488 Chapter 26 Steady-State Molecular Diffusion

reveals that
sffiffiffiffiffiffiffiffiffiffi
DAB
kc ¼ (26-89)
ptexp

In equation (26-89), we see that the convective mass-transfer coefficient, kc, is propor-
tional to the diffusion coefficient raised to the 12 power. This dependency was also
shown earlier in Section 26.2 for the diffusion of a solute into a liquid accompanied
by a rapid chemical reaction. Penetration theory considers that the solute only
penetrates a short distance into the liquid phase due to a short residence time of
exposure of the solute with the liquid, or because the solute rapidly disappears by a
chemical reaction within the liquid. Consequently, penetration theory proposes that
liquid-phase mass-transfer coefficient for transferring species A will assume the form of
equation (26-89).

26.5 CLOSURE
In this chapter, we have considered solutions to steady-state molecular mass-transfer
problems. The defining differential equations were established by simplifying the general
differential equation for mass transfer or through the use of a control volume expression for
the conservation of mass. It is hoped that this two-pronged attack will provide the student
with an insight into the various terms contained in the general differential equation, and thus
enable the reader to decide whether the terms are relevant or irrelevant to any specific
situation.
One-directional systems both with and without chemical production were consid-
ered. Two models of convective mass transfer, film theory and penetration theory, were
introduced. These models will be used in Chapter 28 to evaluate and explain convective
mass-transfer coefficients.

PROBLEMS
26.1 An Arnold cell is to be operated as a pseudo-steady-state
cell to determine the gas diffusivity of benzene in air at 308 K
and 1.0 atm. The 20-cm-long tube, with an inner diameter of
1.0 cm, is initially loaded with liquid benzene to a depth of
1.0 cm from the bottom of the tube. The tube and the liquid are
maintained at a constant temperature of 308 K. At this tem-
perature, benzene exerts a vapor pressure of 0.195 atm. Air is
continually blown over the top of the tube, removing any of
the vaporized benzene vapor; the gas space within the tube
is essentially stagnant. At 308 K, liquid benzene’s density is
0:85 g/cm3 .
a. It was determined that 72.0 h were required to completely
evaporate the benzene initially loaded into the tube. Esti-
mate the binary gas-phase diffusion coefficient for benzene
in air using these data.
b. Compare your evaluated diffusivity with the value reported
in Appendix J.1. What is a possible reason for any differ-
ence in these values?
26.2 Helium gas is seperated from other components of a gas
mixture by its selective diffusion through the wall of a Pyrex
glass tube. Under steady-state conditions, the partial pressures
of helium at the inner and outer surfaces of the Pyrex tube are
1.5 and 1.0 bar, respectively. If the wall thickness of the Pyrex
tubing is 3 mm, determine
a. the flux of He through a tube having an inside diameter of
1.0 cm;
b. the concentration profile, cA (r), of helium within the wall.
26.3 A tank with its top open to the atmosphere contains liquid
methanol (MeOH, molecular weight 32g/mol) at the bottom of
the tank. The tank is maintained at 308C. The diameter of the
cylindrical tank is 1.0 m, the total height of the tank is 3.0 m, and
the liquid level at the bottom of the tank is maintained at 0.5 m.
The gas space inside the tank is stagnant and the MeOH vapors
are immediately dispersed once they exit the tank. At 308C, the
vapor pressure exerted by liquid MeOH is 163 mmHg and at
408C the MeOH vapor pressure is 265 mmHg. We are concerned

that this open tank may be emitting a considerable amount of
MeOH vapor.
a. What is the emission rate of MeOH vapor from the tank in
units of kg MeOH/day when the tank is at a temperature of
308C? State all assumptions and boundary conditions.
b. If the temperature of the tank is raised to 408C, what is the
new methanol emission rate?
26.4 Ethanol is diffusing through a 4-mm stagnant film of
water. The ethanol concentrations of the entrance and the
existing planes are maintained at 0.1 and 0:02 mol/m3 , respec-
tively. If the water film temperature is 283 K, determine the
steady-state molar flux of the ethanol and the concentration
profile as a function of the position z within the liquid film.
