CHEG

3124 Heat and Mass Transfer

Mass Transfer Equa6ons (Ch. 25)
Steady-State Molecular Diusion (Ch. 26)
Instructor: Prof. Anson Ma
 Dieren6al Mass-Transfer Equa6on

' A
) nA + t rA = 0
Mass units: (
) n + B r = 0
B B
* t
rA = rB
& c A
Molar units: ( NA + t RA = 0 Is R rate of produc:on or
A

' consump:on of species A?

( N + c B R = 0
B B
) t
(RA + RB ) depends on the stoichiometry of the reac:on!
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 Recap: Molecular Diusion

Ficks rst law is valid provided that the ux (jA or JA) is dened
rela:ve to the mixture velocity (mass or molar-average velocity):
J A = cA (v A V)
c A v A + c B v B NA + NB
V= =
cA + cB c
The molar ux for species A is given as:

NA = cDAB y A + y A (NA + NB )
= cDAB y A + c A V
We will come back to this equa:on in the next sec:on on dieren:al mass-transfer equa:on 2
 Dieren6al Mass-Transfer Equa6on

& c A
( NA + RA = 0
' t
()N = D c + c V
A AB A A ( cA V) = ( cA ) V + cA ( V)

c A
DAB c A + (c A V) + RA = 0
t
Dc A DT
If no reac:on, diusion
2 coecient and density are
= DAB c A (C.f. )
= 2T
Dt constant
Dt
c A T
= DAB 2c A (C.f. )
= 2T for no uid mo:on
t
t
Ficks second law of diusion Fouriers second law of heat conduc:on
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 Common Boundary Condi6ons

Raoults Law (ideal liquid mixture)

pAs = x A PA

Ideal Gas law

pAs
c As =
RT
pAs Ref: h\p://www.henrys-law.org/
Daltons law y As =
P

Henrys law (A is weakly soluble in the liquid)

pA = kH c A Note Henrys constant can carry dierent units

(see table above)
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 Example 1
Chemical vapor deposi:on (CVD) of silane vapor (SiH4) onto the surface of the wafer.










This surface reac:on is usually carried out at low pressure and high temperature. In many
CVD reactors, the gas phase over the Si lm is not mixed. At high temperature, the surface
reac:on is very rapid. Consequently, the molecular diusion of the SiH4 vapor to the surface
controls the rate of Si lm forma:on.

Consider a simplied CVD reactor shown in the gure above. A mixture of silane and H2 gas
ows into the reactor. A diusor provides a quiescent gas space over the growing Si lm.
Show that the dieren:al model for this process is: cD ! 1+ y $
AB A0
N A,z = ln # &
" 1+ yAs %
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 Example 1

Does the control volume

include the Si thin lm?
Why RA = 0?

Assump:ons:
1) The reac:on occurs only at the surface of growing Si thin lm. No homogeneous
reac:on of silane within the diusion zone, RA = 0.
2) The gas space in the diusion zone is not externally mixed. Molecular diusion
dominates.
3) The feed gas provides silane in high excess rela:ve to that consumed by reac:on.
Silane concentra6on in the gas space at the diusion-zone boundary is constant.
4) The ux of silane is one-dimensional along z.
5) The thickness of the Si lm is very thin rela:ve to . is constant.
6) The mass transfer process within the diusion zone is at steady state.
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 Example 1
The general dieren:al equa:on for mass transfer in terms of rec:linear coordinates is

c
N A + A RA = 0
t

Based on the assump:ons: 1) steady state, 2) 1-D ux, 3) RA = 0, the equa:on could be
reduced to
dNA, z
=0
z
Ficks ux equa:on for the 1-D ux of silane through a binary mixture in the gas phase

Recall: N = D c + y N + N dyA
A( A B) NA, z = cDAB + yA(NA, z + NB, z )
A AB A
dz
Need to nd this rst. How?
Species A: Silane vapor (SiH4). Species B: H2
From the reac:on stoichiometry,
N A,z 1 mol of SiH4 reacted 1
= =
N B,z 2 mol of H2 formed 2 NB, z = 2NA, z
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 Example 1
The Ficks ux equa:on becomes
dyA cDAB dyA
NA, z = cDAB + yA(NA, z 2NA, z ) =
dz 1+ yA dz

Boundary condi:ons:
1) At the Si lm surface, z = , yA = yAs
2) At the diuser, z = 0, yA = yAo
yAs
cDAB

NA, z dz = dyA Is N a func:on of z? Why (not)?
yAo 1+ yA
A,z
0
If T and P are constant, then the total molar concentra:on of the gas, c = P/RT , is constant.
If the diusion coecient DAB is also constant,

cDAB 1+ yAo
NA, z = ln( )
1+ yAs

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 Dieren6al Mass-Transfer Equa6on
If species B is stagnant (non-diusing) within
the diusion cell. What happen to NB,z?

