BATCH REACTOR

Interpretation of rate data

A. SARATH BABU 1
• Simplest reactor – open / closed vessel
• Reactants are placed inside the reactor
and allowed to react over time
• Products and unconverted reactants are
removed and the process is repeated
• Closed system - unsteady state operation
• Fitted with a stirrer
• May have a jacket / cooling or heating
coils inside the reactor
• Generally constant volume / some
designed at constant pressure
• Materials of construction – different
linings
2
3
4
BatchReactorContd. . . 5
BatchReactorAnimation 6
• Used in variety of applications
• Typically for liquid phase reactions that
require long reaction times
• Used only when small amount of product is
required
• Favored when a process is in developmental
stage or to produce expensive products
• Used to make a variety of products at
different times

BatchReactorCont. . . 7
Characteristics of a Batch Reactor

(1) Each batch is a closed system.

(2) The total mass of each batch is fixed.
(3) The reaction (residence) time t for all
elements of fluid is the same.
(4) The operation of the reactor is inherently
unsteady-state; for example, batch
composition changes with respect to time.
(5) It is assumed that, at any time, the batch is
uniform (e.g., in composition, temperature,
etc.), because of efficient stirring.
8
Advantages:
• High conversions can be obtained
• Versatile, used to make many products
• Good for producing small amounts
• Easy to Clean
Dis-advantages:
• High cost of labor per unit of production
• Difficult to maintain large scale production
• Long idle time (Charging & Discharging times) –
leads to periods of no production
• No instrumentation – Poor product quality
BatchReactorContd... 9
 GUIDELINES FOR SELECTING BATCH PROCESSES

• Production rates:
— Sometimes batch process, if the plants have production
capacity less than 10x106 lb/yr (5x106 kg/hr).
— Usually batch process, if the plants have production
capacity less than 1x106 lb/yr (0.5x106 kg/hr).
— Where multiproduct plants are produced using the same
processing equipment.

• Market forces:
— Where products are seasonal (e.g., fertilizers).
— Short product lifetime (e.g., organic pigments).

• Operational problems:
— Long reaction times (when chemical reactions are slow).
— Handling slurries at low flowrates.
— Rapidly fouling materials (e.g., materials foul equipment so
rapidly that shutdown and frequent cleaning are required).
General Mass Balance Equation:

Input = output + accumulation

+ rate of disappearance 11
General Mass Balance Equation:

Input = output + accumulation

+ rate of disappearance
12
Design Equation

General Mass Balance Equation:

Input = output + accumulation

+ rate of disappearance

0 = 0 + dNA/dt + (-rA) V

General Design Equation

-(1/ V) dNA/dt = (-rA)

General Design equation in terms of conversion

(NAo / V) dxA/dt = -rA
13
Design Eqn. for CVBR
-dCA/dt = -rA

CAo dxA/dt = -rA in terms of conversion

Design Eqn. for variable volume batch reactor

CAo /(1+ε AxA) dxA/dt = -rA

Design Eqn. in terms of Total Pressure

(1/δ RT) dPT /dt = (-rA)

14
 Constant Volume Batch Reactor
CA xA
− dCA t dxA
t= ∫ =∫
CA0
− rA C A0 0 − rA

t = CA
0
a
X are
t

15
Stoichiometric Table – Batch Systems
aA + bB → rR + sS
Species Initial Change Final moles

AB N
NAB00 -NA0 xA A0 xA
-(b/a)N N
NAB== N
NAA00(1-x )
(MBA-(b/a)xA)

R NR0 +(r/a)NA0 xA NR= NA0 (MR+(r/a)xA)

S NS0 +(s/a)NA0 xA NS= NA0 (MS+(s/a)xA)
I NI0 0 NI = NI0
Total NT0 NT = NT0 + NA0 δxA

Where: MI = NI0 /NA0

δ = (r/a
For CVBR: CA +=s/a
CA0–(1-x
b/a –);1)C = C [M +(r/a)x ]
A R A0 R A
Constant Volume Batch Reactor
-rA = -dCA/dt = CA0 dxA/dt

1. Zero Order Reaction:

-rA = -dCA/dt = k
CA t

∫ − dC
C A0
A = ∫ k dt
0

CA0 - CA = kt
CA0 xA = kt

Strictly homogenous reactions do not follow zero order. Apparently

the reaction order is made zero w.r.t. a reactant.

