Chapter 2 Principles of Unsteady-State and Convective Mass Transfer

Introduction
In previous chapter, we considered various mass transfer systems where the concentration or partial pressure at any point and the diffusion flux were constant with time, hence at steady state. Before steady state can be reached, time must elapse after the mass transfer process is initiated for the unsteady-state conditions to disappear. In heat transfer course, an unsteady-state equation was derived,

T 2T = 2 t x
In the same manner, an unsteady state mass transfer equation can be derived by applying a mass balance on component A.

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Mass Transfer ChE 461

Chapter 1-2

Consider the elemental solid shown in the drawing where A is diffusing the x-direction Mass balance on component A in terms of moles without generation:
Rate of input

Rate of output

N Ax x

y x

N Ax xx
z x + x

x Rate of input = rate of output + rate of accumulation

c A x x c = DAB A rate of output = N Ax x + x x x + x

rate of inpute = N Ax x = DAB
Rate of accumulation is as follows for the volume xyz m3: c rate of accumulation = (xyz ) A c c t DAB A DAB A x x c A x x + x Combining the three terms and dividing by xyz: = x x c A c A As x approaches zero: = DAB x + x t x x
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Mass Transfer ChE 461

Chapter 1-3

For constant diffusivity DAB:

2c A c A = DAB 2 t x

cA = cA(x,t)

Similar derivation can be obtained for diffusion in all three direction:

2c A 2c A 2c A c A = DAB 2 + 2 + 2 x t y z
Because of mathematical similarity between the equation for heat conduction, mathematical method used for solution of the unsteady-state heat-conduction can be used for unsteady-state mass transfer.

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Mass Transfer ChE 461

Chapter 1-4

Diffusion in a Flat Plate with Negligible Surface Resistance

Consider the unsteady-state diffusion in the x direction for a plate of thickness 2x1. c For a very high mass-transfer coefficient outside the surface, resistance will be negligible and the concentration c at t > 0 at the surface will be equal to that in the fluid, c1 c0 @ t =0 (t = t) Initial and boundary conditions: c c c2 c1 c = c0, t = 0, x = x, Y = 1 0 = 1 c1 c0 c c x Y = 1 1 =0 c = c1, t = t, x = 0, 0 x1 2x1 c1 c0 Define dimensionless conc.: c1 c1 c = c1, t = t, x = 2x1, Y = Y 2Y =0 c1 c = DAB 2 Y= c1 c0 t x c1 c0 Solution is an infinite Fourier series:
32 2 X 3x 1 52 2 X 5x c1 c 4 1 12 2 X 1x 1 sin sin sin = exp + exp + exp + Y= 2 x1 4 4 2 x1 5 4 2 x1 3 c1 c0 1

where:

X = Dt x12
Mass Transfer ChE 461
Chapter 1-5

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Unsteady-State Diffusion in Various Geometries

Solution of unsteady-state mass transfer is time-consuming; convenient charts for various geometries are available. Previously, we discussed the case of negligible convective resistance at the surface. However, in many cases when a fluid is outside the solid, convective mass transfer is occurring at the surface. Convective mass-transfer coefficient (kc) is similar to convective heat transfer (h), and is defined as follows:

N A = kc (cL1 cLi )

[compare with q = h (T1 Ti)]

where kc = mass transfer coefficient, in m/s cL1= bulk fluid concentration, in kg mol A/m3 cLi= fluid concentration just adjacent to the surface, in kg mol A/m3

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Mass Transfer ChE 461

Chapter 1-6

Different interface conditions are shown in the drawing Concentration drop across the fluid is cL1 cLi The concentration of the fluid adjacent to the surface, cLi, is related to the concentration of the fluid in the solid, ci, by the following equilibrium equation:

cLi ci K: equilibrium distribution coefficient K=

(similar to Henrys law coefficient for a gas and liquid)

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Mass Transfer ChE 461

Chapter 1-7

1. Relation between mass and heat Transfer parameter. Charts for unsteady heat transfer can be used to predict concentration in unsteady-state mass transfer by diffusion 2. Chart for diffusion in various geometries Semi infinite solid (Fig 5.3-3) Flat plate (Fig 5.3-5/6) Long cylinder (Fig 5.3-7/8) Sphere (Fig 5.3-9/10) Average concentration (Fig 5.313)

