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Interfacial Transfer

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Mass Transfer Coefficient

Q A  q  h ts tm  
An analogous equation for mass transfer is of the form
Mass Transfer Coefficient
 The driving force is the difference between the
concentration at the phase boundary, CAS and the
concentration at some arbitrarily defined point in the
fluid medium, C A .

 kC is a function of geometry of the system and the


velocity and properties of the fluid similar to the heat
transfer coefficient, h.
Dimensionless Correlations

 The molecular diffusivities of the three transport process


(momentum, heat and mass) have been defined as:

𝑀𝑎𝑠𝑠 𝐷𝑖𝑓𝑓𝑢𝑠𝑖𝑣𝑖𝑡𝑦= 𝐷 𝐴𝐵

 Each of the diffusivities has the dimensions of L2 / t, hence,


a ratio of any of the two of these must be dimensionless.

3
Correlations

 The analogous number in mass transfer is Schmidt number given


as

 The ratio of the molecular diffusivity of heat to the molecular diffusivity


of mass ,the Lewis Number, and is given by

 Lewis number is encountered in processes involving


simultaneous convective transfer of mass and energy. 4
Sherwood number
Consider the mass transfer of solute A from a solid to a fluid
flowing past the surface of the solid.

For such a case, the mass transfer between the solid surface
and the fluid may be written as


N A  k c C As  C A  

5
Analogies among Mass, Heat and
Momentum Transfer
 mathematical description of the effects
 physical parameters used for quantitative description.

Fick’s Law
dCA
J A   D AB
dz
Fourier’s law
dT
q  k
dz
Newton’s law
d
 
dz
6
Convective Mass Transfer Correlations

 Extensive data have been obtained for the transfer of mass


between a moving fluid and certain shapes, such as flat
plates, spheres and cylinders.

 The techniques include sublimation of a solid, vapourization


of a liquid into a moving stream of air and the dissolution of a
solid into water.

 Data correlated in terms of dimensionless parameters and the


equations are used to estimate the mass transfer coefficients.

7
Flat Plate

Sh  0.664 ReL1 2Sc 1 3 laminar Re L  3 * 10 5

Sh  0.036 ReL0.8 Sc 1 3 turbulent Re L  3 * 10 5

Using the definition of j factor for mass transfer in


equation (2.38) and (2.39) we obtain

j D  0.664 ReL 1 2 laminar Re L  3 * 10 5

J D  0.037 ReL 0.2 turbulent Re L  3 * 10 5

These equations may be used if the Schmidt number is in the range


0.6 < Sc < 2500.
8
Single Sphere
Sh  Sh o  C Re m Sc n

Where C, m and n are constants, the value of n is normally taken as 1/3

For very low Reynold’s number, the Sherwood number should approach a
value of 2.

Sh  2  C Re m Sc 1 3

9
Single Sphere
For mass transfer into liquid stream by Brain and Hales


Sh  4  1.21 2 3 12
PeAB 
Peclet number, Pe AB < 10,000 (Brain & Hales).

Pe AB  Re Sc

For Peclet numbers > 10,000, (Levich)

Sh  1.01 Pe1AB3

10
Single Sphere
Sh  2  0.552 Re 1 2 Sc 1 3

Mass transfer into gases


2<Re<800 ; 0.6<Sc<2.7 (Froessling).

For natural convection mass transfer the relation given by Schultz


Sh  2  0.59 Gr AB Sc 1 4
2 * 10 8 < Gr AB Sc < 1.5 * 10 10 (Schultz)

11
Practice Problem
The mass flux from a 5 cm diameter naphthalene ball placed in
stagnant air at 40C and atmospheric pressure, is
1.47*10 –3  mol/m 2. sec. Assume the vapor pressure of naphthalene
to be 0.15 atm at 40C and negligible bulk concentration of
naphthalene in air. If air starts blowing across the surface of
naphthalene ball at 3 m/s by what factor will the mass transfer rate
increase, all other conditions remaining the same?
For spheres :

Sh = 2.0 + 0.6 (Re) 0.5 (Sc)0.33

Where Sh is the Sherwood number and Sc is the Schmidt’s number.


The viscosity and density of air are 1.8 * 10 –5 kg/m.s and 1.123
kg/m 3, respectively and the gas constant is
82.06 cm 3 . atm/mol.K.

