Chemical Reaction Engineering

Chemical Reaction Engineering
Factors affecting rate of reaction

Homogeneous
• Temperature
• Pressure
• Composition
Heterogeneous
• Rate of mass transfer
• Rate of heat transfer
Reaction rate
For homogeneous, V = Vr
• Single
• Multiple
Size Comparison
Batch
• At A=0, Vbatch =V PFR
• Suitable for small
amount
• Multiple products
CHAPTER 3
Interpretation of Batch Reactor Data

TWO STEP PROCEDURE IN THE DETERMINATION
OF THE RATE EQUATION:
1) The concentration dependency is found at fixed temperature.

2) Then the temperature dependence of the rate constants is found,
yielding the complete rate equation.
TWO STEPS OF EQUIPMENT BY WHICH EMPIRICAL
INFORMATION IS OBTAINED:
1) BATCH REACTOR
- Is simply a container to hold the contents while they react.
- Is usually operated isothermally and at constant volume because it
is easy to interpret the results of such runs.
- This is used for obtaining Homogeneous Kinetic Data.
2) FLOW REACTOR
- Is used primarily in the study of the Kinetics of Heterogeneous
Reactions.
TWO PROCEDURES FOR ANALYZING KINETIC DATA:
1) INTEGRAL METHOD
- We guess a particular form of rate equation and, after appropriate
integration and mathematical manipulation, predict that the plot of a
certain concentration function versus time should yield a straight line.
2) DIFFERENTIAL METHOD
- We test the fit of the rate expression to the data directly and without any
integration. However, since the rate expression is a differential equation we
must first find (1/V)(dN/dt) from the data before attempting the fitting
procedure.
3.1 CONSTANT VOLUME BATCH REACTOR
When we mention the constant-volume batch reactor we are really

referring to the volume of reaction mixture, and not the volume of reactor. This
term actually means a constant-density reaction system. Most liquid-phase
reactions as well as all gas-phase reactions occurring in a constant volume
bomb fall in this class.
In a constant-volume system the measure of reaction rate of component i
becomes:
ri = (1/V)(dNi/dt) = d(Ni/V)/dt = dCi/dt
Or for ideal gases, where C = P/RT
ri = (1/RT)(dPi/dt)
The rate of reaction of any component is given by the rate of change of
its concentration or partial pressure; so no matter how we choose to follow
the progress of the reaction, we must eventually relate this measure to the
concentration or partial pressure if we are to follow the rate of reaction.
For the gas reactions with changing numbers of moles, a simple way of
finding the reaction rate is to follow the change in total pressure Π of the
system.
ANALYSIS OF TOTAL PRESSURE DATA OBTAINED IN A
CONSTANT-VOLUME SYSTEM
For isothermal gas reactions where the number of moles of material

changes during reaction, which relates the changing total pressure of the
system Π to the changing concentration or partial pressure of any of the
reaction components.
aA + bB  rR + sS
PA = CART = PAO – (a/ng)( - o)

PB = CBRT = PBO – (b/ng)( - o)
PR = CRRT = PRO + (r/ng)( - o)
PS = CSRT = PSO + (s/ng)( - o)
Where:
 = total pressure at time, t
o = total pressure at time, t = 0
ng = Σ product, gas – Σ reactant, gas
PAO,PBO,PRO,PSO = initial partial pressure of A,B,R,S respectively
CONVERSION
Fractional Conversion or the fraction of any reactant,say A, converted to

something else, or the fraction of A reacted away. We call this simply, the
conversion of A , with symbol XA.
XA = (CAO – CA) / CAO

XA = (PAO – PA) / PAO
Where:
CAO = initial concentration of A
CA = concentration of A at time, t
PAO = initial pressure of A
PA = pressure of A at time, t
IRREVERSIBLE REACTION
• In terms of concentration
- rA = -dca/dt = KCA n
• In terms of fractional conversion or conversion factor, X A

- rA = CAOdXA / dt = K [ CAO (1-XA) ] n
• FOR ZERO ORDER IRREVERSIBLE REACTION, n = 0
In terms of concentration: A  R
CAO – CA = kt
In terms of conversion factor:

CAO XA = kt
Graphical Interpretation:
m = -k m=k
CA XA
t t
• FOR FIRST ORDER IRREVERSIBLE REACTION, n = 1
In terms of concentration: A  R
ln (CAO/CA) = kt

