Chemical Reaction Engineering

Definition of Chemical Reaction

A

chemical reaction has taken place when a detectable number of moles

of chemical molecules of one or more species have lost their identity and
assumed a new form by a change in the kind or number of atoms in the
compound and/or by change in structure or configuration of these atoms.
Types of Reactions

Rate of Reaction (-rA) and Rate Equation

The rate of disappearance of a species say species A, is the number of A
molecules that lose their chemical identity per unit time per unit volume through
the breaking and subsequent reforming of chemical bonds during the course of
the reaction.
The dimensions of rate of reaction for heterogeneous reaction are
number of moles of A reacting per unit time per unit mass of the catalyst.
The rate equation for -rA is an algebraic equation that is solely a function
of the properties of the reacting material and reaction condition, for example,
species concentration, temperature, pressure or types of catalyst) at a point in
the system.

This rate equation is independent of the type of reactor in which the

reaction is carried out. however because the properties and the reaction
conditions of the reacting material may vary with position in a chemical reactor,
-rA can in turn be a function of the position and can vary from point to point in
the system.
Suppose a following reaction where species A reacts to give some
product
A Product
The rate equation for this reaction may have any of the following form
-rA = k CA or
-rA = k1 CA / (1+k2CA) or
any other form depending on the reaction.
In above reaction k or K1 is a constant called as reaction rate constant.
Relative Rates of Reaction
The relative rates of reaction of the various species present in the reaction
can be obtained from the stoichiometric coefficients. Consider following
general reaction,

This can be rearranged in the following form as,

We can see from above equation, for every mole of A consumed c/a moles of C
will get produced. In other word it can be written as,

or

For all species

Reaction Rate Constant

The reaction rare constant is not truly a rate constant; it is merely
independent of the concentration of the reacting species. The quantity k is
referred a specific rate constant or the rate constant.
It is strong function of temperature. It depends whether catalyst is
present or not, and gas phase reaction it depends on total pressure. In liquid
system it also depends on other parameters such as ionic strength and the choice
of the solvent. The other parameters are normally exhibit small effect than the
temperature does, with exception of supercritical solvents.
So we can say k is function of temperature and this assumption works
well for laboratory as well as industrial reactors too. It is great Swedish chemist
Arrhenius who first suggested that the temperature dependence of the specific
reaction rate k, could be correlated by an equation of form

There is rule of thumb that says rate constant doubles for every 10 0C
increase in temperature. However, this hold right only for particle
combination of activation energy and temperature only.
Power Law Model and Elementary Rate Law
Suppose the reaction
aA + bB proudct
-rA =KACAaCBb
For elementary reaction order of reaction refers to the power to which the
concentration are raised in the kinetic rate law
n = a+b
k = (concentration)1-n/time
Units of k for different reaction order
For zero order reaction
k = mol/ dm3.sec
For first order reaction
k = 1/sec
For second order reaction
k = dm3/mol.sec
For third order reaction
k = (dm3/mol) 21/sec

Theories for Rate Constant

Following three theories suggest rate constant and temperature relation.
Arrhenius theory suggest that k directly proportional to e E RT
Collision theory suggest that k directly proportional to T0.5 e E RT
Transition state theory suggest that k directly proportional to T e E RT
A +B AB* AB
Collision theory view the first step is slow and rate controlling, whereas the
transition state theory views the second step to be rate controlling.
Activation Energy
Activation energy term introduced in Arrhenius equation is the
minimum energy required to convert a reactant into a product.
If the reactants are free radicals then they will reactant immediately on
collision. They do not require any activation energy. However, for most of the
atoms and molecules, there is activation energy. Following are reasons to
consider activation energy,
1. The molecules require energy to distort or stretch their bonds so that they
will break them and thus new bonds will form.
2. The steric and electron repulsion forces must be overcome as the
molecules come close to each other.
Activation energy can also be thought as a barrier for the reaction. All
reacting molecules has to pass this barrier in order get converted in to the
product. Following graph plotted with reaction coordinate on x-axis and
potential energy on y-axis.

