Chemical Reaction

Engineering I
(CHE 332)

By
Engr. Dr. O.U. Osazuwa
(AMIChemE)
 COURSE OUTLINE

• Classification and types of reactions.

• Kinetics of reactions.
• Homogenous reactions.
• Rate expressions
• Design equations for single reactions.
• Single ideal reactors: batch, mixed flow and
plug flow reactors.
• Size companion of single reactors. Design for
multiple reactions.

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 REACTION (Rxn)

• A rearrangement of the atoms or molecules

of two or more substances in contact,
resulting in the formation of new substances.

• Chemical reactions: electrons interacting.

• E.g. of reaction: acid with a base, results in

the creation of a salt and water.

• Some, but not all, reactions can be reversed.

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CLASSIFICATION AND TYPES OF REACTIONS

Classified based on:

1. Physical state : i.e. homogenous or heterogenous rxns
(could be catalytic & non-catalytic reactions).

2. Type/nature of chemical reaction:

Combination, Decomposition, Displacement or, Substitution, Double
displacement, Redox and Rearrangement reactions.

3. Direction of the reaction: Reversible and irreversible

reaction.

4. Absorption or Evolution of Heat: Exothermic (heat loss),

or Endothermic (heat gain)reaction.

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HOMOGENOUS AND HETEROGEN0US REACTION.

Homogenous reaction – reactions that occur in one

phase. i.e. reactants are in one phase.
Examples:
• Most gas phase reactions
• most liquid phase reactions
• Fast reactions such as burning of a flame.
• Reactions in colloidal systems, enzyme and microbial
reactions
• Ammonia synthesis
• Burning of coal
• Oxidation of ammonia to produce nitric acid
• Roasting of ores
• Attack of solids by acids

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HOMOGENOUS AND HETEROGEN0US REACTION.

Heterogenous reactions – reactions that occur

in two or more phases. i.e., reactants are in more
than one phase.

Examples:
• gas phase absorption with reaction
• Cracking of crude oil
• reduction of iron ore to iron and steel
• oxidation of SO2 to SO3.

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 Assignment

Classify all the given examples of homogeneous &

heterogenous into catalytic & non-catalytic reactions.
• Most gas phase reactions
• most liquid phase reactions
• Fast reactions such as burning of a flame.
• Reactions in colloidal systems, enzyme and microbial reactions
• Ammonia synthesis
• Burning of coal
• Oxidation of ammonia to produce nitric acid
• Roasting of ores
• Attack of solids by acids
• gas phase absorption with reaction
• Cracking of crude oil
• reduction of iron ore to iron and steel
• oxidation of SO2 to SO3.

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 TYPE/NATURE OF CHEMICAL REACTION

No. Reaction Types Examples

1 Combination Reaction A+B → C

2 Decomposition Reaction AB→ A+B

3 Single Displacement AB + C → AC+B

4 Double Displacement A+B–+C+D– → A+C–+B+D–

5 Combustion Reaction CxHy+ O2 → + OCO + H2O

Heat (energy)

6 Precipitation Reaction AB + CD → AD(Insoluble) +

BC

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 KINETICS OF REACTIONS

Involves the study of the rate of

chemical processes which includes:
1. The change of concentration of
reactants with products.
2. The study of how fast/slow reactants
change into products.
3. Breaking down elementary processes
into Chemical reaction.

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 KINETICS OF REACTIONS

• Elementary processes involves a transition

between two atomic or molecular states
separated by a barrier.
• The Barrier is the activation energy of the
process, which determines the rate at which
the process occurs.
• Activation energy- is the least amount of
energy that must be surpassed in other for a
chemical reaction to take place.

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 KINETICS OF REACTIONS

Therefore :
4. The higher the activation energy the slower
the reaction and the lower the activation
energy the faster the reaction.
5. The barrier is dependent on the
temperature of the reaction.

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 RATE OF REACTION

• The rate at which reactants are used up or

the rate at which products are formed.
• Its unit is concentration per unit time.
(moldm-3s-1)
• Rate of a reaction tells us how many moles
per liter of A is lost per unit of time.