12
Flow Through Pipes
 Mass transfer from the inner wall of a tube to a moving
fluid

 pB,lm is the log mean composition of the carrier gas, evaluated between
the surface and bulk stream composition and P the total pressure.

 The expression is valid over the range


2000 < Re < 35000
0.6 < Sc < 2.5

In the range, 2000 < Re < 70000 and 1000 < Sc < 2260,

13
Example
A solid disc of benzoic acid 3 cm in diameter is spun at 20 rpm and
25C. Calculate the rate of dissolution in a large volume of water.
Diffusivity of benzoic acid in water is 1.0 * 10 –5 cm 2/sec, and solubility
is 0.003 g/cc. The following mass transfer correlation is applicable:
Sh = 0.62 Re ½ Sc 1/3
Where

D2  and  is the angular speed


Re  in radians/time

14
Solution
Dissolution rate = N A S
….. (*1)
Where N A = mass flux, and
S = surface area for mass transfer
N A = k c (C As – C A ) ….. (*2)

Where C As is the concentration of benzoic acid in water at the surface


of the dose.
C A is the concentration of benzoic acid in water for an infinite
distance from the surface of the disc.
Given:
Sh = 0.62 Re ½ Sc 1/3
(i.e.) 1 1
kc D  D 2   2   3
 0.62     ….. (*3)
D AB   
    D AB  

20
 * 2  radian sec
60
1 rotation = 2  radian
15
Therefore 20 rotation per minute = 20 * 2  radian/min
For water  = 1 g/cm 3  = 1 centipoise = 0.01 g/cm.sec.
From (*3),
1 1
    2   

3
k c  0.62 D AB  
     D AB 

1 1
5  40  60 * 1 2  0.01  3
 0.62 * 1.0 * 10 *   5

 0.01   1 * 1.0 * 10 
= 8.973 * 10 –4 cm/sec.
From (*2),
N A = 8.973 * 10 –4 (0.003 – 0)
= 2.692 * 10 –6 g/cm 2.sec
From (*1),
N A S = N­A * (2r 2)
= 2.692 * 10 –6 * (2 * 1.5 2)
= 3.805 * 10 –5 g/sec
= 0.137 g/hr. 16
Interfacial mass transfer
 mass transfer across an interface between a gas and a
liquid or between two liquid phases.

 Such interfaces exist in absorption, distillation, extraction,


and stripping.

 At fluid-fluid interfaces, turbulence may persist to the


interface.

 Several theoretical models to describe mass transfer


between a fluid and such an interface. Water

NA

NH3 +Air 17
 Component A (ammonia), diffuses into Film Theory
nonvolatile liquid B.
pA
 A is absorbed into B without desorption

film
Liq.
of B into gaseous A. CAi
Bulk liquid

 Gas is at total pressure PA, no Gas CAb

resistance to mass transfer in the gas


NA
phase.
Z=δ
Z=0
 At the gas-liquid interface, phase
equilibrium is assumed so the
concentration of A, CAi, is related to the Fick’s Law:
partial pressure of A, PA,

 In the thin, stagnant liquid film of


thickness δ, molecular diffusion only
occurs with a driving force CAi-CAb

 If, in addition, bulk flow of A is


18
neglected, the concentration gradient is
Film Theory
For dilute A, bulk flow can be neglected

𝑫 𝑨𝑩
⟹ 𝒌𝒄 =
𝜹
For significant bulk flow effect,

′ 𝐷 𝐴𝐵
𝑘 =
𝑐
Generally, 𝛿 ( 1 − 𝑥 𝐴 )𝐿𝑀

⇒ 𝒌 𝒄 ∝ 𝑫 𝑨𝑩

Experimental data shows that


0.5<n<0.75 19
Two resistance theory
 An extension of the film theory to two fluid films in
series.

 Each film presents a resistance to mass transfer.

 concentrations in the two fluids at the interface are


assumed to be in phase equilibrium.