Compare these results with a 4-mm stagnant film of air at 283 K
and 1 atm at the same entrance and exit ethanol concentrations.
26.5 Consider the process shown in the figure below. A slab
contains parallel linear channels running through a nonporous
slab of thickness 2.0 cm. The gas space over the slab contains a
mixture of A and B maintained at a constant composition. Gas-
phase species A diffuses down a straight, 1.0-mm-diameter
channel. At the base of the slab is a catalytic surface that
promotes the isomerization reaction A(g) ! B(g). This reaction
occurs very rapidly so that the production of B is diffusion
limited. The quiescent gas space in the channel consists of only
species A and B. The process is isothermal at 1008C and isobaric
at 2.0 atm total system pressure. The bulk composition over
the slab is maintained at 40 mol% A and 60 mol% B. The
molecular weight of species A and its isomer B is 58 g/mol.
Monolith catalyst
Bulk gas phase
40 mol% A, 60 mol% B
z = L = 2.0 cm
1-mm-diameter
channels
(cylindrical pores)
z=0
Catalytic surface
A(g) B(g)
a. Listing all of your assumptions, simplify the general mass-
transfer equation for species A.
b. Develop a final integrated equation for the flux of product B.
Be sure to specify your boundary conditions.
c. The binary gas-phase molecular diffusion coefficient of
species A in species B is 0:1 cm2 /s at 258C and 1.0 atm.
What is a reasonable estimate for the molecular flux of
species B in species A under the conditions of the operation?
d. If the total production rate, WA, is 0.01 mol B/min, what is
the required number of 1.0-mm-diameter channels neces-
sary to accomplish this production rate?
Problems 489
26.6 The following illustrated spherical capsule is used for
long-term, sustained drug release. A saturated liquid solution
containing the dissolved drug (solute A) is encapsulated within a
rigid gel-like shell. The saturated solution contains a lump of
solid A, which keeps the dissolved concentration of A saturated
within the liquid core of the capsule. Solute A then diffuses
through the gel-like shell (the gel phase) to the surroundings.
Eventually, the source for A is depleted, and the amount of solute
A within the liquid core goes down with time. However, as long
as the lump of solid A exists within the core, the source solution
is saturated in A and the concentration cA is constant. The
diffusion coefficient of solute A in the gel phase B is DAB ¼
1:5 " 10#5 cm2 /s. The concentrations of solute A in the gel
phase at the boundaries of the shell are
@ r ¼ R1 ¼ 0:2 cm, cA ¼ cAs ¼ cA ¼ 0:01 g mol/cm3 ,
the solubility limit of A in the gel.
@ r ¼ R0 ¼ 0:35 cm; cA ¼ cAo :
Sustained drug-release spherical capsule
Drug (solute A)
dissolved in liquid
(at saturation)
Lump of
solid species A
Gel capsule
shell r = Rf r = Ro
c A = c As cA = c Ao
a. State the differential forms of the flux equation and the
differential equation for mass transfer for this diffusion
process.
b. Develop the final analytical, integrated equation to deter-
mine the total rate of drug release, WA, from the capsule
under the condition where the concentration of A within the
liquid core of the capsule remains constant.
c. What is the maximum possible rate of drug release from the
capsule, in units of gram moles of A per hour?
26.7 A spherical ball of solid, nonporous naphthalene, a
‘‘moth ball’’, is suspended in still air. The naphthalene ball
slowly sublimes, releasing the naphthalene into the surrounding
air by molecular diffusion-limited process. Estimate the time
required to reduce the diameter from 2 to 0.5 cm when the
surrounding air is at 347 K and 1:013 " 105 Pa. Naphthalene has
a molecular weight of 128 g/mol, a solid density of 1:145 g/cm3 ,
490 Chapter 26 Steady-State Molecular Diffusion
a diffusivity in air of 8:19 " 10#6 m2 /s, and exerts a vapor pres-
sure of 5 Torr (666 Pa) at 347 K.
