PROBLEM 14.

1
KNOWN: Mixture of O2 and N2 with partial pressures in the ratio 0.21 to 0.79. FIND: Mass fraction of each species in the mixture. SCHEMATIC:

pO2 p N2
2

0.21 0.79

MO = 32 kg / kmol M N = 28 kg / kmol
2

ASSUMPTIONS: (1) Perfect gas behavior. ANALYSIS: From the definition of the mass fraction,

mi = i = i i
Hence, with

i =
Hence

pi pi Mp = = i i. R i T ( / M i ) T T

mi =

M i p i / T M i p i / T Mi x i . Mi x i

or, canceling terms and dividing numerator and denominator by the total pressure p,

mi =

With the mole fractions as

x O 2 = pO2 / p =

0.21 = 0.21 0.21 + 0.79

x N 2 = p N 2 / p = 0.79,
find the mass fractions as

mO 2 =

32 0.21 = 0.233 32 0.21 + 28 0.79

< <

m N 2 = 1 mO2 = 0.767.

PROBLEM 14.2
KNOWN: Mole fraction (or mass fraction) and molecular weight of each species in a mixture of n species. Equal mole fractions (or mass fractions) of O2, N2 and CO2 in a mixture. FIND: SCHEMATIC:

x O2 = x N 2 = x CO2 = 0.333
or

mO2 = m N 2 = mCO2 = 0.333

MCO = 44
2

MO = 32, M N = 28
2 2

ASSUMPTIONS: (1) Perfect gas behavior. ANALYSIS: (a) With

mi = i = i

pi / R i T p M / T = i i pi / R i T piMi / T

i i i and dividing numerator and denominator by the total pressure p,

mi =
Similarly,

Mi x i . Mi x i
i

<
( i / M i ) T ( i / Mi ) T
i

xi =

pi RT = i i = p i i R i T
i i

or, dividing numerator and denominator by the total density

xi =
(b) With

m i / Mi . m i / Mi
i

<

MO x O + M N x N + MCO x CO = 32 0.333 + 28 0.333 + 44 0.333 = 34.6 2 2 2 2 2 2

mO 2 = 0.31,
With

m N 2 = 0.27,

mCO2 = 0.42.

<

mO / MO + m N / M N + mCO / M = 0.333 / 32 + 0.333 / 28 + 0.333 / 44 2 2 2 2 2 CO 2

mO2 = 2.987 102.

find

x O 2 = 0.35,

x N 2 = 0.40,

x CO 2 = 0.25.

<

PROBLEM 14.3
KNOWN: Partial pressures and temperature for a mixture of CO2 and N2. FIND: Molar concentration, mass density, mole fraction and mass fraction of each species. SCHEMATIC:

A CO2 , M A = 44 kg / kmol B N 2 , M B = 28 kg / kmol

ASSUMPTIONS: (1) Perfect gas behavior. ANALYSIS: From the equation of state for an ideal gas,

Ci =

pi . T
1 bar 8.314 102 m3 bar / kmol K 298 K

Hence, with pA = pB,

CA = CB =

CA = CB = 0.040 kmol / m3.

With i = Mi Ci , it follows that

< < <

A = 44 kg / kmol 0.04 kmol / m3 = 1.78 kg / m3 B = 28 kg / kmol 0.04 kmol / m3 = 1.13 kg / m3.

Also, with

x i = Ci / i Ci
find

x A = x B = 0.04 / 0.08 = 0.5

and with find

<

m i = i / i

m A = 1.78 / (1.78 + 1.13) = 0.61

< <

m B = 1.13 / (1.78 + 1.13) = 0.39.

PROBLEM 14.4 KNOWN: He-Xe mixture containing 0.75 mole fraction of He at 300 K and 1 atm. FIND: Mass fraction of He and mixture mass density, molar concentration, and molecular
weight. Mass of coolant in 10 liters.

SCHEMATIC:

He-Xe mixture 0.75 mole fraction He T = 300 K, p = 1 atm

ASSUMPTIONS: Ideal gas mixture. PROPERTIES: M He = 4 kg / kmol , M Xe = 131.3 kg / kmol ANALYSIS: The molar concentration of the mixture can be found directly from the ideal gas law, in the form

C=

p 1 atm = = 0.0406 kmol / m3 2 m3 atm / kmol K 300 K T 8.205 10

<

The mass density of one component in a mixture can be related to the mole fraction by combining Eqs. 14.11 and 14.1 to yield

i = Mi x i C
For He this results in

He = 4 kg / kmol 0.75 0.0406 kmol / m3 = 0.1219 kg / m3

Then the total mass density can be found by summing the species mass densities,

= i = C Mi x i = 0.0406 [ 4 kg / kmol 0.75 + 131.3 kg / kmol 0.25]

i i

= 1.455 kg / m3
Thus the helium mass fraction is

<

0.1219 kg / m3 m He = He = = 0.0837 1.455 kg / m3

Finally, the molecular weight of the mixture can be found from

<
Continued

PROBLEM 14.4 (Cont.)

M=

1.455 kg / m3 = = 35.8 kg / kmol C 0.0406 kmol / m3

<

Finally, the mass corresponding to a 10 liter cooling system capacity would be M = V = 1.455 kg/m3 10 liters 10-3 m3/liter = 0.0146 kg

<

COMMENTS: (1) As you may recall from thermodynamics, the molar concentration of an ideal gas is a function only of pressure and temperature, independent of the species. (2) The mass fraction of helium is much less than its mole fraction because its molecular weight is so much less than that of xenon.

PROBLEM 14.5
KNOWN: Mass diffusion coefficients of two binary mixtures at a given temperature, 298 K. FIND: Mass diffusion coefficients at a different temperature, T = 350 K. ASSUMPTIONS: (a) Ideal gas behavior, (b) Mixtures at 1 atm total pressure. PROPERTIES: Table A-8, Ammonia-air binary mixture (298 K), DAB = 0.28 10 m /s; -4 2 Hydrogen-air binary mixture (298 K), DAB = 0.41 10 m /s. ANALYSIS: According to treatment of Section 14.1.4, assuming ideal gas behavior,
-4 2

D AB ~ T3/ 2
where T is in kelvin units. It follows then, that for

NH3 Air :

DAB ( 350 K ) = 0.28 104 m 2 / s ( 350 K / 298 K )

D AB ( 350 K ) = 0.36 104 m 2 / s

3/ 2

<
3/ 2

H 2 Air :

DAB ( 350 K ) = 0.41 104 m 2 / s ( 350 / 298 )

D AB ( 350 K ) = 0.52 104 m 2 / s

<

COMMENTS: Since the H2 molecule is smaller than the NH3 molecule, it follows that

D H 2 Air > D NH3 Air

as indeed the numerical data indicate.

PROBLEM 14.6
KNOWN: Pressure and temperature. Substance A and Substance B.

FIND: Plot of DAB versus MA for NH3, H2O, CO2, H2, O2, acetone, benzene and naphthalene in air.
ASSUMPTIONS: Ideal gas behavior. PROPERTIES: Substance A (T, p) NH3 (298 K, 1 atm) H2O (298 K, 1 atm) CO2 (298 K, 1 atm) H2 (298 K, 1 atm) O2 (298 K, 1 atm) Acetone (273 K, 1 atm) Benzene (298 K, 1 atm) Naphthalene (300 K, 1 atm) DAB* (m2/s) 0.28 10-4 0.26 10-4 0.16 10-4 0.41 10-4 0.21 10-4 0.11 10-4 0.88 10-5 0.62 10-5 MA (kg/kmol) 17.03 ** 18.02 ** 44.01 ** 2.016 ** 32.00 ** 58.08 *** 78.11**** 128.16 *****

* Table A.8 ** Table A.4 *** J.R. Howell and R.O. Buckius, Fundamentals of Engineering Thermodynamics, 2nd ed., McGraw-Hill, 1992. **** M.J. Moran and H.N. Shapiro, Fundamentals of Engineering Thermodynamics, 6th ed., John Wiley and Sons, Hoboken, 2008. ***** Problem 6.63

ANALYSIS: The mass diffusivity values must be corrected to account for the temperature and
pressure dependence. From Table A.8, DAB p 1T 3/ 2 and the corrected mass diffusivity for NH3 is

DABc = 0.28 104 m 2 /s (1atm /1.5atm ) ( 320K / 298K )

3/ 2

= 0.21 104 m 2 /s

Repeating the calculation for the other substances yields the following. Substance A NH3 H2O CO2 H2 O2 Acetone Benzene Naphthalene DABc (m2/s) 0.21 10-4 0.19 10-4 0.12 10-4 0.30 10-4 0.16 10-4 0.93 10-5 0.65 10-5 0.46 10-5

A plot of the corrected mass diffusivities versus molecular weight of Substance A follows. Continued...

PROBLEM 14.6 (Cont.)

35 30 DABc x 10^6 (m^2/s) 25 20 15 10 5 0 0 20 40 60 80 100 120 140

MWA (kg/kmol)

According to kinetic theory, the mass diffusivity decreases with increasing molecular weight. This behavior is readily evident in the plot, and therefore the kinetic theory is consistent with measured values.

<

COMMENTS: Small molecules can diffuse through the host medium more readily than large
molecules.

PROBLEM 14.7
KNOWN: The inner and outer surfaces of an iron cylinder of 100-mm length are exposed to a carburizing gas (mixtures of CO and CO2). Observed experimental data on the variation of the carbon composition (weight carbon, %) in the iron at 1000C as a function of radius. Carbon flow rate under steady-state conditions. FIND: (a) Beginning with Ficks law, show that d c / d ln r

c b gh is a constant if the diffusion

coefficient, DC-Fe, is a constant; sketch of the carbon mass density, c(r), as function of ln(r) for such a diffusion process; (b) Create a graph for the experimental data and determine whether DC-Fe for this diffusion process is constant, increases or decreases with increasing mass density; and (c) Using the experimental data, calculate and tabulate DC-Fe for selected carbon compositions over the range of the experiment. SCHEMATIC:

PROPERTIES: Iron (1000C). = 7730 kg/m .Experimental observations of carbon composition r (mm) Wt. C (%) 4.49 1.42 4.66 1.32 4.79 1.20 4.91 1.09 5.16 0.82 5.27 0.65 5.40 0.46 5.53 0.28

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional, radial diffusion in a stationary medium, and (3) Uniform total concentration. ANALYSIS: (a) For the one-dimensional, radial (cylindrical) coordinate system, Ficks law is

jA = D AB A r

d A dr

(1)

where Ar = 2rL. For steady-state conditions, jA is constant, and if DAB is constant, the product

d A = C1 dr

(2)

must be a constant. Using the differential relation dr/r = d (ln r), it follows that

d A = C1 d ln r

b g

(3)

so that on a ln(r) plot, A is a straight line. See the graph below for this behavior. Continued ...

PROBLEM 14.7 (Cont.)

(b) To determine whether DC-Fe is a constant for the experimental diffusion process, the data are represented on a ln(r) coordinate.