- ln (1-XA) = kt
ln CAO/CA - ln (1-XA) m =k
m=k
t
t
• FOR SECOND ORDER IRREVERSIBLE REACTION ,n = 2
CASE 1: 2A  R
In terms of concentration:
1/CA – 1/CAO = kt

XA/(1-XA) = kCAOt
XA/(1-XA) m =k
1/CA m=k
t
t
CASE 2: A + B  R
(1/M-1) ln((M-XA)/(M(1-XA))) = kCAOt
• FOR nth ORDER

When the mechanism of reaction is not known.
CA 1-n – CAO 1-n

= k (n-1) t n1
RATE EQUATION IN TERMS OF PRESSURE
aA + bB  rR + sS
-(dPa / dt) = k’ Pa n ; k’ = k(RT) 1-n
• For n = 0
PAO –PA = k’t
• For n = 2
• For n = 1 1 / PA – 1 / PAO = k’t
ln ( PAO / PA) = k’t

IRREVERSIBLE REACTION FROM THE HALF LIFE, t1/2
HALF LIFE – time to reduced the amount of ½ the original.
• For n = 0
t1/2 = CAO / 2k
• For n = 1
t1/2 = ln 2 / k
• For n = 2
t1/2 = 1 / CAOk
• For nth order

t1/2 =((((0.5)1-n – 1) (CAO1-n))) / k(n-1)
FRACTIONAL LIFE METHOD, tf
The half life method can be extended to any fractional life method in which
concentration of reactant drops to any fractional value, F= CA / CAO in time tf .
tf =(((F1-n – 1) (CAO1-n))) / k(n-1)
Where:
F = CA / CAO
t = tf
SAMPLE PROBLEM
1) A certain reaction is first order. After 540 min, 67.5 % of the reactant is
decomposed. Determine t when 25% of the reactant has decomposed.
Given:
t = 540 mins
XA = 0.675
Required: t @ 25% conversion

Solution: n =1
-ln( 1 – XA) =kt XA = 0.25
-Ln ( 1- 0.675) = k(540 min) -ln (1-0.25) =(2.08  10 -3 min-1)(t)
k = 2.08  10 -3 min-1 t = 138.31 minutes
2) An aqueous solution of ethyl acetate is to be safonified with NaOH. The
initial concentration of acetate is 5 g/L and that of NaOH is 1M. The value of k
is 92.4 L/ gmolemin. Estimate the time required to saponify 95% of the ester.
Solution:
C2H5C2H302 + NaOH  NaAc + C2H5OOH n =2
MW C2H5C2H302 = 88 g/gmole
CAO = (5g/L) / (88 g/gmole) = 0.0568 M
(1/M-1) ln((M-XA)/(M(1-XA))) = kCAOt
M = 1 / 0.0568 = 17.61
XA= 0.95 k = 92.4 L/gmolemin
(1/17.61-1) ln((17.61-0.95)/(17.61(1-0.95))) = 92.4(0.568)t
t = 0.029 minutes
3) k = 5.3  10-3 L/moles for a certain second order reactions half life is equal to
2500 seconds. Determine the initial concentration of the reactant after 1 hour.
Solution: n=2 ; 2A  products

t1/2 = 1 / CAOk
@ t = t1/2 = 2500s
CA = ½ CAO
2500s = 1 / (CAO(5.3  10-3))
Cao = 0.7547 M
1/CA – 1/CAO = kt
t = 1 hr = 3600s
1/CA – 1 / 0.7547 = 5.3  10-3 (3600s)
CA = 0.3093
4) An artificially produced radioactive isotope decomposes according to the first
order law with a half life period of 15 minutes. In what time will 80% of the
sample be decomposed?
Solution: n = 1; A  R ; t1/2 = 15 minutes(50% of reactant is converted to product.)
For n = 1 : ln (CAO/CA) = kt
CA = 0.5 CAO
ln (CAO / 0.5CAO = k(15 minutes)