26.8 Consider the low-pressure chemical vapor deposition
(LPCVD) diffusion reactor as shown below. It is desired to
lay a thin film of the semiconductor gallium, Ga, onto a silicon
wafer surface. Gallium metal is not volatile, but trimethyl
gallium (TMG; GaðCH3 Þ3 , 114.72 g/g mol) is volatile. In the
presence of an H2 gas, at high temperature, TMG will decom-
pose to solid Ga on a surface by the following reaction:
Ga(CH3)3 vapor 700°C, 0.2 ATM
+ H2 gas (uniform concentration)
Diffuser
Quiescent z=δ
Ga(CH3)3 H2 CH4 gas
Ga thin
film
z=0
Heated plate
Ga(CH3 )3 (g) þ 32H2 (g) ! Ga(s) þ 3CH4 (g)
At 7008C, this surface reaction is diffusion limited. Let gas-
phase species A ¼ TMG; B ¼ H2 and C ¼ CH4 .
a. Develop an integral model to predict the flux of TMG to
the wafer surface. Keep your final model in algebraic
form. Provide appropriate assumptions and boundary con-
ditions. At this point, you may not assume that the process
is dilute.
For parts (b) and (c), consider a process where the feed
gas consists of 99.98 mol% H2 and 0.02 mol% TMG. The
temperature and total system pressure are 7008C and
0.20 atm, respectively. The binary diffusion coefficient of
TMG in H2 at 7508C and 1.0 atm is known to be 2:0 cm2 /s.
b. What is the simplified form of the model previously devel-
oped in part (a)?
c. What is the value of an appropriate diffusion coefficient for
this process?
26.9 Microelectronic devices are fabricated by forming many
layers of thin films onto a silicon wafer. For example, thin films
of arsenic as a common dopant for silicon are commonly
deposited onto silicon by chemical vapor deposition, or CVD,
of arsine (AsH3) vapor onto the surface of the wafer. The
chemical reaction for this CVD process is
AsH3 (g) ! As(s) þ 32H2 (g)
It is proposed to allow this process to take place at a pressure
of 303.9 Pa and a temperature of 6008C. In many CVD reactors,
the gas phase over the thin film is not mixed. Furthermore,
at high temperatures, the surface reaction is very rapid. Con-
sequently, the molecular diffusion of AsH3 vapor to the
surface often controls the rate of As(s) formation. Consider
the very simplified CVD reactor illustrated in Chapter 25,
Problem 25.11.
A mixture of arsine and hydrogen gas continuously flows
into the reactor. The mixture contains 20 mol% arsine. A diffuser
provides a quiescent gas space over the growing As film. The
distance from the diffuser to the film surface is 6.0 cm. The gas
mixture may be assumed to behave as an ideal gas. The
molecular weight of arsenic, As, is 75 g/g mol. The Lennard–
Jones parameters for SiH4 are s A ¼ 4:08 A8 and eA/k ¼ 207:6.
a. What is the molecular diffusion coefficient of arsine vapor
in hydrogen gas at 6008C and 303.9 Pa?
b. Develop a model to predict the diffusion-limited flux of
arsine to the surface of the wafer. State at least three
assumptions relevant to this process.
c. The diameter of the wafer is 15 cm. Estimate the initial
deposition rate of arsenic onto the surface of the wafer, in
units of grams of As per minute.
26.10 Consider a hemispherical droplet of liquid water resid-
ing on a flat surface. Still air surrounds the droplet. At an
infinitely long distance from the gas film, the concentration
of water vapor is effectively zero. At a constant temperature of
308C and 1.0 atm total pressure, the evaporation rate of the
droplet is controlled by the rate of the molecular diffusion
through the still air. Determine the time it will take for the
water droplet to completely evaporate at 308C and 1.0 atm total
system pressure if the initial droplet radius is 5 mm. The vapor
pressure of water at 308C can be found in the steam tables.
26.11 Consider the metallurgical refining process illustrated in
the following figure.