17
2. First Order Reaction: A → Products
-rA = -dCA/dt = kCA
CA t
− dC A
∫C C A = ∫0 k dt
A0

-ln (CA/CA0 ) = kt
-ln(1-xA) = kt
Example: N2O5 → 2NO2 + ½O2

-rA = k CA0.6 CB0.4 ??

Unimolecular – Collision theory ??

18
First Order Reaction kinetics
Influence of k

19
3. Second Order Reaction:
2A → Products
A + B → Products CA0 = CB0

-rA = -dCA/dt = kCA2

CA t
− dC A
∫C C A2 = ∫0 k dt
A0

1/CA – 1/CA0 = kt
xA/(1-xA) = kCA0 t

20
4. Second Order Reaction:
A + B → Products CA0 ≠ CB0

-rA = -dCA/dt = kCACB

C C 
ln B A0  K(CB0 -CA0 )
 C B 0C A 

t
 M − xA   C B C A0 
ln  = ln  = (C B 0 − C A0 )kt
 1 − xA   C B 0C A 

Example: CH3COOC2H5 + NaOH → CH3COONa+C2H5OH

21
5. Third Order Reaction:
3A → Products
2A + B → Products CA0 = 2CB0
A + B + C → Products CA0 = CB0 = CC0

-rA = -dCA/dt = kCACBCC = k′ CA3

1 1
2
− 2 = 2k ′t
C A C A0
Example: 2NO + H2 → H2O +N2O
2NO + Cl2 → 2NOCl

22
6. Third Order Reaction:

2A + B → Products CA0 ≠ 2CB0

-rA = -dCA/dt = kCA2CB

2
CB M C B 0 M M kt
ln − = ln − −
CA CA C A0 C A0 2

23
7. Third Order Reaction:

A + B + C → Products CA0 ≠ CB0 ≠ CC0

-rA = -dCA/dt = kCACBCC

C A0 ln(1 / 1 − x A ) C B 0 ln(M B / M B − x A )
+
(C A0 − C B 0 )(C A0 − CC 0 ) (C B 0 − C A0 )(C B 0 − CC 0 )
CC 0 ln(M C / M C − x A )
+ = kt
(CC 0 − C B 0 )(CC 0 − C A0 )

24
8. nth Order Reaction:
nA → Products

-rA = -dCA/dt = kCAn

1 1
n −1
− n −1 = (n − 1)kt
CA C A0

C 1A− n − C 1A−0n = (n − 1)kt

25
The reciprocal of rate approaches infinity as CA → 0

26
Integrated forms – Constant density

27
Note that for a II
order reaction with a
large ratio of feed
components, the order
degenerates to a first
order (pseudo first
order).

28
Differential Method of analysis

CA -rA
k

t f(c)

− dC A
− rA = = f (k , C ) = k f (C )
dt

29
Differential Method of analysis
− dC A
− rA = = k C An
dt
ln(− rA ) = ln(k ) + n ln( C A ) n
ln(-rA)

If –rA = kCAaCBb, how to use DM? ln k

• Use stoichiometric ratio of reactants ln(CA)

• Use method of excesses

• Use method of least squares
ln(−rA ) = ln(k ) + a ln( C A ) + b ln(C B )