k = 0.046 / minute
If XA = 0.8 ; CA = CAO(1-XA) = CAO(1-0.8) = 0.2CAO

ln (CAO / 0.2CAO) = (0.046)(t)
t = 35 minutes
5) At 100°C the gaseous reaction A  2B+C is observed to be first order reaction.
On starting with pure A it is found that at the end of 10 minutes the total
pressure of the system is 176 mmHg, and after a long time 270 mmHg. From
these data find (a) the initial pressure of A, (b) the pressure of A at the end of 10
minutes,© the rate constant of the reaction and (d) the half life period of the
reaction.
Solution:
A  2B + C
n = 1, @ t = 10 mins
PA = 0, PB = 2PAO, PC = PAO
P= PA + PB + PC = 0 + 2PAO + PAO ln ( PAO / PA) = k’t
P= 270 mmHg ln ( 90 / 47) = k’( 10 min)
3PAO = 270 mmHg k’ = 0.065 / minutes
PAO = 90 mmHg
PA = CART = PAO – (a/ng)( - o)
@ t = 10 mins ,  = 176 mmHg t1/2 = ln 2 / k
PA = 90 – (1/2)(176-90) t1/2 = ln 2 / 0.065mins

PA = 47 mmHg t1/2 = 10.66 minutes
6) At 25°C, the specific rate constant for the hydrolysis of ethyl acetate by sodium
hydroxide is found by experiments to be 6.36 L/ molmin. At 40°C, the hydrolysis is
nearly three times faster. Starting with the concentration of base and ester at 0.05
mol/L. What proportion of ester will be hydrolyzed after 10 minutes at 35 °C?
Soluiton:
T1 = 25°C  298K ,K1 = 6.36
T2 = 40°C  313 K, K2 = 3K1
Ln(K2 / K1) =(E / R) (1 / T1 – 1 / T2)
Ln(3K1/ K1) =(E / 8.314) (1 / 298 – 1 / 313)
E = 56,796.79 J / mol
T3 = 35°C  308K
Ln(K3/ K2) =(E / R) (1 / T2 – 1 / T3)
Ln(K2 / 19.08) =(56,796.79 / 8.314) (1 / 313 – 1 / 308)
K3 = 13.39
@ t = 10 mins
1/CA – 1/CAO = kt
CAO = 0.05 mol / L
1/(CAO(1-XA)) – 1/CAO = kt
1/(0.05(1-XA)) – 1/0.05 = 13.39(10)
XA = 0.87  87 %
CAOXA = 0.05( 0.87)
CAOXA = 0.0435
7) At 25°C, the half life of N2O5 decomposition is 5.7 hrs and is independent of
the initial pressure of N2O5. Calculate (a) k, (b) time required for a 95%
decomposition of N2O5.
Solution:
t1/2 = 5.7 hrs  342 mins
For n = 1: t1/2 = ln 2 / k
342 mins = ln2 / k
k = 2.027  10-3
For n = 1: -ln (1-XA) = kt

-ln (1-0.95) = 2.027  10-3 t
t = 1477.91 mins  24.63 hrs

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Chemical Reaction Engineering

Factors affecting rate of reaction

Interpretation of Batch Reactor Data

1) The concentration dependency is found at fixed temperature.

When we mention the constant-volume batch reactor we are really

For isothermal gas reactions where the number of moles of material

PA = CART = PAO – (a/ng)( - o)

Fractional Conversion or the fraction of any reactant,say A, converted to

XA = (CAO – CA) / CAO

• In terms of fractional conversion or conversion factor, X A

In terms of conversion factor:

In terms of conversion factor:

In terms of conversion factor:

(1/M-1) ln((M-XA)/(M(1-XA))) = kCAOt

• FOR nth ORDER

CA 1-n – CAO 1-n

• For n = 1 1 / PA – 1 / PAO = k’t

ln ( PAO / PA) = k’t

HALF LIFE – time to reduced the amount of ½ the original.

• For nth order

tf =(((F1-n – 1) (CAO1-n))) / k(n-1)

Required: t @ 25% conversion

(1/17.61-1) ln((17.61-0.95)/(17.61(1-0.95))) = 92.4(0.568)t

Solution: n=2 ; 2A  products

Solution: n = 1; A  R ; t1/2 = 15 minutes(50% of reactant is converted to product.)

ln (CAO / 0.5CAO = k(15 minutes)

If XA = 0.8 ; CA = CAO(1-XA) = CAO(1-0.8) = 0.2CAO

PA = 90 – (1/2)(176-90) t1/2 = ln 2 / 0.065mins

For n = 1: -ln (1-XA) = kt

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