100% H2 gas
(Constant concentration along outer surface)
z=0
Porous Fe layer
2.0 cm
z=d
Nonporous FeO layer
Iron oxide, FeO, ore is being reduced to iron, Fe, by hydrogen
gas according to the reaction
FeO(s) þ H2 (g) ! Fe(s) þ H2 O(g)
The FeO layer is nonporous, but the Fe layer is porous. Pure
hydrogen gas flows over the surface of the slab. As FeO is
reduced to Fe, the path length for diffusion of H2 gas through the
porous slab from the surface to the FeO/Fe boundary increases
with time. In making your model, you may assume that (1) the
process operates under constant conditions of 400 K and 1.0 atm;
(2) the reaction is very rapid so that the reduction of FeO is
limited by the diffusion of H2 to the FeO/Fe boundary; (3) the
diffusion process is pseudo-steady state along the path length;
and (4) the effective gas-phase diffusion coefficient of water in
hydrogen is 1:7 cm2 /s within the porous solid under the condi-
tions of the process. The bulk density of the FeO solid is
2:5 g/cm3 , and the molecular weight of FeO is 71.85 g/g mol.

a. Reduce the general differential equation for mass transfer to
describe the diffusion of H2.
b. Determine the molar flux of H2 to the FeO/Fe boundary
when d ¼ 1 cm.
c. Determine the minimum time necessary for FeO to be
converted to Fe from d ¼ 1 to d ¼ 2:0 cm.
26.12 Condsider the timed drug-release pill illustrated below.
(Essentially water)
cA,∞ ≈ 0
cA,∞ ≈ 0
Initially 0.4 mm
NA
Cross-sectional
view of pill
z yH =1.0, yH
Lt =
0.36cm 2.0 mm
At a Lo =
later time 1.2 mm
Solid
drug A
r
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 2:0 "
10#4 g mol/cm3 (i.e., not very soluble) and the diffusion coeffi-
cient of the drug is 2:0 " 10#5 cm2 /s at body temperature of
378C. 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 ¼ 0, and the drug does not chemi-
cally degrade inside the pore.
b. From your model, determine the 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?
26.13 Hydrogen (H2) gas is commonly used to reduce iron
oxide ores to metallic ores. Consider the following heteroge-
neous reduction reactions on a nonporous flat surface of the
following ores:
FeO(s) þ H2 (g) ! Fe(s) þ H2 O(g)
TiO2 (s) þ 2H2 (g) ! Ti(s) þ 2H2 O(g)
Fe2 O3 (s) þ 3H2 (g) ! 2Fe(s) þ 3H2 O(g)
Mn3 O4 (s) þ 4H2 (g) ! 3Mn(s) þ 4H2 O(g)
Problems 491
Write the integrated form of the flux equation, assuming
(1) steady-state one-dimensional flux through a gas film of
thickness d along the coordinate z; (2) constant gas composition
at the edge of the gas film; (3) instantaneous reaction at the
surface; and (4) constant temperature and pressure. Which
reactions result in an equimolar-diffusion flux of the gas-phase
species? Hint: Carefully consider the stoichiometry associated
with each reaction.
26.14 As part of the manufacturing process for the fabrication
of titanium-oxide-based solar panels, a layer of nonporous
titanium oxide must be reduced to metallic titanium, Ti, by
hydrogen gas as shown in the following figure.
100% H2 gas at z = 0
≈0
2 2O
Z=0
Nanoporous solid Ti layer
0.1 CM
Z=d
Nanoporous TiO2 layer
The reaction at the Ti/TiO2 boundary is given by
TiO2 (s) þ 2H2 (g) ! Ti(s) þ 2H2 O(g)
Pure H2 gas flows rapidly over the surface of the nanoporous
TiO2 slab. As TiO2(s) is reduced to Ti (molecualr weight
Ti ¼ 47:9 g/g mol), the path length for mass transfer of H2
and H2O gas through the porous slab from the surface to the
Ti/TiO2 boundary increases with time. You may assume that
(1) the process operates at 1.0 atm and 900 K; (2) the reaction is
very fast so that the concentration of H2 gas at the Ti/TiO2
boundary is zero and the reduction of TiO2(s) is limited by the
diffusion of TiO2(g) away from the Ti(s)/TiO2 boundary; (3) the
diffusion process is pseudo-steady state along the diffusion path;
and (4) the effective gas-phase diffusion coefficient of H2 within
the porous Ti(s) containing a mixture of H2(g) and H2O(g) is
0:031 cm2 /s at the temperature and pressure of the process,
whereas the effective diffusion coefficient of H2O(g) within the
nanoporous Ti(s) containing a mixture of H2(g) and H2O(g) is
0:01 cm2 /s at the temperature and pressure of the process. The
density of the nanoporous Ti(s) is 2:6 g/cm3 .
