Chemical Reaction Engineering -II

Spring 2023

Instructor:

Dr. Sushant Kumar

Department of Chemical and Biochemical Engineering
Indian Institute of Technology, Patna 1
Mon, 10/04/23

NH3(g) +Na(l) → NaNH2(s) +1/2H2

Heterogeneous fluid-fluid reactions are made because of following reasons:

1. Numerous can be found in all areas of chemical industry where organic/inorganic syntheses are employed.

2. Facilitate the removal of an unwanted component from a fluid.

3. To obtain a vastly improved product distribution for homogeneous multiple reactions

Following factors will determine how to approach this process:

a. The overall rate expression: since materials in the two separate phases must contact each other before reaction can
can occur, both the mass transfer and the chemical rates will enter the overall rate expression.

b. Equilibrium stability: The solubility of the reacting components will limit their movement from phase to phase. The factor
will certainly influence the form of the rate equation since it will determine whether the reaction takes place in one
or both phases.

c. The contacting scheme: In gas-liquid systems, semibatch and countercurrent contacting schemes predominate. In liquid-
liquid systems mixed flow and batch contacting are used in addition to counter and concurrent contacting.
The rate equation
The rate equation for straight mass transfer (absorption) of A

Here, we have two resistances in series, of the gas film and of the liquid film. The rate transfer of A from gas to liquid is
given by the rate expressions, for the gas film
Tue, 11/04/23

Setting up the rate equation for absorption of A in the liquid, and reaction in the liquid, based on the two-film theory.

Using Henry’s law 𝑝𝐴𝑖 = 𝐻𝐴 𝐶𝐴𝑖 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.
 The rate equation for mass transfer and reaction

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 the main body but with

Film resistance

Case H: Slow reaction, no mass transfer resistance

Interface behaviour for the liquid-phase reaction

Wed, 12/04/23

The general 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

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡𝑎𝑘𝑒 𝑢𝑝 𝑜𝑓 𝐴 𝑤ℎ𝑒𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑐𝑐𝑢𝑟𝑠

𝐿𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚 𝑒𝑛ℎ𝑎𝑛𝑐𝑒𝑚𝑒𝑛𝑡 𝑓𝑎𝑐𝑡𝑜𝑟 , 𝐸 =
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡𝑎𝑘𝑒 𝑢𝑝 𝑜𝑓 𝐴 𝑓𝑜𝑟 𝑠𝑡𝑟𝑎𝑖𝑔ℎ𝑡 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟
(note: same CAi, CA, CBi, CB in the two cases

The value of E is always greater or equal to one.

 𝑡ℎ𝑒 𝑒𝑛ℎ𝑎𝑛𝑐𝑒𝑚𝑒𝑛𝑡 𝑓𝑎𝑐𝑡𝑜𝑟 𝑓𝑜𝑟 𝑎𝑛 𝑖𝑛𝑓𝑖𝑛𝑖𝑡𝑒𝑙𝑦
𝐸𝑖 =
𝑓𝑎𝑠𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑖𝑛 𝑡ℎ𝑒

𝑀𝐻2 = 𝑓𝑖𝑙𝑚 𝑐𝑜𝑚𝑝𝑎𝑟𝑒𝑑 𝑤𝑖𝑡ℎ 𝑚𝑎𝑥𝑖𝑚𝑢𝑚
𝑡𝑟𝑎𝑛𝑠𝑝𝑜𝑟𝑡 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑡ℎ𝑒 𝑓𝑖𝑙𝑚
Case A: Instantaneous reaction with respect to mass transfer.