Wt. carbon distribution - experimental observations

1.6

1.4 Exp data 1.2

Wt Carbon (%)

0.8

0.6

0.4

0.2

0 1.45 1.5 1.55 1.6 ln (r, mm) 1.65 1.7 1.75

Since the plot is not linear, DC-Fe is not a constant. From the treatment of part (a), if DAB is not a constant, then

D AB

d A = C2 d ln r

b g

must be constant. We conclude that DC-Fe will be lower at the radial position where the gradient is higher. Hence, we expect DC-Fe to increase with increasing carbon content. (c) From a plot of Wt - %C vs. r (not shown), the mass fraction gradient is determined at three locations and Ficks law is used to calculate the diffusion coefficient,

jc = A r D C Fe
where the mass flow rate is

Wt % C r

jc = 3.6 103 kg / 100 h 3600 s / h = 1 108 kg / s

and = 7730 kg/m , density of iron. The results of this analysis yield, Wt - C (%) 1.32 0.955 0.37 r (mm) 4.66 5.04 5.47 Wt-C/r (%/mm) -0.679 -1.08 -1.385 DC-Fe 10
11 3 2

(m /s)

6.51 3.79 2.72

PROBLEM 14.8
KNOWN: Air is enclosed at uniform pressure in a vertical, cylindrical container whose top and bottom surfaces are maintained at different temperatures. FIND: (a) Conditions in air when bottom surface is colder than top surface, (b) Conditions when bottom surface is hotter than top surface. SCHEMATIC:

ASSUMPTIONS: (1) Uniform pressure, (2) Perfect gas behavior. ANALYSIS: (a) If T1 > T2, the axial temperature gradient (dT/dx) will result in an axial density gradient. However, since d/dx < 0 there will be no buoyancy driven, convective motion of the mixture. There will also be axial species density gradients, d O / dx and d N / dx. However, there is no

gradient associated with the mass fractions dmO / dx = 0, dm N / dx = 0 . Hence, from Ficks 2 2 law, Eq. 14.12, there is no mass transfer by diffusion.

(b) If T1 < T2 , d / dx > 0 and there may be a buoyancy driven, convective motion of the mixture. However, dm O / dx = 0 and dm N / dx = 0, and there is still no mass transfer. Hence, although
2 2

there is motion of each species with the convective motion of the mixture, there is no relative motion between species.
COMMENTS: The commonly used special case of Ficks law,

jA = DAB

d A dx

would be inappropriate for this problem since is not uniform. If applied, this special case indicates that mass transfer would occur, thereby providing an incorrect result.

PROBLEM 14.9 KNOWN: Dimensions of rubber stopper in medicine jar. Molar concentration of medicine
vapor at top and bottom surfaces. Mass diffusivity of medicine vapor in rubber.

FIND: Rate at which medicine vapor exits through the stopper. SCHEMATIC:
D2 = 20 mm CA,2 = 0

L = 20 mm CA,1 = 2 10-3 kmol/m3 x

D1 = 10 mm

ASSUMPTIONS: (1) Glass neck is impermeable to medicine vapor, thus there is negligible
mass loss out of slanted surface, (2) One-dimensional mass diffusion, (3) Steady state, (4) Constant properties, (5) No chemical reaction.

PROPERTIES: Medicine vapor-rubber (given): DAB = 0.2 10-9 m2/s. ANALYSIS: The analysis follows the alternative conduction analysis approach. For onedimensional diffusion in the x-direction, Ficks Law in molar form, Eq. 14.13, reduces to

J* = CD AB A

dx A dC = D AB A dx dx

(1)

where the total concentration, C , has been assumed constant. The transfer rate of species A through the entire stopper cross-section, N A , can be expressed as N A = J* Ac , where Ac is A the cross-sectional area. For steady-state, one-dimensional diffusion with no chemical reaction, the species transfer rate must be constant. We multiply Eq. (1) by Ac , separate variables, and integrate between the top and bottom of the stopper, as follows

N A = J* Ac = D ABAc A
NA

dCA dx
(2)

L dx x = D AB A2 dCA = D AB (CA1 CA2 ) = D ABCA1 0 Ac x A1

The cross-sectional area is given by

Ac = R 2 , where R = R1 + (R 2 R1)x / L
Continued

PROBLEM 14.9 (Cont.)

Thus dx = LdR/(R2 R1), and Eq. (2) becomes R dR L NA 2 = D ABCA1 R1 R 2 R 2 R1 NA 1 1 L = D ABCA1 R1 R 2 R 2 R1 Thus

NA = =

D ABCA1R1R 2 L 0.2 109 m2 / s 2 103 kmol / m3 0.005 m 0.01 m 0.02 m

N A = 3.14 1015 kmol / s

COMMENTS: (1) The assumption of constant concentration, C, is excellent because the

<

mixture of rubber and medicine vapor would be dominated by the rubber. (2) Using the properties of water for the medicine, we can estimate how much the liquid would be depleted per year. The molar loss in one year is 3.14 10-15 kmol/s 3.15 107 s/yr = 9.9 10-8 kmol/yr. If the molecular weight is 18 kg/kmol, the loss would be 1.8 10-6 kg/yr. If the liquid density is 1000 kg/m3, the volume loss would be 1.8 10-9 m3/yr. For a bottle cross-sectional area of 2 10-3 m2, the liquid level would drop by less than 1 m per year.

PROBLEM 14.10

KNOWN: Evaporation of liquid A into a column containing vapor A and B. Species B cannot
be absorbed in liquid A.

FIND: The relationship between the ratio of the molar-average velocity to the species velocity of
species A to the mole fraction of species A.

SCHEMATIC:

Binary gas mixture, A + B

NA,x

vx,B = 0

Liquid B

ASSUMPTIONS: (1) Steady, one-dimensional diffusion, (2) No chemical reactions. ANALYSIS: From Section 14.2.2, we know that N" = 0 . From Eq. 14.27, B,x
N " = C A v A,x and N " = C B v B,x = 0 or v B,x = 0 A,x B,x

(1) (2)

From Eq. 14.29,

v * = x A v A,x x

Therefore

v* x = xA v A,x

<

The relationship is shown in the graph below.

Ratio of molar-average to species velocity, vx*/vA,x 1

0.8

0.6

0.4

0.2

0 0 0.2 0.4 0.6 0.8 1

Mole Fraction of Species A, xA

Continued

PROBLEM 14.10 (Cont.)

COMMENTS: (1) When the mole fraction of Species A is small and Species B is not in
motion, the molar-average velocity is dominated by Species B and is negligible compared to the non-zero species velocity of A. In other words, the vapor in the column can be treated as a stationary medium since, although Species A is in motion, there is very little species A present. (2) When the mole fraction of Species A is large, there is very little Species B present, and the velocity of the mixture is dominated by the velocity of Species A. Hence, the velocity ratio approaches unity as mixture becomes dominated by Species A.

PROBLEM 14.11
KNOWN: Water in an open pan exposed to prescribed ambient conditions. FIND: Evaporation rate considering (a) diffusion only and (b) convective effects. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional diffusion, (3) Constant properties, (4) Uniform T and p, (5) Perfect gas behavior. PROPERTIES: Table A-8, Water vapor-air (T = 300 K, 1 atm), DAB = 0.26 10 m /s; Table A-6, 3 Water vapor (T = 300 K, 1 atm), psat = 0.03531 bar, vg = 39.13 m /kg. ANALYSIS: (a) The evaporation rate considering only diffusion follows from Eq. 14.32 simplified for a stationary medium. That is,
-4 2

N A,x = N A = D ABA A,x

dCA . dx
=

Recognizing that pA/pA,sat = CA/CA,sat, the rate is expressed as

N A,x = D ABA
N A,x = 0.26 10
4 2

CA, CA,s L
2

D ABA CA,sat (1 ) L
1
3

m / s ( / 4 )( 0.2 m ) 80 10
3

where CA,s = 1/ vg MA with M A = 18 kg / kmol.

39.13 m / kg 18 kg / kmol

(1 0.25 ) = 1.087 108 kmol / s

(b)The evaporation rate considering convective effects using Eq. 14.40 is

N A,x = N A = A,x

CDABA 1 x AL ln . L 1 x A,0

Using the perfect gas law, the total concentration of the mixture is C = p / T = 1.0133 bar / 8.314 102 m3 bar / kmol K 300K = 0.04063 kmol / m3

where p = 1 atm = 1.0133 bar. The mole fractions at x = 0 and x = L are

x A,0 =
Hence
N A,x =

p A,s p

0.03531 bar = 0.0348 1.0133 bar

3 4 2

x A,L = x A,0 = 0.0087.

0.04063 kmol / m 0.26 10 80 10

m / s ( / 4 )( 0.2 m )

ln

1 0.0087 1 0.0348

= 1.107 10

kmol / s.

<

COMMENTS: For this situation, the advective effect is very small but does tend to increase (by 1.5%) the evaporation rate as expected.

PROBLEM 14.12
KNOWN: Spherical droplet of liquid A and radius ro evaporating into stagnant gas B. FIND: Evaporation rate of species A in terms of pA,sat, partial pressure pA(r), the total pressure p and other pertinent parameters. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional, radial, species diffusion, (3) Constant properties, including total concentration, (4) Droplet and mixer air at uniform pressure and temperature, (5) Perfect gas behavior. ANALYSIS: From Eq. 14.32 for a radial spherical coordinate system, the evaporation rate of liquid A into a binary gas mixture A + B is

N A,r = DABA r
2

dCA CA + N A,r dr C

where Ar = 4r and NA,r = NA, a constant,

C N A 1 A C

2 dCA . = DAB 4 r dr p dp A T dr

From perfect gas behavior, CA = p A / T and C = p / T,

N A ( p p A ) = D AB 4 r 2

Separating variables, setting definite limits, and integrating

NA
find that

r dr pA,r dp A T 1 ro r 2 = p A,r p pA p 4 DAB o

N A = 4 ro D AB

p pA ( r ) p 1 ln T 1 ro / r p p A,o

<

where p A,o = p A ( ro ) = p A,sat , the saturation pressure of liquid A at temperature T.

COMMENTS: Compare the method of solution and result with the content of Section 14.2.2, Evaporation in a Column.

PROBLEM 14.13
KNOWN: Clean surface with pure steam has condensate rate of 0.020 kg/m s for the prescribed conditions. With the presence of stagnant air in the steam, the condensate surface drops from 28C to 24C and the condensate rate is halved. FIND: Partial pressure of air in the air-steam mixture as a function of distance from the condensate film. SCHEMATIC:
2

ASSUMPTIONS: (1) Steady-state conditions, (2) Constant properties including pressure in air-steam mixture, (3) Perfect gas behavior. PROPERTIES: Table A-6, Water vapor: psat (28C = 301 K) = 0.03767 bar; psat (24C = 297 K) = -4 2 0.02983 bar; Table A-8, Water-air (298 K, 1 bar): DAB = 0.26 10 m /s. ANALYSIS: The partial pressure distribution of the air as a function of distance y can be found from the species (A) rate expression, Eq. 14.40,

N = ( CDAB / y ) ln 1 x A,y / 1 x A,0 . A,y

)(

With C = p / T, x B,y = 1 x A,y and x B,0 = 1 x A,0, recognizing that xB = pB/p, find

T p B ( y ) = p B,0 exp N y A,y pDAB p B,0 = p p A,0 = psat ( 28C ) psat ( 24C ) = ( 0.03767 0.02983) bar = 0.00784 bar.
2 4 2 With N A,y = ( 0.020 / 2 ) kg / m s / 29 kg / kmol = 3.45 10 kmol / m s,

8.314 102 m3 bar / kmol K 299 K p B ( y ) = 0.0784 bar exp 3.45 104 kmol / m2 s y 0.03767 bar 6.902 104 m2 / s

p B ( y ) = 784 kPa exp ( 0.330y )

with pB in [kPa] and y in [mm], where T = 26C = 299 K, the average temperature of the air-steam -1 3/2 -4 2 3/2 -4 2 mixture, and DAB p T = 0.26 10 m /s (1/0.03767) (299/298) = 6.902 10 m /s. Selected values for the pressure are shown below and the distribution is shown above: y (mm) pB(y) (kPa) 0 784 5 151 10 29.0 15 5.6

COMMENTS: To minimize inert gas effects, the usual practice is to pass vapor over the surfaces so that the inerts are eventually collected near the outlet region of the condenser. Our estimate shows that the effective region to be swept is approximately 10 mm thick.