a. Determine the flux of H2 to the Ti/TiO2 boundary when
d ¼ 0:05 cm, assuming yAo ¼ 1:0.
b. Determine the number of hours necessary for all the TiO2 to
be converted to Ti(s).
c. At z ¼ d ¼ 0:05 cm, determine the concentration profile for
H2(g).
26.15 Two very large tanks, maintained at 323 K and 1 atm
total system pressure, are connected by a 0.1-m-diameter
circular duct which is 5 m in length. Tank 1 contains a uniform
gas of 60 mol% acetone and 40 mol% air, whereas tank
2 contains a uniform gas of 10 mol% acetone and 90 mol%
air. Determine the initial rate of acetone transfer between the
two tanks. The gas diffusivity of acetone in air at 298 K and
1 atm is 0:093 cm2 /s.
492 Chapter 26 Steady-State Molecular Diffusion
26.16 Consider the novel ‘‘nanostructured’’ catalyst shown in
the following figure.
Nonostructured ordered catalyst support
Detail for one “nanowell”
Bulk gas (473 K, 1.25 atm)
H2(g), O2(g), H2O(g) 50m nm
Still
gas
z H2 O2 H2 O
Ordered catalyst support
r 19 g/mol, and the density of solid tungsten is 19:4 g/cm3 .
Catalytic
surface
The catalyst support consists of an ordered array of cylindrical
‘‘nanowells’’ of 50nm diameter and 200 nm depth (1 nm ¼
10#9 m). A catalytic surface coats of the bottom of each well.
Although gas flows over the catalyst surface, the gas space
within each ‘‘well’’ is stagnant, that is, not well mixed. In the
present application, the catalyst surface is used to convert
unreacted H2 gas (species A) and O2 gas (species B) from a
fuel cell into water vapor (species C) according to the reaction
2H2 (g) þ O2 (g) ! 2H2 O(g)
For our first approximation, consider the reaction diffusion
limited within the catalyst well. The process is isothermal at
473 K and isobaric at 1.25 atm total system pressure.
a. State reasonable assumptions for this process. What is the
simplified form of the general differential equation for the
mass transfer of hydrogen? What is the simplified form of
Fick’s equation for hydrogen? Consider O2 is the dominant
species and both H2 and H2O are dilute.
b. What is the effective diffusion coefficient of H2 gas inside
each nanowell if we have a dilute system with bulk gas
mole fraction compositions for yH2 ¼ 0:01 and yH2 O ¼
0:01. What is the flux of H2?
26.17 ‘‘Microvia’’ are microscopic passages between two thin
films on a microelectronic device. Often, microvia are filled
with a conductive metal to make a microscopic conductor for
the flow of electrons between the two thin films. In one particular
process, tungsten is deposited onto the base of the microvia by
the following chemical vapor deposition reaction:
WF6 (g) þ 3H2 (g) ! W(s) þ 6HF(g)
As the tungsten metal forms, it fills the microvia (2:0 mm depth,
0:5 mm diameter) as illustrated in the following figure:
Gas phase
WF6 + H2 + HF + He
0.5 µm
microvia
z at 208C is also shown below. Other experiments showed that the
L = 2.0 µm
W(S) Si
z=δ
z=L
SiO2
The tungsten metal does not coat the side walls of the microvia; it
only grows upward from the base of the microvia where the
tungsten was initially seeded. The reactants are significantly
diluted in inert Helium (He) gas to lower the deposition rate.
The temperature is 700 K, the total system pressure is 75 Pa, and
Z = L = 200 nm the concentrations of WF6 and H2 in the bulk gas space over the
microvia are each 0.001 mol. Assume that the tungsten deposi-
tion is limited by molecular diffusion. The molecular weight of
tungsten, W, is 184 g/mol, the molecular weight of fluorine is
z=0
a. Develop a pseudo-steady-state model to predict the depth of
tungsten metal within the microvia as a function of time.
b. Estimate the time required to completely fill the microvia
assuming Knudsen diffusion for WF6 vapor.
26.18 In the distillation of a benzene/toluene mixture, a
vapor richer in benzene is produced from a benzene/toluene
liquid solution. Benzene is transferred from the liquid to the
vapor phase and the less-volatile toluene is transferred in the
opposite direction. At the system temperature and pressure,
the latent heats of vaporization of benzene and toluene are
30 and 33 kJ/mol, respectively. Both components are diffusing
through a gas film of thickness d. Develop an equation to
predict the steady-state flux of benzene through the gas film.
The equation must include terms for the bulk gas-phase
mole fraction of benzene, the gas-phase mole fraction of
benzene in equilibrium with the liquid solution, the diffusion
coefficient of benzene/toluene, the diffusion path d, and the
total molar gas concentration. Assume the distillation is an
adiabatic process.
26.19 An important step in the purification of uranium iso-
topes involves the conversion of uranium to uranium hexa-
fluoride, UF6. In the present process, UF6 is prepared by
exposing uranium pellets, spherical in shape, to fluorine gas
at 1000 K and 1 atm pressure. The molecular diffusion of the
fluorine gas to the pellet surface is thought to be the controlling
step. If the reaction
U(s) þ 3F2 (g) ! UF6 (g)
occurs irreversibly and instantaneously on the pellet surface, and
the diffusivity of fluorine gas through uranium hexafluoride gas
is 0:273 cm2 /s at 1000 K and 1 atm, determine the production
rate of UF6 when the pellet diameter is 0.4 cm.
26.20 Consider the ‘‘drug patch’’shown below. The drug patch
looks like a sandwich consisting of a pure drug source mounted
on top of a gel diffusion barrier. The gel diffusion barrier has a
thickness of 2.0 mm. The gel barrier is in direct contact with the
skin. The drug release vs. time profile for a 3.0-cm square patch
drug was immediately taken up into the body after exiting the
patch. The maximum solubility of the drug in the gel diffusion
barrier is 0:5 mmol/cm3 . The drug is only slightly soluble in the
gel material. The solubility of the drug in the gel diffusion barrier
is not affected by the temperature.
 Problems 493

where DA2 is the diffusivity of A2 through the membrane.

Drug patch
When standard pressures are employed with a membrane of
Drug reservoir
Impermeable standard thickness, JA2 is called the permeability of A2.
barrier L Gel diffusion barrier
b. A piece of laboratory equipment operating at 7008C con-
Skin surface tains hydrogen gas at 8 atm that is separated from a continu-
ously evacuated space by an 8 cm2 nickel disk, 2 mm thick.
Infected body tissue The solubility of hydrogen in nickel at 1 atm pressure
(sink for drug) and 7008C is approximately 7:0 cm3 /100 g of nickel. The
diffusivity of hydrogen through nickel at 7008C is
0.20
6 " 10#5 cm2 /s, and the density of nickel at 7008C is
9:0 g/cm3 . Calculate the number of cubic centimeters of
hydrogen per hour that diffuses through the nickel.
Drug released (m mol A)

0.15 26.22 Living cells homogeneously distributed (immobilized)

with an agarose gel require glucose to survive. An important
aspect of the biochemical system design is the effective diffusion
0.10 coefficient of glucose (species A) into the cell-immobilized gel.