Show that:
cDAB (1 yA2 )
N A,z = ln
z2 z1 (1 yA1 )

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 Dieren6al Mass-Transfer Equa6on

Show that: cDAB (1 yA2 )
N A,z = ln
z2 z1 (1 yA1 )
c
N A + A RA = 0
t
N = cD y + y (N + N )
A AB A A A B

cDAB dyA
N A,z =
1 yA dz
z2 yA2 1
z1
N A,z dz = cDAB
yA1

1 yA
dyA
Is NA,z a func:on of z? Why (not)?
cDAB 1 yA2
N A,z = ln
z2 z1 1 yA1

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 Example 2
A vapor degreaser (as shown) is used for cleaning
metal parts. Liquid solvent rests at the bo\om of
the degreaser tank. A hea:ng coil immersed in the
solvent (trichloroethylene, TCE) vaporizes a small
por:on of the solvent. What is the TCE emission
rate (in kg/day) to the surrounding atmosphere?

The tank has a diameter of 2 m and a height of 5 m.
The solvent level height is kept constant at 0.2 m.
The solvent and headspace temperatures are
constant at 35 C. The pressure is 1 atm and the air
is stagnant. TCE has a molecular weight of 131.4
kg/ kmol, a vapor pressure of 0.152 atm at 35C,
and a mass diusivity of of 0.088 cm2/s through air.

cDAB (1 yA2 )
N A,z = ln
z2 z1 (1 yA1 )

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 Example 2
The total molar concentra:on of the gas, c is determined from the ideal gas law.
P 1atm kmol
c = = = 0.0396
RT m 3 atm m3
0.08206 (273+ 35)K
kmol K

The mole frac:on of TCE vapor at the solvent surface (yA1) is determined from the vapor
pressure of the solvent at 35C
PA 0.152 atm
yA1 = = = 0.152
P 1 atm
At the exit of the degreaser tank, the mole frac:on of TCE vapor is taken as zero. yA2=0.
The path length for diusion
z2 - z1 = 5.0m 0.2m = 4.8m N = cDAB ln (1 yA2 )
A,z
The ux of TCE vapor from the degreaser is z2 z1 (1 yA1 )
kmol
(0.0396 3 )(0.088
cm 2 1m 2
)
NA, z =
m s (100cm) 2
ln(
1 0
) = 1.197 10 8
kmol TCE
4.8 m 1 0.152 m2 s
The TCE emission rate (WA)
D 2 8 kmol TCE (2m)
2
131.4kg TCE 3600s 24h
WA = NA, z = 1.197 10 2
( )( )
4 m s 4 kmol TCE 1h 1day
kg TCE
= 0.427 12
day
 How about the concentra6on prole?
dN A,z
=0
dz ln ((1 yA2 ) (1 yA1 )) ln ((1 yA1 ) (1 yA ))
=
N = cDAB dyA z1 z2 z z1
A,z 1 yA dz 1 yA z z1 1 yA2
ln = ln
d 1 dyA 1 y A1 z 2 z1 1 y A1
=0
dz 1 yA dz zz1
1 yA 1 yA2 z2 z1
1 dyA =
=
1 C 1 y A1 1 y A1
1 yA dz
ln(1 yA ) = C1z + C2 (1)
ln(1 y ) = C z + C (2)
A1 1 1 2

ln(1 yA2 ) = C1z2 + C2 (3)
ln(1 yA2 ) ln(1 yA1 ) ln ((1 yA2 ) (1 yA1 )) from (2) (3)
C1 = =
z1 z2 z1 z2

ln ((1 yA1 ) (1 yA ))
C1 = z z1
from (1) (2)

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 Pseudo-Steady-State Diusion

Note previously NA,z does not have any

:me dependence
cDAB 1 yA2
N A,z = ln
z2 z1 1 yA1
because we assume steady state!
Pseudo-Steady-State Diusion: Slow
deple:on of the source or sink for the
mass-transfer process, where the
expression above is s:ll okay.
Lets consider an Arnold diusion cell
with a moving liquid surface.

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 Pseudo-Steady-State Diusion

Goal: To derive an expression for DAB for an Arnold diusion cell

cDAB 1 yA2 cDAB yB2
N A,z = ln = ln
z 1 yA1 z yB1
z is the length of diusion path (z2 z1) at :me t.
Show that:

A,L
DAB =
2M A c ln(yB2 yB1 )t
( zt
2
zt0 )
2

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 Pseudo-Steady-State Diusion

Molar ux (NA) is related to the amount of A leaving the liquid

dz S: cross-sec:on area
WA = N A,z S = A,L S MA: molecular weight
M A dt

cDAB yB2
Recall: N A,z = ln
z y
B1
A,L dz cDAB yB2
N A,z = = ln
M A dt z yB1
A,L zt yB2 t
MA
zt0
zdz = cDAB ln
yB1
0 dt

A,L 2 2
2M A
( zt z t0 ) = cDAB ln ( yB2 yB1 ) t

A,L
DAB =
2M A c ln(yB2 yB1 )t
( zt2 zt20 )
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 Example 3

A B
As shown in the gure above, assuming that the diusion of O2 through the SiO2 lm
limits the oxida:on process, develop a model to predict the thickness of the SiO2 layer, ,
as a func:on of :me at 1000 C.

