minutes

k1 10
ln 1 0.6
0.958
0.958

k1 0.0839 s 1

Once k1 is determined, k2: is determined after K is determined at the experimental data:

For t = 45 oC from the table in (i), K = 24.372. The value of k2 is thus:
K

k1
0.0839
24.372
k2
k2

k2 = 0.00344 s-1.

k1 p

ln 1 X A
X Ae

X Ae
Summarised data:
Temperature

Conversion Space
of A
Time

Xae

k1

k2

C
45
85

318
358

0.60
0.581

11.24
2.34

0.958
0.622

0.084 24.372 0.00344

1.858 1.563
1.189

Using Arrheniuslaw, the relationship between the rate constant and temperature is
determined:

E1

k1,358 K 1.858 k1,0 e RT1

E
1
k1,318 K 0.084
k1,0 e RT2

Substituting all values, E1 = 73269 and k1,o = 9.12 E+10

In the same fashion E2 and k2,o is determined:

k 2,358 K
k 2,318 K

E2

k 2,0 e RT1
1.189

E
2
0.00344
k 2,0 e RT2

E2 = 1.383 x 105 and k2,o = 1.808 x 1020

Thus

k1,T k1, 0 e
k 2,T k 2,0 e

E1
E2

73269

RT1

9.12 x1010 e

RT

1.808 x 10 e
20

RT1

5
1.383 x10

RT

Question 2

A)

i)

PFR:

1
C Ao C Af

C A

dC

C Ao

Where is the instantaneous yeild of (3)

k1C A CB0.6

k1CBCB0.6 k 2C0A.6C1B.7

1
PFR:
C Ao C Af

C A

dC

as above

C Ao

max CSTR

b)

rs k 2 C 0A.6 C1B.7

rR
k 1C A CB0.6

For the sake of the investigation assume k1 k2

So

rs k 2 C 0A.6 C1B.7

C A0.4 C1B.1
0. 6
rR
k 1C A C B

C1B.1
C 0A.4

We want to minimise

rs
in order to maximise this reaction for desired product.
rR

Firstly, the concentration of CB could be kept small in order to minimise the ratio.
However, since 1.1 does not affect the ratio substantially we need to focus on CA. CA is
fractional and the fraction below the denominator must be maximised in order to
rs
minimise
.
rR
Hence CA must be maximised.

Distributed
Feed of B

B
OR
A
B

Question 3
3.1 The model assumes that
(1)
(2)
(3)

the reactant is a non porous unreacted solid

reaction occurs in an infinitely thin zone separating the core from
the completely reacted product;
pseudo-steady state exists.

3.2 The five consecutive steps may be distinguished as

(1)
(2)
(3)

diffusion of gaseous reactant through gas film surrounding

the particle to particle surface
penetration of A by diffusion through pores and cracks in
the layer of product to the surface of unreacted core,
chemical reaction at surface of core

(4)
(5)

diffusion of any gaseous products back through product

layer to exterior surface of the solid
mass transfer of gaseous product through gas film, back
into the main body of gas