Real Reactor

➢Bypassing
Effect of
Flow ➢Inefficient mixing
Pattern ➢Presence of dead zones

CRE-I

Kinetic Reactor Heat ➢ Non-isothermal

Design & Transfer
Study
Operation Effects ➢ Presence of hot spots

Mass
Transfer ➢Internal and external
Effects
➢Heterogeneous Catalytic / Non-Catalytic
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 2𝑁𝑎2 𝑆𝑂3 (𝑙) + 𝑂2 (𝑔) → 2𝑁𝑎2 𝑆𝑂4 (𝑙)

2𝑍𝑛𝑆 𝑠 + 3𝑂2 → 2𝑍𝑛𝑂 𝑠 + 2𝑆𝑂2 (𝑔)

𝐴𝑙𝐶𝑙3 𝑁𝑖
𝐶2 𝐻4 (𝑔) + 𝐶6 𝐻6 (𝑙) 𝐶6 𝐻5 𝐶2 𝐻5 → 𝐶6 𝐻5 𝐶𝐻2 + 𝐻2

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FLUID-FLUID
REACTIONS
Prof. Anand Tiwari

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Overview
■ Fluid–fluid reactions contribute to more than 70% of industrial applications
■ Heterogeneous fluid-fluid reactions are made to take place for one of three reasons.
1. The product of reaction may be a desired material – Nitration, Chlorination
2. Removal of undesired product – reactive absorption of unwanted gases
3. Improving product distribution
■ Three factors dominate such reactions
1. The Overall Rate Expression - 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.
2. 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.
3. The Contacting Scheme - In gas-liquid systems semi-batch and countercurrent
contacting schemes predominate.

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THE RATE EQUATION
Take G/L reactions for (Applies equally for (L/L) reactions as well).

Component A in gas phase and component B is in Liquid phase

A gets dissolved in the liquid, B does not enter the gas.

From bulk gas A enters and move into the liquid phase before it can react

Reaction occurs in the Liquid phase only.

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Consider Vr is the unit volume of the contactor contains gas, liquid and solid

Rate of reaction can

be written in a
number of ways

𝒅𝑵𝑨
𝒓′′′′
𝑨 𝑽𝒓 = 𝒓𝑨 𝑽𝒍 = 𝒓′′
𝑨𝑺 =
𝒅𝒕
Here two resistances are operating in series, the gas film and the liquid film

Rate Equation for Straight Mass

Transfer (Absorption) of A (no
reaction)
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The rate equation for
absorption of A in the
liquid, and reaction in the
liquid, based on the two-
film theory

Combining Eqs. with Henry's law pAi= HACA to

eliminate the unknown interface conditions pAi
and CAi we obtain the final rate expression for
straight mass transfer at any point in the
absorber
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Rate Equation for Mass Transfer and
Reaction
■ Three factors to consider:
– the gas film;
– the liquid film;
– the main body of the liquid
■ All sorts of special forms of the rate equation can result depending on the relative
values of the rate constants k, kg, and kl, the concentration ratio of reactants pA/CB,
and Henry's law constant HA
■ These 8 regimes are given below
– Very slow reactions: regime 1
– Slow reactions: regime 2
– Fast reactions: regime 3
– Instantaneous reactions: regime 4
■ These cases are further sub-catagorized in to 8 cases based on reaction rates

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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

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■ 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

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■ Case A: Instantaneous Reaction with Respect
to Mass Transfer (Low CB)
■ An element of liquid can contain either A or B,
but not both
■ Reaction will occur at a plane between A-
containing and B-containing liquid.
■ Both Reactants must diffuse towards this
reaction plane
■ The rate of diffusion of A and B will determine
the rate,
■ Change in pA or CB will move the plane one
way or the other.
■ At steady state the flow rate of B toward the
reaction zone will be b times the flow rate of A
toward the reaction zone

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■ where kAg and kAl, kBl are the mass transfer coefficients in gas and liquid phases.
■ The liquid side coefficients are for straight mass transfer without chemical reaction
and are therefore based on flow through the whole film of thickness x0.
■ At the interface the relationship between pA and CA is given by the distribution
coefficient, called Henry's law constant for gas-liquid systems
■ The movement of material within the film is visualized to occur by diffusion alone,
the transfer coefficients for A and B are related by