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Mass Transfer ChE 461

Chapter 1-8

Example: Unsteady-State Diffusion in a Slab of Agar Gel

A solid slab of 5.15 wt% agar gel at 278 K is 10.16 mm thick and contains a uniform concentration of urea of 0.1 kgmol/m3. Diffusion is only in the x-direction through two parallel flat surfaces 10.16 mm apart. The slab is suddenly immersed in pure turbulent water, so the surface resistance can be assumed to be negligible; that is, the convective coefficient kc is very large. The diffusivity of urea in the agar is 4.72 1010 m2/s. 1) Calculate the concentration at the midpoint of the slab (5.08 mm from the surface) and 2.54 mm from the surface after 10 h. 2) If the thickness of the slab is halved, what would be the midpoint concentration in 10 h?

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Mass Transfer ChE 461

Chapter 1-9

CONVECTIVE MASS-TRANSFER COEFFICIENT

In previous chapter emphasis molecular diffusion in stagnant fluids or fluids in laminar flow. In many cases, the rate of diffusion is slow and more rapid transfer is desired. So, to achieved it the fluid velocity is increased until turbulent mass transfer occurs. To have fluid in convective flow usually requires the fluid to be flowing past another immiscible fluid or a solid surface. Example: flowing in a pipe Laminar flow: fluid flows in streamlines and its behavior can usually be described mathematically Turbulent flow: no streamlines and large eddies or chunks of fluid exist moving rapidly in seemingly random fashion
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Mass Transfer ChE 461

Chapter 1-10

Three regions of mass transfer can be visualized when a solute is dissolving from a solid to a fluid: cA2 Fluid Laminar sub-layer: a thin viscous sublayer eddies which is adjacent to the surface Characterized by molecular diffusion Transition zone No eddies present Solid surface Large concentration drop
Laminar sub-layer

z cA1

Transition or buffer zone: a region adjacent to the laminar layer where gradual transition from molecular diffusion to mainly turbulent at the end occurs. Some eddies present Mass transfer is the sum of turbulent + diffusion Turbulent region: adjacent to the buffer zone where most cA1 of the transfer is by turbulent with very small diffusion concentration decrease very small cA eddies motion cA2 Typical plot for mass transfer of a dissolving solid from a surface to a turbulent fluid in a conduit
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z
Chapter 1-11

Mass Transfer ChE 461

Definition of Mass-Transfer coefficient

Previously, for molecular diffusion in stagnant fluid and fluid in laminar flow:
* J A = DAB

dcA dz

N A = cDAB

dxA cA + ( N A + NB ) dz c

For turbulent flow, mass transfer is increased by eddy diffusivity, (m/s)

* J A = (DAB + )

dcA dz

varied with distance, average will be used; J*A1 is normally used which is flux of A on surface area A1 (since the cress sectional area may vary) relative to the whole bulk surface.

DAB + M J = (cA1 cA2 ) z2 z1

* A1

* ' In terms of convective mass transfer coefficient: J A1 = kc (cA1 cA2 )

where kc is mass transfer coefficient: k ' = DAB + M c

z2 z1

[Kgmol/s.m2.(kgmol/m3)] or [m/s]
Chapter 1-12

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Mass Transfer ChE 461

Mass-transfer coefficient for equimolar counterdiffusion

NA = -NB
Since N A = c DAB + M

) dxA + cA ( N A + NB )
dz c
Defining equation for the mass-transfer coefficient

N A = kc' (cA1 cA2 )

DAB + M where k = z2 z1
' c

Other definitions for mass transfer coefficient depending on concentrations: Gases:

' ' N A = kc' (cA1 cA2 ) = kG ( pA1 pA2 ) = k y ( yA1 cA2 )
' ' ' Liquids: N A = kc (cA1 cA2 ) = kL (cA1 cA2 ) = kx ( xA1 xA2 )

Mass transfer coefficients are related to each other, eg.

c A2 k y ' ' ' cA1 N A = kc (cA1 cA2 ) = k y ( yA1 cA2 ) = k y = (cA1 cA2 ) c c c ' ' Hence, kc = k y / c (Also see Table 7.2-1 with corresponding units)
Mass Transfer ChE 461
Chapter 1-13

'

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Mass-transfer coefficient for A diffusing through stagnant, nondiffusing B NB = 0 DAB cav NA = ( x A1 x A2 ) was derived Previously, the expression

( z2 z1 ) xBM With eddy diffusivity, N A = ( DAB + M )cav ( x A1 x A 2 ) = ( DAB + M ) (c A1 c A 2 ) ( z2 z1 ) xBM ( z2 z1 ) xBM

kc' or N A = (cA1 cA2 ) = kc (cA1 cA2 ) xBM ' kx or N A = ( xA1 xA2 ) = kx ( xA1 xA2 ) xBM

DAB + M where k = z2 z1
' c

kc Mass transfer coefficient for A diffusing through stagnant B

Rewriting using other units: Gases: N A = kc (cA1 cA2 ) = kG ( pA1 pA2 ) = k y ( y A1 cA2 ) Liquids: N A = kc (cA1 cA2 ) = kL (cA1 cA2 ) = k ( x x ) x A1 A2 Again, mass transfer coefficients are related to each other, eg.
' c

cA1 cA2 = kx (c c ) N A = (k / xBM )(cA1 cA2 ) = kx ( xA1 xA2 ) = kx A1 A2 c c c ' Hence, kc / xBM = kx / c (Also see Table 7.2-1 with corresponding units)
Mass Transfer ChE 461
Chapter 1-14

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Example: Vaporizing A and Convective Mass Transfer

A large volume of pure gas B at 2 atm pressure is flowing over a surface from which pure A is vaporizing. The liquid A completely wets the surface, which is a blotting paper. Hence, the partial pressure of A at the surface is the vapor pressure of A at 298 K, which is 0.2 atm. The ky has been estimated to be 6.78 10-5 kgmol/s.m2.mol frac. Calculate NA, the vaporization rate, and also the values of ky anf kG.

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Mass Transfer ChE 461

Chapter 1-15

Mass Transfer Coefficient for General Case of A and B diffusing and Convective flow using Film Theory
In this case mass transfer is assumed to occur through a thin film next to the Fluid z wall of thickness f and by molecular diffusion. xA2 f The experimental value of kc for dilute DAB xA1 ' Solid surface kc = solutions is used to determine f:
f

Convective term dxA cA + ( N A + NB ) Since N A = c(DAB + M ) dz c dx with molecular diffusion only: N A = cDAB A + xA ( N A + NB ) dz x A2 1 z= f dxA dz = Rearranging and integration: xA1 N x ( N + N ) cDAB z=0 A A A B N / ( N A + N B ) x A2 NA NA = kc' c ln A N A + NB N A /( N A + NB ) xA1

' when NB = 0 N A = kc / xBM (cA1 cA2 )

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Mass Transfer ChE 461

Chapter 1-16

Mass Transfer Coefficient under High Flux Conditions

The previous case assumes that film thickness is unaffected by high flux and bulk or convective flow (diffusion-induced convection) Other definitions of the mass transfer coefficient which includes effect of diffusion-induced convection will be derived assuming stagnant nondiffusing B

dxA N A = cDAB + xA ( N A + N B ) dz z=0 0

Defining a mass-transfer coefficient in terms of the diffusion flux,

dx cDAB A = kc0c( xA1 xA2 ) dz z=0

kc0c( xA1 xA2 ) NA = (1) 1 xA1

In general, kc may be defined without regard to convective flow:

0 Combining (1) and (2): kc = (1 xA1 )kc

N A = kc c( xA1 xA2 )

(2)

kc0 and kc for high flux

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kc for low flux

Mass Transfer ChE 461
Chapter 1-17

Relationship between kc0 and kc for high flux and kc for low flux
The following expressions have previously derived using the film theory foe transfer of A by molecular diffusion and convective flow, with B being stagnant and nondiffusing

kc' NA = (cA1 cA2 ) = kc (cA1 cA2 ) xBM kc k 1 = = x Hence, ' ' kx kc xBM 0 kc0 1 xA1 kx 0 = ' = But, kc = (1 xA1 )kc ' kx xBM kc

Correction factor for high flux

Note: correction factors obtained by film theory give results reasonably close to those using more complex theory, eg. penetration theory or boundary layer theory

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Mass Transfer ChE 461

Chapter 1-18

Example: High Flux Correction Factors

Toluene A is evaporating from a wetted porous slab by having inert pure air at 1 atm flowing parallel to the flat surface. At a certain point the mass-transfer coefficient kc for very low fluxes has been estimated as 0.2 lb mol/h.ft2. The gas composition at the interface at this point is xA1 = 0.65. Calculate the flux NA and the ratio kc/kc or kx/kx and k0c/kc or k0x/kx to correct for high flux.

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Mass Transfer ChE 461

Chapter 1-19

Mass-Transfer Coefficients for Various Geometries

Dimensionless Numbers
Reynolds number

Re =

: mass average velocity if in pipe : superficial velocity in the empty cross section of a packed bed ( = /)
Schmidt number Sherwood number

L Dp for sphere L D for pipe L L length for plate

Sc =

DAB

y shear component for diffusivit (/ ) Diffusivit for mass transfer(DAB ) y

=...

' kc' L kc yBM L kx L = = Sc = c DAB DAB DAB

' kG P Stanton number = = . . . GM = /Mav = c St = = GM GM ' kc' kG P 2/3 (Sc )2 / 3 = Sc / (Re Sc1/3 ) J D = ( N Sc ) = JD factor GM

kc'

' ky

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Mass Transfer ChE 461

Chapter 1-20

Analogies among Mass, Heat and Momentum transfer

Why analogies? Similarity of molecular diffusion equation for momentum, Fouriers for heat and Fick for mass Data for pressure drop and heat transfer are available more than mass transfer In case of turbulent flow, the differential equations will contain time average velocities and in addition the eddy diffusivities of momentum (), mass (D), and heat transfer (H). The resulting equations can not be solved for lack of information about the eddy diffusivities, but one might expect results of the form:

f Sh f =1 , Sc, = 2 , Sc, D 2 D Re Sc 2 f Nu f =1 , Pr, = 2 , Pr, H 2 H Re Sc 2

Equations or correlations for heat transfer can be used for mass transfer by replacing dimensionless number of the former by the later. See next slide
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Mass Transfer ChE 461

Chapter 1-21

Corresponding dimensionless groups of mass and heat transfer

Mass Transfer
cA cA1 cA2 cA1

Reynolds number:

Re =

Schmidt number: Sc =

DAB

DAB

Heat Transfer T T1 T2 T1 L Re = Reynolds number: C Pr = p = Prandtl number: k Nusselt number:

Nu = hL k
2

' kc' L kx L Sherwood number: Sc = = DAB c DAB

gL3 Grashof number: GrD = L PeD = ReSc = Peclet: DAB

Grashof number: GrH = gL3T C p L L Peclet: PeH = Re Pr = = k

' Sh Sh kG P h Nu Nu = = Stanton number: St D = = = Stanton number: St H = Re Sc PeD GM Re Pr PeH C p

JD factor:

J D = St D Sc 2/3

JH factor:
Mass Transfer ChE 461

J H = St H Pr 2/3
Chapter 1-22

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Derivation of Mass-Transfer Coefficients in Laminar Flow

When a fluid flowing in laminar flows and mass transfer by molecular diffusion is occurring, the equations are very similar to those for heat transfer by conduction in laminar flow. In theory it is not necessary to have experimental mass-transfer coefficients for laminar flow, since the equations for momentum transfer and diffusion can be solved Consider mass transfer of solute A into a laminar falling film as shown in the drawing Solute A in the gas is absorbed at the interface and then diffuses a distance into the liquid so that it does not penetrate the whole distance x = Concentration profile at point z distance is shown in the drawing
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Mass Transfer ChE 461

Chapter 1-23

Consider the mass balance on the elemental system: For steady-state: Rate of input = rate of output

N Ax x (1z) + N Az z (1x) N Ax x+x (1z) + N Az z+z (1x) = 0

For dilute solution:

cA N Ax = DAB + zero convection x

N Az = zerodiffusion+ cAz
Substituting, dividing by xz, letting xz and approaches zero leads to:

x 2 z is needed and has been derived in fluid mechanics: z = z,max 1 Also z,max = (3/2)z,av
If solute A penetrates only a short distance into the fluid: z = z,max = max
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cA 2c A z = DAB 2 z x

Mass Transfer ChE 461

Chapter 1-24

cA 2cA max = DAB 2 z x

Solution by Laplace transform:

Boundary conditions: z=0 cA = 0 x=0 cA = cA0

x=

cA = 0

cA x = erf 4D z / cA0 AB max

Local molar flux at the surface x = 0 at position z:

N Ax ( z) x=0 = DAB

cA D = cA0 AB max x x=0 z

Total moles of A transferred per second to the liquid over the entire length: 1/ 2 L L 4DABmax DABmax 1 = (1) cA0 dz = (L.1)cA0 N A (L 1) = (1) ( N Ax x=0 )dz L 0 0 z1/ 2

where L/max = tL time of exposure of the liquid to the solute A in the gas
0.5 0 Rate of mass transfer DAB and 1/ tL.5

Basis for penetration theory in turbulent mass transfer

Chapter 1-25

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Mass Transfer ChE 461

Mass Transfer for Laminar Flow inside Pipes

For laminar flow of a liquid or gas inside a pipe: Re =

Experimental data for mass transfer from the wall for gases are presented graphically

D < 2100

cA: exit concentration cA0: inlet concentration cAi: concentration at the interface between the gas and the gas W: flow in kg/s L: length of mass transfer section
For liquids with small values of DAB:

W cA cA0 = 5.5 D L cAi cA0 AB

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2 / 3

Mass Transfer ChE 461

Chapter 1-26

Mass Transfer for Turbulent Flow inside Pipes

For laminar flow of a liquid or gas inside a pipe: Re = For gases or liquids flowing inside a pipe:
1 kc' D (kc pBM ) D 0.83 Sh = = = 0.023 Re Sc 3 DAB DAB

D > 2100
Re > 2100 0.6 <Sc < 3000

Mass Transfer for Flow inside Wetted-Wall Towers

When a gas is flowing inside the core of a wetted-wall tower, the same correlations that are used for mass transfer of a gas in laminar or turbulent flow in a pipe are applicable For the mass transfer in the liquid film flowing down the wetted-wall tower use: D 4DABmax N Ax ( z) x=0 = cA0 AB max and N A (L 1) = (L.1)cA0 z L

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Mass Transfer ChE 461

Chapter 1-27

Example: Mass Transfer Inside a Tube A tube is coated on the inside with naphthalene and has an inside diameter of 20 mm and a length of 1.1 m. Air at 318 K and an average pressure of 101.3 kPa flows through this pipe at a velocity of 0.8 m/s. Assuming that the absolute pressure remains essentially constant, calculate the concentration of naphthalene in the exit air.

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Mass Transfer ChE 461

Chapter 1-28

Mass Transfer in Flow Outside Solid Surface

For gases or evaporation of liquids in the gas phase Laminar region; ReL= L/ < 15, 000

J D = 0.664 Re

0. 5 L

NA L
A

In terms of Sherwood number:

kc' L = Sh = 0.664 Re 0.5 Sh1 / 3 L D AB

For gases and 15,000 < ReL < 300,000:

J D = 0.036 Re 0.2 L
For liquids and 600 < ReL < 50,000:

J D = 0.99 Re 0.5 L

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Mass Transfer ChE 461

Chapter 1-29

Example: Mass Transfer from a Flat Plate

A large volume of pure water at 26.1oC is flowing parallel to a flat plate of solid benzoic acid, where L = 0.244 m in the direction of flow. The water velocity is 0.061 m/s. The solubility benzoic acid in water is 0.02948 kgmol/m3. The diffusivity of benzoic acid is 1.245 10-9 m2/s. Calculate the mass transfer coefficient kL and the flux NA.

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Mass Transfer ChE 461

Chapter 1-30

Mass Transfer for Flow Past Single Sphere

Previously, the following equation was derived for stagnant medium

N A1 = 2DAB k = Dp
' c

2DAB (cA1 cA2 ) Dp

Mass-transfer coefficient kc, which is kc for a dilute solution is:

Rearranging,

kc' Dp DAB

= Sh = 2.0

Only for very low Re= Dp/

0.53

Gases; 0.6 < Sc < 2.7; 1 < Re = Dp/ < 48 000 Sh = 2.0 + 0.552Re Liquids; 2 < Re = Dp/ < 2000

Sc1/ 3

Sh = 2.0 + 0.95Re0.5 Sc1/ 3 Sh = 0.347Re0.62 Sc1/ 3

Liquids; 2,000 < Re = Dp/ < 17,000

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Mass Transfer ChE 461

Chapter 1-31

Example: Mass Transfer from a Sphere

Calculate the value of the mass-transfer coefficient and the flux for mass transfer from a sphere of naphthalene to air at 45oC and 1 atm flowing at a velocity of 0.305 m/s. The diameter of the sphere is 25.4 mm. The diffusivity of naphthalene in air at 45oC is 6.9210-6 m2/s and the vapor pressure of solid naphthalene is 0.555 mm Hg.

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Mass Transfer ChE 461

Chapter 1-32

Mass Transfer to Packed Beds

Typical processing operation including packed beds Drying operations Adsorption or desorption of gases or liquids by solid particles, eg. charcoal Mass transfer of gases and liquids to catalyst particles Void fraction of the bed, , is an important parameter in the bed:

volume of voids pace, in m3 = = Sh = 2.0 3 Total volume of thebed,in m

Gases in packed bed of spheres; 10 < Re < 10,000: where, Re =

Dp'

JD = JH =

0.4548 0.4069 Re

: superficial velocity (mass average velocity in the empty tube without packing
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Mass Transfer ChE 461

Chapter 1-33

Liquid in packed bed; 0.0016 < Re < 55 ; 165 < Sc < 70 000:

JD =

1.09

Re2 / 3

Liquid in packed bed; 55 < Re < 1 500 ; 165 < Sc < 10 690:

JD =

0.250

Re0.31

Gases or Liquid in Fluidized bed of spheres; 10 < Re < 4 000:

0.4548 0.4069 JD = Re

Liquid in Fluidized bed; 1 < Re < 10 :

1.1068 0.72 JD = Re

Correction factor is introduced for non-spherical particles

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Mass Transfer ChE 461

Chapter 1-34

Calculation Method for Packed Beds

Select proper correlation for JD and then calculate kc in m/s. Calculate the total external surface area A m2 of the solids

A = aVb =

6(1 ) Vb Dp

a: m2 surface area/m3 total volume Vb: total volume of the bed, in m3

Calculate the log mean driving force at the inlet and outlet of the bed:

N A A = Akc

(c Ai c A1 ) (c Ai c A2 ) ln[(c Ai c A1 ) /(c Ai c A2 )]

cAi: concentration at the surface of the solid, kg mol/m3; cA1: inlet bulk fluid concentration, kg mol/m3; cA2: outlet bulk fluid concentration, kg mol/m3;

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Mass Transfer ChE 461

Chapter 1-35

Example: Mass Transfer of a Liquid in a Packed Bed

Pure water at 26.1oC flows at the rate of 5.51410-7 m3/s through a packed bed of benzoicacid spheres having a diameter of 6.375 mm. The total surface area of the spheres in the bed is 0.01198 m2 and the void fraction is 0.436. The tower diameter is 0.0667 m. The solubility of benzoic acid in water is 2.94810-2 kg mol/m3. 1. Predict the mass-transfer coefficient kc. Compare with the experimental value of 4.66510-6 m/s. 2. Using the experimental value of kc, predict the outlet concentration of benzoic acid in the water

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Mass Transfer ChE 461

Chapter 1-36

Mass Transfer to Suspensions of Small Particles

Examples Liquid-liquid hydrogenation -hydrogen diffuse from gas bubbles through an organic liquid then to small suspended catalyst particles. Fermentation-oxygen diffuses from small gas bubbles through the aqueous medium then to the small suspended particles.

1. Mass Transfer to small particles <0.6 mm

To predicts mass transfer coefficients from small gas bubbles such as oxygen or air to the liquid phase from liquid phase to the surface of small catalyst particles, microorganisms, solids or liquids.

2 DAB 2 / 3 c g + 0.31Sc k 'L = p2 DP c

Molecular diffusion
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= c - p c: density of continuous phase

Due to free fall or rise of the sphere due to gravitation

Mass Transfer ChE 461
Chapter 1-37

Example: Mass Transfer from Air Bubbles in Fermentation

Calculate the maximum rate of absorption of O2 in a fermenter from air bubbles at 1 atm pressure having diameters of 100 m at 37oC into water having a zero concentration of dissolved O2. The solubility of O2 from air in water at 37oC is 2.2610-7 g mol O2/cm3 liquid or 2.2610-4 kg mol O2/m3. The diffusivity of O2 in water at 37oC is 3.2510-9 m2/s. Agitation is used to produce the air bubbles.

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Mass Transfer ChE 461

Chapter 1-38

2. Mass Transfer to Large Gas Bubbles > 2.5 mm

For large bubbles or liquid drops >2.5 mm, the mass coefficient can be predicted by

c g k ' L = 0.42Sc 0.5 2 c

Large bubbles are produced when pure liquids are aerated in mixing vessels and sieve plate columns.

3. Mass Transfer to Particles in Transition Region

In mass transfer in the transition region between small and large bubbles in the size range 0.6-2.5 mm, the mass coefficient can be approximated by assuming that it increases linearly with bubbles diameter.

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Mass Transfer ChE 461

Chapter 1-39

4. Mass Transfer to Particles in Highly Turbulent Mixers

When agitation power is increased beyond that needed for suspension of solid or liquids particles and the turbulence force become larger than the gravitational forces, so mass transfer coefficient

k ' L Sc

2/3

( P / V ) c g = 0.13 2 c

P/V: power input per unit volume

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Mass Transfer ChE 461

Chapter 1-40

Molecular Diffusion Plus Convection and Chemical Reaction

N A = cA A (kg mol A/s.m2) or

J*A: molar flux of A in kg mol A/s.m2 relative to molar average velocity M NA: molar flux of A relative to stationary coordinate

nA = A A (kg A/s.m2)

Assuming to be the mass average velocity of the stream relative to stationary coordinate and can be obtained from A and B as:

= wA A + wA A =
where wA = A/

A A + B B

(weight fraction of A)

A: velocity of A relative to stationary coordinate

Molar average velocity M in m/s relative to stationary coordinate is:

M = x A A + xB B =
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cA cB A + B c c
Chapter 1-41

Mass Transfer ChE 461

Molar diffusion flux relative to the molar average velocity M is:

J * = c A ( A M ) A
or

(kg mol A/s.m2)

j * = A ( A M ) (kg A/s.m2) A J A = c A ( A )
(kg mol A/s.m2) (kg A/s.m2) Prove that jA + jB = 0

Molar diffusion flux relative to the mass average velocity M is:

or

j A = A ( A )

j A = A ( A ) jB = B ( B ) dx J * = cDAB A j A + jB = A dz A A A + B B B Ficks law to terms of a mass flux relative to : = A A + B B ( A + A )

Ficks law as given relative to M:

dw j A = DAB A dz
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Use: =

A A + B B Identity is proved

Mass Transfer ChE 461

Chapter 1-42

Equation of Continuity for a Binary Mixture

Objective: Derive general equation for a binary mixture of A and B for diffusion and convection including unsteady state diffusion and chemical reaction Consider the element xyx fixed in space General mass balance on A is:
rate of rate of + mass A in mass A out rate of rate of = generation of mass A accumulation
nAzz+z

z y
nAxx z x

y nAxx+x

x
nAzz

n Ax x yz + n Ay y xz + n Az z xy n Ax x + x yz n Ay y + y xz n Az z + z xy + rA xyz = dm dt

Divide by xyz and letting xyz approach zero:

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Mass Transfer ChE 461

Chapter 1-43

 A n Ax n Ay n Az + x + y + z = rA t In vector notation: A + ( n ) = r A A t
Dividing both sides by MA:

c A N Ax N Ay N Az + x + y + z = RA t
dz

RA: kmol A/s.m3

Substituting NA and Ficks law from: N = cD dxA + c Az AB A M

c A + ( c A M ) ( cDAB x A ) = RA Final General equation t

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 1-44

Equation for constant c and DAB:

c A + (c A M ) + ( M c A ) (DAB 2 c A ) = RA t

Equimolar counterdiffusion for gases:

dcA N Az = DAB dz
(or M = 0)

