Zulamita Zapata, UPB

Chapter 5

Differential Equations of Mass Transfer:

Steady and Unsteady State Diffusion
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What is mass transfer?

Mass transfer is mass in transit as the result of a species concentration difference in a

mixture (actually, it is the chemical potential difference which causes the mass transfer)

Since molecular motion is random, there is equal probability any molecule moving to the
left or the right. Accordingly, more molecules of species A cross the plane from the left that
from the right.
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Molecular and convective mass transfer

Velocities – In a mixture of different chemical species, each specie moves at
different total velocity vi, therefore is important to define an average velocity of
the mixture:

Mass average velocity Molar average velocity

n n
v =  A v A + B v B + =  i v i v = x A v A + xB v B +
M
=  xi v i
i =1 i =1

The velocity of a specie relative to the average velocity of the mixture defines its
velocity of diffusion.

vi − v the diffusion velocity of species i relative to the mass-average velocity

vi − v M the diffusion velocity of species i relative to the molar-average velocity

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Molecular and convective mass transfer

Fluxes – The flux of a given species is a vector quantity denoting the amount of the
particular species, in either mass or molar units, that passes per given increment of time
through a unit area normal to the vector.

N𝑖 = 𝑐𝑖 v𝑖
ቊ Total molar (mass) flux of species i (relative to fixed axes)
Total fluxes n𝑖 = 𝜌𝑖 v𝑖

 J i = ci ( v i − v )
( )
Difusive molar flux of species i
J i = ci v i − v  M
( )
relative to the mass (molar) average
 J
 i = c v − v M velocity
 i i
Difusive fluxes 
  ji = i ( v i − v )
( )
Difusive mass flux of species i
 ji = i v i − v  M
( )
relative to the mass (molar) average
 j
 i =  i v i − v M
velocity
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Molecular and convective mass transfer

Therefore, from the expressions for the total flux, we have:

Ni = J i + ci v
total flux diffusive flux advective flux

In this way, for the different

average velocities:

N i = J i + ci v = J iM + ci v M
ni = ji + i v = jiM + i v M
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Fick’s law for binary mixtures of A and B

Reference velocity Mass units Molar units

 DAB
v j A = −  DAB A (A) JA = −  A (B)
MA

vM jMA = −CM A DABxA (C) J MA = −CDABxA (D)

From equation (B)

J A = − DAB c A Isothermal liquid solution ( constant)

From equation (D)

J MA = − DABcA Isobaric and isothermal gas mixture (C

constant)
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Binary system 𝑐𝐴 v𝐴,𝑧 = −𝑐𝐷𝐴𝐵

𝑑𝑦𝐴
+ 𝑦𝐴 𝑐𝐴 v𝐴,𝑧 + 𝑐𝐵 v𝐵,𝑧
𝑑𝑧
𝑁𝐴,𝑧 = 𝐽𝐴,𝑧 + 𝑐𝐴 v𝑧
𝑁𝐴,𝑧 = 𝑐𝐴 v𝑧 𝑁𝐵,𝑧 = 𝑐𝐵 v𝑧
𝑑𝑦𝐴 𝑑𝑦𝐴
𝑐𝐴 v𝐴,𝑧 = −𝑐𝐷𝐴𝐵 + 𝑐𝐴 v𝑧 𝑁𝐴,𝑧 = −𝑐𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴,𝑧 + 𝑁𝐵,𝑧
𝑑𝑧 𝑑𝑧
𝑑𝑦𝐴
𝑐𝐴 𝑉𝐴,𝑧 = −𝑐𝐷𝐴𝐵 + 𝑐𝐴 v𝑧 𝑆𝑖 𝑁𝐵,𝑧 = 0
𝑑𝑧
𝑑𝑦𝐴
σ𝑛𝑖=1 𝑐𝑖 v𝑖 σ𝑛𝑖=1 𝜌𝑖 v𝑖 𝑁𝐴,𝑧 = −𝑐𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴,𝑧 + 0
v= v= 𝑑𝑧
σ𝑛𝑖=1 𝑐𝑖 σ𝑛𝑖=1 𝜌𝑖 𝑑𝑦𝐴
𝑁𝐴,𝑧 = −𝑐𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴,𝑧
𝑑𝑧
σ𝑛𝑖=1 𝑐𝑖 v𝑖 σ𝑛𝑖=1 𝜌𝑖 v𝑖
v= v= −𝑐𝐷𝐴𝐵 𝑑𝑦𝐴
𝑐 𝜌 𝑁𝐴,𝑧 =
1 − 𝑦𝐴 𝑑𝑧
1
v = 𝑐𝐴 v𝐴,𝑧 + 𝑐𝐵 v𝐵,𝑧 𝑁𝐴,𝑧 = −𝑐𝐷𝐴𝐵 ∇𝑦𝐴 + 𝑦𝐴 𝑁𝐴 + 𝑁𝐵
𝑐
𝑑𝑦𝐴 𝑐𝐴 𝑛𝐴,𝑧 = −𝜌𝐷𝐴𝐵 ∇𝑤𝐴 + 𝑤𝐴 𝑛𝐴 + 𝑛𝐵
𝑐𝐴 v𝐴,𝑧 = −𝑐𝐷𝐴𝐵 + 𝑐 v + 𝑐𝐵 v𝐵,𝑧
𝑑𝑧 𝑐 𝐴 𝐴,𝑧
Forma generalizada
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Equimolar counter diffusion (EMCD)