Concentration of reactants as visualized by the two-film theory for an infinitely fast irreversible reactions of any order,
A +bB-> products. Case A→ low CB, Case B→ high CB

• Since an element of liquid can either A or B, but not both, reaction will occur at a plane between A-containing and B-
containing liquid. Also, since reactants must diffuse to this reaction plane the rate of diffusion of A and B will determine
the rate, so that a 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.
Thus,

where, 𝑘𝐴𝑔 𝑎𝑛𝑑 𝑘𝐴𝑙 , 𝑘𝐵𝑙 are the mass transfer coefficients in gas and liquid phases.
At the interface, the relationship between 𝑝𝐴 𝑎𝑛𝑑 𝐶𝐴 is given by the distribution coefficient, called Henry’s law constant
for gas-liquid systems. Thus,

𝑝𝐴𝑖 = 𝐻𝐴 𝐶𝐴𝑖

In addition, since the movement of material within the film is visualized to occur by diffusion alone, the transfer coefficients
for A and B are related by
𝑘𝐴𝑙 𝐷𝐴𝑙 /𝑥0 𝐷𝐴𝑙
= =
𝑘𝐵𝑙 𝐷𝐵𝑙 /𝑥0 𝐷𝐵𝑙
For negligible gas-phase resistance,
𝑝𝐴 = 𝑝𝐴𝑖 ⇒ 𝑘𝑔 → ∞
Eliminating the unmeasured intermediates (𝑥, 𝑥0 , 𝑝𝐴𝑖 and 𝐶𝐴𝑖 )
The equation reduces to

For case A:

𝑘𝐵𝑙 𝐶𝐵 Hence, the rate expression for infinitely fast

𝑘𝑔 𝑝𝐴 >
𝑏 reaction and no gas phase resistance is
−𝑟𝐴" = 𝑘𝐴𝑙 𝐶𝐴𝑖 𝐸𝑖
Tue, 18/04/23

Case B: Instantaneous reaction; High CB.

If the concentration of B is raised, or more precisely, if

𝑘𝐵𝑙 𝐶𝐵
𝑘𝑔 𝑝𝐴 ≤
𝑏

In this condition, the reaction zone move to and stay at the interface rather than remain in the liquid film.

Here, the resistance of the gas-phase controls, and the rate is not affected by any further increase in concentration of B.
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, reaction is fast enough so
that this reaction zone remains totally within the liquid film. Thus, 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,
Case D: Fast Reaction; High CB. Hence, Pseudo First-Order rate with respect to A.

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 first-order rate expression.
Thus, the general rate expression reduces to
Case E and F: Intermediate Rate with respect to mass transfer

In this case, 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.

Case G: Slow reaction with respect to mass transfer

It is an interesting 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,

Case H: Infinitely Slow reaction.

In the case, 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.
Wed, 19/04/23

Hatta Number, 𝑴𝑯
To determine whether the reaction is fast or slow, we focus on unit surface of gas-liquid interface, we assume that gas-phase
is negligible, and we define a film conversion parameter

𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑝𝑜𝑠𝑠𝑖𝑏𝑙𝑒 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑖𝑛 𝑡ℎ𝑒 𝑓𝑖𝑙𝑚

𝑀𝐻2 =
𝑀𝑎𝑥𝑖𝑚𝑢𝑚 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛𝑎𝑙 𝑡𝑟𝑎𝑛𝑠𝑝𝑜𝑟𝑡 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑡ℎ𝑒 𝑓𝑖𝑙𝑚

𝑘𝐶𝐴𝑖 𝐶𝐵 𝑥0 𝑘𝐶𝐵 𝐷𝐴𝑙

= =
𝐷𝐴𝑙 𝑘 2
𝑥0 ∙ 𝐶𝐴𝑖
𝐴𝑙

If 𝑴𝑯 >>1, all reaction occurs in the film and surface area is the controlling rate factor.

If 𝑴𝑯 ≪1, no reaction occurs in the film, and bulk volume becomes the controlling rate factor.

Among the cases,

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.

• Gas film resistance controls for highly soluble gases
(no need to add a liquid-phase reactant to promote the adsorption)

• Liquid film resistance controls for slightly soluble gases (chemical reaction helps)
Q. 1 It is proposed to remove CO2 from air by counter-current contact with water at 25°C
(i) Find the resistances of the gas and liquid films for this operation?
(ii) Suggest the simplest form of rate equation for tower design.

