Fluid-Fluid Reactions: Kinetics

• This deals with the kinetics of reactions which

include gas-liquid and liquid-liquid reactions.
• Fluid-fluid reactions are made to take place
due to one of the two reasons;

Separation-process point of view

Fluid-fluid reactions are intended to enhance
the separation i.e. adsorption of a solute gas by
water adding a suitable material to the water
which will react with the solute being adsorbed.
 Fluid-Fluid Reactions: Kinetics
• This is used for the formation of a desired
product or set of products.
• A solid catalyst may be involved as a third
phase.
Examples include;
(a) Removal of H2S or CO2 from a gas stream
by contact with MEA or DEA in aqueous
phase.
H2S(g) + MEA(l) → HS- + HOCH2CH2NH3+

CO2(g) + 2DEA(l) → (HOCH2CH2)2NCOO- +(HOCH2CH2)2NH2+

 Fluid-Fluid Reactions: Kinetics
• Other reagents may also be used for various
solute gases are;
 Fluid-Fluid Reactions: Kinetics
Reaction-process point of view
• The formation of desired product or set of
products.
• Such reactions are numerous and can be
found practically in all area of the chemical
industry where organic synthesis are
employed.
• Examples include;
 Fluid-Fluid Reactions: Kinetics
(a) Production of ethanolamines from ethylene
oxide and ammonia
C2H4O + NH3 → HOCH2CH2NH2 (MEA)
C2H4O + MEA → (HOCH2CH2)2NH2 (DEA)
C2H4O + DEA → (HOCH2CH2)3NH2 (TEA)

(b) Hydrogenation of benzene to cyclohexane

C6H6(l) + 3H2(g) → C6H12(l)
 Fluid-Fluid Reactions: Kinetics
(c) Production of ammonium carbonate

CO2(g) + 2NH3(g) + H2O(l) → (NH4)2CO3(aq)

(d) In inorganic field we have manufacturing of

sodium amide from gaseous ammonia and
liquid sodium.

NH3(g) + Na(l) → NaNH3(s) + ½ H2

 Factors involved
The factors which we will have consider before
approaching this process are;

(i) The overall rate expression

Since the materials in the two separate phases must contact
each other before reaction can occur; both mass transfer and
the chemical rates will enter in the overall rate expression.
(ii) Equilibrium solubility
The solubility of the reacting components will limit their
movement from phase to phase.
This factor will certainly influence the form of rate equation
since it will determine whether the reaction take place in one
or both phases.
 Factors involved
(iii) The contacting scheme
• In gas-liquid systems semi-batch and counter-current
contacting schemes predominate.
• In liquid-liquid systems mixed flow and batch
contacting schemes are used in addition to counter and
cocurrent contacting.

Other possibilities of rate, equilibrium and contacting

patterns can also be imagine.
 Types of fluid-fluid reactors
Fluid-fluid reactors are generally of two types:

• Column type reactors, or

• Tank type reactors

These reactors are either with energy addition

(mechanically agitated) or without energy
addition.
Various types of contactors
 Types of fluid-fluid reactors
Column type reactors without energy addition
are commonly employed for gas-liquid
systems while with energy additions are
commonly used for liquid-liquid systems.
Contacting patterns for gas-liquid reactors
Selected column type contactors
 Packed columns
 Tray towers
 Spray towers
 Wetted wall or falling film columns
 Bubble columns
Packed column
Random packings for packed columns

a) Raschig ring, b) Lessing ring, c) Cross-partition ring, d) Berl saddle,

e) Intalox saddle, f) Tellerette, and g) Pall ring
 Features of packed column
Both phases are considered to be in plug flow
(PF).
 Tray towers
 Gas is dispersed while the liquid phase is
continuous.
 “The gas-liquid interfacial area is relatively large,
and the gas-liquid contact time is typically greater
than that in a packed tower”
Tray towers
 Spray tower

 Small contact time.