Two constituents whose molar latent heats of vaporization are essentially equal.
(e.g. Distillation). This physical situation stipulates that the flux of one gaseous
component is equal to but acting in the opposite direction from the other
gaseous component.
𝑁𝐴 = −𝑁𝐵
0

𝑁𝐴,𝑧 = −𝑐𝐷𝐴𝐵 ∇𝑦𝐴 + 𝑦𝐴 𝑁𝐴 + 𝑁𝐵

𝑁𝐴,𝑧 = −𝑐𝐷𝐴𝐵 ∇𝑦𝐴

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Differential equation for mass transfer

For a given fixed control volume, the total mass conservation equation in integral form is
given by


t   dV = −  (v  n)dS
rate of accumulation net rate of mass in
of mass

From the divergence theorem and the mean value theorem, we obtain that:


+   (  v) = 0 continuity equation
t
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Now, for a component A we have (in molar units)


t  c dV = − c (v
A A A  n)dS +
 R dV A

rate of increase net rate of moles in rate of production

of moles of moles

As before, from the divergence theorem and the mean value theorem, we obtain that:

c A RA is the net formation rate, and occurs

+   N A − RA = 0 throughout the volume of the mixture -
t homogeneous reaction
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c A
+   N A − RA = 0
t

Conservation equations for a specie in different coordinate systems.

Rectangular
ci N i , x N i , y N i , z
+ + + − Ri = 0
t x y z
Cylindrical
ci 1  1 N i , N i , z
+
t r r
( rN i ,r ) +
r 
+
z
− Ri = 0

Spherical
ci 1  2  1 N i ,
+
t r 2 r
(
r N i ,r + )1
r sin  
( Ni , sin  ) + r sin   − Ri = 0
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Special cases of chemical species conservation equation:

ci
+ v  ci = Di  2 ci + Ri
t
ci
= Di  2 ci Fick's second law
t
 2 ci = 0 Laplace equation

Conservation equations for a specie in a binary or pseudobinary mixture in different coordinate systems assuming
ρ y Di constants.

Rectangular
ci ci ci ci   2ci  2ci  2ci 
+ vx + vy + vz = Di  2 + 2 + 2  + Ri
t x y z  x y z 
Cylindrical
ci c v c c  1   ci  1  2ci  2ci 
+ vr i +  i + vz i = Di  r + 2 + 2  + Ri
t r r  z  r r  r  r  2
z 
Spherical
ci ci v ci v ci  1   2 ci  1   ci  1  2ci 
+ vr + + = Di  2  r + 2  sin  + 2 2 2 
+ Ri
t r r  r sin    r r  r  r sin      r sin   
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Boundary conditions

1. Dirichlet boundary condition: The concentration value is

given on a surface

cA (0) = cA,s

2. Neumann boundary condition: The flux normal to a

surface is given

 N A, s

x=0 n  N A =  − RAs
 0

3. Robin boundary condition: The component diffusing
throughout the material is transferred from/to the surface
by convective mass transfer

x=0 n  N A = kc (c A , s − c A ,  )

Note: The unit normal n is directed out from surface

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In many cases the concentration of a specie is discontinuous in a gas-solid or a gas-liquid

interface. We have to relate the concentration on both sides of the interface.

• Evaporation and sublimation

p A (0) = x A (0) p Asat Raoult's law

p A (0) = p Asat Pure liquid

• Solubility of gases in liquids

p A (0)
x A (0) = Henry's law
H
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Unsteady-state molecular diffusion

The time-dependent equations are simple to derive from the general differential equations of mass transfer.

c A  A
+   N A − RA = 0 or +   n A − rA = 0
t t
The solution to the resulting partial differential equation is generally difficult, involving relative advanced
mathematics techniques.

