Non-Catalytic Systems

Fluid-Fluid Reactions: Kinetics

1
Fluid-Fluid Reactions: Kinetics
 Heterogeneous fluid-fluid reactions are widely found in industry
– Formation of a desired compound
• An example of liquid-liquid reactions is the nitration of
organics with a mixture of nitric and sulfuric acids to form
materials such as nitroglycerin

– Removal of an unwanted component from a fluid

• Absorption of a solute gas, e.g. CO2 capturing with amines

– Improved product distribution for homogeneous multiple

reactions compared to using the single phase alone.

2
 Fluid-Fluid Reactions: Kinetics
 Important factors
– The Overall Rate Expression. Since materials in the two separate
phases must contact each other before reaction can occur, both the
mass transfer and the chemical rates will enter the overall rate
expression.

– Equilibrium Solubility. The solubility of the reacting components

will limit their movement from phase to phase. This factor will
certainly influence the form of the rate equation since it will
determine whether the reaction takes place in one or both phases.

– The Contacting Scheme. In gas-liquid systems semibatch and

countercurrent contacting schemes predominate. In liquid-liquid
systems mixed flow (mixer-settlers) and batch contacting are used
in addition to counter and concurrent contacting.

3
 Fluid-Fluid Reactions: Kinetics
 The rate equation
– In the following we assume a G/L reaction (but everything holds
true for L/L as well)

4
 Fluid-Fluid Reactions: Kinetics
 The rate equation
– Consider a unit volume of a contactor Vr

5
 Fluid-Fluid Reactions: Kinetics
 The rate equation for straight mass transfer (absorption) of A

6
 Fluid-Fluid Reactions: Kinetics
 The rate equation for straight mass transfer (absorption) of A
1 dN A
rA   k Ag  p A  p Ai   k Al  C Ai  C A  
S dt
k Ag p A  k Al C A
k Ag  p A  H AC Ai   k Al  C Ai  C A   C Ai 
k Ag H A  k Al
Elimination of interface concentration CAi from the rate equation
1 dN A  k Ag p A  k Al C A 
rA   k Al  C Ai  C A   k Al   CA  
S dt  
 k Ag H A  k Al 
 k Ag p A  k Al C A k Ag H AC A  k Al C A   k Ag p A  k Ag H AC A 
rA  k Al     k Al   
 k H k k Ag H A  k Al 
 Ag A Al  k Ag H A  k Al 
k Ag k Al 1
rA   A A A H
p  H C 
1
 pA  H ACA   K Ag  pA  H ACA 
k Ag H A  k Al A

k Al k Ag

KAg: Total mass transfer coefficient based on gas phase

The equation above gives the rate of physical absorption of A in liquid 7
phase based on measurable quantities.
 Fluid-Fluid Reactions: Kinetics
 The rate equation for straight mass transfer (absorption) of A
1 dN A
rA   k Ag  p A  p Ai   k Al  C Ai  C A  
S dt
k Ag p A  k Al C A
k Ag  p A  p Ai   k Al  p Ai / H A  C A   p Ai 
k Al / H A  k Ag
Elimination of interface pressure pAi from the rate equation

1 dN A  k Ag p A  k Al C A 
rA   k Ag  p A  p Ai   k Ag  p A   
S dt  k / H  k
 Al A Ag 

  k Al / H A  p A  k Ag p A k Ag p A  k Al C A    k Al / H A  p A  k Al C A 
rA  k Ag     k Ag   
 k Al / H A  k Ag k Al / H A  k Ag  k Al / H A  k Ag
  
k Ag k Al 1
rA   pA / H A  CA   1 1
 pA / H A  C A   K Al  pA / H A  C A 
k Al / H A  k Ag 
k Ag H A k Al

KAl: Overall mass transfer coefficient based on liquid phase

The equation above gives the rate of physical absorption of A in liquid 8
phase based on measurable quantities.
 Fluid-Fluid Reactions: Kinetics
 The rate equation for straight mass transfer (absorption) of A

1 1
rA 
HA 1
 p A  H AC A   K Ag  pA  H AC A   1 1
 pA / H A  C A   K Al  pA / H A  C A 
 
k Al k Ag k Ag H A k Al

or
1 1
rA
HA 1
 pA  H AC A   K Ag  p A  H AC A   1 1
 pA / H A  C A   K Al  p A / H A  C A 
 
k Al k Ag k Ag H A k Al
9
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and (slow) reaction in the main
body (bulk) of the liquid (outside the film)

