Reaction Engineering

CGC035 / CGC052

Reaction rate expressions for

Gas / Liquid systems III

Department of Chemical Engineering

Dr Stella Georgiadou

1
Outline of Subject area – Gas / Liquid reactions and reactors

1. Development of rate expressions for G/L systems

1.1. Develop rate expressions for straight mass transfer in G/L systems by
using the two film theory
1.2. Describe pressure and concentration profiles according to two film theory
1.3. Develop rate expressions to account for both mass transfer + reaction

2. Development of design equations for G/L contactors

3. Solution of design equations

2
Gas/Liquid reactions III
Rate expressions fo Mass transfer & Chemical Reaction

Learning outcomes

1. Rate expressions to account for both Mass transfer and reaction for Gas
Liquid reactions categorized as

• Instantaneous reactions
• Fast reactions and Enhancement factor
• Intermediate reactions and Hatta number
• Slow reactions

Outline (Chapter 23 Levenspiel, Section 9.2 Missen)

3
Reaction rates for Mass Transfer and Chemical Reaction
1. Instantaneous reaction
If the rate of reaction between A and B is so high as to result in instantaneous reaction, then A and B
cannot coexist anywhere in the liquid phase. Reaction occurs at some point in the liquid film, the location
(reaction plane) of which is determined by the relative concentrations and diffusivities of A and B.
The entire process is mass-transfer controlled, with
A diffusing to the reaction plane from the bulk gas,
Bulk Film Film Bulk
first through the gas film and then through the gas gas liquid liquid
portion of the liquid film of thickness 𝛿, and B CB
diffusing from the bulk liquid through the remaining
PA0
portion of the liquid film 𝛿! − 𝛿.
CAi
This applies to PAi

Case A: Instantaneous reaction, low CB

𝜹 𝜹𝒍 − 𝜹
Case B: Instantaneous reaction, high CB, 𝛿 = 0 Reaction plane

4
Reaction rates for Mass Transfer and Chemical Reaction
1. Instantaneous reaction
The three diffusion steps can be treated
as series processes with the fluxes or Other relationships:
rates given by
• pAi and CAi are related
𝑁# = 𝑘#$ (𝑝# − 𝑝#% ) (1) through Henry’s law
𝑝#% = 𝐻# 𝐶#% (4)

𝐷#& 𝛿& • From stoichiometry

𝑁' = 𝑏𝑁# (5)
𝑁# = 𝐶#% − 0 = 𝑘#& 𝐶#% (2)
𝛿 𝛿

• The liquid phase diffusivities 𝑘#& 𝐷#&

𝐷'& 𝛿& = (6)
𝑁' = 𝐶' − 0 = 𝑘'& 𝐶' (3) and mass transfer 𝑘'& 𝐷'&
𝛿& − 𝛿 𝛿& − 𝛿 coefficients are related

5
Reaction rates for Mass Transfer and Chemical Reaction
1. Instantaneous reaction
These six governing equations may be solved for NA with elimination of pAi, CAi, NB, kBl, and 𝛿" /𝛿 to result in the rate
law, in terms of −𝑟# ≡ 𝑁#
𝐷"# 𝐻!
𝑝! + 𝐶
𝐷!# 𝑏 "
𝑁! ≡ (−𝑟! ′) =
1 𝐻!
+
𝑘!$ 𝑘!#

1 1 HA 1 1 1
If we combine = + = + with the rate
K Ag k Ag k Al K Al H A k Ag k Al expression above

𝐷"# 𝐻! 𝑝! 𝐷"#
(−𝑟! ′) = 𝐾!$ 𝑝! + 𝐶 = 𝐾!# + 𝐶
𝐷!# 𝑏 " 𝐻! 𝐷!# 𝑏 "

6
Reaction rates for Mass Transfer and Chemical Reaction
1. Instantaneous reaction
Gas
𝐷"# 𝐻! 𝑝! 𝐷"# film
(−𝑟! ′) = 𝐾!$ 𝑝! + 𝐶" = 𝐾!# + 𝐶
𝐷!# 𝑏 𝐻! 𝐷!# 𝑏 " control

Two extreme cases arise from the above equation corresponding to

• gas-film control if CB is very high (−𝑟# ) = 𝑘#$ 𝑝# For high CB the rate depends only on pA
• liquid-film control if CB is low
Similar to those cases for mass transfer without chemical reaction Liquid
film
control
The case of gas film control has implications for the location of the reaction plane
(at distance 𝛿 from the interface)

7
Mass Transfer and Chemical Reaction
Enhancement factor, E
For reaction occurring only in the liquid film, whether instantaneous or fast, the rate law can be written in terms of a
factor that measures the enhancement of the rate relative to the rate of physical absorption of A in the liquid without
reaction.