PROBLEM 14.14
KNOWN: Column containing liquid phase of water (A) evaporates into the air (B) flowing over the mouth of the column. FIND: Evaporation rate of water (kg/hm ) using the known value of the binary diffusion coefficient for the water vapor - air mixture. SCHEMATIC:
2

ASSUMPTIONS: (1) Steady-state, one-dimensional diffusion in the column, (2) Constant properties, (3) Uniform temperature and pressure throughout the column, (4) Water vapor exhibits ideal gas behavior, and (5) Negligible water vapor in the chamber air. PROPERTIES: Table A-6, water (T = 320 K): psat = 0.1053 bar; Table A-8, water vapor-air (0.25 -1 3/2 atm, 320 K): Since DAB ~ p T find

D AB = 0.26 104 m2 / s 1.00 / 0.25 320 / 298 3/ 2 = 1157 104 m2 / s .

ANALYSIS: From Eq. 14.40, the molar flow rate per unit area is

gb

N A,x =

C DAB 1 x A,L ln L 1 x A,0

where C is the mixture concentration determined from the ideal gas law as

C=

where R = 8.205 102 m3 atm/kmol K. The mole fractions at x = 0 and x = L are x A,L = 0 (no water vapor in air above column)

p 0.25 atm = = 0.009397 kmol/m3 2 m3 atm/kmol K 320 K RT 8.205 10

x A,0 = p A / p = 01053 / 0.25 = 0.4212 .

where pA is the saturation pressure for water at T = 320 K. Substituting numerical values 1 0 0.009397 kmol / m3 1157 104 m2 / s . N A,x = ln

0.150 m

b1 0.4212g

b g

N A,x = 3.964 106 kmol / m2 s

or, on a mass basis, m = N M A A,x A,x

mA,x = 3.964 106 kmol / m2 s 3600 s / h 18 kg / kmol mA,x = 0.257 kg / m2 h

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PROBLEM 14.15
KNOWN: Molar concentrations of helium at the inner and outer surfaces of a plastic membrane. Diffusion coefficient and membrane thickness. FIND: Molar diffusion flux. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional diffusion in a plane wall, (3) Stationary medium, (4) Uniform C = CA + CB. ANALYSIS: The molar flux may be obtained from Eq. 14.54,

N = A,x

D AB 109 m 2 / s CA,1 CA,2 = ( 0.02 0.005 ) kmol / m3 L 0.001 m

N = 1.5 108 kmol / s m 2 . A,x

COMMENTS: The mass flux is

<

n = M A N = 4 kg / kmol 1.5 108 kmol / s m 2 = 6 108 kg / s m 2 . A,x A,x

PROBLEM 14.16
KNOWN: Three-dimensional diffusion of species A in a stationary medium with chemical reactions. FIND: Derive molar form of diffusion equation. SCHEMATIC:

ASSUMPTIONS: (1) Uniform total molar concentration, (2) Stationary medium. ANALYSIS: The derivation parallels that of Section 14.4.2, except that Eq. 14.43 is applied on a molar basis. That is,

& & N A,x + N A,y + N A,z + N A,g N A,x + dx N A,y + dy N A,z + dz = N A,st .
With

N A,x + dx = N A,x +

N A,x x

dx,

N A,y + dy = ....

N A,x = D AB ( dydz )

CA , x

N A,y = ....

& & N A,g = N A ( dxdydz ) ,

It follows that

C & N A,st = A dxdydz t CA & CA . + DAB + NA = z t z

CA CA DAB + D AB x x y y

<

COMMENTS: If DAB is constant, the foregoing result reduces to Eq. 14.48b.

PROBLEM 14.17
KNOWN: Gas (A) diffuses through a cylindrical tube wall (B) and experiences chemical reactions at & a volumetric rate, N A . FIND: Differential equation which governs molar concentration of gas in plastic. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional radial diffusion, (2) Uniform total molar concentration, (3) Stationary medium. ANALYSIS: Dividing the species conservation requirement, Eq. 14.43, by the molecular weight, MA, and applying it to a differential control volume of unit length normal to the page,

& & N A,r + N A,g N A,r + dr = N A,st

where

N A,r = ( 2 r 1) N = 2 rD AB A,r N A,r + dr = N A,r + N A,r r dr

CA r

& & N A,g = N A ( 2 r dr 1)

Hence

CA ( 2 rdr 1) . & N A,st = t

& N A ( 2 rdr ) + 2 D AB
or

CA r r r

CA dr = 2 rdr t

DAB CA r r r r

CA & . NA = t

<

COMMENTS: (1) The minus sign in the generation term is necessitated by the fact that the reactions deplete the concentration of species A.

& (2) From knowledge of N A ( r, t ) , the foregoing equation could be solved for CA (r,t).

(3) Note the agreement between the above result and the one-dimensional form of Eq. 14.49 for uniform C.

PROBLEM 14.18
KNOWN: One-dimensional, radial diffusion of species A in a stationary, spherical medium with chemical reactions. FIND: Derive appropriate form of diffusion equation. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional, radial diffusion, (2) Uniform total molar concentration, (3) Stationary medium. ANALYSIS: Dividing the species conservation requirement, Eq. 14.43, by the molecular weight, MA, and applying it to the differential control volume, it follows that

& & N A,r + N A,g N A,r + dr = N A,st

where

N A,r = DAB 4 r 2 N A,r + dr = N A,r +

CA r r dr
CA 4 r 2dr . & N A,st = t

N A,r

& & N A,g = N A 4 r 2dr ,

Hence

C & N A 4 r 2dr + 4 D ABr 2 A r r

or

2 CA dr dr = 4 r t

2 CA DABr r r 2 r 1

CA & . + NA = t

<

COMMENTS: Equation 14.50 reduces to the foregoing result if C is independent of r and variations in and are negligible.

PROBLEM 14.19
KNOWN: Pressure and temperature of hydrogen stored in a spherical steel tank of prescribed diameter and thickness. FIND: (a) Initial rate of hydrogen mass loss from the tank, (b) Initial rate of pressure drop in the tank. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional species diffusion in a stationary medium, (2) Uniform total molar concentration, C, (3) No chemical reactions. ANALYSIS: (a) From Table 14.1

N A,r =

CA,o CA,L R m,dif

(1/ 4 DAB ) (1/ ri 1/ ro )

CA,o

N A,r =
or

4 0.3 1012 m 2 / s 1.5 kmol / m3

(1/ 0.05 m 1/ 0.052 m )

= 7.35 1012 kmol / s

n A,r = M A N A,r = 2 kg / kmol 7.35 1012 kmol / s = 14.7 1012 kg / s.

(b) Applying a species balance to a control volume about the hydrogen,

<

& & M A,st = M A,out = n A,r

d ( A V ) D3 d A D3 dp A D3M A dp A & M A,st = = = = dt 6 dt 6R A T dt 6T dt

Hence

6 0.08314 m3 bar / kmol K ( 300 K ) dp A 6T = n A,r = 14.7 1012 kg / s 3M 3 2 kg / kmol dt D A (0.1m)

dp A = 3.50 107 bar / s. dt

2

<

COMMENTS: If the spherical shell is appoximated as a plane wall, Na,x = DAB(CA,o) D /L = 7.07 -12 10 kmol/s. This result is 4% lower than that associated with the spherical shell calculation.

PROBLEM 14.20
KNOWN: Temperature of atmospheric air and water. Percentage by volume of oxygen in the air. FIND: (a) Mole and mass fractions of water at the air and water sides of the interface, (b) Mole and mass fractions of oxygen in the air and water. SCHEMATIC:

Mw = 18, Mair = 29
ASSUMPTIONS: (1) Perfect gas behavior for air and water vapor, (2) Thermodynamic equilibrium at liquid/vapor interface, (3) Dilute concentration of oxygen and other gases in water, (4) Molecular weight of air is independent of vapor concentration. PROPERTIES: Table A-6, Saturated water (T = 290 K): pvap = 0.01917 bars. Table A-9, O2/water, H = 37,600 bars. ANALYSIS: (a) Assuming ideal gas behavior, pw,vap = (Nw,vap/V) T and p = (N/V) T, in which case

x w,vap = p w,vap / pair = ( 0.01917 /1.0133) = 0.0189

With mw,vap = (w,vap/air) = (Cw,vap M w/Cair M air) = xw,vap ( M w/ M air). Hence, mw,vap = 0.0189 (18/29) = 0.0120 Assuming negligible gas phase concentrations in the liquid,
xw,liq = mw,liq = 1

< < < < < <

(b) Since the partial volume of a gaseous species is proportional to the number of moles of the species, its mole fraction is equivalent to its volume fraction. Hence on the air side of the interface

x O 2,air = 0.205
mO
2,air

= xO

2,air

(MO2 / Mair ) = 0.205 (32 / 29) = 0.226

The mole fraction of O2 in the water is

x O 2,liq = pO2,air / H = 0.208 bars / 37, 600 bars = 5.53 106

where pO = x O2,air patm = 0.205 1.0133 bars = 0.208 bars. The mass fraction of O2 in the 2,air water is mO = xO M0 / M w = 5.53 106 ( 32 /18 ) = 9.83 106 2,liq 2,liq 2

<

COMMENTS: There is a large discontinuity in the oxygen content between the air and water sides of the interface. Despite the low concentration of oxygen in the water, it is sufficient to support the life of aquatic organisms.

PROBLEM 14.21
KNOWN: Pressure and temperature of hydrogen inside and outside of a circular tube. Diffusivity and solubility of hydrogen in tube wall of prescribed thickness and diameter. FIND: Rate of hydrogen transfer through tube per unit length. SCHEMATIC:

ASSUMPTIONS: (1) Steady diffusion in radial direction, (2) Uniform total molar concentration in wall, (3) No chemical reactions, (4) Stationary medium. ANALYSIS: The mass transfer rate per unit tube length is

N = A,r

ln ( r2 / r1 ) / 2 DAB

CA ( r1 ) CA ( r2 )

where from Eq. 14.62, CA,s = Spa,

CA ( r1 ) = Sp A,1 = 160 kmol / m3 atm 2 atm = 320 kmol / m3

CA ( r2 ) = Sp A,2 = 160 kmol / m3 atm 0.1 atm = 16 kmol / m3.

Hence,

N = A,r

( 320 16 ) kmol / m3 304 kmol / m3 = ln ( 20.5 / 20 ) / 2 1.8 1011 m 2 / s 2.18 108 s / m 2

N = 1.39 106 kmol / s m. A,r

COMMENTS: If the wall were assumed to be plane,

<
= 2.21 108 s / m 2

R m,dif =

L DAB D

5 104 m 1.8 1011 m 2 / s ( 0.04 m )

8 2

which is close to the value of 2.18 10 s/m for the cylindrical wall.

PROBLEM 14.22
KNOWN: Oxygen pressures on opposite sides of a rubber membrane. FIND: (a) Molar diffusion flux of O2, (b) Molar concentrations of O2 outside the rubber. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional, steady-state conditions, (2) Stationary medium of uniform total molar concentration, C = CA + CB, (3) Perfect gas behavior. PROPERTIES: Table A-8, Oxygen-rubber (298 K): DAB = 0.21 10 m /s; Table A-10, Oxygen-3 3 rubber (298 K): S = 3.12 10 kmol/m bar. ANALYSIS: (a) For the assumed conditions
-9 2

N = J = DAB A,x A,x

From Eq. 14.62,

C ( 0 ) CA ( L ) dCA = D AB A . dx L

CA ( 0 ) = Sp A,1 = 6.24 103 kmol / m3

CA ( L ) = Sp A,2 = 3.12 103 kmol / m3.

Hence

( 6.24 103 3.12 103 ) kmol / m3 N = 0.21 109 m 2 / s A,x

0.0005 m
N = 1.31109 kmol / s m 2 . A,x

<

(b) From the perfect gas law

CA,1 =

p A,1 T

2 bar

0.08314 m3 bar / kmol K 298 K

= 0.0807 kmol / m3

< <

CA,2 = 0.5CA,1 = 0.0404 kmol / m3.

COMMENTS: Recognize that the molar concentrations outside the membrane differ from those within the membrane; that is, CA,1 CA(0) and CA,2 CA(L).