Data: For CO2 between air and water,

𝑘𝑔 𝑎 = 0.80 𝑚𝑜𝑙/ ℎ ∙ 𝑚3 ∙ 𝑃𝑎

𝑘𝑙 𝑎 = 25 ℎ−1
𝐻 = 3000 𝑚3 ∙ 𝑃𝑎 /𝑚𝑜𝑙
Q. 2 Gaseous A absorbs and reacts with B in liquid according to

A(g->l) + B(l) -> R (l) −𝑟𝐴𝑙 = 𝑘𝐶𝐴 𝐶𝐵

in a packed bed.

(i) Calculate the rate of reaction

(ii) Determine the location of the major resistance (gas film, liquid film, and bulk liquid) and behaviour in the liquid film
(pseudo first order reaction, instantaneous etc.) at a point in the reactor where 𝑝𝐴 = 100 𝑃𝑎 and 𝐶𝐵 = 100 𝑚𝑜𝑙 Τ𝑚3 .

𝑙𝑖𝑞𝑢𝑖𝑑
Data: 𝑘 = 108 𝑚3 𝑚𝑜𝑙∙ℎ
1.0 𝑃𝑎 ∙ 𝑚3 𝑙𝑖𝑞𝑢𝑖𝑑
𝐻𝐴 =
𝑚𝑜𝑙
𝑘𝐴𝑔 𝑎 = 0.10𝑚𝑜𝑙/(ℎ ∙ 𝑚3 reactor ∙ 𝑃𝑎)
𝑘𝐴𝑙 𝑎 = 100𝑚3 liquid/( 𝑚3 reactor ∙ ℎ)
𝑓𝑙 = 0.01𝑚3 liquid/ 𝑚3 reactor
𝑎 = 100𝑚2 / 𝑚3 reactor
𝐷𝐴𝑙 = 𝐷𝐵𝑙 = 10−6 𝑚2 /ℎ
𝑀𝐻
Hint: For 𝐸𝑖 < , 𝑤𝑒 ℎ𝑎𝑣𝑒 𝑖𝑛𝑠𝑡𝑎𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑎𝑛𝑑 𝐸~𝐸𝑖
5
Q. 3 Air with gaseous A bubbles through a tank containing aqueous B. Reaction occurs as follows:

A(g->l) +2B(l) -> R(l), −𝑟𝐴𝑙 = 𝑘𝐶𝐴 𝐶𝐵2 , 𝑘 = 106 𝑚6 /𝑚𝑜𝑙 2 ∙ ℎ

For this system,

𝑘𝐴𝑔 𝑎 = 0.010𝑚𝑜𝑙/(ℎ ∙ 𝑚3 reactor ∙ 𝑃𝑎)
𝑘𝐴𝑙 𝑎 = 20𝑚3 liquid/( 𝑚3 reactor ∙ ℎ)
𝑓𝑙 = 0.98𝑚3 liquid/ 𝑚3 reactor
𝑎 = 20𝑚2 / 𝑚3 reactor
𝐷𝐴𝑙 = 𝐷𝐵𝑙 = 10−6 𝑚2 /ℎ
105 𝑃𝑎 ∙ 𝑚3 𝑙𝑖𝑞𝑢𝑖𝑑
𝐻𝐴 = , 𝑣𝑒𝑟𝑦 𝑙𝑜𝑤 𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦
𝑚𝑜𝑙
For a point in the absorber-reactor where, 𝑝𝐴 = 5000 𝑃𝑎 and 𝐶𝐵 = 100 𝑚𝑜𝑙 Τ𝑚3

(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 behaviour in the liquid film (whether pseudo first-order reaction, instantaneous, physical transport, etc.)
(d) Calculate the rate of reaction (𝑚𝑜𝑙/𝑚3 reactor ∙ ℎ)