30
31
32
Integral Method of analysis

• Guess the reaction order

• Integrate and Derive the equation

• Check whether the assumed order is

correct or not by plotting the necessary
graph

33
34
 Integral Method Differential Method
• Easy to use and is • Useful in complicated
recommended for testing cases

specific mechanism • Require large and more

• Require small amount of accurate data
data • No trial and error
• Involves trial and error • Can be used for
• Cannot be used for fractional orders
fractional orders • Less accurate
• Very accurate
Generally Integral Method is attempted first and
if not successful, the differential method is used.
35
Method of Excesses
Consider –rA = kCAaCBb
• Perform the experiment with CB0 >> CA0 and
measure CA as a function of t.
–rA = kCAaCBb = kCB0 b CAa = k′ CAa
Use either differential method or integral
method and evaluate k’ & a
• Perform the experiment with CA0 >> CB0 and
measure CB as a function of t.
–rA = kCA0 a CBb = k’′ CBb
Use either differential method or integral
method and evaluate k’’ & b
Require multiple experiments 36
Method of Half lives
1 1
n −1
− n −1 = (n − 1)kt (n ≠ 1)
CA C A0 (1-n)
ln(t1/2 )
At t = t1/2 , CA = CA0 /2
1− n n −1 K’
C (2 − 1)
t1/ 2 = A0
(n − 1)k ln(CA0 )

 (2 n −1 − 1) 
ln(t1/ 2 ) = (1 − n) ln(C A0 ) + ln 
 (n − 1)k 
For I Order reactions: t1/2 = ln(2)/k
t1/2 does not depend on CA0
Require multiple experiments 37
Check the value of dimensionless rate constant kCA0 (n-1) t
for each order at t = t½ 38
39
Method of Half lives

40
Method of Fractional lives
The half-life, or half-period, of a reaction is the time
necessary for one half of the original reactant to
disappear.
At t = t1/n , CA = (1- 1/n) CA0
n −1
C 1A−0n (2 n −1 − 1) C 1− n
(3 − 1)
t1/ 2 = t1/ 3 =
A0 2
(n − 1)k (n − 1)k
t1/ 2 (2 n −1 − 1) t1/ 2 ln 2
= = for n = 1
t1/ 3 ( 3 n −1
− 1) t1/ 3 ln 3
2 2
The ratio of any two fractional lives is
characteristic of the order. 41
42
Method of Initial Rates

The order of the reaction with respect to an individual

component can be determined by making an initial rate
measurement at two different initial concentrations of
this species while holding all other concentrations
constant between the two runs.

Advantage of the initial rate method is that complex rate functions

that may be extremely difficult to integrate can be handled in a
convenient manner. Moreover, when initial reaction rates are used,
the reverse reactions can be neglected and attention can be
focused solely on the reaction rate function for the forward
reaction. 43
 Method of Initial Rates
(CA0 )1

(CA0 )2
(-rA0 )1 = slope at (CA0 )1, t = 0

(CA0 )3 (-rA0 )2 = slope at (CA0 )2, t = 0

(-rA0 )3 = slope at (CA0 )3, t = 0

Time, t

-rA0 = k (CA0 )n ln(-rA0 ) = ln(k) + n ln(CA0 ) 44

Method of Initial Rates

d er
o r
es
ln (-rA0 ) g i v
p e
o
Sl

ln CA0
45
46
CA/CA0

DA= kCA0 n-1 t

Comparison of Different order

Reactions in a Batch reactor 47
Variable Volume Batch Reactor
1 dN i 1 d (CiV ) 1  dCi dV 
ri = = = V + Ci
V dt V dt V  dt dt 
dCi Ci dV
ri = + Volume Change with time ??
dt V dt
Fractional Change in Volume or Expansion factor(ЄA):
Change in total no. of moles when reaction is completed
εA =
Total no. of moles fed
Vx A =1 − VX A =0
εA =
VX A =0
Expansion factor can be obtained if we know the initial
volume and the volume at any X. Similarly X can be obtained
given expansion factor. 48
V NT
=
V0 NT 0
NT N A0
=1 + δ x A =1 +δ y A0 x A =1 +εA x A
NT 0 NT 0
r s b
εA =δ y A0 δ = + − −1
a a a

Example: A → 3R, starting with pure A

Since pure A, y = 1.
AO

Also δ = 3/1 -1 = 3-1 = 2.