PROBLEM 14.23
KNOWN: Water vapor is transferred through dry wall by diffusion. FIND: The mass diffusion rate through a 0.01 3 5 m wall. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional species diffusion, (3) Homogeneous medium, (4) Constant properties, (5) Uniform total molar concentration, (6) Stationary medium with xA << 1, (7) Negligible condensation in the dry wall. ANALYSIS: From Eq. 14.42,

N = CD AB A,x
From Eq. 14.62

CA,1 CA,2 dx A dC = DAB A = DAB . dx dx L

CA,1 = Sp A,1 = 0.15 103 kmol / m3

CA,2 = Sp A,2 = 0 kmol / m3.

Hence

N = 109 m 2 / s A
Therefore

0.15 103 kmol / m3 = 0.15 1010 kmol / s m 2 . 0.01 m

n A = M A ( A N ) = 18 kg / kmol 15 m 2 0.15 1010 kmol / s m 2 A

or

n A = 4.05 109 kg / s.

<

PROBLEM 14.24
KNOWN: Pressure and temperature of helium in a glass cylinder of 100 mm inside diameter and 5 mm thickness. FIND: Mass rate of helium loss per unit length. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional radial diffusion through cylinder wall, (3) Negligible end losses, (4) Stationary medium, (5) Uniform total molar concentration, (6) Negligible helium concentration outside cylinder. PROPERTIES: Table A-8, He-SiO2 (298 K): DAB 0.4 10 -3 3 K): S 0.45 10 kmol/m bar. ANALYSIS: From Table 14.1,
-13

m /s; Table A-10, He-SiO2 (298

N = A,r

ln ( r2 / r1 ) / 2 DAB

CA,S1 CA,S2

where, from Eq. 14.62, CA,S = SpA. Hence

CA,S1 = Sp A,1 = 0.45 103 kmol / m3 bar 4 bar = 1.8 103 kmol / m3

CA,S2 = SPA,2 = 0.
Hence

N = A,r

1.8 103 kmol / m3 ln ( 0.055 / 0.050 ) / 2 0.4 1013 m 2 / s

N = 4.75 1015 kmol / s m. A,r

The mass loss is then

n = M A N = 4 kg / kmol 4.75 1015 kmol / s m A,r A,r

n = 1.90 1014 kg / s m. A,r

<

PROBLEM 14.25
KNOWN: Temperature and pressure of helium stored in a spherical pyrex container of prescribed diameter and wall thickness. FIND: Mass rate of helium loss. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) Helium loss by one-dimensional diffusion in radial direction through the pyrex, (3) C = CA + CB is independent of r, and xA << 1, (4) Stationary medium. PROPERTIES: Table A-8, He-SiO2 (293 K): DAB = 0.4 10 -3 3 K): S = 0.45 10 kmol/m bar.
-13

m /s; Table A-10, He-SiO2 (293

ANALYSIS: From Table 14.1, the molar diffusion rate may be expressed as

N A,r =
where

CA,S1 CA,S2 R m,dif

R m,dif =
with

1 1 1 1 1 1 12 3 = = 1.81 10 s / m 4 DAB r1 r2 4 0.4 1013 m 2 / s 0.1m 0.11m

CA,S1 = Sp A = 0.45 103 kmol / m3 bar 4 bar = 1.80 103 kmol / m3

CA,S2 = 0
find

N A,r =
Hence

1.80 103 kmol / m3 1.811012 s / m3

= 1015 kmol / s.

n A,r = M A N A,r = 4 kg / mol 1015 kmol / s = 4 1015 kg / s.

2 = 0.01 m and A 4 rm = 0.139 m 2 . From Table 14.1,

<

COMMENTS: Since r1 r2, the spherical shell could have been approximated as a plane wall with L

R m,dif =

L DABA

0.01 m

0.4 1013 m 2 / s 0.137 m 2

)(

= 1.8 1012 s / m3 and

N A,x =

CA,S1 CA,S2 R m,dif

1.80 103 kmol / m3 1.8 1012 s / m3

= 1015 kmol / s.

Hence the approximation is excellent.

PROBLEM 14.26

KNOWN: Thickness of polymer packaging material, temperature and humidity conditions in

gas on either side of the material.

FIND: (a) Solubility of the packaging material, (b) Total water vapor transfer rate for a material
that has 10% of the diffusivity of the material in Example 14.3, (c) Total water vapor transfer rate for a material that has 10% the solubility of the material in Example 14.3, (d) Total water vapor transfer rate after coating the exterior surface with a thin film to reduce its solubility by a factor of 9, leaving the interior surface untreated.

SCHEMATIC:

Polymer material

Exterior T = 295 K 1 = 0.9

pA(x = 0) CA,s(x = 0) = C A,s1

pA(x = L) Interior CA,s(x = L) = C A,s2 T = 295 K 2 = 0.1

Surface 2 Surface 1 x L

ASSUMPTIONS: (1) Constant properties and steady-state conditions, (2) Stationary medium. PROPERTIES: Table A.6, water (T = 295 K): psat = 0.02617 bars. ANALYSIS:
(a) For the exterior Surface 1, p A (x = 0) = 1pA,sat = 0.9 0.02617 bars = 0.02355 bars. For the

interior Surface 2, p A (x = L) = 2 p A,sat = 0.1 0.02617 bars = 0.002617 bars. From Example 14.3, CA,s2 = CA,s (x = L) = 0.5 10-3 kmol/m3 so that S=

0.5 103 kmol / m3 -3 kmol 0.002617 bar = 191 10 p A (x = L) m3bar

C A,s2
=

<

(b) From Example 14.3, N A,x,p = 0.32 1015 kmol/s . If the diffusivity is reduced to 10% of its
original value,
N A,x = 0.1N A,x,p = 0.1 0.32 1015 kmol / s = 0.32 1016 kmol / s

<
Continued

PROBLEM 14.26 (Cont.)

(c) If the solubility is reduced to 10% of its original value at both surfaces, CA,s1 = 0.5 104 kmol / m3 and CA,s2 = 4.5 104 kmol / m3 . Hence, N A,x = 0.1N A,x,p = 0.32 1016 kmol/s

<

(d) If the solubility of exterior Surface 1 is reduced by a factor of 9, CA,s1 = CA,s1,p/9 = 4.5 10-3 kmol/m3/9 = 0.5 10-3 kmol/m3 = CA,s2. Hence, CA,s1 CA,s2 = 0 and NA,x = 0

<

COMMENT: (1) The same value of the solubility may be found in part (a) by considering conditions at Surface 1. (2) By manipulating the solubilities of the surfaces independently, one may eliminate concentration gradients in the material and, in turn, completely eliminate water vapor transfer by diffusion. Materials that have properties designed to change through their thickness in order to promote desired behavior are known as functionally-graded materials.

PROBLEM 14.27

KNOWN: Dimensions of sphere containing a pharmaceutical product. Mass loss of sphere over
specified time period, mass diffusivity, external conditions.

FIND: The value of the partition coefficient, K. SCHEMATIC:

Do = 5.1 mm Di = 5 mm M = 8.3 mg t = 1 week p = 1250 kg/m3 p,1 p,2 p, = 0

r Polymer material DAB = 0.2 10-11 m2/s

ASSUMPTIONS: (1) Constant properties and steady-state conditions, (2) Stationary medium. PROPERTIES: Pharmaceutical product (given): p = 1250 kg/m3, DAB = 0.2 10-11 m2/s, ANALYSIS: By the definition of the partition coefficient provided in the problem statement,
p,1 = K p and p,2 = K p, . The mass transfer rate through the polymer is found using the onedimensional species diffusion resistance approach
n p,r = p,1 p,2 R m,dif = K p 1 1 1 4D AB r1 r2 = M t

Hence,

K=

M t p

1 1 1 4 D AB r1 r2

8.2 106 kg 1 2 2 3 11 2 3 3 7 days 24 h/day 3600 s/h 1250 kg/m 4 0.2 10 m /s 5 10 m 5.1 10 m

= 0.0034

<

PROBLEM 14.28

KNOWN: Dimensions of N =100 closed-end palladium tubes. Hydrogen (H2) pressures and temperature on either side of tube wall. Mass diffusivity of atomic hydrogen (H) through the palladium, and Sieverts constant. FIND: Hourly production rate of pure hydrogen (H2). SCHEMATIC:
L = 80 mm

NH

t = 75 m

Pure H2 T = 600 K, P = 6 bar CH,i

Di = 1.6 mm

CH,o Impure hydrogen, H2 T = 600 K, P = 15 bar, xH2 = 0.85

N = 100 tubes

ASSUMPTIONS: (1) Constant properties and steady-state conditions, (2) Stationary medium. PROPERTIES: Hydrogen (H) in palladium, given: DAB = 7 10-9 m2/s. ANALYSIS: The concentration of atomic hydrogen (H) on the outer and inner surfaces of the
tube are

C H,o = 1.4 and C H,i = 1.4

kmol (0.85 15 bar)1/2 = 5.00 kmol/m3 3 1/2 m bar kmol (6 bar)1/2 = 3.43 kmol/m3 3 1/2 m bar

The one-dimensional species diffusion resistances for the wall and end of one tube are
3 6 3 ln(r2 / r1 ) ln (0.8 10 m + 75 10 m) / 0.8 10 m = 25.5106 s/m3 = = 2LD AB 2 80 10-3 m 7 10-9 m 2 /s

R m,dif ,w

and
R m,dif ,e = t D ABA c = 75 106 m = 5.33 109 s/m3 7 10-9 m 2 /s (0.8 10-3 m)2

The molar transfer rate of atomic hydrogen (H) in one tube is therefore

Continued

PROBLEM 14.28 (Cont.)

(5.00 3.43) kmol m3
s 25.5 106 m3

NH =

(5.00 3.43) kmol m3

s 5.33 109 m3

= 61.9 109

kmol s

The molar transfer rate of molecular hydrogen (H2) is therefore NH2 = 0.5NH = 30.95 kmol/s The total production rate, NH2,t, in kg/h is NH2,t = NH2 MH2 N t = 30.95 kmol/s 2kg/kmol 3600 s/h 100 tubes = 0.022 kg/h

<

Comments: (1) The concentrations of hydrogen (H2) in the gas streams are 0.25 kmol/m3 and
0.12 kmol/m3, respectively. (2) Palladium and other nanostructured materials, such as carbon nanotubes, can store very high concentrations of hydrogen within their atomic matrix.

PROBLEM 14.29
KNOWN: Conditions of the exhaust gas passing over a catalytic surface for the removal of NO. FIND: (a) Mole fraction of NO at the catalytic surface, (b) NO removal rate. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional species diffusion through the film, (3) Effects of bulk motion on NO transfer in the film are negligible (stationary medium), (4) No homogeneous reactions of NO within the film, (5) Constant properties, including the total molar concentration, C, throughout the film. ANALYSIS: Subject to the above assumptions, the transfer of species A (NO) is governed by diffusion in a stationary medium, and the desired results are obtained from Eqs. 14.69 and 14.70. Hence

x A,s x A,L
Also

1 1 + ( Lk1 / D AB )

x A,s =

0.15 1 + 0.001 m 0.05 m / s 104 m 2 / s

= 0.10.

<

N = A,s

1 + ( Lk1 / D AB )

k1Cx A,L

where, from the equation of state for a perfect gas,

C=
Hence

p 1.2 bar = = 0.0187 kmol / m3. T 8.314 102 m3 bar / kmol K 773 K 0.05 m / s 0.0187 kmol / m3 0.15 1 + 0.001 m 0.05 m / s 104 m 2 / s = 9.35 105 kmol / s m 2

N = A,s
or

n = M A N = 30 kg / kmol 9.35 105 kmol / s m 2 = 2.80 103 kg / s m 2 . A,S A,S

The molar rate of NO removal for the entire surface is then

N A,s = N A = 9.35 105 kmol / s m 2 0.02 m 2 = 1.87 106 kmol / s A,s

or

n A,S = 5.61 105 kg / s.