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 RATE OF REACTION

For a single phase reaction:

aA + bB rR + sS

reaction rate for reactant A is:

The rate of all materials is

-rA/a = -rB/b = rR/r = rS/s----------------(2)

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 RATE LAW

Rate is proportional to the concentration of the

reactants each raised to some power.
i.e. r = kAn ------------3

K = rate constant (s-1)

n = order of the reaction (integer or non-integer)
A = concentration of the reactant
r = rate of reaction

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 TERMS IN CHEMICAL REACTION STUDIES

To determine a reactors capacity we must study

its:
1. Kinetics : Rate (speed) of the reaction
2. Contacting pattern : degree of mixing/ flow.
3. Performance equation:
output = f(input , kinetics, contacting pattern).

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VARIABLES AFFECTING THE RATE OF REACTION (KINETICS).

For homogenous system:

(volume of reactor is same as volume of fluid in the reactor)
Temperature
Pressure
composition.

For heterogeneous system :

Temperature
Pressure
Composition
Mass transfer

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 KINETICS OF HOMOGENEOUS REACTIONS

To determine a reactors capacity we must study

its:
1. Kinetics : Rate (speed) of the reaction
2. Contacting pattern : degree of mixing/ flow.
3. Performance equation:
output = f(input , kinetics, contacting pattern).

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 KINETICS OF HOMOGENEOUS REACTIONS

REACTORS – a reactor is a system (volume) with

boundaries which allows mass to enter and leave
its boundaries.

Reactors could be ideal or non-ideal

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 CHARACTERISTICS OF IDEAL REACTORS

1. Closed systems :No mass enters or leaves

during reaction – semi batch reactors
2. Open system :Mass enters or leaves during
reaction- continuous flow reactors.
3. When the mass is homogeneous through out
the systems and completely mixed– batch
/semi-batch reactors are used, cstr are also
used.
4. When the mass does not mix, and also
heterogeneous conditions-plug flow reactor
are used

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 NON -IDEAL REACTORS

Reasons why we say reactors are non ideal are :

• Dispersion deviates from ideal plug flow

conditions.
• Dead spaces deviate from ideal mixing and
flow conditions.
• Filling deviates from ideal batch conditions.

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 FLOW PATTERNS OF THE IDEAL REACTOR

Three ideal flow patterns exist for ideal

reactors:
1. Batch
2. plug flow
3. mixed flow
Batch flow system :
• uniform composition of reactant exist all
through the reactor
• Composition changes with time.

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FLOW PATTERNS OF THE IDEAL REACTOR CONTD.

Plug flow:
• Fluid passes through the reactor with no
mixing of entering or exiting fluid.
• Assume that the fluid moves in single file
through the reactor.

Mixed flow:
• Composition are uniformly mixed . i.e. same
composition all through the reactor.

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 FLOW PATTERNS OF THE IDEAL REACTOR

Plug flow:
• Fluid passes through the reactor with no
mixing of entering or exiting fluid.
• Assume that the fluid moves in single file
through the reactor.

Mixed flow:
• Composition are uniformly mixed . i.e. same
composition all through the reactor.

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ELEMENTARY REACTIONS AND MOLECULARITY.

Unimolecular
A products, rA = K [A]1

Bimolecular
A + A products, rA = K[A]2
A + B products, r = K [A]1[B]1
Trimolecular
A+ A + A Products, r = K[A]3
A + A +B products, r = K[A]2[B]1
A + B + C products, r = K[A]1[B]1[C]1

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TEMPERATURE DEPENDENT TERM OF A RATE EQUATION.

For elementary reaction the rate expression can be written as

r1 = F1 (temperature) . F2 (composition)------4
recall :
k [CA]n ------------------5
Using Arrhenius law to represent the rate constant :
k = koe-E/RT ----------------6

k = rate constant, n = order of reaction.

ko = frequency or pre-exponential factor
E = activation energy of the reaction
R=constant

NB

Arrhenius suggested that rate constants vary exponentially with the

reciprocal of the absolute temperature.