Physical proper:es:

Density of solid SiO2, B=2.27 g/cm3
Molecular weight of SiO2, MB = 60 g/mol
Molecular diusion coecient of O2 in SiO2 (1000 C), DAB = 2.7 x 10-9 cm2/s
Maximum solubility of O2 in SiO2, cAs = 9.6 x 10-8 mol/cm3

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 Example 3

Assump:ons:
1) The oxida:on of Si to SiO2 only occurs at the Si/SiO2 interface.
2) The O2 in the gas phase above the wafer represents an innite source for O2 transfer.
3) The rate of SiO2 forma:on is controlled by the rate of molecular diusion of O2
(species A) through the solid SiO2 layer(species B) to the unreacted Si layer.
4) The reac:on is very fast, CA=0.
5) 1-D ux
6) Pseudo-steady state.
7) Overall thickness of the wafer does not change.
8) The process is isothermal.

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 Example 3
The general dieren:al equa:on for mass transfer
dNA, z
cA =0 Why RA = 0?
NA + RA = 0
t dz
Ficks ux equa:on for 1-D diusion of O2 (species A) through crystalline solid SiO2
(species B)
dcA dcA
NA, z = DAB + yA (NA, z + NB, z ) = DAB + yA NA, z
dz dz

The concentra:on of molecular O2 in the SiO2 layer is dilute enough that yA term is
negligible. dcA
N A, z DAB
dz

0
As NA is constant along z
0 NA, zdz = DAB cAs dcA

DAB cAs
N A, z =

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 Example 3
However, this process is operated under pseudo-steady state assump:on. The
thickness will increases slowly with :me. In order to discover how increases with
:me, consider the unsteady-state material balance for SiO2 within the wafer.
BS
d( )
NA, z S = MB
dt
B is the density of solid SiO2 (2.27 g/cm3), MB is the molecular weight of SiO2 layer
(60 g/mol), S is the surface area of the wafer. DAB cAs
NA, z =

Combine the material balance with the ux equa:on

B d DAB cAs
=
MB dt
Ini:al condi:on: t = 0, = 0.
t
MBDAB cAs
d = B dt
0 0

2MBDABcAs
= t
B 20
 Example 4
A uidized coal reactor has been proposed for a new power plant. The process is
operated at 1145 K and is limited by the diusion of oxygen to the par:cle surface.
Assume that the coal is pure solid carbon with a density of 1.28 x 103 kg/m3 and the
par:cle is spherical with an ini:al diameter of 1.5 x 10-4 m, surrounded by air (21% O2
and 79% N2). Diusivity of oxygen through the gas mixture is: 1.3 x 10-4 m2/s. If pseudo-
steady state is assumed, calculate the :me necessary to reduce the diameter of the
par:cle to 5 x 10-5 m.
dyO2
N O2 ,r = cDO2 mix + yO2 (N O2 ,r + N CO2 ,r + N N2 ,r )
dr
yO2
R
N O2 ,r dr = yO2S
cDO2 mix dyO2
1
(r NO2 ,r )
2
R
r 2
dr = cDO2 mix ( yO2 yO2S )

NO2,r is a func:on of r, but r2NO2,r
C(s) + O2(g) CO2(g)
is not. Why?

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 Example 4
1
(r N )
2
O2 ,r R 2
r
dr = cDO2 mix ( yO2 yO2S )

1
( O2 ,r ) R = cDO2 mix yO2 assume fast reac:on
r 2
N

WO2 = 4r 2 N O2 ,r = 4RcDO2 mix yO2

WC = WO2 = 4RcDO2 mix yO2
From material balance,
C dR
WC = 4R 2
MC dt C(s) + O2(g) CO2(g)
C dR
4R 2 = 4RcDO2 mix yO2
MC dt P 1 atm kmol
c= = 3
= 0.0106
C RdR RT m atm m3
0.08206 1145 K
dt = kmol K
M C cDO2 mix yO2
1.28 10 3 kg / m 3 ((7.5 10 5 m)2 (2.5 10 5 m)2 )
tf C Rf tf =
0
dt =
M C cDO2 mix yO2
Ri
RdR 2(12 kg / kmol)(0.0106 kmol / m 3 )(1.310 4 m 2 / s)(0.21)
= 0.92 s
C
tf =
2M C cDO2 mix yO2
( Ri2 R 2f )
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 Prof. Mas Checklist: What do you really need to know?
Working equa:ons:
c
N A + A RA = 0 (1)
t
N = D c + y (N + N ) (2)
A AB A A A B

For Eqn (1), RA = 0 when there is no homogeneous reac:on (in the gas phase) even though
there is a heterogeneous reac:on at the surface (e.g., CVD or combus:on)
Simplify Eqn (2) by rela:ng NA and NB based on:
Stoichiometry (for reac:ons)
NB = 0 if gas B is stagnant or B is a solid
yA 0 if A has low solubility in solid B
Pseudo-steady-state problems:
Assume NA remains the same as that in steady state
Combine that with material balance to determine temporal change in height,
thickness, radius, etc. (Examples 3 & 4).
For spherical coordinate, r2NA,r is constant and can be taken out of the integral.

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