<

COMMENTS: Because bulk motion is likely to contribute significantly to NO transfer within the film, the above results should be viewed as a first approximation.

PROBLEM 14.30
KNOWN: Radius of coal pellets burning in oxygen atmosphere of prescribed pressure and temperature. FIND: Oxygen molar consumption rate. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional diffusion in r, (2) Steady-state conditions, (3) Constant properties, (4) Perfect gas behavior, (5) Uniform C and T, (6) Stationary medium. ANALYSIS: From Equation 14.57,

d 2 dCA r dr dr

=0 or CA = C1 / r + C2 .

dCA / dr = C1 / r 2
CA ( ) = C C2 = C

The boundary conditions at r and r = ro are, respectively,

dx dC & N = N ( ro ) = CD AB A = D AB A A A dr r dr r o o
Hence

2 k1 ( C1 / ro + C ) = DABC1 / ro
2 k1 ( C1 / ro ) + DAB C1 / ro = k1C The oxygen molar consumption rate is

or

C1 =

k1C ( k1 / ro ) +

2 D AB / ro

N ( ro ) = D AB A
where

C=

p = = 8.405 103 kmol / m3. 2 m3 atm / kmol K 1450 K T 8.205 10

dCA k1C = D AB dr r k1ro + DAB o 1 atm

Hence,

N ( ro ) = 1.71 104 m 2 / s A

0.1 m / s 8.405 103 kmol / m3

104 + 1.71104 m 2 / s
2

= 5.30 104 kmol / s m 2

2 N A ( ro ) = 4 ro N ( ro ) = 4 ( 0.001 m ) 5.30 104 kmol / s m 2 A

N A ( ro ) = 6.66 109 kmol / s.

<

COMMENTS: The O2 consumption rate would increase with increasing k1 and approach a limiting finite value as k1 approaches infinity.

PROBLEM 14.31
KNOWN: Pore geometry in a catalytic reactor. Concentration of reacting species at pore opening and order of catalytic reaction. FIND: (a) Differential equation which determines concentration of reacting species, (b) Distribution of reacting species concentration along the pore. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional diffusion in x direction, (3) Stationary medium, (4) Uniform total molar concentration, (5) Stationary medium. ANALYSIS: (a) Apply the species conservation requirement to the differential control volume, N A,x k1CA ( D ) dx N A,x + dx = 0, where

N A,x + dx = N A,x + dN A,x / dx dx

and from Ficks law

dx N A,x = CD AB A dx
Hence

2 D2 dC D D AB A . = 4 dx 4

dN A D2 d 2C A dx k1CA ( D ) dx = DAB k1CA ( D ) dx = 0 dx 4 dx 2 4 k1 CA = 0. DD AB

d 2C A dx 2

<

(b) A solution to the above equation is readily obtained by recognizing that it is of exactly the same form as the energy equation for an extended surface of uniform cross section. Hence for boundary conditions of the form

CA ( 0 ) = CA,0 ,

D AB ( dCA / dx ) x = L = k1CA ( L )

the solution must be analogous to that obtained for a fin with a convection tip condition. With the analogous quantities 1/ 2 1/ 2 CA T T , m ( 4 k1 / DD AB ) ( 4h / Dk )

D AB k,
the solution is, by analogy to Eq. 3.75

k1 h

CA ( x ) =

cosh m ( L x ) + ( k1 / mD AB ) sinh m ( L x ) . cosh mL + ( k1 / mD AB ) sinh mL

2

<

COMMENTS: The total pore reaction rate is DAB(D /4) (dCA/dx)x=0, which can be inferred by applying the analogy to Eq. 3.76.

PROBLEM 14.32
KNOWN: Pressure, temperature and mole fraction of CO in auto exhaust. Diffusion coefficient for CO in gas mixture. Film thickness and reaction rate coefficient for catalytic surface. FIND: (a) Mole fraction of CO at catalytic surface and CO removal rate, (b) Effect of reaction rate coefficient on removal rate. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state, (2) One-dimensional species diffusion in film, (3) Negligible effect of advection in film (stationary medium), (4) Constant total molar concentration and diffusion coefficient in film. ANALYSIS: From Eq. (14.69) the surface molar concentration is

x A ( 0) =

1 + ( Lk1 / DAB )

x A,L

1 + 0.01m 0.005 m / s /104 m 2 / s

-2 3

0.0012

= 0.0008
3

<

With C = p/RT = 1.2 bar/(8.314 10 m bar/kmolK 773 K) = 0.0187 kmol/m , Eq. (14.70) yields a CO molar flux, and hence a CO removal rate, of

N = N ( 0 ) = A,s A N = A,s

1 + ( Lk1 / DAB )

k1C x A,L

0.005 m / s 0.0187 kmol / m3 0.0012 1 + 0.01m 0.005 m / s /104 m 2 / s

= 7.48 108 kmol / s m 2

<

If the process is diffusion limited, Lk1 / D AB >> 1 and

N = A,s C D AB x A,L L
=

0.0187 kmol / m3 104 m 2 / s 0.0012 0.01m

= 2.24 107 kmol / s m 2

<

COMMENTS: If the process is reaction limited, N 0 as k1 0. A,s

PROBLEM 14.33 KNOWN: Mass flow rate of gas containing palladium (species A), which flows through a tube
and deposits into pores of tube wall. Inlet mass concentration of palladium. Mass transfer coefficient between gas and tube surface. Deposition rate is proportional to mass concentration of palladium at tube surface.

FIND: (a) Expression for variation of mean species density of palladium with x. Expression for
local deposition rate for tube of diameter D. (b) Ratio of deposition rates at x = L and x = 0.

SCHEMATIC: D Gas & m , A,m,i A,m, hm x=0 x=L

n = k1 A,s A,s

ASSUMPTIONS: (1) Steady state, (2) Constant properties, (3) Constant mass flow rate, (4) Negligible leakage of gas through porous walls. ANALYSIS: (a) Section 8.9 develops the variation of mean species density, A,m, for the case in
which the surface species concentration, A,s, is uniform. Here, however, the surface concentration will vary as the mean species density decreases with x. Under steady-state conditions, the mass flux of palladium reaching the surface must equal the mass flux of palladium depositing into the pores. Referring to Equation 8.82, where n is the mass flux from the A,s

surface,

n = h m ( A,s A,m ) = k1 A,s A,s

Solving for the surface concentration yields A,s = hmA,m/(hm + k1). Then substituting this into either expression for n yields A,s

n = U m A,m , A,s

1 U m = 1/ h m + 1/ k1

Comparing this result with Equation 8.82, we see that they are analogous if we replace h m with Um and A,s with 0. Applying the same analogy to Equation 8.86, the distribution of the mean species density is

A,m (x)

U P = exp m x & m A,m,i

(1)

<

where P is the perimeter, P = D. Note that we could have found this same result by expressing mass species conservation for species A. Noting that the rate at which species A is carried & downstream by the flow is m A,m / , and assuming to be constant, we have Continued

PROBLEM 14.33 (Cont.)

& m d A,m = n P = U m P A,m A,s dx
Integrating with respect to x and applying the inlet condition yields the same result as Equation (1). The local deposition rate is

x U P n = U m A,m = U m A,m,i exp m x = U m A,m,i exp B (2) A,s & m L

<

& where B = UmPL/ m .

(b) The ratio of deposition rates at x = L and x = 0 is

ratio of deposition rates = exp ( B)

<

COMMENT: From Eq. (2), the deposition rate decreases exponentially with distance x. Therefore, as the tube length increases, the deposit thickness at the outlet end will become thinner, and the variation in deposit thickness between the inlet and outlet will increase.

PROBLEM 14.34
KNOWN: Radius of a spherical organism and molar concentration of oxygen at surface. Diffusion and reaction rate coefficients. FIND: (a) Radial distribution of O2 concentration, (b) Rate of O2 consumption, (c) Molar concentration at r = 0. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state, one-dimensional diffusion, (2) Stationary medium, (3) Uniform total molar concentration, (4) Constant properties (k0, DAB). ANALYSIS: (a) For the prescribed conditions and assumptions, Eq. (14.50) reduces to

DAB d 2 d CA r dr r 2 dr

k0 = 0

r2

k r3 d CA = 0 + C1 dr 3D AB k 0 r 2 C1 + C2 6 D AB r

CA =

With the requirement that CA(r) remain finite at r = 0, C1 = 0. With CA(ro) = CA,o

C2 = CA,o

2 k 0 ro 6 DAB

2 CA = CA,o ( k 0 / 6 D AB ) ro r 2

<

Because CA cannot be less than zero at any location within the organism, the right-hand side of the foregoing equation must always exceed zero, thereby placing limits on the value of CA,o. The smallest possible value of CA,o is determined from the requirement that CA(0) 0, in which case 2 CA,o k 0 ro / 6 DAB

<

(b) Since oxygen consumption occurs at a uniform volumetric rate of k0, the total respiration rate is & R = k 0 , or
3 & R = ( 4 / 3) ro k 0 Continued

<

PROBLEM 14.34 (Cont.)

(c) With r = 0, 2 CA ( 0 ) = CA,o k 0 ro / 6 D AB

CA ( 0 ) = 5 105 kmol / m3 1.2 104 kmol / s m3 104 m

CA ( 0 ) = 3 105 kmol / m3

/ 6 108 m 2 / s

<

COMMENTS: (1) The minimum value of CA,o for which a physically realistic solution is possible is 2 CA,o = k 0 ro / 6 D AB = 2 105 kmol / m3.

(2) The total respiration rate may also be obtained by applying Ficks law at r = ro, in which case
2 2 & R = N A ( ro ) = + D AB 4 ro d CA / dr r = r = D AB 4 R o o The result agrees with that of part (b).

) ( ko / 6 DAB ) 2ro = ( 4 / 3) ro3k 0 .

PROBLEM 14.35
KNOWN: Radius of a spherical organism and molar concentration of oxygen at its surface. Diffusion and reaction rate coefficients. FIND: (a) Radial distribution of O2 concentration, (b) Expression for rate of O2 consumption, (c) Molar concentration at r = 0 and rate of oxygen consumption for prescribed conditions. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state, one-dimensional diffusion, (2) Stationary medium, (3) Uniform total molar concentration, (4) Constant properties (k1, DAB). ANALYSIS: (a) For the prescribed conditions and assumptions, Eq. (14.50) reduces to

1 d d CA D r2 2 dr AB dr r

k1 CA = 0
2

With y r CA, d CA/dr = (1/r) dy/dr y/r and

2 1 d 2 d CA = D AB d r dy y = D AB r d y D AB r dr r 2 dr r 2 dr dr r 2 dr 2
The species equation is then

d2y dr 2

k1 y=0 D AB
1/ 2

The general solution is of the form

y = C1 sinh ( k1 / DAB )
or

r + C2 cosh ( k1 / DAB )

1/ 2

C C 1/ 2 1/ 2 CA = 1 sinh ( k1 / DAB ) r + 2 cosh ( k1 / DAB ) r r r

Because CA must remain finite at r = 0, C2 = 0. Hence, with CA (ro) = CA,o,

C1 =
and

CA,o ro sinh ( k1 / DAB )

1/ 2

ro

Continued

PROBLEM 14.35 (Cont.)

ro sinh ( k1 / D AB )1/ 2 r CA = CA,o r 1/ 2 sinh ( k1 / D AB ) ro

<

(b) The total O2 consumption rate corresponds to the rate of diffusion at the surface of the organism.

2 & R = N A ( ro ) = + DAB 4 ro d CA / dr ro

1 1 1/ 2 1/ 2 2 & R = 4 ro D AB CA,o ro + ( k1 / DAB ) cot ( k1 / D AB ) ro 2 ro ro

& R = 4 ro DAB CA,o ( coth 1)
1/ 2 2 where k1 ro / D AB .
1/2

<

(c) For the prescribed conditions, (k1/DAB)

5 10
5

= (20 s 10 m /s)
1/ 2

-1

-8

1/2

= 44,720 m and = 4.472.