Reaction occurring only in liquid film is characterised by 𝐶# → 0 somewhere in the liquid film and the enhancement
factor E, is defined by

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑟 𝑓𝑙𝑢𝑥 𝑜𝑓 𝐴

𝐸=
𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚

𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡𝑎𝑘𝑒 𝑢𝑝 𝑜𝑓 𝐴 𝑤ℎ𝑒𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑐𝑐𝑢𝑟𝑠

𝐸=
𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡𝑎𝑘𝑒 𝑢𝑝 𝑜𝑓 𝐴 𝑓𝑜𝑟 𝑠𝑡𝑟𝑎𝑖𝑔ℎ𝑡 𝑚𝑎𝑠𝑠 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟
−𝑟! −𝑟!
𝐸= = −𝑟# = 𝑘#& 𝐸𝐶#%
𝑘!# (𝐶!% − 𝐶! ) 𝑘!# 𝐶!%
 Mass Transfer and Chemical Reaction
Enhancement factor, E
To express the reaction rate in terms of E we follow the following steps

−𝑟# = 𝑘#& 𝐸𝐶#% (1)

𝑝#%
If we combine (1) and (2) −𝑟# = 𝑘#& E (3)
𝑝!% = 𝐻! 𝐶!% (2) 𝐻#

(−𝑟# ) 𝑟# (4)
Also 𝑁# = −𝑟# = 𝑘#$ 𝑝# − 𝑝#% → 𝑝#% = 𝑝# − = 𝑝# +
𝑘#$ 𝑘#$

𝑟! 𝑝!
𝑝! + −𝑟! =
𝑘!# 1 𝐻 (5)
If we substitute (4) in (3) −𝑟! = 𝑘!" E + !
𝐻! 𝑘!# 𝑘!" E
Reaction rates for Mass Transfer and Chemical Reaction
2. Fast reaction Cases C and D
Bulk Film Film Bulk
gas gas liquid liquid
𝑝' CB
−𝑟' = PA0
1 𝐻'
+ CAi
𝑘'( 𝑘') E PAi

Reaction zone
 Summary

§ Discussed the rate expressions for instantaneous, and fast reactions

§ Defined Enhancement factor

11
 Reaction Engineering
CGC035 / CGC052

Reaction rate expressions for

Gas / Liquid systems III

Department of Chemical Engineering

Dr Stella Georgiadou

12
Outline of Subject area – Gas / Liquid reactions and reactors

1. Development of rate expressions for G/L systems

1.1. Develop rate expressions for straight mass transfer in G/L systems by
using the two film theory
1.2. Describe pressure and concentration profiles according to two film theory
1.3. Develop rate expressions to account for both mass transfer + reaction

2. Development of design equations for G/L contactors

3. Solution of design equations

13
Gas/Liquid reactions III
Rate expressions fo Mass transfer & Chemical Reaction

Learning outcomes

1. Rate expressions to account for both Mass transfer and reaction for Gas
Liquid reactions categorized as

• Instantaneous reactions
• Fast reactions and Enhancement factor
• Intermediate reactions and Hatta number
• Slow reactions

Outline (Chapter 23 Levenspiel, Section 9.2 Missen)

14
Mass Transfer and Chemical Reaction 𝐷!#
𝛿# =
𝑘!#
Hatta number, Ha
The Hatta number, Ha, is the dimensionless group defined by

0/1 0/1 0/1

𝑘# 𝐷#& 𝑘# 𝐷#& 𝑘#
𝐻𝑎 = 𝛿& = =
𝐷#& 𝑘#& 𝐷#& 𝑘#&
𝑎$ = 𝑖𝑛𝑡𝑒𝑟𝑎𝑐𝑖𝑎𝑙 𝑎𝑟𝑒𝑎 𝑚 % /𝑚 &
& & 𝑘! 𝑘! 𝑎% 𝐶!% 𝑣' 𝑘! 𝐶!%
𝐻𝑎 = 𝛿# = 𝛿# = 𝑣' = 𝑡ℎ𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚, 𝑚 &
𝐷!# 𝑘!# 𝑎% 𝐶!% 𝑎% 𝑘!# 𝐶!%

Ha is a measure of the maximum rate of reaction in the liquid film to the maximum rate
of transport of A through the liquid film.

𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝐻𝑎 =
𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡𝑟𝑎𝑛𝑠𝑝𝑜𝑟𝑡 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚
Mass Transfer and Chemical Reaction

Hatta number, Ha
Ha is a measure of the maximum rate of reaction in the liquid film to the maximum rate
of transport of A through the liquid film.
𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝐻𝑎 =
𝑚𝑎𝑥𝑖𝑚𝑢𝑚 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡𝑟𝑎𝑛𝑠𝑝𝑜𝑟𝑡 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚

Ø 𝐼𝑓 𝐻𝑎& ≫ 1, 𝑡ℎ𝑒𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑐𝑐𝑢𝑟𝑠 𝑖𝑛 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚 𝑜𝑛𝑙𝑦 𝐻𝑎 > 3

Ø 𝐼𝑓 𝐻𝑎& ≪ 1, 𝑡ℎ𝑒𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑐𝑐𝑢𝑟𝑠 𝑖𝑛 𝑏𝑢𝑙𝑘 𝑙𝑖𝑞𝑢𝑖𝑑 𝐻𝑎 < 0.1

Ø 𝐼𝑓 0.1 < 𝐻𝑎 < 3,

𝑡ℎ𝑒𝑛 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑐𝑐𝑢𝑟𝑠 𝑖𝑛 𝑏𝑜𝑡ℎ 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚 𝑎𝑛𝑑 𝑏𝑢𝑙𝑘 𝑙𝑖𝑞𝑢𝑖𝑑
Reaction rates for Mass Transfer and Chemical Reaction
3. Intermediate reaction rate
Consider material balances for A and B across a thin strip dx in the liquid film at a distance x
from the gas-liquid interface.
Since the gas-film mass transfer is in series with combined diffusion and reaction in the liquid
film, its effect can be added as a resistance in series. Bulk Film Film Bulk
gas gas liquid liquid

CA - curved profile (falling gradient) CB0

because the amount that diffuses is CB
PA0
decreased by reaction
CAi
CB - curved profile PAi CA0
Let’s assume a rate law first-order in A and n-order in B dg dL

C −𝑟'
−𝑟# = 𝑘𝐶# 𝐶' = 𝑥
𝑏
𝑑𝑥
 Bulk Film Film Bulk Bulk Film Film Bulk Bulk Film Film Bulk
gas gas liquid liquid gas gas liquid liquid gas gas liquid liquid
CB CB CBi CB0
PA0 CA PA0 CA PA0
CAi
PAi PAi PAi
CA CA CA0
dg dl

Reaction zone
Reaction zone 𝑧=0 𝑧 = 𝛿!
𝑧=0 𝑧 = 𝛿! 𝑧=0 𝑧 = 𝛿!

Note that −𝑟!" in mol m-2 s-1 represents the rate of reaction per unit interfacial area! −𝑟!" and NA are
equal only in the cases where reaction takes place in the film only, or in the bulk liquid only! If the
reaction takes place in both the film and bulk liquid, we need to distinguish between the flux of A
into the liquid film at the gas- liquid interface 𝛿# = 0, and the flux from the liquid film to the bulk
liquid interface 𝛿# =z.

18
Reaction rates for Mass Transfer and Chemical Reaction
3. Intermediate reaction rate
Mass Balances on A and B Bulk Film Film Bulk
gas gas liquid liquid
According to Fick’s second law
CB0
#
𝑑 𝐶" CB
𝐷"! #
= −𝑟" ′ = 𝑘𝐶" 𝐶$ % PA0
𝑑𝑥
CAi
𝑑 # 𝐶$ PAi CA0
𝐷$! = −𝑟$ ′ = 𝑏(−𝑟" ) dg dL
𝑑𝑥 # 𝑑𝐶$
𝐶" = 𝐶"& and = 0 at 𝑥 = 0
Boundary conditions: 𝑑𝑡 𝑥
𝐶" = 𝐶"' and 𝐶$ = 𝐶$' at 𝑥 = 𝛿( 𝑑𝑥