 Interfacial area is large.
 Each phase in plug flow (PF).
 Liquid phase is dispersed and gas phase is
continuous.
 It offers low pressure drop on the gas side while
liquid pressure may be high.
Spray tower
 Wetted wall column
 Each phase in plug flow (PF).
 Each phase is continuous, no discontinuous phase.
 Gas-liquid contact not efficient.
 Low interfacial area and therefore low mass transfer
efficiencies.
 Low pressure drop for the gas phase.
 Usually used for experimental determination of mass
transfer coefficients as interfacial area may be easy to
control and measure.
 Heat removal is easy and therefore may be used industrially
for highly exothermic reactions.
Wetted wall column
 Bubble column
 High pressure drop for the gas phase.

 Gas phase is dispersed and liquid phase is

continuous.

 The plug flow is assumed for the gas flow and

backmixed flow is assumed for the liquid phase.
Bubble column
 Tank type reactors
 Usually a mechanical agitator is used. Gas phase is usually
dispersed and the liquid phase is in continuous phase.

 Each phase may be considered in backmixed flow.

 They are suitable for a reaction that needs a large liquid

holdup or a long residence time.

 “In comparison with non-agitated tank reactors equipped

only with spargers, mechanically agitated tank reactors
have the advantage of providing a greater interfacial area
for efficient mass transfer”
Agitated tank contactor

Disc blade turbine

Open blade turbine

 The rate equation
For this we will only discuss G/L reactions which is equally
holds good for L/L reactions

Consider a second order reaction;

A(g→l) + bB(l) → R (s, l or g) -rA = kCACB

Assumptions are;
(i) ‘A’ is gas which is soluble in liquid ‘B’
(ii) ‘B’ is not soluble in ‘A’.
(iii) ‘A’ must enter and move into liquid phase before it can
react and the reaction will occur in liquid phase.
 The rate equation
• The reaction can occur close to interface, within the
interface or in the main body of liquid.
• If ‘A’ is present in gas phase and is soluble in ‘B’ then
solubility of ‘A’ in ‘B’ can be represented by;

pAi = HA CAi (Henry’s Law)

• For overall rate expression for the said reaction we have to

consider two resistances;

(a) Mass transfer resistance (to bring the reactants together)

(b) Chemical reaction resistance

• The relative magnitudes of these resistances may greatly

varied.
 The rate equation
Consider a unit volume of contactor Vr with its gas, liquid
and solid phases.

We know from our previous knowledge that

Fractional volume of liquid phase = fl = Vl/Vr
Fractional volume of gas phase = fg = Vg/Vr
 The rate equation

In case of presence of solids,

Void fraction = ԑ = fl + fg
So,
Interfacial area/volume of liquid = al = S/Vl
Interfacial area/volume of contactor = a = S/Vr
 The rate equation
We also know that the rate expression can be written as,

1 dN A 1 dN A 1 dN A
 rA////   ,  rAl   ,  rA//  
Vr dt Vl dt S dt

These rates can be related as,

 r ////Vr  rl Vl  r // S
or
r ///  f l rl  ar //
The rate expression: when only gas ‘A’ is moving
into liquid phase (mass transfer only)
As we know that only gas ‘A’ is soluble in liquid phase, so
diffusional resistance enters in the rate equation.
• According to two film theory, there will be two resistances
in series,
(a) Gas film and
(b) Liquid film
The rate expression: when only gas ‘A’ is moving
into liquid phase (mass transfer only)
So, the rate expression for the mass transfer of ‘A’ from gas
to liquid phase is given below;

For gas film

rA//  k Ag  p A  p Ai  or  rA////  k Ag a  p A  p Ai  (1)
mol mol
m 2 . Pa . s m 3 contactor . Pa . s

For liquid film

rA//  k Al C Ai  C A  or  rA////  k Al a C Ai  C A  ( 2)
m 3liquid m 3liquid
m 2 surface . s m 3 contactor . s
The rate expression: when only gas ‘A’ is moving
into liquid phase (mass transfer only)