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For the special case of negligible gas-phase resistance, for example, if you
used pure reactant A in the gas phase, then pA = pAi or kg → ∞

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Case B: Instantaneous Reaction; High CB

This condition requires that the reaction zone move to and stay 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

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■ 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.
■ Reaction is fast enough so that this reaction zone remains totally within the liquid
film.
■ No A enters the main body of liquid to react there. Since the last resistance term in
the general rate equation, is negligible (large k), the rate form for this case is

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■ Case D: Fast Reaction; High CB, Hence Pseudo First-Order Rate with
Respect to A.
■ CB does not drop appreciably within the film, it can be taken to be constant
throughout, second-order reaction rate (Case C) simplifies to the more
easily solved first-order rate expression

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■ Cases E and F: Intermediate Rate with Respect to Mass Transfer.
■ Here 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. Here we have to use the general rate
expression with its three resistances

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Case G: Slow Reaction with Respect to Mass Transfer.

Though all the 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,

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■ Case H: Infinitely Slow Reaction.
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

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 Basic Rate Equation

■ The absorption of A from gas is larger when reaction occurs within the
liquid film than for straight mass transfer. Thus for the same
concentrations at the two boundaries of the liquid film we have

E≥1

How to evaluate E, the enhancement factor?

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The enhancement factor for fluid-fluid reactions as a function of MH and Ei

𝐷𝐴𝑘𝐶𝐵
MH, is Hatta modulus or Number 𝑀𝐻 =
𝑘𝐴𝑙

This dimensionless number correlates the rate of reaction in a liquid film

to the rate of diffusion through the film. The maximum rate of reaction
assumes that the liquid film is saturated with gas at the interfacial
concentration
The enhancement factor for fluid-
fluid reactions as a function of MH
and Ei,

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■ Whether reaction is fast or slow, consider unit surface of gas-liquid
interface, assume gas-phase resistance is negligible,

Film conversion
Parameter

If MH >>1, all reaction occurs in the film, surface area controls overall rate
If M << 1 no reaction occurs in the film, bulk volume controls overall rate

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■ 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.
■ 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 of no benefit here

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 General Reaction
−𝑟𝐴 = 𝑘𝑚𝑛 𝐶𝐴𝑚 𝐶𝐵𝑛

𝑀𝐻1
■ For a pseudo-first-order reaction, the enhancement factor 𝐸=
tanh 𝑀𝐻1

𝑀𝐻𝑚
■ For a pseudo-mth-order reaction, the enhancement factor 𝐸=
tanh 𝑀𝐻𝑚

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Kinetic Regime from Solubility Data
■ For reactions occurring in the film, the phase distribution coefficient H can suggest
whether the gas-phase resistance is likely to be important or not
■ The expression for straight mass transfer of A across the gas and liquid films

■ For slightly soluble gases HA is large; hence, with all

other factors unchanged, the liquid film resistance
term is large. The reverse holds for highly soluble
gases.
■ Highly soluble gases - Gas film resistance controls f
■ Slightly soluble gases - Liquid film resistance controls
■ When temperatures are taken in to account consider
that gases are more soluble at lower temperatures

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Example-1
■ Air with gaseous A bubbles through a tank containing aqueous B. Reaction occurs
as given. For this system data is provided below.
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)

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Assume the reaction is not elementary and follow second order kinetics

First evaluate E, and MH.

Assume pAi = pA

Check Ei < or > 5MH

For any other smaller guess for pAi Ei > 5MH

Pseudo first-order reaction in the film with E = MH = 100

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 ■ Calculate

■ Check

(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) reaction proceeds by a pseudo first-order reaction of A, at the interface
(d) the rate is calculated

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 General Reaction
−𝑟𝐴 = 𝑘𝑚𝑛 𝐶𝐴𝑚 𝐶𝐵𝑛

𝑀𝐻1
■ For a pseudo-first-order reaction, the enhancement factor 𝐸=
tanh 𝑀𝐻1

𝑀𝐻𝑚
■ For a pseudo-mth-order reaction, the enhancement factor 𝐸=
tanh 𝑀𝐻𝑚

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