Second order reaction rate:

rA
 rA kC ACB fl  C A 
kCB f l

Mass transfer rate in the film:

 p   p rA   K Al  K Al p A

 rA K Al  A  C A   K Al  A     r 
A 1   
H
 A  H
 A kC f
B l   kCB f l  HA
K Al p A
HA 1 1 1 1
 rA  pA ,  
K  HA HA K Al k Ag H A k Al
1  Al 
kCB fl K Al kCB fl
10
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction (cont’d)

Substituting the righthand side of 1/KAl equation into the rate equation yields:

1 1
 rA pA  pA
HA HA HA 1 HA HA
   
k Ag H A K Al kCB fl k Ag k Al kCB fl

gas film liquid film liquid bulk

resistance resistance resistance

11
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction. General case:
reaction occurs in the liquid film and the bulk of liquid.

12
Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction
– Enhancement factor E (always greater or equal to one)

– The enhancement factor E depends on 2 quantities, the

enhancement factor for an infinitely fast reaction Ei, and the
Hatta modulus MH.

13
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction

14
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction

15
 Fluid-Fluid Reactions: Kinetics
 Case A: Instantaneous reaction, low CB
– Since the reactants must diffuse to the
reaction plane the rate of diffusion of
A and B will determine the rate

In addition, since the movement of material within the film occurs by diffusion
alone, the transfer coefficients for A and B are related by

Also, at the G/L interphase:

16
 Fluid-Fluid Reactions: Kinetics
 Case A (cont’d):

Eliminating the unmeasured intermediates xo, x, pAi

and CAi, using the equations in the previous slide,
yields:

– For the special case of negligible gas-phase resistance, e.g. if

pure reactant A is used in the gas phase

Ei

17
 Fluid-Fluid Reactions: Kinetics
 Case A (cont’d):
The enhancement factor for an infinitely fast reaction (Ei) is the ratio of the rate of
chemical absorption in the case of an infinitely fast reaction (previous slide) and the
maximum rate of physical absorption in the liquid film. The latter is attained when the
concentration of A in the bulk liquid is 0, so we have the maximum driving force for
physical absorption.
DBl CB p A

DAl b H A
1 1 DBl CB p A DBl CB p A
  
k Ag H A k Al DAl b H A DAl b H A D C H
Ei     1  Bl B A
 pA  pA pA DAl b p A
  C A
 C A  0
H
 A  HA HA
1 1

k Ag H A k Al
For the case of negligible gas-phase resistance, pA=pAi and so HA/pA= HA/pAi=1/CAi.
Therefore:
D C
Ei  1  Bl B
bDAl C Ai 18
 Fluid-Fluid Reactions: Kinetics
 Case B: Instantaneous reaction, high CB
– This condition requires that the
reaction zone moves to and stays at
the interface rather than remain in
the liquid film
– When this happens, the resistance
of the gas-phase controls, and the
rate is not affected by any further
increase in concentration of B

19
 Fluid-Fluid Reactions: Kinetics

 Case C: Fast reaction, low CB

– The plane of reaction for case A
now spreads into a zone of reaction in
which A and B are both present.
– However, the reaction is fast enough
so that this reaction zone remains
totally within the liquid film. Thus, no
A enter the main body of liquid to
react there.

20
 Fluid-Fluid Reactions: Kinetics

 Case D: Fast reaction, high CB

– For the special case where CB does
not drop appreciably within the film,
it can be taken to be constant
throughout, and the second-order
reaction rate (Case C) simplifies to
the more easily solved (pseudo) first-
order rate expression
– Thus, the general rate expression
reduces to

21
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction

Case E and F: Intermediate rate with reaction in the film and in the main
body of the liquid

22
 Fluid-Fluid Reactions: Kinetics
 Case E & F: Intermediate rate with respect to mass transfer
– Here the reaction is slow enough for some A to diffuse through the film
into the main body of the fluid.
– Consequently, A reacts both within the film and in the main body of the
fluid.
– In these cases we have to use the general rate expression with its
three resistances

23
 Fluid-Fluid Reactions: Kinetics
 The rate equation for mass transfer and reaction

Case G: Slow reaction in main body but with film resistance

Case H: Slow reaction, no mass transfer resistance 24
 Fluid-Fluid Reactions: Kinetics
 Case G: Slow reaction with respect to
mass transfer, but with film resistance
– This represents the somewhat curious
case where all reaction occurs in the
main body of the liquid; however, the
film still provides a resistance to the
transfer of A into the main body of
liquid
– Thus, three resistances enter into the rate expression, and the general
rate expression reduces to

25
 Fluid-Fluid Reactions: Kinetics
 Case H: Slow reaction with respect to mass transfer, no mass
transfer resistance
– Here the mass transfer resistance is
negligible, the compositions of A and
B are uniform in the liquid, and the
rate is determined by chemical
kinetics alone

26
 Fluid-Fluid Reactions: Kinetics
 Role of the Hatta number, MH
– To tell whether reaction is fast or slow, we focus on a unit surface of
gas-liquid interface, we assume that gas-phase resistance is negligible,
and we define a film conversion parameter

– If MH>>1 all reaction occurs in the film, and the surface area is the
controlling rate factor
– If MH<<1 no reaction occurs in the film, and the bulk volume becomes
the controlling rate factor
27
 Fluid-Fluid Reactions: Kinetics
 Role of the Hatta number, MH
– More precisely, it has been found that:
1. If MH >>2 the reaction occurs in the film and we have Cases A, B, C, D
2. If 0.02 < MH < 2 we then have the intermediate Cases E, F, G
3. If MH << 0.02 we have the infinitely slow reaction of Case H

– When MH is large, we should pick a contacting device which develops

or creates large interfacial areas; energy for agitation is usually an
important consideration in these contacting schemes
– When MH is very small, all we need is a large volume of liquid.
Agitation to create large interfacial areas is of no benefit here
– Spray or plate columns should be efficient devices for systems with
fast reaction (or large MH), while bubble contactors should be more
efficient for slow reactions (or small MH)

28
Problem
Air with gaseous A bubbles through a tank containing aqueous B. Reaction occurs as
follows:

For this system:

For a point in the absorber-reactor where

(a) locate the resistance to reaction (what % is in the gas film, in the liquid film,
in the main body of liquid)
(b) locate the reaction zone
(c) determine the behavior in the liquid film (whether pseudo first-order
reaction, instantaneous, physical transport, etc.)
(d) calculate the rate of reaction (mol/m3 hr) 29
 Solution

Since no analysis is available for other than second-order reactions, let us replace our
third-order reaction with a second order approximation. Thus,

To find the rate from the general expression, we need to first evaluate Ei, and MH. Let
us do this:

Since (Ei)firstguess > 5 MH, then for any other smaller guess for pAi we will still
have Ei > 5 MH. Therefore, from Fig. 23.4 we have pseudo first-order reaction in the
film with E = MH = 100.
30
 Solution

Now the rate expression will be

Thus,
(a) 2/3 of the resistance is in the gas film, 1/3 is in the liquid film.
(b) The reaction zone is in the liquid film
(c) The reaction proceeds by a pseudo first-order reaction of A, at the interface
(d) the rate is –r’’’’= 33 mol/m3 hr

31
Problem
Gaseous A absorbs and reacts with B in liquid according to

in a packed bed under conditions where

At a point in the reactor where

(a) calculate the rate of reaction in mol/hr‧m3 of reactor.

(b) describe the following characteristics of the kinetics: location of the major
resistance (gas film, liquid film, main body of liquid) behavior in the liquid film
(pseudo first-order reaction, instantaneous, second-order reaction, physical
transport) for the following values of reaction rate and Henry's law constant.

1) k =10 m3 liquid/mol‧hr and HA= 1000 Pa ‧ m3 liquid/mol

2) k =10-2 m3 liquid/mol‧hr and HA= 1 Pa ‧ m3 liquid/mol 32
 Solution

DkCB 106 10  102 

1)      0.0316  E=1 (Figure 23.4, Book Levenspiel)
k Al 1
'''' pA 102 3
r 
A  3 3
 3.33 mol/m  hr
1 HA HA 1 10 10
   2 
k Ag k Al E kCB f l 0.1 10 (1) 10 102 101

33% 33% 33%

• 1/3 of the resistance is in the gas film, 1/3 is in the liquid film and 1/3 in the main
liquid body
• The location of the reaction zone is in the main body of liquid.
• The behavior in the liquid film is physical transport

33
 Solution

DkCB 106 102 102 

2)      103  E=1 (Figure 23.4, Book Levenspiel)
k Al 1
'''' pA 102
r 
A   5 mol/m3  hr
1 HA HA 1 1 1
   2  2 2 1
k Ag k Al E kCB fl 0.1 10 (1) 10 10 10

~50% ~50%

• 1/2 of the resistance is in the gas film and 1/2 in the main liquid body
• The location of the reaction zone is in the main body of liquid.
• The behavior in the liquid film is physical transport

34