These two equations are coupled through equation −𝑟#E = −𝑟# (𝐶# , 𝐶' , 𝑇)
Analytical solutions may not exist. The equations can be uncoupled only if the reaction is pseudo-first order.
3. Intermediate reaction rate
Negligible Depletion of B in the Film, Pseudo - first order reaction Cases E and F

There is no analytical solution except for the case n = 0 Bulk Film Film Bulk
gas gas liquid liquid
Two asymptotic approximation (van Krevelen & Hoftijzer) can be found CBi CB0
1. Infinitely rapid reaction - instantaneous reaction PA0
(This will often occur when A is CAi
2. Negligible depletion of B
only moderately soluble) PAi CA0
dg dl
The mass balances reduce to

𝐶$& ≈ 𝐶$' 𝑑& 𝐶! ( ( Same equation as for diffusion on a

𝐷!# = −𝑟! = 𝑘𝐶! 𝐶" = (𝑘𝐶") )𝐶! catalytic slab, however, the boundary
𝑑𝑥 &
conditions are different
𝐶"& << 𝐶$'
𝑑 # 𝐶$ 𝐶" = 𝐶"' at 𝑥 = 𝛿(
𝐷$! = −𝑟$ = 𝑏(−𝑟" )
𝑑𝑥 # 𝐶" = 𝐶"& at 𝑥 = 0

20
Reaction rates for Mass Transfer and Chemical Reaction
3. Intermediate reaction rate Cases E and F
𝐷!#
𝛿# =
𝑑 # 𝐶" If we transform the balance into a dimensionless 𝑘!#
𝐷"! #
= (𝑘𝐶$' % )𝐶" = 𝑘" 𝐶" from
𝑑𝑥

& 𝑑& 𝐶! & 𝑑& 𝐶!

𝛿# 𝐷!# = 𝛿# 𝑘! 𝐶! → & = 𝛿# & (𝑘! /𝐷!# )𝐶!
𝑑𝑥 & 𝑥
𝑑
𝛿#

𝑥 𝐶! 𝑑& 𝐶!
In dimensionless form 𝑧= and λ= − 𝛿 &
(𝑘! /𝐷!# )𝐶! = 0
𝛿# 𝐶!% 𝑑𝑧 & #

0/1 0/1 0/1

Where the Hatta number, Ha, is the 𝑘# 𝐷#& 𝑘# 𝐷#& 𝑘#
dimensionless group defined by 𝐻𝑎 = 𝛿& = =
𝐷#& 𝑘#& 𝐷#& 𝑘#&
3. Intermediate reaction rate Cases E and F
Negligible Depletion of B in the Film, Pseudo - first order reaction
The boundary conditions become Bulk Film Film Bulk
gas gas liquid liquid
𝑎𝑡 𝑧 = 0, λ=1
𝐶! CBi CB0
𝑎𝑡 𝑧 = 1, λ= = λ* PA0
𝐶!%
CAi
The solution of the mass balance is
PAi CA0
λ* sinh 𝐻𝑎 𝑧 + sinh[𝐻𝑎 1 − 𝑧 ] dg dl
λ=
sinh(𝐻𝑎)
𝑧=0 𝑧 = 𝛿#
𝐻! 𝐶!
𝑝! −
cosh(𝐻𝑎)
And the rate expression for overall transfer through the film at z=0 is 𝑁! (𝑧 = 0) =
1 𝐻 tanh(𝐻𝑎)
+ !
𝑘!$ 𝑘!# 𝐻𝑎
3. Intermediate reaction rate Cases E and F

Negligible Depletion of B in the Film, Pseudo - first order reaction

Bulk Film Film Bulk
gas gas liquid liquid
CBi CB0
And the rate expression for overall transfer
through the interface at 𝑧 = 1 is PA0
CAi
PAi CA0
𝑘!# tanh 𝐻𝑎 𝐶!+ dg dl
𝑘!# 𝐻𝑎 𝑘!# 𝐻𝑎 𝑝! +
cosh 𝐻𝑎
𝑁! 𝑧 = 1 = − 𝑝!
tanh 𝐻𝑎 𝑘!$ 𝐻! tanh 𝐻𝑎
cosh 𝐻𝑎 1 + 𝑧=0 𝑧=1
𝑘!# 𝐻𝑎
Reaction rates for Mass Transfer and Chemical Reaction
4. Slow reaction
If the resistance to mass transfer of A through the gas and liquid films is not negligible &
We assume that the reaction is second order, first order for each one of the reactants
Bulk Film Film Bulk
gas gas liquid liquid Note that −𝑟") in mol m-2 s-1 represents the
Please note the units for CB rate of reaction per unit interfacial area!
− 𝑟") and NA are equal only in the cases
• NA are mol m-2 s-1 PA0 CA
where reaction takes place in the film only, or
• −𝑟") are mol m-2 s-1 in the bulk liquid only! If the reaction takes
PAi
• -rA are mol m-3 s-1 CA place in both the film and bulk liquid, we need
• 𝛼 are m2 / m-3 to distinguish between the flux of A into the
liquid film at the gas- liquid interface 𝛿! = 0,
Reaction zone and the flux from the liquid film to the bulk
liquid interface 𝛿! =z.
𝑁# = −𝑟# ′ = −𝑟# /𝑎 = (𝑘8𝑎 )𝐶# 𝐶' = 𝑘# 𝐶# 𝐶'

24
Reaction rates for Mass Transfer and Chemical Reaction
4. Slow reaction
Since the system is usually specified in terms of pA and CB, rather than CA and CB, we eliminate CA in favor
of pA by combining the rate expressions for mass transfer through the gas and liquid films with the rate
expression for reaction and Henry’s law, 𝑝!$ = 𝐻! 𝐶!$

N A = -rA ' = k Ag ( p A - p Ai ) N A = -rA ' = k Al (C Ai - C A ) 𝑁# = −𝑟# ′ = −𝑟# /𝛼 = 𝑘# 𝐶# 𝐶'

Bulk Film Film Bulk
These four equations can be solved simultaneously to obtain : gas gas liquid liquid
CB
𝑝#
−𝑟# ′ = This applies to cases: PA0 CA
1 𝐻 𝐻
+ #+ # G and H
𝑘#$ 𝑘#& 𝑘# 𝐶' PAi
CA

Gas film Liquid film

resistance Reaction
resistance Reaction zone

25
 Summary

§ Described and discussed the effect of the relative magnitude of the mass transfer and reaction
rates on the position of the reaction plane or zone.

§ Described and discussed the effect of the relative magnitude of the mass transfer and reaction
rates on the concentration and pressure profiles.

§ Developed rate expressions for instantaneous, fast, intermediate and slow reaction rates compared
to mass transfer.

26
Nomenclature
𝑎$ = 𝑖𝑛𝑡𝑒𝑟𝑎𝑐𝑖𝑎𝑙 𝑎𝑟𝑒𝑎 𝑚 % /𝑚 &
PA = partial pressure of A
H A = Henry' s law constant
C A = concentrat ion of A
i = conditions at the interface
D = Diffusivity
DAl = molecular diffusion coefficient of A in Liquid phase (m 2 / s )
DAg = molecular diffusion coefficient of A in Liquid phase (m 2 / s )
dg , dl = thickness of gas film and liquid film respective ly
Ha = Hatta number (ratio of reaction rate/diffu sion rate)
E = enhancemen t factor
k Ag = gass film mass transfer coefficient
k Al = liquid film mass transfer coefficient
K Ag , K Al = overall mass transfer coefficient for gas and liquid
𝑣' = 𝑡ℎ𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑 𝑓𝑖𝑙𝑚, 𝑚 &
 Nomenclature
a = area of gas - liquid interface per unit volume of liquid m2/m3
p A = partial pressure of A
H A = Henry' s law constant
C A = concentrat ion of A
i = conditions at the interface
D = Diffusivity
D Al = molecular diffusion coefficient of A in Liquid phase (m2 / s )
D Ag = molecular diffusion coefficient of A in Liquid phase (m2 / s )
δg , δl = thickness of gas film and liquid film respective ly
k Ag = gas - film mass transfer coefficient
k Al = liquid - film mass transfer coefficient
te = time liquid spends at the interface
K Ag , K Al = overall mass transfer coefficient for gas and liquid
−𝑟# ′= rate of diffusion / mass transfer mol /(m2 s1 )

−𝑟# = rate of diffusion / mass transfer mol /(m3 s1 )

28