𝑁 𝐴=𝑘𝑐 ( 𝐶 𝐴𝑖 −𝐶 𝐴𝑏 ) AND 𝑁 𝐴=𝑘𝑝 ( 𝑝 𝐴𝑏 −𝑝 𝐴𝑖 )


liquid phase gas phase 20
Overall transfer coefficients
𝑁 𝐴=𝐾 𝑐 ( 𝑝 𝐴𝑏 − 𝐶 𝐴𝑏 )

pAb and CAb are different entities


(concepts) and cannot be simply
subtracted from each other

 Define = a fictitious liquid phase concentration which is


the concentration that would be in equilibrium with the
partial pressure in the bulk gas

 Kc = overall mass transfer coefficient based on the liquid


phase resistance (KL)

𝑁 𝐴=𝐾 𝑐 ( 𝐶 𝐴 −𝐶 𝐴𝑏 )

21
Overall transfer coefficients
An overall transfer equation can also be written based
on the gas phase

Not a consistent
𝑁 𝐴=𝐾 𝑝 ( 𝑝 𝐴𝑏 −𝐶 𝐴𝑏 ) .............(160)
equation!

 Define = a fictitious gas phase partial pressure


which is the partial pressure that would be in
equilibrium with the bulk liquid concentration.

 Kp = overall mass transfer coefficient based on the


gas phase (KG)
𝑁 = 𝐾 𝑝 −𝑝 ∗
𝐴 𝑝 ( 𝐴𝑏 𝐴 ) ......................(161)

At steady state, NA = constant

........(162)
22
Transfer coefficients
Assume Henry’s law is valid,

and ....................................(163)
Also and

Equation can be written as

..........(164)

(𝐶¿¿ 𝐴 −𝐶 𝐴𝑏 )=( 𝐶 𝐴 −𝐶 𝐴𝑖 ) + ( 𝐶 𝐴𝑖 −𝐶 𝐴𝑏 ) ¿
∗ ∗
......................(165)
¿(𝑝 ¿ ¿ 𝐴𝑏 𝐻 𝐴 − 𝑝 𝐴𝑖 𝐻 𝐴 )+ ( 𝐶 𝐴𝑖 −𝐶 𝐴𝑏 ) ¿
¿ 𝐻 𝐴 (𝑝 ¿ ¿ 𝐴𝑏− 𝑝 𝐴𝑖 )+ ( 𝐶 𝐴𝑖 − 𝐶 𝐴𝑏 ) ¿ = the overall resistance to
mass transfer
𝑁𝐴 𝐻 𝐴𝑁 𝐴 𝑁 𝐴
⇒ = + = resistance due to the liquid
𝐾𝑐 𝑘𝑝 𝑘𝑐 film
= resistance due to the gas
1 1 𝐻 𝐴........................(166) film
⇒ = +
𝐾 𝑐 𝑘𝑐 𝑘𝑝
23
Transfer coefficients
Similarly,
......................(167)

................................................(168)

 kp, kc are called individual or local mass transfer


coefficients since they are applicable only in the
individual phases concerned.

 KG, kG, KL, kL also used in place of Kp, kp, Kc, kc 24


Transfer coefficients
Driving force can also be expressed in mole fractions

................(169)
Using K values to express the equilibrium,

...........................................(170)

......................(171)

.....................(172)

25
Mass Transfer rate
 Area coefficients are difficult to determine

 Volume coefficients are usually used

 Goal of the design is to determine the total volume


of absorber

Define
................(173)

 Actual value of a difficult to predict


 Accurate prediction not necessary since design is
usually based on the volumetric coefficients.

26
Mass Transfer rate

27
Alternate forms of
transfer coefficients
.........(174)

.........(175)

.........(176)
Units
m/s
.........(177)
kmol/s.m2.kPa
, kmol/s.m2
.........(178)

.........(179) 28
Equilibrium stage operations
 A class of mass-transfer devices consisting of assemblies of
individual units or stages

 Connected so that the materials being processed pass through each


stage in turn.

 Called cascades.

 Streams entering each stage must NOT be in equilibrium with each


other for any mass transfer to take place.

 For the ideal stage, the leaving streams are in equilibrium.

29
Equilibrium stage operations

 A batch mass transfer operation is equivalent to a single stage.

 For more than one equilibrium stage, the stages must be connected for
counter current flow.

 This is the most efficient arrangement requiring the fewest stages for a
given change of composition

30
Phase equilibria
 Two phases involved in almost all mass transfer operations.

 The rate of mass transfer is proportional to the departure from


equilibrium.