By combining eq (1) and (2) and introduction of Henry’s

Law (to eliminate unknown interface conditions), the final
rate expression from straight mass transfer at any point in
the absorber is,

 rA//// 
1
 pA  H AC A 
1 HA

k Ag a k Al a
Pa . m 3 liquid
mol
The rate expression: when only gas ‘A’ is moving
into liquid phase
(mass transfer followed by reaction)

For this, we have to consider three factors;

(a) What happens in the gas film
(b) What happens in the liquid film, and
(c) What happens in the main body of liquid.
The rate expression: when only gas ‘A’ is moving
into liquid phase
(mass transfer followed by reaction)

All sort of possibilities can be considered depending upon

the,

(a) Relative values of rate constants (k, kg, kl)

(b) The concentration ratio of reactants (pA/CB and HA)

There are almost eight possibilities to consider going from

instantaneous to extremely slow reactions (no mass transfer
resistance to be considered).
Occurrence of reaction in liquid phase
side
Depending upon the rate of a chemical reaction,
the reaction may

• take place within a narrow plane of the film

(mass transfer control),
• spread within the film,
• spread in liquid film and main body of liquid
or
• take place within the main body of the liquid
(no mass transfer resistance to be considered).
Occurrence of reaction in liquid
phase side
Case A: Instantaneous reaction with low CB
Case B: Instantaneous reaction with high CB
Case C: Fast reaction in liquid film, with low CB
Case D: Fast reaction in liquid film, with high CB
Case E and F: Intermediate rate with reaction in the
film and in the main body of the liquid
Case G: Slow reaction in main body but with film
resistance
Case H: Slow reaction, no mass transfer resistance
 General rate equation for mass
transfer and reaction of gas (A) in
liquid
 Henry’s constants

HA is large HA is small
(Liquid film resistance is large) (Liquid film resistance is small)
Enhancement factor and its evaluation

rate of take up of A when reaction occurs

E
rate of take up of A for straight mass transfer

E is always greater or equal to 1.

The value of E depends on Ei and MH.

Enhancement factor and its evaluation
 Hatta modulus, MH
maximum possible conversion in the film
M 
2
H
maximum diffusiona l transport through the film
k  C B  DAl
 2
k Al
k  C B  DAl
Hatta modulus  M H  2
k Al

o If MH >> 1: reaction occurs in the film, and we have

cases A, B, C, D.
o If 0.02<MH<2: Cases E, F, G (intermediate cases)
o If MH < 0.02: Infinitely slow reaction (Case H)
Enhancement factor and its evaluation
 Hatta modulus, MH

•“When MH is large, we should pick a contacting

device which develops or creates interfacial areas;
energy for agitation is usually an important
consideration in these contacting schemes. On the
other hand, if MH is very small, all we need is a large
volume of liquid. Agitation to create large interfacial
areas is 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).”
 Interface behavior for the reaction in
liquid phase

•Reaction plane will spread. •Conc of B will not drop in film.

•Reaction is fast enough to stay in film. •The second order rate will simplify to first
•Liquid bulk resistance in negligible in rate equation. order w.r.t. A
Interface behavior for the reaction in
liquid phase
oAn element of liquid can contain either A or B but not
both, so the reaction will occur at a plane between A-
containing liquid and B-containing liquid.

oReactants will have to diffuse for the reaction to occur

then rate of diffusion of A and B or in order words
change in pA or CB will move the plane one way or other.

oAt steady state, from chemical equation, the flow rate of

B towards the reaction zone is b times faster than A.

o So,
(EQUATION)
 Interface behavior for the reaction in
liquid phase
•Reaction is slow enough for A to
diffuse into bulk liquid.
•“A” reacts both in liquid film and
bulk.

Liquid film is still

providing resistance
for transfer of A in
bulk of liquid.

•Mass transfer is
negligible
•The compositions are
uniform.
•Rate is determine by
chemical kinetics
alone.
 Rate equations for selected cases

For Case C:

For Cases E and F:

For Case G:

For Case H: