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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.
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
Chapter 1-3
2c A c A = DAB 2 t x
cA = cA(x,t)
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.
Chapter 1-4
where:
X = Dt x12
Mass Transfer ChE 461
Chapter 1-5
N A = kc (cL1 cLi )
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
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:
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)
Chapter 1-8
Chapter 1-9
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
JUST Department of Chemical Engineering
z
Chapter 1-11
dcA dz
N A = cDAB
dxA cA + ( N A + NB ) dz c
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.
z2 z1
[Kgmol/s.m2.(kgmol/m3)] or [m/s]
Chapter 1-12
) dxA + cA ( N A + NB )
dz c
Defining equation for the mass-transfer coefficient
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
'
Mass-transfer coefficient for A diffusing through stagnant, nondiffusing B NB = 0 DAB cav NA = ( x A1 x A2 ) was derived Previously, the expression
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
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
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
Chapter 1-16
N A = kc c( xA1 xA2 )
(2)
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
Note: correction factors obtained by film theory give results reasonably close to those using more complex theory, eg. penetration theory or boundary layer theory
Chapter 1-18
Chapter 1-19
Re =
: mass average velocity if in pipe : superficial velocity in the empty cross section of a packed bed ( = /)
Schmidt number Sherwood number
Sc =
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
Chapter 1-20
Chapter 1-21
Reynolds number:
Re =
Schmidt number: Sc =
DAB
DAB
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
Chapter 1-23
Consider the mass balance on the elemental system: For steady-state: Rate of input = rate of output
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
JUST Department of Chemical Engineering
cA 2c A z = DAB 2 z x
Chapter 1-24
x=
cA = 0
N Ax ( z) x=0 = DAB
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
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:
2 / 3
Chapter 1-26
D > 2100
Re > 2100 0.6 <Sc < 3000
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.
Chapter 1-28
J D = 0.664 Re
0. 5 L
NA L
A
J D = 0.036 Re 0.2 L
For liquids and 600 < ReL < 50,000:
J D = 0.99 Re 0.5 L
Chapter 1-29
Chapter 1-30
N A1 = 2DAB k = Dp
' c
Rearranging,
kc' Dp DAB
= Sh = 2.0
Gases; 0.6 < Sc < 2.7; 1 < Re = Dp/ < 48 000 Sh = 2.0 + 0.552Re Liquids; 2 < Re = Dp/ < 2000
Sc1/ 3
Chapter 1-31
Chapter 1-32
Dp'
JD = JH =
0.4548 0.4069 Re
: superficial velocity (mass average velocity in the empty tube without packing
JUST Department of Chemical Engineering
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
0.4548 0.4069 JD = Re
1.1068 0.72 JD = Re
Chapter 1-34
A = aVb =
6(1 ) Vb Dp
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;
Chapter 1-35
Chapter 1-36
Chapter 1-38
Large bubbles are produced when pure liquids are aerated in mixing vessels and sieve plate columns.
Chapter 1-39
k ' L Sc
2/3
( P / V ) c g = 0.13 2 c
Chapter 1-40
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)
M = x A A + xB B =
JUST Department of Chemical Engineering
cA cB A + B c c
Chapter 1-41
J * = c A ( A M ) A
or
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
or
j A = A ( A )
dw j A = DAB A dz
JUST Department of Chemical Engineering
Use: =
A A + B B Identity is proved
Chapter 1-42
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
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
Chapter 1-44
2c A 2c A 2c A c A = DAB 2 + 2 + 2 x t y z
(previously derived)
Chapter 1-45
NA NB
z1 z z2
z2 =
z1=0
dz = cDAB
x A2
xA1
dxA 1 + xA
1 + xA1 ln NA = 1 + xA2
cDAB
Instantaneous xA2 = 0
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:
NA =
cDAB
ln
1 + xA1 1 + xA2
NA =
cDAB
ln
1 + xA1 1 + N A / k1'c
Chapter 1-47
Chapter 1-48
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 =
) sinh (
NA =
(Stefan-Maxwell method)
where pim is the log mean of pi1 = P pA1 and Pi2 = P pA2 Also,
DAm =
xB , 1 xA
' xC =
xC 1 xA
Mass Transfer ChE 461
Chapter 1-50
Chapter 1-51