Consider the experiment shown below where a slab of the
cell-immobilized gel of 1.0 cm thickness is placed within a
0.05

0.00
0 5 10 15 20 25 Living cells in
agarose gel Well-mixed
Time (h) Well-mixed RA= –0.05 mmol/cm3 min glucose solution
glucose solution (1.0 cm thick) constant
a. From the data in the drug release vs. time profile, estimate constant
concentration
concentration
the effective diffusion coefficient of the drug in the diffusion (50 mmol/L)
(50 mmol/L)
barrier.
b. When used on the body, heat transfer raises the temperature
Sampling
of the drug patch to about 358C. What is the new drug syringe
delivery rate, WA, at this temperature in units of mmol/day? (center of gel)
You may assume that the gel-like diffusion barrier material
approximates the properties of water. The viscosity of liquid well-mixed aqueous solution of glucose maintained at a con-
water is 0.00993 g/cm s at 208C and 0.00742 g/cm s at 358C. centration of 50 mmol/L. The glucose consumption within the
cell-immobilized gel proceeds by a zero-order process given by
26.21 The permeability of solids by gases is experimentally
determined by steady-state diffusion measurements. The diffus- RA ¼ #m ¼ #0:05 mmol/L min (26-70)
ing solute is introduced at one side of the membrane and The solubilities of the glucose in both water and the gel are the
removed from the other side as a gas. same; that is, the concentration of glucose on the water side of
For a diatomic gas, A2, which dissociates upon dissolving the water–gel interface is equal to the concentration of glucose
into a solid, Sievert’s law relates the concentration of A atoms in on the gel side of the water–gel interface. A syringe mounted at
the surface layer of the membrane, cA1 , in equilibrium with the the center of the gel carefully excises a tiny sample of the gel for
applied pressure, p1, of the diatomic gas by the relation glucose analysis.
cA ¼ k( p1 )1/ 2 1
Develop a model in final integrated form to predict the
concentration profile of glucose within the gel. Be careful with
This same equation also holds at the other surface of the specification of boundary conditions, so that your model is truly
membrane for the off-gas pressure, p2. Sievert’s law is a variant predictive and is based only on process input parameters, not
of Henry’s law for gases that dissociate upon dissolving. measured parameters.
a. Prove that the rate of diffusion of a diatomic gas from a
high-pressure reservoir, p1, through a membrane of thick- 26.23 A cylindrical graphite (pure carbon) rod of length 25 cm
ness z, into a low-pressure reservoir, p2, is and initial diameter of 2 cm is inserted into a flowing air stream at
1100 K and 2 atm total pressure. The flowing gas creates a
DA2 k( p11/2 # p21/2 ) stagnant gas boundary layer 5 mm thick around the external
JA2 ¼ surface of the rod. At this high temperature, the solid carbon
z
494 Chapter 26 Steady-State Molecular Diffusion

oxidizes to carbon dioxide, CO2, gas

Z =d
C(s) þ O2 (g) ! CO2 (g)
Oxygen CO and/or CO2
The oxidation reaction is limited by the molecular diffusion of
O2 through the stagnant gas film surrounding the surface of the Z =0
rod. Outside of the gas film, the bulk composition of the air Carbon
stream prevails.
a. Estimate the initial rate of CO2 production from the rod, Determine the rate of oxygen diffusion per hour through one
assuming that the surface reaction is diffusion limited. square meter of area if
b. How long will it take for the rod to disappear? The density a. only carbon monoxide, CO, is produced at the carbon
of solid graphite is 2:25 g/cm3 . surface;
26.24 Ammonia, NH3, is selectively removed from an b. only carbon dioxide, CO2, is produced at the carbon surface;
air–NH3 mixture by absorption into water. In this steady-
c. the following instantaneous reaction occurs at the carbon
state process, ammonia is transferred by molecular
surface:
diffusion through a stagnant gas layer 2 cm thick, and then
through a stagnant water layer 1 cm thick as shown in the 4C(s) þ 3O2 (g) ! 2CO(g) þ 2CO2 (g):
figure. The concentration of ammonia at the upper boundary
26.26 The data provided in Figure 26.5 are based on the
of the
diffusion of O2 into SiO2 formed from the oxidation of (100)
crystalline silicon at 10008C. Estimate the diffusion coefficient
Source for NH3 z = 0 cm of O2 in SiO2 formed from the oxidation of (111) crystalline
yA∞ = 0.0342 silicon at 10008C, using the following data provided by Hess9:
NA
Gas film
Measured SiO2 film thickness (mm)
z = 2 cm
Gas–liquid interface Time (h) (100) Si (111) Si
Liquid film
z = 3 cm
1 0.049 0.070
Sink for NH3 CA = 0
2 0.078 0.105
4 0.124 0.154
7 0.180 0.212
gas layer is 3.42 mol%, and the concentration at the lower
16 0.298 0.339
boundary of the water layer is essentially zero. The tempera-
ture of the system is 158C and the total pressure on the system
is 1 atm. The concentration of ammonia (species A) at the The maximum solubility of O2 in the SiO2 is 9:6 "
interface between the gas and the liquid phase is given by the 10#8 mol O2 =cm3 solid at 10008C and 1 atm O2 gas partial
following equilibrium data: pressure.