Pseudo-steady-state diffusion

In many mass-transfer operations, one of

the boundaries may move with time. If
the length of the diffusion path changes a NAr
small amount over a long period of time,
Liquid evaporation
a pseudo-steady state diffusion model
may be used.

Solid dissolution
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Example
Consider the timed drug-release pill illustrated below. The pill is ingested into the stomach. The pill is a slab, 0.36 cm
per side, that has an array of 16 cylindrical pores in it. Each pore is 0.4 mm in diameter and 2.0 mm deep. Pure solid
drug A is loaded into each pore to a depth of 1.2 mm, which provides a total initial drug loading of 2.65 mg in all of
the pores. The density of the solid drug A is 1.10 g/cm3. The drug dissolves into the fluid inside the stomach, which
approximates the properties of water (component B). The maximum solubility of drug A in water is 2×10-4 gmol/cm3
(i.e., not very soluble) and the diffusion coefficient of the drug is 2×10-5 cm2/s at body temperature of 37 °C. The
molecular weight of the drug is 120 g/mol.

a. Starting with the general differential equation for mass

transfer and Fick’s flux equation, develop a simple model,
in final integrated form, for predicting the flux of the drug
from one pore. You may assume that the diffusion process
is pseudo-steady state, the stomach fluid serves as an
infinite sink for the drug so that cA, = 0, and the drug does
not chemically degrade inside the pore.
b. From your model, determine the initial total transfer rate
of the drug from the whole pill, WA, to the body when each
0.2 cm pore is filled to a depth of 0.12 cm with solid drug.
c. How many hours will it take for all of the drug to be
released?
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Example
The formation of a silicon oxide (SiO2) thin film on a silicon (Si) wafer surface is an important step in
the fabrication of solid-state microelectronic devices. A thin film of SiO2 serves as a dielectric insulator
to isolate various devices being formed on the wafer. In one common process, silicon is oxidized by
exposure to oxygen (O2) gas at temperatures above 700 ºC.

Molecular O2 dissolves into de SiO2 solid, diffuses through the SiO2 film, and then reacts with Si at the
Si/SiO2 interface, as shown in figure. Assuming that the diffusion of O2 through the SiO2 film limits the
oxidation process, develop a model to predict the thickness of the SiO2 layer () as a function of time at
1000 ºC. The density of solid SiO2 is 2.27 g/cm3, and the molecular weight of SiO2 is 60 g/mol. The
molecular diffusion coefficient of O2 in SiO2 is 2.7  10-9 cm2/s at 1000 ºC, and the maximum
solubility of O2 in SiO2 is 9.6  10-8 mol O2/cm3 solid at 1000 ºC and 1 atm O2 partial pressure.
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𝑡=0 𝑡>0
Suposiciones

• Inicialmente no hay 𝑆𝑖𝑂2 sobre 𝑆𝑖.

• La concentración de 𝑂2 en la interfase se aproxima a cero
porque se consume rápidamente.
• Densidad constante
• El 𝑆𝑖 se va consumiente y el espacio librado es ocupado por el
𝑆𝑖𝑂2 .
• No hay reacción del 𝑂2 con el 𝑆𝑖𝑂2 .
• La concentración de 𝑂2 no cambia, cA,, por lo tanto, se puede
suponer estado pseudo-estacionario para el 𝑂2 .
• 𝑂2 gas ideal
 Zulamita Zapata, UPB
Ecuación diferencial de transferencia de masa VC1: 𝑂2
0
VC1:
c A
0

𝐴: 𝑂2 +   N A − RA = 0
t 𝑆𝑖𝑂2
∇ ∙ NA = 0
0
0 𝐶+𝐴→𝐵
𝜕𝑁𝐴,𝑥 𝜕𝑁𝐴,𝑦 𝜕𝑁𝐴,𝑧 𝑁𝐴,𝑧 𝑁𝐵,𝑧
+ + =0 =
𝜕𝑥 𝜕𝑦 𝜕𝑧 −1 1
𝑑𝑁𝐴,𝑧 𝑧=𝛿 𝑐𝐴2 =0
=0 𝑁𝐴,𝑧 → 𝑘𝑡𝑒 න 𝑁𝐴 𝑑𝑧 = −𝐷𝐴𝐵 න 𝑑𝑐𝐴
𝑑𝑧
𝑧=0 𝑐𝐴 =𝑐𝐴∞
𝑑𝑐𝐴 𝑧=𝛿 𝑐𝐴2 =0
𝑁𝐴 = −𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴,𝑧 + 𝑁𝐵,𝑧
𝑑𝑧 𝑁𝐴 න 𝑑𝑧 = −𝐷𝐴𝐵 න 𝑑𝑐𝐴
0 𝑧=0 𝑐𝐴 =𝑐𝐴∞
𝑑𝑐𝐴
𝑁𝐴 = −𝐷𝐴𝐵 + 𝑦𝐴 𝑁𝐴,𝑧
𝑑𝑧 𝑁𝐴 𝑧𝛿0 = −𝐷𝐴𝐵 𝑐𝐴 0𝑐𝐴∞
La 𝑐𝐴 en la capa de 𝑆𝑖𝑂2
es los suficientemente 𝑁𝐴,𝑧 𝛿 = 𝐷𝐴𝐵 𝑐𝐴∞
diluida. 𝑑𝑐𝐴
𝑁𝐴 = −𝐷𝐴𝐵 𝐷𝐴𝐵 𝑐𝐴∞
𝑑𝑧 𝑁𝐴,𝑧 =
𝛿𝑡
 Zulamita Zapata, UPB
Balance de masa para 𝑆𝑖𝑂2 (VC2):
𝑂2
𝑑 𝜌𝐵 𝛿𝐴
VC2 𝑁𝐵 𝑀𝑤𝐵 𝐴 =
𝑑𝑡
:
−𝑁𝐴,𝑧 = 𝑁𝐵,𝑧
𝑆𝑖𝑂2