-1

CA =

kmol / m 10

sinh ( 4.472 )

sinh ( k1 / D AB ) r

= 1.136 10

1/ 2 r 10 kmol sinh ( k1 / D AB ) 3 r

In the limit of r 0, the foregoing expression yields

CA ( r 0 ) = 5.11106 kmol / m3
& R = 4 104 m 108 m 2 / s 5 105 kmol / m3 ( 4.472 coth 4.472 1)

<

= 2.18 1015 kmol / s

COMMENTS: The total respiration rate may also be obtained by integrating the volumetric rate of r & & consumption over the volume of the organism. That is, R = N A d = o k1 CA ( r ) 4 r 2dr. 0

PROBLEM 14.36
KNOWN: Combustion at constant temperature and pressure of a hydrogen-oxygen mixture adjacent to a metal wall according to the reaction 2H2 + O2 2H2O. Molar concentrations of hydrogen, 3 oxygen, and water vapor are 0.10, 0.10 and 0.20 kmol/m , respectively. Generation rate of water -2 3 vapor is 0.96 10 kmol/m s. FIND: (a) Expression for CH as function of distance from wall, plot qualitatively, (b) CH at the 2 2 wall, (c) Sketch also curves for CO ( x ) and CH O ( x ) , and (d) Molar flux of water at x = 10mm.
2 2

SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional diffusion, (3) Stationary medium, (4) Constant properties including pressure and temperature. PROPERTIES: Species binary diffusion coefficient (given, for H2, O2 and H2O): DAB = 0.6 10 2 m /s. ANALYSIS: (a) The species conservation equation, Eq. 14.48b, and its general solution are & & d 2C A N A NA + =0 CA ( x ) = x + C1x + C2 . D AB 2D AB dx 2
-5

(1,2)

The boundary condition at the wall must be dCA(0)/dx = 0, such that C1 = 0. For the species & & hydrogen, evaluate C2 from knowledge of CH (10 mm ) = 0.10 kmol / m3 and N H = N H O , 2 2 2 according to the chemical reaction. Hence,

0.10 kmol / m3 =

( 0.96 102 kmol / m3 s ) ( 0.010 m )2 + 0 + C2

2 0.6 105 m 2 / s

C2 = 0.02 kmol / m3.

Hence, the hydrogen species concentration distribution is

CH 2 ( x ) =

& NH2 2DAB

x 2 + 0.02 = 800x 2 + 0.02

<

which is parabolic with zero slope at the wall; see sketch above. (b) The value of CH at the wall is, 2

CH 2 ( 0 ) = ( 0 + 0.02 ) kmol / m3 = 0.02 kmol / m3.

Continued

<

PROBLEM 14.36 (Cont.)

(c) The concentration distribution for water vapor species will be of the same form,

& N H 2O 2 CH 2O ( x ) = x + C1x + C2 2D AB
With C1 = 0 for the wall condition, find C2 from CH O (10 mm ) , 2
3

(3)

0.20 kmol / m

( 0.96 10 =

kmol / m
5 2

2 0.6 10

) ( 0.010 m )

+ C2

C 2 = 0.28 kmol / m .

m /s

Hence, CH O at the wall is, 2

CH 2O ( 0 ) = 0 + 0 + C2 = 0.28 kmol / m3
& & and its distribution appears as above. Recognizing that N O = 0.5N H O , by the same analysis, find 2 2

CO2 ( 0 ) = 0.06 kmol / m3

and its shape, also parabolic with zero slope at the wall is shown above. (d) The molar flux of water vapor at x = 10 mm is given by Ficks law

N 2O,x = D AB H

dCH 2O dx

and using the concentration distribution of Eq. (3), find

& d N H 2O 2 & N 2O,x = D AB x = + N H 2O x H dx 2D AB

and evaluation at the location x = 10 mm, the species flux is

N O, (10 mm ) = + 0.96 102 kmol / m3 s 0.010 m = 9.60 105 kmol / m 2 s. H2 x

<

COMMENTS: Note that the generation rate of water vapor is a positive quantity. Whereas for H2 & & and O2, species are consumed and hence N H and N O are negative. According to the chemical
2 2

reaction one mole of H2 and 0.5 mole of O2 are consumed to generate one mole of H2O. Therefore,

& & & & N H 2 = N H 2O and N O 2 = 0.5 N H 2O .

PROBLEM 14.37
KNOWN: Molar concentrations of oxygen at inner and outer surfaces of lung tissue. Volumetric rate of oxygen consumption within the tissue. FIND: (a) Variation of oxygen molar concentration with position in the tissue, (b) Rate of oxygen transfer to the blood per unit tissue surface area. SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional species transfer by diffusion through a plane wall, (3) Homogeneous, stationary medium with uniform total molar concentration and constant diffusion coefficient. ANALYSIS: (a) From Eq. 14.71 the appropriate form of the species diffusion equation is d 2C A D AB k o = 0. 2

dx

Integrating,

dCA / dx = ( k o / DAB ) x + C1

CA =

With CA = CA ( 0 ) at x = 0 and CA = CA ( L ) at x = L,

ko x 2 + C1x + C2 . 2DAB

C2 = CA ( 0 )
Hence

C ( L ) CA ( 0 ) k L C1 = A o . L 2DAB

CA ( x ) =

ko x x ( x L ) + CA ( L ) CA ( 0 ) + CA ( 0 ) . L 2D AB

<

(b) The oxygen assimilation rate per unit area is

N ( L ) = D AB ( dCA / dx ) x = L A,x
k L k L D N ( L ) = D AB o o AB CA ( L ) CA ( 0 ) A,x L DAB 2DAB

k L D N = o + AB CA ( 0 ) CA ( L ) . A,x 2 L
COMMENTS: The above model provides a highly approximate and simplified treatment of a complicated problem. The lung tissue is actually heterogeneous and conditions are transient.

<

PROBLEM 14.38
KNOWN: Ground level flux of NO2 in a stagnant urban atmosphere. FIND: (a) Vertical distribution of NO2 molar concentration, (b) Critical ground level flux of NO2, N A,0,crit . SCHEMATIC:

ASSUMPTIONS: (1) Steady-state conditions, (2) One-dimensional diffusion in a stationary medium, (3) Total molar concentration C is uniform, (4) Perfect gas behavior. ANALYSIS: (a) For the prescribed conditions the molar concentration of NO2 is given by Eq. 14.73, subject to the following boundary conditions.

CA ( ) = 0,

dCA dx

N A,0 . = D AB x =0

From the first condition, C1 = 0. From the second condition,

mC2 = N / DAB . A,0 N A,0 mDAB

1/2

Hence

CA ( x ) =

e mx

<

where m = (k1/DAB)

(b) At ground level, CA ( 0 ) =

N A,0 mDAB

. Hence, from the perfect gas law,

p A ( 0 ) = C A ( 0 ) T =

TN A,0

mD AB
-4 1/2 -1

.
-1

Hence, with m = (0.03/0.15 10 )

m = 44.7 m .

N A,0,crit =

mD ABpA ( 0 )crit
T

44.7 m 1 0.15 104 m 2 / s 2 106 bar 8.314 102 m3 bar / kmol K 300 K

11 kmol / s m 2 . N A,0,crit = 5.38 10

<

COMMENTS: Because the dispersion of pollutants in the atmosphere is governed strongly by convection effects, the above model should be viewed as a first approximation which describes a worst case condition.

PROBLEM 14.39
KNOWN: Ground level flux of NO2 in a stagnant urban atmosphere. FIND: (a) Governing differential equation and boundary conditions for the molar concentration of NO2, (b) Concentration of NO2 at ground level three hours after the beginning of emissions. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional diffusion in a stationary medium, (2) Uniform total molar concentration, (3) Constant properties. ANALYSIS: (a) Applying the species conservation requirement, Eq. 14.43, on a molar basis to a unit area of the control volume,

N ( k1CA ) dx N + dx = A,x A,x

CA dx. t

With N + dx = N A,x A,x + N / x dx and N A,x A,x = D AB ( CA / x ) , it follows that

D AB

2CA x 2

k1CA =

CA . t

< <
CA ( , t ) = 0.

Initial Condition:
Boundary Conditions:

CA ( x, 0 ) = 0.

DAB

CA x

= N , A,0 x =0

<

(b) The present problem is analogous to Case (2) of Fig. 5.7 for heat conduction in a semi-infinite medium. Hence by analogy to Eq. 5.62, with k D AB and D AB ,

t CA ( x, t ) = 2N A,0 DAB
At ground level (x = 0) and 3h,

1/ 2

x 2 N x x A,0 exp erfc 4D AB t D AB 2 ( D t )1/ 2 AB

t CA ( 0,3h ) = 2N A,0 D AB
C A ( 0, 3h ) = 2 3 10

1/ 2

11

kmol / s m

)(10, 800 s / 0.15 10

m /s

1/ 2

= 9.08 10

kmol / m .

<

COMMENTS: The concentration decays rapidly to zero with increasing x, and at x = 100 m it is, for all practical purposes, equal to zero.

PROBLEM 14.40
KNOWN: Initial concentration of hydrogen in a sheet of prescribed thickness. Surface concentrations for time t > 0. FIND: Time required for density of hydrogen to reach prescribed value at midplane of sheet. SCHEMATIC: CA(x,0) = 3 kmol/m = CA,i 3 CA(0,tf) = 1.2 kg/m /2 kg/kmol 3 CA(0,tf) = 0.6 kmol/m = CA CA(20 mm,t) = 0 = CA,s
3

ASSUMPTIONS: (1) One-dimensional diffusion in x, (2) Constant DAB, (3) No internal chemical reactions, (4) Uniform total molar concentration, (5) Stationary medium. ANALYSIS: The mass transfer Biot number is Bim = hmL/DAB . Hence, Bi 1 = 0. By analogy to m Equation 5.44, the approximate solution, it follows that
2 = = 0.2 o C1 exp 1 Fo m = CA,i CA,s 3.0 0.0

CA CA,s

0.6 0.0

Using values of 1 = 1.57 and C1 = 1.27 from Table 5.1, it follows that
2 1.27 exp (1.57 ) Fo m = 0.2 from which

Fo m = 0.75
Hence, tf = 0.75(0.02m)2/910-7 m2/s = 333 s
COMMENT: Fom > 0.2. Hence, the approximate, one-term solution is valid.

<

PROBLEM 14.41
KNOWN: Radius and temperature of air bubble in water. FIND: Time to reach 99% of saturated vapor concentration at center. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional radial diffusion of vapor in air, (2) Constant properties, (3) Air is initially dry, (4) Stationary medium. PROPERTIES: Table A-8, Water vapor-air (300 K): DAB = 0.26 10 m /s. ANALYSIS: If the one-term approximation to the infinite series solution (Eq. 5.53),
-4 2

* 2 0 = C1 exp( 1 Fo) is used, it follows that,

2 = = 0.01. o C1 exp 1 Fom = CA,i CA,s 0.0 1

CA CA,s

0.99 1

Using values of C1 = 2.0 and 1 = 3.1415 for Bi m , it follows that 2 0.01 = 2.0 exp ( 3.1415 ) Fo m

or

Fo m = 0.54

Hence, t = FomD2/DAB = 0.54(0.001m)2/0.26 10-4 m2/s = 0.02 s

COMMENT: Since Fo > 0.2, the approximate solution is valid.

<

PROBLEM 14.42
KNOWN: Radius and temperature of air bubble.

FIND: (a) Time to reach 95% of the maximum average water vapor concentration, (b) Time to reach 50% of the maximum average water vapor concentration.
SCHEMATIC:
ro = 1 mm Water T = 25C Air CA,s

ASSUMPTIONS: (1) One-dimensional radial diffusion of vapor in air, (2) Constant properties, (3) Air is initially dry, (4) Stationary medium. PROPERTIES: Table A.8, Water vapor-air (300 K): DAB = 0.26 10-4 m2/s.