26.27 A 20-cm-long, cylindrical graphite (pure carbon) rod is
inserted into an oxidizing atmosphere at 1145 K and 1:013 "
PA(mmHg) 5.0 10.0 15.0 20.0 25.0 30.0 105 Pa pressure. The oxidizing process is limited by the diffu-
cA(mol/m3) 6.1 11.9 20.0 32.1 53.6 84.8 sion of oxygen counterflow to the carbon monoxide that is
formed on the cylindrical surface. Under the conditions of
the combustion process, the diffusivity of oxygen in the gas
mixture may be assumed to be 1:0 " 10#5 m2 /s.
a. Determine the moles of CO that are produced at the surface
Determine the flux of ammonia across both the gas and liquid
of the rod per second at the time when the diameter of the
films. At 158C, the diffusivity of ammonia in air is 0:215 cm2 /s,
rod is 1.0 cm and the oxygen concentration that is 1.0 cm
and the diffusivity of ammonia in liquid water is 1:77 "
radial distance from the rod is 40 mol%. Assume a steady-
10#5 cm2 /s.
state process.
26.25 In a combustion chamber, oxygen diffuses through air
b. What would be the composition of oxygen 1.0 cm from the
to the carbon surface where it reacts to make CO and/or CO2.
center of the rod.
The mole fraction of oxygen at z = 0 is 0.21. The reaction at the
surface may be assumed to be instantaneous. No reaction occurs
9
in the gas film. D. W. Hess, Chem. Eng. Educ., 24, 34 (1990).

26.28 Please refer to Example 4. Consider now that the
biofilm is a homogeneous sphere of 2.0 mm diameter. First,
verify that the concentration profile of phenol within the sphere
is
pffiffiffiffiffiffiffiffiffiffiffiffi
R sinh(r k1 DAB )
cA ¼ cAo pffiffiffiffiffiffiffiffiffiffiffiffi
r sinh(R k1 DAB )
for 0 ' r ' R. From this expression, derive an appropriate
expression for the flux NA at the surface of the sphere (r =
R). Then calculate NA using the values for cAo ; k1, and DAB given
in Example 4. Compare your results to the flux obtained in
Example 4 and discuss any differences.
Hint: Define a new lumped parameter y ¼ cA r to reduce the
second-order differential equation for cA (r) from a ‘‘variable
coefficients’’ form to a ‘‘constant coefficients’’ form.
26.29 The following problem illustrates the gas-phase diffu-
sion in the neighborhood of a flat catalytic surface. Component
Problems 495
A diffuses through a stagnant film containing only A and B.
Upon reaching the catalytic surface, it is instantaneously con-
verted into species B by the reaction A ! B. When B diffuses back
into the stagnant film, it begins to decompose by the first-order
reaction B ! A. The rate of formation of component A with the
film is equal to RA ¼ k1 yB , moles A produced/(time) (volume),
where yA is the concentration of B expressed in mole fraction.
Determine the rate at which A enters the gas film if this is a
steady-state process.
26.30 Reconsider Problem 26.29 and determine the concen-
tration profile of compound A in the stagnant film if in the film B
decomposes to form A and if A reacts to form B, both by first-
order reactions
k10
A ! B; RA ¼ k1 yB # k10 yA
k1
Simultaneously, A is instantaneously reacting to form B on the
flat catalytic surface.