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TEMPERATURE DEPENDENT TERM OF A RATE EQUATION
CONTD..

From :[6]
k = koe-E/RT---------------------------6
taking log of both sides :
ln k = ln ko – E/RT------------------7
Comparing with equation of a straight line
Y = Mx + C----------------------------8
A plot of ln K vs 1/ T will yield a straight
Slope = -E/R
Intercept = ln ko

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TEMPERATURE DEPENDENT TERM OF A RATE EQUATION.

NB
E can be obtained from rate constants measured
at two different temperatures :

lnk1 = ln A – E/RT1 and ln K2 = ln A -E/RT2------9

ln k2/k1 = E/R [1/T1 – 1/T2] = ln r2/r1-----------10

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TEMPERATURE DEPENDENT TERM OF A RATE EQUATION.

NB
E can be obtained from rate constants measured
at two different temperatures :

lnk1 = ln A – E/RT1 and ln K2 = ln A -E/RT2------9

ln k2/k1 = E/R [1/T1 – 1/T2] = ln r2/r1-----------10

• The temperature dependency of reactions is

determined by the activation energy and
temperature level of the reaction.

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 INTERPRETATION OF BATCH REACTOR DATA

Two methods to interpret batch reactor data exist:

Integral method & differential method

Steps for integral method:

1. Guess the order of the reaction.

2. Make use of its rate equation.

3. Carry out mathematical manipulation (by integration)

4. Check if the plot of concentration vs time yields a straight line.

5. If the data yields a straight line then the guessed rate

equation is correct.

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 INTERPRETATION OF BATCH REACTOR DATA CONTD.

Differential method

1. Insert data into your rate expression.

2. Plot the curve and compare with already

known trends.

Note – no integration is carried out.

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 CONSTANT VOLUME BATCH REACTOR

• This refers to the volume of the reacting

mixture and not the volume of the reactor.

• Same as a constant density system.

Rate expression in a constant –volume system:

i = component, r= rate of reaction, N = no. of

moles, C= concentration, t = time, v = volume.

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 IRREVERSIBLE UNIMOLECULAR REACTION- First order.

A P

(1)

Recall : (2)

• Using boundaries CA and CAO, i.e. final initial

concentration, with time from t and 0.

Integrating (1)

-ln (3) (in terms of concentration)

-ln (4) (in terms of conversion)

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IRREVERSIBLE UNIMOLECULAR REACTION- First order.

A P

• A plot of -lnor -lnvs t gives a straight line

through the origin.

• With Slope k

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IRREVERSIBLE BIMOLECULAR REACTIONS – Second Order.

A+B P

(1)

(2)

CAOXA = amount of A that reacted

CBOXA = amount of B that reacted

Assumptions

CBO/CAO = M (3)

(4)
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IRREVERSIBLE BIMOLECULAR REACTIONS – Second Order.

Rearranging :

(5)

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IRREVERSIBLE BIMOLECULAR REACTIONS – Second Order.
CONTD.

Different forms of the rate equation exist:

= =

M≠ 1

• A plot of any of the parameter above vs. T

gives a straight line.

• With slope (CBO-CAO)k

• Intercept = ln M
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 TEST FOR BIMOLECULAR MECHANISM

EXTREME CASE

1. If CBO is much higher than CAO,

• The eqn. approaches a pseudo first order reaction.

2. For a second order rxn with equal initial

concentration of A and B

2A P

(7)

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 TEST FOR BIMOLECULAR MECHANISM

Integrating (7):

(8)

• Plotting concentration against time in (8) gives a

straight line with slope k and CAOk

respectively.

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 TEST FOR BIMOLECULAR MECHANISM

EXTREME CASE

3. A + 2B P

(9)

Integrating :

ln M-2XA/M(1-XA)= ln CBCAO/CBOCA= CAO(M-2) (10)

Where M≠2

• A plot of any of the parameter above vs Time gives a

straight line through the origin

• With slope CAO(M-2)k

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 IRREVERSIBLE TRIMOLECULAR-TYPE THIRD ORDER
REACTIONS

A+B+D P

In terms of XA

(1-)( (15)

Breaking down into partial fractions and

integrating :

(16)
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 IRREVERSIBLE TRIMOLECULAR-TYPE THIRD ORDER
REACTIONS CONTD.