 A limit to mass transfer is reached when the two phases come


into equilibrium.

 The number of independent variables (or degrees of freedom)


in a system under equilibrium is given by the phase rule.

.........(180)

For 2 phase (vapour – liquid) binary system,

31
Phase equilibria
 At constant pressure, only 1 variable (liquid phase composition,
temperature and gas phase composition) can be changed independently.

 The equilibrium data for such systems are displayed as temperature-


composition diagrams or y-x diagrams.

32
Vapour Liquid Equilibrium
Consider a two component, two phase system

At equilibrium, temperatures, pressure and compositions


of the 2 phases cease to change.

For each component,

.........(181)

 In general, the concentrations of the components in


the two phases are not equal at equilibrium.

 Several thermodynamic models developed to relate the 33


Models of Vapour/Liquid
Equilibrium (VLE)
 Several thermodynamic models developed to
relate the concentrations in the two phases

 The goal is to find by calculations the


temperature, pressures and compositions of
phases in equilibrium.

 There are several ways to represent VLE data.

 Pxy diagrams at constant T ;


 Txy diagrams at constant P
 y-x diagrams at 1 atm.

34
VLE Diagrams

35
Raoult’s law
The law is valid at moderately low pressures and applies
to a system composed of chemically similar components

Assumptions

1. Vapour phase is an ideal gas


2. The liquid phase is an ideal solution

For any component A,


................(182)
 
where is the vapour pressure of the component A
 
Raoult’s law is limited to species with known vapour
pressure (temperatures below critical temperature).

The law is applicable to species that are present at mole


fractions approaching 1 provided the vapour phase is an
36
ideal gas.
Example (practice)
Raoult’s law may be used to determine phase
compositions for the binary system benzene-toluene, at
low temperatures and pressures.
Determine the composition of the vapor in equilibrium
with a liquid containing 0.4 mole fraction of benzene at
300 K,
and calculate the total equilibrium pressure. Estimate the
vapor pressure of benzene and toluene at 300 K from the
Antoine equation,

where Pi is the vapor pressure of component i, in mmHg,


and T is the temperature, in K. The Antoine constants for
benzene and toluene are given in the following table:

37
Modified Raoult’s Law
If the liquid solution is not ideal,
.........(183)
 
 -activity coefficient; an experimental value that is a
function of temperature and liquid phase composition

 Obtained from fugacities.

Example
The binary system acetonitrile (2.)/nitromethane(2) conforms closely with
Raoult’s law. Vapour pressure for the pure species are given by the
following Antoine equations
2,945.47
ln P1sat  14.2724 
T  224.0

2,972.64
ln P2sat  14.2043 
T  209.0
Psat in kPa and T in °C
Prepare a graph showing P vs. xi and P vs. yi for a temperature of 75 °C
Prepare a graph showing T vs xi and T vs yi for a pressure of 70 kPa 38
Henry’s Law
 The partial pressure of a species in the vapour phase is
directly proportional to its liquid phase mole fraction.

.........(184)

 Henry’s law is valid for very dilute solutions (2.0% or less).

 Henry’s constant is tabulated for a number of components at


different conditions.

39
K-value correlations
 A simple and convenient measure of the tendency of a
species to distribute in the vapour and liquid phase at
equilibrium is given by the K-value.
.........(185)
 K values are functions of temperature and pressure

 Compared with Raoult’s law and Henry’s law

.........(186)

.........(187)

.........(188) 40
41
Dilute Solutions

 In general, for dilute solutions, the


equilibrium curve is approximated by a
straight line with equation

𝒚 ∗ =𝒎𝒙 .........(189)

42
Example (practice)
• In an experimental study of the absorption of ammonia by
water in a wetted wall column, the value of KG was found to be
2.75 x 10-6 kmol/m2-s-kPa.
• At one point in the column, the composition of the gas and
liquid phases were 8.0 and 0.115 mole% NH3 respectively. The
temperature was 300K and the total pressure was1 atm. Eighty-
five percent of the total resistance to mass transfer was found
to be in the gas phase.
• At 300K, ammonia-water solutions follow Henry’s law up to 5
mole % in the liquid with m = 1.64 when the total pressure is 1
atm.
• Calculate the individual film coefficients and the interfacial
concentrations

43

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