ЄA = (3 - 1)/1 = 2
With 50% inerts: y = 0.5 & δ = 3/1 -1 = 2.
AO

ЄA= (4-2)/2 = 1
= 0.5 (3-1) = 1
49
Variable Volume Batch Reactor
− 1 dN A −1 − N A0 dx A C A0 dx A
− rA = = =
V dt V0 (1 + ε A x A ) dt 1 + ε A x A dt

N A N A0 (1 − x A ) C A0 (1 − x A )
CA = = =
V V0 (1 + ε A x A ) 1 + ε A xA
C A0 [ M R + (r / a ) x A ]
CR =
1 + ε A xA
CA 1 − xA 1 − C A / C A0
= xA =
C A0 1 + ε A x A 1 + ε AC A / C A 0

50
 CVBR xA
VVBR
CA t dxA
t = ∫ − dCA / − rA =∫
C A0 0 − rA (1 + ε A x A )
C A0

t / CA0
t
1
1 /-rA
− rA (1 + ε A x A )

CA CA0
xA

51
Variable Volume Batch Reactor
1. Zero Order Reaction:
C A0 dx A
− rA = =k
1 + ε A x A dt

Ln(1+ЄAxA)
xA t
dx A
C A0 ∫ = ∫ k dt kЄA/CA0
0
1 + ε A xA 0

C A0 ln(1 + ε A x A ) = kε At t

C A0 ln(V / V0 ) = kε At

52
Variable Volume Batch Reactor
2. First Order Reaction:
C A0 dx A C A0 (1 − x A )
− rA = = kC A = k
1 + ε A x A dt 1 + ε A xA
xA t
dx A
∫0 1 − x A = ∫0 k dt

-ln(1-xA)
− ln(1 − x A ) = kt

* Performance equation is similar to that of CVBR

53
Variable Volume Batch Reactor
3. Second Order Reaction:
2
C A0 dx A  C A0 (1 − x A ) 
− rA = = kC A = k 
2

1 + ε A x A dt  1 + ε A xA 
xA
(1 + ε A x A )dx A
t

∫0 (1 − x A ) 2 = ∫0 k C A0 dt
x A (1 + ε A ) /(1 − x A ) + ε A ln(1 − x A ) = kC A0t

54
Variable Volume Batch Reactor
4. Higher Order Reactions:
n
C A0 dx A  C A0 (1 − x A ) 
− rA = = kC A = k 
n

1 + ε A x A dt  1 + ε A xA 
xA
(1 + ε A x A ) dx A
n −1 t

∫0 (1 − x A ) n ∫0 A0 dt
n −1
= k C

Analytical integration would be difficult.

Resort to either graphical / numerical integration.

55
Constant Volume Batch Reactor (PT vs. t)
PT NT
= =1 +εA x A
PT 0 NT 0

ε A Fractional Volume / Pressure Change ??

1  PT 
xA =  −1
εA PT 0 
N A0 dx A N A0 d 1
− rA = = ( PT − PT 0 )
V0 dt V0 dt ε A PT 0
N A0 dPT N T 0 dPT 1 dPT
= = =
V0ε A PT 0 dt V0δPT 0 dt δRT0 dt
Design equation for CVBR in terms of PT 56
 CVBR – Concentrations in terms of PT
N A0 p A0
C A = C A 0 (1 − x A ) = (1 − x A ) = (1 − x A )
V0 RT 0
1  PT 
xA =  −1
εA PT 0 
1 y A0
p A 0 x A = y A 0 PT 0 ( PT − PT 0 ) = ( PT − PT 0 )
εA PT 0 δy A0
= ( PT − PT 0 ) / δ
p A0 p A 0 −[( PT − PT 0 ) / δ]
CA = (1 − x A ) =
RT 0 RT 0
p B 0 −b [( PT − PT 0 ) / δ]
CB = a
RT 0
57
CVBR – Complex reactions:
1. First Order Reversible Reaction:A ⇔ R
dx A
− rA = C A0 = k1C A − k 2C R = k1C A0 (1 − x A ) − k 2C A0 ( M + x A )
dt
CRe C A0 ( M + x Ae ) k1
KC = = =
C Ae C A0 (1 − x Ae ) k2
dx A k1 (1 − x Ae )
= k1 (1 − x A ) − (M + xA )
dt ( M + x Ae )

Integrating:
x Ae ( M + 1)
ln = k1t
x Ae − x A ( M + x Ae )
58
 CVBR – Complex reactions:
2. Irreversible Reactions in parallel:
A →B
A →C C A CC

− dC A
− rA = = k1C A + k 2C A = (k1 + k 2 )C A CB
dt
CA
Integrating: − ln = (k1 + k 2 )t
C A0 t
dC B dCC CB
rB = = k1C A rC = = k 2C A
dt dt
K1/k2
dC B C B − C B 0 k1
= k1 / k 2 =
dCC CC − CC 0 k 2 CC
59
60
 CVBR – Complex reactions:
3. Homogenous Catalytic Reactions:
A →R
A + C →R + C
CA
− dC A − ln
− rA = = k1C A + k 2C ACC C A0
kobs
dt
Integrating:
t
CA
− ln = (k1 + k 2CC )t = kobs t
C A0
kobs k2

k1

CC
61
 CVBR – Complex reactions:
4. Auto Catalytic Reactions:
A + R →R + R
− dC A
− rA = = kC AC R = kC A (C0 − C A ) kC0
dt
Integrating: t

CA
− ln + ln( C0 − C A )
C A0
-rA
C A0 (C0 − C A )
= ln = kC 0t
C A (C0 − C A0 )

CA = CR =0.5 C0
62
CVBR – Complex reactions:
5. Irreversible Reactions in series:
A → B → C CB0 = CC0 = 0

CC/CA0
CA/CA0

CB/CA0

CB, max and topt - ?? 63

 − dC A
− rA = = k1C A
dt
CA
Integrating: − ln = kt (or ) C A = C A0 e −k1t
C A0
dC B
rB = = k1C A − k 2C B
dt
dC B
+ k 2C B = k1C A0 e −k1t
dt
Solving: B C =
k1C A0 −k1t
k 2 − k1
(e − e −k 2t
)
CC = C A 0 − C A − C B
k2
dC B ln( k 2 / k1 ) C B ,max  k1  ( k 2 −k1 )
= 0 ⇒ topt = =  
dt k 2 − k1 C A0  k2 
If k1 = k2, find topt and CR, max 64
 Consecutive I-order reactions
Conc. vs. time for various ratios of k2/k1

65
 Concept of Rate Determining Step (RDS)
Consider the irreversible reactions in series: A → R → S

− dC A dC R dC S
− rA = = k1C A rR = = k1C A − k 2C R rS = = k 2C R
dt dt dt
I. When k1 >> k2  
 
dC S  dC R  e −k1t  ~  − dC R 
rS = = k 2C R =  −  1−
dt  dt  k2
e − k 2t
−
k1
e −k1t
  dt 
 k 2 − k1 k 2 − k1 
 
Overall rate of product formation is dominated by reaction - 2
II. When k2 >> k1
dC S  dC A  k 2 ( k1 − k 2 ) t  dC A 
rS = = −  (1 − e ) ~ − 
dt  dt  k 2 − k1  dt 
Overall rate of product formation is dominated by reaction - 1