Assuming DAB = constant and RA = 0

2c A 2c A 2c A c A = DAB 2 + 2 + 2 x t y z

(previously derived)

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 1-45

Diffusion and Chemical Reaction at the Boundary

Consider gas A diffusing from the bulk gas phase to the catalyst surface, where it reacts instantaneously and reversibly as follows: A 2B Gas B then diffuses back, see the drawing At steady state, NA = - 2NB
catalyst surface

NA NB
z1 z z2

dx Since, N Az = cDAB A + xA ( N A + NB ) dz dx N Az = cDAB A + xA ( N A 2NB ) dz

Rearranging and integration, N A or,

z2 =

z1=0

dz = cDAB

x A2

xA1

dxA 1 + xA

1 + xA1 ln NA = 1 + xA2
cDAB

Instantaneous xA2 = 0

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 1-46

For Slow surface reaction If the reaction A 2B is not instantaneous, but is rather slow and describes by the first order kinetic:

N Az= = k1'cA = k1'cxA

where k1 is first order homogeneous reaction velocity constant in m/s. In this case the flux is still given by:

NA =

cDAB

ln

1 + xA1 1 + xA2

' But replacing xA2 by xA2 = N Az= / k1'c = N Az= / kc

NA =

cDAB

ln

1 + xA1 1 + N A / k1'c

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 1-47

Example: Diffusion and Chemical Reaction at a Boundary

Pure gas A diffuses from point 1 at a partial pressure of 101.32 kPa to point 2 a distance 2.0 mm away. At point 2 it undergoes a chemical reaction at the catalyst surface and A 2B. Component B diffuses back at steady state. The total pressure is P = 101.32 kPa. The temperature is 300 K and DAB = 0.1510-4 m2/s. (a) For instantaneous rate of reaction, calculate xA2 and NA. (b) For a slow reaction where k1 = 5.6310-3 m/s, calculate xA2 and NA.

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 1-48

Diffusion and Homogeneous Reaction in a Phase

Consider component A undergoes an irreversible chemical reaction in the homogeneous phase B while diffusing, as follows: A C. Assuming A is very dilute in phase B, which can be a gas or a liquid, thus at steady state the bulk term is dropped (no movement):

dcA N Az = DAB +0 dz Since for this case, c A + N Ax + N Ay + N Az = R A x t y z d dc A DAB = RA dz dz d 2c A k' For first order reaction (RA = -kcA) and constant DAB: = cA 2 DAB dz
For the boundary conditions cA = cA1 @ z = 0 and cA = cA2 @ z = L:

cA =

c A2 sinh k ' / DAB z + c A1 sinh k ' / DAB ( L z ) k / DAB L

'

) sinh (

cA = cA(z) for reactions in gases, liquids, or solids

Chapter 1-49

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Multi-component Diffusion of Gases

Multicomponent component diffusion occurs when three or more components A, B, C, are present. Example: diffusion of A through a stagnant nondiffusing mixture of B, C, D, For NB = NC = = 0

NA =

DAm P ( p A1 p A2 ) RT ( z2 z1 ) piM 1 ' ' xB / DAB + xC / DAC +

(Stefan-Maxwell method)

where pim is the log mean of pi1 = P pA1 and Pi2 = P pA2 Also,

DAm =

where xB = mol B/mole inerts:

' xB =

xB , 1 xA

' xC =

xC 1 xA
Mass Transfer ChE 461
Chapter 1-50

JUST Department of Chemical Engineering

Example: Diffusion of A Through Nondiffusing B and C

At 298 K and 1 atm total pressure, methane (A) is diffusing at steady state through nondiffusing argon (B) and helium (C), At z = 0, the partial pressures in atm are pA1 = 0.4, pB1 = 0.4, and pC1 = 0.2, and at z2 = 0.005 m, pA2 = 0.1, pB2 = 0.6, and pC2 = 0.3. The binary diffusivities from Table 6.2-1 are DAB = 2.0210-5 m2/s, DAC = 6.7510-5 m2/s, DBC = 7.2910-5 m2/s. Calculate NA.

JUST Department of Chemical Engineering

Mass Transfer ChE 461

Chapter 1-51