Commonly used tri-molecular reaction are of the form:

A+2B P

(1-)(2 (17)

Integrating with M = CBO/CAO

(18) where M ≠ 2

(19), where M =2
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 RATE EQUATIONS OF THE Nth ORDER.

Integrating : n≠1

(20)

• When using the empirical rate equation (20) we test

different values of n (2,3) using different runs (CA &

CAO) to see the one that gives us the least variation in k.

• The order with the least variation in k is the desired

order.

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 ZERO ORDER REACTIONS

• A reaction is of zero order when the rate of reaction

is independent of the concentration of materials .

• For this kind of reactions the rates are determined

by other factors apart from the concentration of

reacting materials.

Integrating :

(21)

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 IRREVERSIBLE REACTIONS IN PARALLEL

A R

A S

(22) (W.R.T. A)

(23) (W.R.T. R)

(24) (W.R.T. S)

To find the values of K we make use of the 3 rate

equations (22 -24):

Relating to (3), after integrating (22) becomes -ln (24)

With Slope = k1 + k2
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 IRREVERSIBLE REACTIONS IN PARALLEL

Dividing (23) by (24):

(25)

Integrating we have :

(26)

Slope :

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HOMOGENOUS CATALYSED REACTIONS.

READ UP.

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 IRREVERSIBLE REACTIONS IN SERIES

Considering a uni-molecular type first order

reaction:

A R S

(27)

- (28)

(29)
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 IRREVERSIBLE REACTIONS IN SERIES

ASSIGNMENT

Derive the expression for CR, CS ,CS when

K2> k1, CS when k1 > k2, tmax ,CRmax

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 FIRST ORDER REVERSIBLE REACTIONS

A R
• A reversible process in kinetics means the backward reaction is significant.

• When a reaction does not go to completion the rate equation is of the form:

r = rF – rb (1)
rF = rate of forward reaction

rb = rate of backward reaction

For a reversible reaction :

Kc = equilibrium constant.

M=
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 FIRST ORDER REVERSIBLE REACTIONS

A R

- (2)

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 FIRST ORDER REVERSIBLE REACTIONS CONTD.

CA = CAO – CAOXA (3a)

CR = CRO + CAOXA (3b)

substituting [3] into [2]

At equilibrium = 0

Note

Equilibrium occurs when the rate of formation of

products equals the rate of formation of reactants.

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 FIRST ORDER REVERSIBLE REACTIONS CONTD.

k1 (CAO-CAOXA) = K2 (MCAO +CAOXA) (4)

= or (5)

At equilibrium: fractional conversion = XAe and Kc

Kc = = (6) in terms of equilibrium constant

CRe = concentration of products at equilibrium

CAe = concentration of reactant at equilibrium

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 FIRST ORDER REVERSIBLE REACTIONS CONTD.

The rate equation in terms of fractional conversion of A at

equilibrium

(7)

Factor out CAO

(1-(M+ (8)

Recall Kc = = substitute (6) into (8)

) = (9)

Integrating (9)

-ln(1- (10)
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 FIRST ORDER REVERSIBLE REACTIONS CONTD.

Testing for unimolecular type reversible

reactions is a plot of -ln(1-vs t.

The plot is true if the test give a straight line

through the origin.

Slope =

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 SECOND ORDER REVERSIBLE REACTIONS

A + B R+S

2A R+S

2A 2R

A+B 2R

Note: initial conditions : CAO, CBO, CRO,CSO =0

After integrating:

ln= 2((

• For the reversible bimolecular reaction the test give a straight line
through the origin.

• Because of the difficulty in integration for order other than one or two, we make

use of the differential method.

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VARYING – VOLUME BATCH REACTOR

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