Overall rate of a reaction is always governed by the slowest

step, which is known as the rate determining step (RDS). 66
6. Reactions with shifting order:
A →R − dC A k1C A
− rA = =
dt 1+ k 2C A
The order shifts from low to high (zero to one)
as the reactant concentration drops.

ln(C A0 / C A ) + k 2 (C A0 − C A ) = k1t

k1
-rA

t/(CA0 -CA)
k2

CA
67
7. Reactions with shifting order:
A → R − rA = − dC A = k1 + k 2C A
dt
The order shifts from high to low (one to zero)
as the reactant concentration drops.
k1 + k 2C A0
ln = k 2t
k1 + k 2C A

-rA k2 CA

k1

CA t
68
Guggenheim's Method for First-Order Reactions

• A special method to obtain the rate constant for a

first-order reaction when an accurate value of the
initial reactant concentration is not available.
• Requires a series of readings of the parameter used
to follow the progress of the reaction at times t1, t2,
t3, etc. and at times t1 + ∆, t2 + ∆, t3 + ∆ etc.
• The time increment ∆ should be two or three times
the half life of the reaction.

For a I order reaction: ln(1-xA) = -kt ⇒ xA = 1 - e-kt

At t1 and t1 + ∆, (xA)t1 – (xA)t1+∆ = e-kt1 (1-ek∆ )
Similar equations are valid at times t2, t3, etc. In all cases,
the right side will be a constant, since the time increment
is a constant. 69
• applicable to systems that give apparent first-order
rate constants.
• also applicable to irreversible first order reactions in
parallel and reversible reactions that are first-order in
both the forward and reverse directions.
• the technique provides an example of the advantages
that can be obtained by careful planning of kinetics
experiments instead of allowing the experimental design
to be dictated entirely by laboratory convention and
experimental convenience.
• Guggenheim's technique can also be extended to other
order reactions, but the final expressions are somewhat
cumbersome.

70
Example:

Note that k can be determined without a knowledge of the

dilatometer readings at times zero and infinity.

71
Batch reactors are charged with reactants, closed, and
heated to the reaction temperature, maintained
isothermally for the duration of the reaction. After the
reaction is completed, the mixture cooled, and the reactor
opened, the product is discharged and the reactor is
cleaned for the next batch. In industrial operations, the
cycle time is constant from one batch to the next.

The time required for filling, discharging, heating, cooling,

and cleaning the reactor is referred to as the turnaround
time (tt).

The total batch cycle time tb is the reaction tr time plus

the turnaround time tt.
tb = tr + tt

The total batch cycle time tb is used in batch reactor 72

design to determine the productivity of the reactor.

Design of Batch Reactor

What do you mean by Design ??

− 1 dN A N A0 dx A
− rA = =
V dt V dt

Can we Design the Batch Reactor using the

Above equation ??

How can you call the above equation as

Design equation of a Batch Reactor ??
73
Design Problem
The reaction 2A → R takes place in a batch
reactor. Pure A is to be taken initially in the
reactor. It is required to produce 3 tons of R per
day. The molecular weight of R is 120. The
density of A is 0.8 kg/lit. The expected
conversion of A is 75%. A time of 30 min must be
allowed for filling the reactor and 45 min for
discharging and cleaning the reactor. Kinetic
calculations show that a reaction time of 4hr 45
min is needed for the required conversion.

What size reactor must be used??

74
Solution
Total batch time = ½ + ¾ + 4¾ = 6 hrs.
Number of batches / day = 4
Required production /batch = ¾ tons = 750kg
750 kg of A is required, if xA = 100%
For 75% conversion:
Amount of A to be fed /batch = 750/0.75
= 1000kg
Volume of 1000 kg of A = 1250 lit.
∴ Size of the vessel = 1250 lit.
Is the above Design always valid ??

What is the use of the Design equation ?? 75

 ANY
CLARIFICATIONS ?

Gauss, Karl
I have had my results for a long time;
but I do not yet know how I am to arrive at them.
76