ANALYSIS: (a) We may employ the one-term approximation to the infinite series solution (Eq.
5.55)
* Q 3 o * = 1 3 [sin( 1 ) 1 cos( 1 )] ; o = C1 exp 12 Fo Qo 1

) ( )

By analogy, the preceding equations may be written as CA CA,max = 1

* 3 o

13

[sin( 1 ) 1 cos( 1 )]

* ; o =

CA CA,s CA,i CA,s

= C1 exp 12 Fom

Using values of C1 = 2.000 and 1 = 3.1415 from Table 5.1 for Bim , it follows that

CA CA,max

= 0.95 = 1

* 3 o [sin(3.1415) 3.1415cos(3.1415)] ; 3.14153

* o =

CA CA,s CA,i CA,s

= 2.0exp 3.14152 Fom

* Solving the two equations yields o = 0.1645, Fom = 0.2531. Since Fom > 0.2, the approximate solution is valid. Hence,

t = Fom ro2 / DAB = 0.2531( 0.001m ) / 0.26 104 m 2 / s = 9.7 103 s = 9.7 ms
2

<

(b) The time associated with an average water vapor concentration of 50% is expected to be significantly shorter than in part (a). Hence, Fom may be less than 0.2 and the one-term approximation to the exact solution may not be valid. Therefore, we employ the approximate solution of Section 5.8 and apply the analogy between heat and mass transfer.

Continued

PROBLEM 14.42 (Cont.)

From Table 5.2a for Fo < 0.2,
q* = qs ro 1 t = 1 ; Fo = 2 k (Ts Ti ) Fo ro

Substituting the expression for Fo into the first equation yields qs = k (Ts Ti ) ro 1/2 1 t ro

We desire an expression for Q/Qo. Hence,

Q 3 ro 1/2 t =0 = = 1 dt t Qo (4 / 3) ro3 c(Ts Ti ) ro2 t =0

4 ro2

qsdt

or Q 3 2ro 1/ 2 = t t Qo ro2

2 = 3

Fo Fo

Applying the analogy between heat and mass transfer,

CA CA,max

2 = 0.50 = 3

Fom Fom

from which Fom = 0.0305. Hence, t = Fom ro2 / DAB = 0.0305 ( 0.001m ) / 0.26 104 m 2 / s = 1.17 103 s = 1.17 ms
2

<

COMMENTS: (1) Use of the approximate solution of Section 5.8 is not valid for part (a) since its use yields Fom = 0.366, which does not satisfy the criterion Fom < 0.2. (2) Use of the one-term approximation to the exact solution for part (b) yields a mass transfer Fourier number of Fom = 0.0198, which does not satisfy the criterion Fom > 0.2.

PROBLEM 14.43
KNOWN: Initial carbon content and prescribed surface content for heated steel. FIND: Time required for carbon mole fraction to reach 0.01 at a distance of 1 mm from the surface. SCHEMATIC:

ASSUMPTIONS: (1) Steel may be approximated as a semi-infinite medium, (2) One-dimensional diffusion in x, (3) Isothermal conditions, (4) No internal chemical reactions, (5) Uniform total molar concentration, (6) Stationary medium. ANALYSIS: Conditions within the steel are governed by the species diffusion equation of the form 2C A 1 CA = DAB t x 2

or, in molar form,

2x A x 2

x A . D AB t 1

The initial and boundary conditions are of the form

x A ( x, 0 ) = 0.001

x A ( 0, t ) = x A,s = 0.02

x A ( , t ) = 0.001.

The problem is analogous to that of heat transfer in a semi-infinite medium with constant surface temperature, and by analogy to Eq. 5.60, the solution is

x A ( x, t ) x A,s x A,i x A,s

where

x = erf 2 ( D t )1/ 2 AB

D AB = 2 105 exp [ 17, 000 /1273] = 3.17 1011 m 2 / s.

Hence

0.01 0.02 0.001 m = 0.526 = erf 0.001 0.02 2 3.17 1011 t 1/ 2

where erf w = 0.526 w 0.51,

0.51 = 0.001/ 2 3.17 1011 t

1/ 2

or

t = 30,321 s = 8.42 h. <

PROBLEM 14.44
KNOWN: Thick plate of pure iron at 1000C subjected to a carburizing process with sudden exposure to a carbon concentration CC,s at the surface. FIND: (a) Consider the heat transfer analog to the carburization process; sketch the mass and heat transfer systems; explain correspondence between variables; provide analytical solutions to the mass and heat transfer situation; (b) Determine the carbon concentration ratio, CC (x, t)/CC,s, at a depth of 1 mm after 1 hour of carburization; and (c) From the analogy, show that the time dependence of the 1/ 2 mass flux of carbon into the plate can be expressed as n C = C,s D C Fe / t ; also, obtain an expression for the mass of carbon per unit area entering the iron plate over the time period t.

SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional transient diffusion, (2) Thick plate approximates a semiinfinite medium for the transient mass and heat transfer processes, and (3) Constant properties, (4) Stationary medium. ANALYSIS: (a) The analogy between the carburizing mass transfer process in the plate and the heat transfer process is illustrated in the schematic above. The basis for the mass - heat transfer analogy stems from the similarity of the conservation of species and energy equations (Eqs. 14.77 and 5.29, respectively), the general solution to the equations, and their initial and boundary conditions. For both processes, the plate is a semi-infinite medium with initial distributions, CC (x, t 0) = CC,i = 0 and T (x, t 0) = Ti, suddenly subjected to a surface potential, CC (0, t > 0) = CC,s and T (0, t > 0) = Ts. The heat transfer situation corresponds to Case 1, Figure 5.7, from which the following relations were obtained. Heat transfer Distributions
T ( x, t ) Ts x = erf Ti Ts 2 t

Mass transfer

Cc ( x, t ) Cc,s 0 Cc,s

x = erf 2 DC-Fe t

or
Cc ( x, t ) x = erfc 2 DC-Fe t Cc,s

Fluxes
q" ( t ) = s k (Ts Ti ) t
" nC ,s (t ) =

DC-Fe ( C ,s )

DC-Fet

Continued

PROBLEM 14.44 (Cont.)

(b) Using the concentration distribution expression above, with L = 1 mm, t = 1 h and -11 2 DC-Fe = 3 10 m /s, find the concentration ratio,

CC 1 mm, 1 h = erfc CC,s

F I GG JJ = 0.0314 0.001 m GH 2e3 10-11 m2 / s 3600 sj1/ 2 JK

<

(c) From the species flux expression above, the mass flux of carbon can be written as
n" = C,s ( DC Fe / t ) C,s
1/ 2

<

The mass per unit area entering the plate over the time period follows from the integration of the rate expression

mC ( t ) =

t 0

n" dt = C,s C,s

( DC-Fe / )

1/ 2

0 t

-1/2 dt = 2 C,s

( DC Fe t/ )1/ 2

<

PROBLEM 14.45
KNOWN: Radius of pharmaceutical product, density of the active ingredient, partition coefficient, and binary diffusion coefficient of the active ingredient in the gastrointestinal tract.

FIND: (a) Dosage delivered over 5 hours from a D = 6 mm diameter tablet, (b) Dosage delivered
over 5 hours from N = 200 small, spherical tablets of the same mass. SCHEMATIC:
A = 15 kg/m3
Medication ro = 3 mm or 0.513 mm Gastrointestinal fluid CA, = 0, D AB = 0.4 10-10 m2/s

A,s , K = 3 10-2

ASSUMPTIONS: (1) One-dimensional radial diffusion of active ingredient, (2) Constant properties, (3) Stationary medium, (4) Constant sphere radius. PROPERTIES: Given: DAB = 0.40 10-10 m2/s, K = 3 10-2.

ANALYSIS: (a) The approximate solution of Chapter 5 for external conduction from an isothermal sphere and the heat-mass transfer analogy will be used. From Table 5.2a,
q * ( Fo) = 1 + 1 or, Fo
qs ro r = o +1 k (Ts T ) t

(1,2)

By analogy, Eq. 2 may be written as

nA,s ro DAB ( A,s A, ) Rearranging, = ro +1 DABt

(3)

nA,s =

DAB / ( A,s A, ) t

DAB ( A,s A, ) ro

For A, = 0, the dosage (for As = 4ro2) is D ( ) D = 4 ro2nA,s dt = 4 ro2 DAB / ( A,s )t 1/2 + AB A,s dt ro o 0

With A,s = KA, the preceding expression yields

D = 4 ro K A 2ro DAB / t1/ 2 + DABt (4) Continued

PROBLEM 14.45 (Cont.)

Substituting the appropriate values into Eq. 4 results in 2 3 103 m 0.4 1010 m 2 / s 18000s / D = 4 3 103 m 3 102 15kg/m3 +0.4 1010 m 2 / s 18000s D = 60.9 10-9 kg = 60.9 10-6 g = 60.9 g (b) For the same initial mass and N = 200 tablets,
4 3 N4 3 ro,1 = ro, N or ro, N = ro,1 / N 1/ 3 = 3 103 m / 2001/ 3 = 0.513 mm 3 3

<

The dosage is D = ND1 where D1 is the dosage for one tablet. Hence, 2 0.513 103 m 0.4 1010 m 2 / s 18000s / D = ND1 = 200 4 0.513 103 m 3 102 15kg/m3 +0.4 1010 m 2 / s 18000s D = 703 10-9 kg = 703 10-6 g = 703 g

<

COMMENTS: (1) The dosage is controlled by the tablet size. In this example, the medication dosage is increased by over an order of magnitude by replacing the single tablet with the encapsulated, smaller diameter spherical tablets. (2) The initial mass of the medication is M = 4/3ro3 = 4/315kg/m3(310-3m)3 = 1.69610-6 kg = 1.69610-3 g = 1.696 mg = 1696 g. For the smaller tablets, the mass of medication left after 5 hours is 1696 g 703 g = 993 g. Hence, the tablet radius after 5 hours is r5h = 0.513mm(993/1696)1/3 = 0.429 mm. The assumption of a constant radius is marginally valid.

PROBLEM 14.46
KNOWN: Thickness, initial condition and bottom surface condition of a water layer. FIND: (a) Time to reach 25% of saturation at top, (b) Amount of salt transfer in that time, (c) Final concentration of salt solution at top and bottom. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional diffusion, (2) Uniform total mass density, (3) Constant DAB, (4) Stationary medium. ANALYSIS: (a) With constant and DAB and no homogeneous chemical reactions, Eq. 14.47b reduces to 2 A 1 A = . D AB t x 2

with the origin of coordinates placed at the top of the layer, the dimensionless mass density is

x , Fo m =

A A,s = = 1 A i A,i A,s A,s

Hence, 0, Fo m,1 = 1 0.25 = 0.75. The initial condition is x , 0 = 1, and the boundary conditions are

( )

=0

x = 0

(1, Fo m ) = 0

where the condition at x = 1 corresponds to Bim = . Hence, the mass transfer problem is analogous to the heat transfer problem governed by Eq. 5.38 through 5.40. Assuming applicability of a one-term approximation (Fom > 0.2), the solution is analogous to Eq. 5.43.

2 = C1 exp 1 Fo m cos 1x . With Bi m = , 1 = / 2 = 1.571 rad and, from Table 5.1, C1 1.273. Hence, for x = 0, 2 0.75 = 1.273exp (1.571) Fom,1

) ( )

Fo m,1 = ln ( 0.75 /1.274 ) / (1.571) = 0.214.

2 Hence,

(1 m ) L2 t1 = Fo m,1 = 0.214 = 1.79 108 s = 2071 days. 9 m 2 / s DAB 1.2 10

2 Continued

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PROBLEM 14.46 (Cont.)