𝑑 𝜌𝐵 𝛿𝐴
0 𝑁𝐴 𝑀𝑤𝐵 𝐴 =
0 𝑑𝑡
𝐵: 𝑆𝑖𝑂2 𝐸−𝑆+𝐺 =𝐴
𝜌𝐵 𝑑 𝛿
𝑁𝐴 𝑀𝑤𝐵 =
𝑑𝑡
𝑑 𝑚𝐵
Ñ𝐵 𝑀𝑤𝐵 =
𝑑𝑡 𝑁𝐴 𝑀𝑤𝐵 𝑑𝑡 = 𝜌𝐵 𝑑𝛿
𝑑 𝑚𝐵
𝑁𝐵 𝑀𝑤𝐵 𝐴 = 𝐷𝐴𝐵 𝑐𝐴∞
𝑑𝑡 𝑀𝑤𝐵 𝑑𝑡 = 𝜌𝐵 𝑑𝛿
𝛿
𝑑 𝜌𝐵 𝑉
𝑁𝐵 𝑀𝑤𝐵 𝐴 = 𝐷𝐴𝐵 𝑐𝐴∞
𝑑𝑡 𝑀𝑤𝐵 𝑑𝑡 = 𝛿𝑑𝛿
𝜌𝐵
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𝐷𝐴𝐵 𝑐𝐴∞
𝑀𝑤𝐵 𝑑𝑡 = 𝛿𝑑𝛿 The figure compares the predicted film thickness
𝜌𝐵 vs. time to process data provided by Hess*
𝑡 𝛿
𝐷𝐴𝐵 𝑐𝐴∞
𝑀𝑤𝐵 න 𝑑𝑡 = න 𝛿𝑑𝛿
𝜌𝐵 𝑡=0 𝛿=0

𝐷𝐴𝐵 𝑐𝐴∞ 𝛿2
𝑀𝑤𝐵 𝑡 =
𝜌𝐵 2

𝑃𝐴
𝑐𝐴∞ =
𝑅𝑇

2 2𝐷𝐴𝐵 𝑐𝐴∞ 𝑀𝑤𝐵 𝑡

𝛿=
𝜌𝐵

*D. W. Hess, Chem. Eng. Educ., 24, 34 (1990)

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Transient diffusion (Analytical solution) – Most solutions to these equations have been
limited to situations involving simple geometries and boundary conditions, and a constant
diffusion coefficient.

Many solutions are for one-dimensional mass transfer as defined by Fick’s second law of
diffusion (no bulk motion contribution, v = 0, and no chemical reaction)*

cA ( x,0) = cA,0 c A  2cA

= DAB 2
t x

c A, , kc c A, , kc 
cA ( x,0) = cA,0
 c
 A =0
 x x=0

− D cA = kc cA ( L, t ) − cA, 
 AB x
 x= L

*J. Crank, The mathematics of diffusion, Oxford, 1975

 Zulamita Zapata, UPB
Plane Wall

c A − c A , 4sin  n
c A,0 − c A,
= 
n =1
2 n + sin(2 n )
 2 DAB t 
 L 
 x
exp  − n 2  cos   n  ,
 L

where  n tan  n = Bi
Cylinder
∞
𝐶𝐴 − 𝐶𝐴,∞ 2 𝐽1 𝑛 2 𝐷𝐴𝐵 𝑡
=෍ 𝐽  𝑟 ∗
𝑒𝑥𝑝 − ,
𝐶𝐴,0 − 𝐶𝐴,∞ 𝑛 𝐽0 2 𝑛 + 𝐽1 2 𝑛 0 𝑛 𝑛
𝑅2
𝑛=1

where

Sphere
4 sin( n ) −  n cos( n )   R 

c A − c A ,
c A,0 − c A,
= 
n =1
2 n − sin(2 n )
 
  nr 
exp
 2 DAB t   r 
 − n

2 
sin   n ,
R   R

where 1 −  n cot( n ) = Bi
kc L
For mass transfer the Biot number is defined as Bi =
DAB
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Exact solutions
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Exact solutions
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Example
One way to deliver a timed dosage of a drug within the human body is to ingest a capsule and allow it to settle in the
gastrointestinal system. Once inside the body, the capsule slowly releases the drug by a diffusion-limited process. A
suitable drug carrier is a spherical bead of a nontoxic gelatinous material that can pass through the gastrointestinal
system without disintegrating.

Consider a limiting case where the resistance mass transfer of the drug through the liquid boundary layer surrounding
the capsule surface to the bulk fluid is negligible. Furthermore, assume that the drug is immediately consumed or
swept away once it reaches the bulk solution. It is desired to design a spherical capsule for the timed release of the
drug commonly called Dramamine, which is used to treat motion sickness. A conservative total dosage for one
capsule is 10 mg, where 50% of the drug must be released to the body within 3 h. Determine the size of the bead and
the initial concentration in the bead necessary to achieve this dosage. The diffusion coefficient of Dramamine in the
gel matrix is 3  10-7 cm2/s at 37ºC. The solubility limit of Dramamine in the gel is 100 mg/cm3, whereas the
solubility in water is only 3 mg/cm3.
 Zulamita Zapata, UPB

Calcular:
- El diámetro de la “perla”.
- Concentración inicial, 𝐶𝐴,𝑜

Suposiciones:
- No hay resistencia en la capa límite
𝐶𝐴,𝑠 = 𝐶𝐴,𝑏𝑢𝑙𝑡𝑜 = 𝐶𝐴,∞ = 0

Balance de masa de A en la perla (VC):

0 0
𝑑𝜔𝐴
𝐸−𝑆+𝐺 =𝐴 𝑛𝐴,𝑟 = 𝑗𝐴ሶ = −𝜌𝐷𝐴𝐵 ቤ
𝑑𝑟 𝑟=𝑅
𝑑𝑚𝐴 𝑑𝜌𝐴
−𝑛෤𝐴,𝑟 = 𝑛𝐴,𝑟 = 𝑗𝐴ሶ = −𝐷𝐴𝐵 ቤ
𝑑𝑡 𝑑𝑟 𝑟=𝑅
𝑛෤𝐴,𝑟 = 𝑛𝐴,𝑟 𝑆 = 𝑛𝐴,𝑟 4𝜋𝑟 2

𝑑𝑚𝐴 Cambia en el tiempo, utilizar soluciones

−𝑛𝐴,𝑟 4𝜋𝑟 2 =
𝑑𝑡 exactas ya que hay cambio en el espacio (r) y
𝑑𝑚𝐴 = −𝑛𝐴,𝑟 4𝜋𝑟 2 𝑑𝑡 en el tiempo (t)
 Zulamita Zapata, UPB

4 sin( n ) −  n cos( n )   R 

𝑀𝑤,𝐴 c A − c A,
×
𝑀𝑤,𝐴 c A,0 − c A,
= 
n =1
2 n − sin(2 n )
 
  nr 
exp
 2 DAB t   r 
 − n

2 
sin   n ,
R   R

where 1 −  n cot( n ) = Bi

𝜌𝐴 − 𝜌𝐴∞ 𝑅 𝐷𝐴𝐵 𝑡 𝑟
= 𝐶𝑛 𝑒𝑥𝑝 −𝜉𝑛 2 2 sin 𝜉𝑛
𝜌𝐴,𝑜 − 𝜌𝐴∞ 𝜉𝑛 𝑟 𝑅 𝑅

0
𝑛𝐴 = 𝑘𝑐 𝜌𝐴,𝑠 − 𝜌𝐴,∞ 𝑛𝐴
= 𝜌𝐴,𝑠 − 𝜌𝐴,∞ 𝑘𝑐 → ∞
𝑘𝑐

kc L
Bi = ∴ 𝐵𝑖 → ∞ 𝜉𝑛 = 𝑛𝜋
DAB
𝜌𝐴 𝑛
𝑅 2
𝐷𝐴𝐵 𝑡 𝑛𝜋𝑟
= ෍ −2 −1 ∙ 𝑒𝑥𝑝 − 𝑛𝜋 sin
𝜌𝐴,𝑜 𝑛𝜋𝑟 𝑅2 𝑅
𝑛
𝜕𝜌𝐴 −2𝑅𝜌𝐴,𝑜 −1 2
𝐷𝐴𝐵 𝑡 1 𝑛𝜋𝑟 𝑛𝜋 𝑛𝜋𝑟 1
= ෍ ∙ 𝑒𝑥𝑝 − 𝑛𝜋 cos − sin
𝜕𝑟 𝜋 𝑛 𝑅2 𝑟 𝑅 𝑅 𝑅 𝑟2
 Zulamita Zapata, UPB

Reorganizando y evaluando en r=R:

0
𝑛
𝑑𝜌𝐴 −2𝑅𝜌𝐴,𝑜 −1 2
𝐷𝐴𝐵 𝑡 1 𝑛𝜋𝑅 𝑛𝜋 𝑛𝜋𝑟 1
ቤ = ෍ 𝑒𝑥𝑝 − 𝑛𝜋 cos − sin
𝑑𝑟 𝑟=𝑅 𝜋 𝑛 𝑅2 𝑟 𝑅 𝑅 𝑅 𝑅2

𝑑𝜌𝐴 −2𝜌𝐴,𝑜 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡

ቤ = ෍ 𝑒𝑥𝑝
𝑑𝑟 𝑟=𝑅 𝑅 𝑅2

Reemplazando en la definición del flux:

−2𝜌𝐴,𝑜 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡 2𝜌𝐴,𝑜 𝐷𝐴𝐵 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡
𝑛𝐴,𝑟 = −𝐷𝐴𝐵 ∙ ෍ 𝑒𝑥𝑝 𝑛𝐴,𝑟 = ෍ 𝑒𝑥𝑝
𝑅 𝑅2 𝑅 𝑅2

Reemplazando en el balance de masa:

𝑚𝐴 ,𝑡 𝑡
න 𝑑𝑚𝐴 = − න 𝑛𝐴,𝑟 4𝜋𝑟 2 𝑑𝑡
𝑚𝐴 ,𝑜 0

𝑚𝐴 ,𝑡 𝑡
2𝜌𝐴,𝑜 𝐷𝐴𝐵 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡 2 𝑑𝑡
න 𝑑𝑚𝐴 = − න ෍ 𝑒𝑥𝑝 ∙ 4𝜋𝑅
𝑚𝐴 ,𝑜 0 𝑅 𝑅2
 Zulamita Zapata, UPB
𝑡
−𝑅2 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡
𝑚𝐴,𝑡 − 𝑚𝐴,𝑜 = −8𝜌𝐴,𝑜 𝐷𝐴𝐵 𝜋𝑅 ෍ 2 𝑒𝑥𝑝 อ
𝐷𝐴𝐵 𝑛𝜋 𝑅2
𝑡=0

𝑚𝐴,𝑜 4
𝜌𝐴,𝑜 = 𝑚𝐴,𝑜 = 𝜌𝐴,𝑜 ∙ 𝜋𝑅3
𝑉 3

÷ 𝑚𝐴,𝑜 𝑚𝐴,𝑡 8𝐷𝐴𝐵 𝜋𝑅 1 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡 1

−1=− ෍ 2 𝑒𝑥𝑝 −
𝑚𝐴,𝑜 4 3 𝑛 𝑅2 𝑛2
𝜋𝑅
3
1
2
𝑚𝐴,𝑡 6 1 −𝐷𝐴𝐵 𝑛𝜋 𝑡 6
= 2 ෍ 2 𝑒𝑥𝑝 −෍ 2 2+1
𝑚𝐴,𝑜 𝜋 𝑛 𝑅2 𝑛 𝜋

𝑚𝐴,𝑡 6 1 −𝐷𝐴𝐵 𝑛𝜋 2 𝑡
= ෍ 2 𝑒𝑥𝑝
𝑚𝐴,𝑜 𝜋 2 𝑛 𝑅2
𝑚𝐴,𝑡
Para un 50% de liberación correspondiente a 3 h (10800 s) = 0.5
𝑚𝐴,𝑜

𝑛=4 𝑅 = 0.326 𝑐𝑚
𝑚𝑔 𝑚𝑔
𝑛=1 𝑅 = 0.4 𝑐𝑚 𝑉 = 0.26 𝑐𝑚3 𝜌𝐴,𝑜 = 37.3 < 100
𝑐𝑚3 𝑐𝑚3
 Zulamita Zapata, UPB

Example
A cylinder of clay, 30 cm long and 10 cm in diameter to be dried in a stream of
dry air. The initial uniform composition is 14 wt%, and the final center
composition desired will be 7 wt%. Under the specified drying conditions, the
drying will be controlled by the internal diffusion of liquid water to the surface.
The diffusivity of water through the clay is estimated to be 1.310-8 m2/s. The
surface moisture content will remain constant throughout the process at 3 wt%.
Determine the drying time required.
z
𝜔𝐴, 𝑟=𝑅,∀𝑡 =3%
𝜔𝐴, ∀𝑟,𝑡=0 = 14 %
Aire
seco r

𝜔𝐴, 𝑟=0,𝑡=? =7%

 Zulamita Zapata, UPB

Solución: coordenadas cilíndricas

?
∞
𝐶𝐴 − 𝐶𝐴,∞ 2 𝐽1 𝑛 2 𝐷𝐴𝐵 𝑡
=෍ 𝐽  𝑟 ∗
𝑒𝑥𝑝 − ∴
𝐶𝐴,0 − 𝐶𝐴,∞ 𝑛 𝐽0 2 𝑛 + 𝐽1 2 𝑛 0 𝑛 𝑛
𝑅2
𝑛=1

∞
𝑀𝑤,𝐴 𝐶 − 𝐶𝐴,𝑠 2 𝐽1 𝑛 𝐷 𝑡
× 𝐴 =෍ 𝐽  𝑟 ∗ 𝑒𝑥𝑝 − 2 𝐴𝐵
𝑀𝑤,𝐴 𝐶𝐴,0 − 𝐶𝐴,𝑠 𝑛 𝐽0 2 𝑛 + 𝐽1 2 𝑛 0 𝑛 𝑛
𝑅2
𝑛=1
∞
𝐶𝑠𝑙𝑛 𝜌𝐴 − 𝜌𝐴,𝑠 2 𝐽1 𝑛 2 𝐷𝐴𝐵 𝑡
× =෍ 𝐽  𝑟 𝑒𝑥𝑝 −𝑛
∗
𝐶𝑠𝑙𝑛 𝜌𝐴,0 − 𝜌𝐴,𝑠 𝑛 𝐽0 2 𝑛 + 𝐽1 2 𝑛 0 𝑛 𝑅2
𝑛=1

∞
𝜔𝐴 − 𝜔𝐴,𝑠 2 𝐽1 𝑛 ∗ 𝑒𝑥𝑝 − 2 𝐴𝐵
𝐷 𝑡
=෍ 𝐽  𝑟
𝜔𝐴,0 − 𝜔𝐴,𝑠 𝑛 𝐽0 2 𝑛 + 𝐽1 2 𝑛 0 𝑛 𝑛
𝑅2
𝑛=1
?
𝜔𝐴 − 𝜔𝐴,𝑠 𝐷𝐴𝐵 𝑡 𝑘𝑐 𝑟
= 𝐶1 𝐽0 1 𝑟 ∗ 𝑒𝑥𝑝 −1 2 2 ∴ 𝐵𝑖𝑚 =
𝜔𝐴,0 − 𝜔𝐴,𝑠 𝑅 𝐷𝐴𝐵
 Zulamita Zapata, UPB

𝒏𝑨
𝑁𝐴 = 𝑘𝑐 ∆𝐶𝐴
∙ 𝜔𝐴,𝑠 Aire seco
𝜔𝐴,∞ 𝑛𝐴 = 𝑘𝑐 𝜔𝐴,𝑠 − 𝜔𝐴,∞

𝑛𝐴 ∴ 𝜔𝐴, =3%
↑↑↑ 𝑘𝑐 = 0 𝑟=𝑅,∀𝑡
𝜔𝐴,𝑠 − 𝜔𝐴,∞
𝐶1 = 1.6018
𝑘𝑐 ↑↑↑ → 𝐵𝑖 ↑↑↑ 1 = 2.4050

𝜔𝐴 − 𝜔𝐴,𝑠 𝐷𝐴𝐵 𝑡
= 𝐶1 𝐽0 1 𝑟 ∗ 𝑒𝑥𝑝 −1 2 2
𝜔𝐴,0 − 𝜔𝐴,𝑠 𝑅

𝑅2 𝜔𝐴 − 𝜔𝐴,𝑠 1
𝑡= ∙ 𝑙𝑛 ∙
𝐴,𝑠 𝐶1 𝐽0 1 𝑟
2 𝜔 − 𝜔 ∗
−1 𝐷𝐴𝐵 𝐴,0

𝑡 = 49297.9 𝑠 = 13.7 ℎ
 Zulamita Zapata, UPB

Unsteady-state diffusion in a semi-infinite medium

cA,s c A  2cA
= DAB 2
t x

c A (0, x) = c A,0

c A (t ,0) = c A, s
c (t , ) = c
cA,s  A A,0

c A − c A,0  x 
= erfc 
c A, s − c A,0  2 D t 
 AB 

cA,0
N A, s =
DAB
t
( c A, s − c A,0 )
Zulamita Zapata, UPB
 Zulamita Zapata, UPB

Example
A pond with an initial oxygen content of zero is to be oxygenated by forming a tent over
the water surface and filling the tent with oxygen gas at 25 °C and 130 kPa. Determine
the mole fraction of oxygen at a depth of 1 cm from the surface after 24 h. The Henry’s
constant for dissolution of oxygen in water at 25 °C is 1.310-3 mol/(atmL).
 Zulamita Zapata, UPB

Solución
Un estanque con un contenido inicial de oxígeno de
cero se debe oxigenar formando una tienda sobre la
superficie del agua y llenándola con gas oxígeno a 25 °
C y 130 kPa. Determine la fracción molar de oxígeno a
una profundidad de 1 cm de la superficie después de 24
𝑁𝐴 𝑥
h. La constante de Henry para la disolución de oxígeno
en agua a 25 ° C es 1.310-3 mol/(atmL).

Nota:
- Identificar la condición de frontera en x=0.
- Verificar en que dirección hay un cambio de 𝑐𝐴,𝑠 =?
concentración. 𝑃𝐴 Fase
- ¿Qué pasa con los cambios de concentración muy 𝑐𝐴,𝑠 =
𝑅𝑇 gaseosa
lejos de la superficie después de cierto tiempo?
130 𝑘𝑃𝑎
𝑐𝐴,𝑠 =
ccA (0, 𝑘𝑃𝑎 ∙ 𝑚3
c AA (0, (0, xxx))) = = ccc AA,0,0
=
C.I. 8.314
𝑘𝑚𝑜𝑙 ∙ 𝐾
∙ 298 𝐾
c A  2cA ccA ((tt ,0)
A,0

= DAB 2  =
= cc A, s
 A c A ( t ,0)
,0) = c AA,, ss C.F.1 𝑘𝑚𝑜𝑙
t x 𝑐𝐴,𝑠 = 0.052
cccAA (((ttt ,,, 


)) =
=
=
cc A,0 𝑚3
 A ) c AA,0,0 C.F.2
 Zulamita Zapata, UPB
• Solubility of gases in liquids ? 1 cm
0
𝑐𝐴,𝑠 =? c A − c A,0  x 
= erfc 
c A, s − c A,00  2 D t  24 h
 AB 
Fase líquida?
𝑥
p (0)
x A (0) = A Henry's law
A, s
DAB
N𝐶𝐴 ==𝐶𝐴,𝑠 ∙ erfc
t
( c2√ −𝐷 c 𝑡 )
A, s
𝐴𝐵
A,0


H
= 𝑘𝑃𝑎 𝑜 𝑎𝑡𝑚 1 𝑐𝑚
𝜙= 2 = 0.35
𝐶𝐴 𝐶𝐴 𝑐𝑚
2√ 2.41 × 10−5 𝑠 ∙ 86400 𝑠
𝑃𝐴 = 𝐻𝑥𝐴 ∴ 𝑥𝐴 = 𝑃𝐴 = 𝐻
𝐶 𝐶
𝐻 𝐶𝐴 𝑚𝑜𝑙 erfc 𝜙 = 1 − erf 𝜙
𝑃𝐴 = 𝐶𝐴 = ∴ 𝐻 = 1.3 × 10−3
𝐶 𝐻 𝑎𝑡𝑚. 𝐿
erfc 𝜙 = 1 − 0.3794 = 0.6206
Constante
𝑚𝑜𝑙 𝑚𝑜𝑙
∗
𝐶𝐴,𝑠 = 𝐻𝑃𝐴 = 1.3 × 10−3 ∙ 1.28 𝑎𝑡𝑚 𝐶𝐴 = 1.67 × 10−3 ∙ 0.6206
𝑎𝑡𝑚. 𝐿 𝐿
𝑚𝑜𝑙
𝑚𝑜𝑙 𝐶𝐴 = 1.04 × 10−3
𝐶𝐴,𝑠 ∗ = 1.67 × 10−3 𝐿
𝐿
Zulamita Zapata, UPB
c A − c A,0  x 
= erfc  Zulamita Zapata, UPB
c A, s − c A,0  2 D t 
 AB 

N A, s =
DAB
t
( c A, s − c A,0 ) ????

𝑥𝐴 =? ? ? ? ?