Design Equation for Different Reactors

Following table gives design equation for different reactor types.
CSTR (continuous stirred tank reactor) also know as Back Mix
reactor. It assumes that, reactant lost their identity as soon as they enter into
the reactor and their concentration becomes equal to the exit concentration of
reactant from the reactor.
PFR (plug flow reactor) assumes that there is no axial mixing and
there is no gradient if any kind in radial direction in small volume of the
reactor.
Hence in CSTR the rate of reaction is same at all location or point
inside the reactor, but in PFR the rate continuously changes along the
direction of the flow.
PBR (packed bed reactor) is used for heterogeneous reaction mostly
involving catalyst in solid form and reactant may be gas, liquid or both.
Batch reactor is used in cases when, reaction is highly exothermic or it is
difficult to carry out reaction in continuous mode

Arrangement of Reactors
Two equal size CSTRs in series will give a higher conversion than two
CSTRs in parallel of the same size, when the reaction order is greater than zero,
i.e. conversion in the series arrangement is greater than in parallel for CSTRs.
For reaction whose rate concentration curve rises monotonically, the
reactor should be ordered so as to keep the concentration of reactant as high as
possible.
When n>1, the ordering of the units should be PFR Small CSTR
large CSTR

Questions From Previous GATE paper

1. The half life of an nth order reaction in a batch reactor depends on
a) Only the rate constant
b) Only the rate constant and order of the reaction
c) Only the rate constant and the initial reactant concentration
d) The rate constant, initial reactant concentration and the order of the
reaction

2. Dehydrogenation of ethane, C2H6 (g) C2H4 (g) + H2 (g), is carried out

in a continuous stirred tank reactor (CSTR). The feed is pure ethane. If

the reactor exit stream contains unconverted ethane along with the
products, then the number of degrees of freedom for the CSTR is
A) 1,
B) 2,
C) 3,
D) 4
3. For a homogeneous reaction system, where
Cj is the concentration of j at time t
Nj is the number of moles of j at time t
V is the reaction volume at time t
t is the reaction time.
The rate of reaction for species j is defined as
(A)

(B)

(C)

(D)

4.The liquid phase reaction A Products is governed by the kinetics- rA= k

CA1/2. If the reaction undergoes 75% conversion of A in 10 minutes in an
isothermal batch reactor, the time (in minutes) for complete conversion of A is
A) 40/3
B) 20
C) 30
D)
5. A well-stirred reaction vessel is operated as a semi-batch reactor in which it
is proposed to conduct a liquid phase first order reaction of the type A
B. The reactor is fed with the reactant A at a constant rate of 1 liter/min having
feed concentration equal to 1 mol/liter. The reactor is initially
empty. Given k = 1 min-1, the conversion of reactant A based on moles of A fed
at t = 2 min is
A) 0.136

B) 0.43

C) 0.57

D) 0.864

6. A packed bed reactor converts A to R by first order reaction with 9 mm

pellets in strong pore diffusion regime to 63.2% level. If 18 mm pellets are
used what is the conversion.
A) 0.39

B) 0.61

C) 0.632

D) 0.865

7. An irreversible gas phase reaction A 5B is conducted in an isothermal

batch reactor at constant pressure in the presence of an inert. The feed contains
no B. If the volume of the gas at complete conversion must not exceed three
times the initial volume, the minimum mole percent of the inert in the feed must
be
(A) 0
(B) 20
(C) 33
(D) 50
8. Consider the following reactions between gas A and two solid spherical
particles, B and C of the same size.
A+B
gaseous product,
A+C
ash
The ash does not leave the particle C, Let t1 and t2 be the times required for A to
completely consume particles B and C, respectively, If k1 and k2 are equal at all
temperatures and the gas phase mass transfer resistance is negligible, then
(A) t1 = t2 at all temperatures
(B) t1 = t2 at high temperatures
(C) t1 > t2 at high temperatures
(D) t1 < t2 at high temperatures
9. Consider the following elementary reaction network
A 1
B
2
3

4
C
D
The activation energies for the individual reactions are E1 = 100 kJ/mol, E2 =
150 kJ/mol, E3 = 100 kJ/mol, and E4 = 200kJ/mol. If the feed is pure A and the
desired product is C, then the desired temperature profile in a plug flow reactor
in the direction of flow should be
(A) constant at low temperature
(B) constant at high temperature
(C) increasing
(D) decreasing.
10. The first order liquid phase reaction A P is to be carried out isothermally
in the following ideal reactor configurations.
(P) A 1 m3 CSTR followed by a 1 m3 PFR,
(Q) A 2 m3 CSTR
(R) A 1 m3 PFR followed by a 1 m3 CSTR,
(S) A 1 m3 CSTR followed by a 1 m3 CSTR,
The overall exit conversions X, for the above configurations P, Q, R and S,
assuming identical inlet conditions and temperature, are related as

(a) XP > XR > XS > XQ

(c) XP = XS = XQ = XR

(b) XP = XR > XS > XQ

(d) XQ > XP > XR > XS