(b) The change in the salt mass within the water is

M A = M A ( t1 ) M A,i = A A,i dV = A A dx 0
Hence, L

M = A,s A / A,s dx A 0

M = A,s L 1 dx A 0
1

1 2 M = A,s L 1 C1 exp 1 Fo m,1 cos 1x dx A 0 2 M = A,s L 1 C1 exp 1 Fo m,1 sin 1 / 1 . A Substituting numerical values,

) ( )

M = 380 kg / m3 (1 m ) 1 A

2 1.274 exp (1.571) 0.214 1 1.571rad

M = 198.3 kg / m 2 . A
(c) Steady-state conditions correspond to a uniform mass density in the water. Hence,

< <

A ( 0, ) = A ( L, ) = M / L = 198.3 kg / m3. A
COMMENTS: (1) The assumption of constant is weak, since the density of salt water depends strongly on the salt composition.

(2) The requirement of Fom > 0.2 for the one-term approximation to be valid is barely satisfied.

PROBLEM 14.47
KNOWN: Temperature distribution expression for a semi-infinite medium, initially at a uniform temperature, that is suddenly exposed to an instantaneous amount of energy, Q o J / m2 .

Analogous situation of a silicon (Si) wafer with a 1-m layer of phosphorous (P) that is placed in a furnace suddenly initiating diffusion of P into Si.
FIND: (a) Explain the correspondence between the variables in the analogous temperature and concentration distribution expressions, and (b) Determine the mole fraction of P at a depth of 0.1 m in the Si after 30 s. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional, transient diffusion, (2) Wafer approximates a semi-infinite medium, (3) Uniform properties, and (4) Diffusion process for Si and P is initiated when the wafer reaches the elevated temperature as a consequence of the large temperature dependence of the diffusion coefficient, (5) Stationary medium. PROPERTIES: Given in statement: DP-Si = 1.2 10 m /s; Mass densities of Si and P: 2000 and 3 2300 kg/m ; Molecular weights of Si and P: 30.97 and 28.09 kg/kmol. ANALYSIS: (a) For the thermal process illustrated in the schematic, the temperature distribution is
-17 2

T x, t Ti =

b g

c t

b g

Qo

1/ 2

exp x2 / 4t

(HT)

where Ti is the initial, uniform temperature of the medium. For the mass transfer process, the P concentration has the form

C P x, t =

b g

b D P Si tg

M P,o

1/ 2

exp x 2 / 4 D P Si t
2

(MT)

where M is the molar area density (kmol/m ) of P represented by the film of concentration CP and P,o
thickness do. The correspondence between mass and heat transfer variables in the equations HT and MT involves the following conditions. The LHS represents the increase with time of the temperature or concentration above the initial uniform distribution. The initial concentration is zero, so only the CP (x, t) appears. On the RHS note the correspondence of the terms in the exponential parenthesis and in the denominator. The thermal diffusivity and diffusion coefficient are directly analogous; this can be seen by comparing the MT and HT diffusion equations, Eq. 2.21 and 14.77. The terms Q o / c and M for HT and MT represent the energy and mass instantaneously appearing at the surface. The P,o

product c is the thermal capacity per unit area and appears in the storage term of the HT diffusion equation. For MT, the capacity term is the volume itself. Continued

PROBLEM 14.47 (Cont.)

(b) The molar area density (kmol/m ) of P associated with the film of thickness do = 1 m and concentration CP,o is
2

M = C P,o d o = P / M P d o P,o

M = 2000 kg / m3 / 30.97 kmol / kg 1 106 m P,o

M = 6.458 105 kmol / m2 P,o
Substituting numerical values into the MT equation, find
Cp ( 0.1 m, 30 s ) =

( 1.2 10

6.458 105 kmol/m 2

-17

m 2 / s 30 s

exp 0.1 10-6 m 1/ 2

) / ( 4 1.2 10
2

17

m 2 / s 30 s

Cp = 1.85 kmol/m3 The mole fraction of P in the Si wafer is x P = CP / CSi = CP / ( Si / MSi ) x P = 1.85 kmol/m3 / 2300 kg/m3 / 28.09 kmol/kg x P = 0.023

)
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PROBLEM 14.48
KNOWN: Carbon dioxide concentration at water surface and reaction rate constant. FIND: (a) Differential equation which governs variation with position and time of CO2 concentration in water, (b) Appropriate boundary conditions and solution for a deep body of water with negligible chemical reactions. SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional diffusion in x, (2) Constant properties, including total density , (3) Water is stagnant, (4) Stationary medium. ANALYSIS: (a) From Eq. 14.47b, it follows that, for the prescribed conditions, 2 A D AB k1 A = A . 2

<

The first term on the left-hand side represents the net transport of CO2 into a differential control volume by diffusion. The second term represents the rate of CO2 consumption due to chemical reactions. The term on the right-hand side represents the rate of increase of CO2 storage within the control volume. (b) For a deep body of water, appropriate boundary conditions are

A ( 0, t ) = A,0

A ( , t ) = 0
and, with negligible chemical reactions, the species diffusion equation reduces to

2 A x 2

A . D AB t 1

With an initial condition, A(x,0) A,i = 0, the problem is analogous to that involving heat transfer in a semi-infinite medium with constant surface temperature. By analogy to Eq. 5.60, the species concentration is then

A ( x, t ) A,0 x = erf 2 ( D t )1/ 2 A,0

AB

x . A ( x, t ) = A,0erfc 2 ( D t )1/ 2 AB

<

PROBLEM 14.49

KNOWN: Solubility and diffusivity of oxygen (O2) in polycarbonate. Distance of thin reacting film of polymer from DVD surface. Initial O2 distribution. Critical concentration needed to start reaction in the thin film. FIND: Elapsed time before reaction begins in the thin film. SCHEMATIC:
Atmospheric conditions Cs

Thin reacting film

Polycarbonate DAB = 6.5 10-12 m2/s S = 8.9 10-3 kmol/m3bar

ASSUMPTIONS: (1) Constant properties and steady-state conditions, (2) Stationary medium.
(3) Presence of thin, reacting film does not affect the diffusion process, (4) Semi-infinite media.

PROPERTIES: Oxygen (O2) in polycarbonate, given: DAB = 6.5 10-12 m2/s, S = 8.9 10-3
kmol/m3bar.

ANALYSIS:
The mole fraction of oxygen in air is 0.21. Therefore, the partial pressure of O2 in the atmosphere is

P02 = 0.21 atm 1.0133 and the surface concentration is

bar = 0.213 bar atm

Cs = C(x=0) = SPO2 = 8.9 10-3

kmol kmol 0.213 bar = 1.89 10-3 3 m bar m3

Incorporating the heat and mass transfer analogy and using Eq. 5.60, 5 105 kmol kmol 1.89 103 3 3 0.5 10 m m3 m = erf 2 3 kmol m 0 1.89 10 2 6.5 1012 3 t m s

C(x, t) Cs x = erf 2 D t Ci Cs AB which yields

t = 3940 s COMMENT: The thin film will convert O2 to a product of the reaction. A more detailed analysis would include the effects of O2 conversion on the process.

<

PROBLEM 14.50 KNOWN: DVD with reacting polymer throughout, undergoing first-order homogeneous
reaction between polymer and oxygen, with reaction rate proportional to oxygen molar concentration.

FIND: (a) Governing equations and boundary and initial conditions for oxygen molar
concentration. (b) Expression for volume-averaged molar concentration of product of reaction.

SCHEMATIC:
x
& NA

pA

2L

ASSUMPTIONS: (1) Constant properties, (2) One-dimensional mass diffusion with

heterogeneous chemical reaction. (3) Reaction rate is proportional to molar concentration of oxygen.

ANALYSIS: (a) From Eq. 14.48b for one-dimensional diffusion of species A (oxygen), CA 2C A & = D AB + NA t x 2

& For a first-order reaction that consumes oxygen, we can write N A = k1CA . Thus, CA 2C A = DAB k1CA t x 2
`

<

The boundary conditions express symmetry about the midplane and relate the molar concentration at the surface to the partial pressure of oxygen in the environment, pA.

CA = 0, x x =0

CA (L, t) = SpA

<

The initial condition expresses that there is no oxygen initially in the DVD before the pouch is opened, that is,

CA (x,0) = 0

<

(b) Since each mole of oxygen that reacts with the polymer results in p moles of product, we can & & write the following expression for the rate of generation of product: N prod = pN A = pk1CA . Continued

PROBLEM 14.50 (Cont.)

The volume-averaged molar concentration of product is just the rate of generation integrated over time and averaged over the volume. Thus,

Cprod =

t & 1 1 L t& 1 L t V 0 N proddtdV = 2AL L 0 N proddt(Adx) = L 0 0 pk1CAdtdx V pk L t Cprod = 1 CA (x, t)dtdx L 0 0

<

PROBLEM 14.51
KNOWN: Sheet material has high, uniform concentration of hydrogen at the end of a process, and is then subjected to an air stream with a specified, low concentration of hydrogen. Mass transfer parameters specified include: convection mass transfer coefficient, hm, and the mass diffusivity and solubility of hydrogen (A) in the sheet material (B), DAB and SAB, respectively. FIND: (a) The final mass density of hydrogen in the material if the sheet is exposed to the air stream for a very long time, A,f, (b) Identify and evaluate the parameter that can be used to determine whether the transient mass diffusion process in the sheet can be characterized by a uniform concentration at any time; Hint: this situation is analogous to the lumped capacitance method for a transient heat transfer process; (c) Determine the time required to reduce the hydrogen concentration to twice the limiting value calculated in part (a). SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional diffusion, (2) Stationary medium, (3) Constant properties, (4) Uniform temperature in air stream and material, and (5) Ideal gas behavior. ANALYSIS: (a) The final content of H2 in the material will depend upon the solubility of H2 (A) in the material (B) and its partial pressure in the free stream. From Eq. 14.62,

CA,f = SAB p A, = 160 kmol / m3 atm 0.1 atm = 16 kmol / m3

f = M A CA,f = 2 kg/kmol 16 kmol/m3 = 32 kg/m3

<

(b) The parameters associated with transient diffusion in the material follow from the analogous treatment of Section 5.2 (Fig. 5.3) and are represented in the schematic.

In the material, from Ficks law, the diffusive flux is

N A,dif = DAB CA,1 CA,2 / L

At the surface, x = L, the rate equation, Eq. 6.8, convective flux of species A is

(1)

N A,conv = h m CA,s CA,

i
Continued

PROBLEM 14.51 (Cont.)

and substituting the ideal gas law, Eq. 14.9, and introducing the solubility relation, Eq. 14.62,
N A,conv = N A,conv = hm SAB R T hm SAB R T

(SAB pA,s SAB pA, ) ( C2,s CA, )

(2)

where CA, = CA,f, the final concentration in the material after exposure to the air stream a long time. Considering a surface species flux balance, as shown in the schematic above, with the rate equations (1) and (2),

D AB ( C A,1 CA,2 ) L

hm SAB R T

( CA,s CA,f )
(3)

CA,1 CA,2 CA,s CA,f

R h m / SAB R T m,dif = = Bi m DAB / L R m,conv

and introducing resistances to species transfer by diffusion and convection. Recognize from the analogy to heat transfer, Eq. 5.10 and Table 14.2, that when Bim < 0.1, the concentration can be characterized as uniform during the transient process. That is, the diffusion resistance is negligible compared to the convection resistance,

Bi m = Bi m =

h mL < 01 . SAB Ru T D AB

(4)

. b15 m / h 3600 s / hg 0.003 m

160 kmol / m3 atm 8.205 10-2 m3 atm / kmol K 555 K 2.68 10-8 m2 / s Bi m = 6.60 103 < 0.1

Hence, the mass transfer process can be treated as a nearly uniform concentration situation. From conservation of species on the material with uniform concentration,

& N A,conv = N A,st

hm C ( CA CA,f ) = L d dtA SAB R T

Integrating, with the initial condition CA (0) = CA,i, find

CA CA,f CA,i CA,f hm t = exp L SAB R T

(5)

<

Continued ..

PROBLEM 14.51 (Cont.)

which is similar to the analogous heat transfer relation for the lumped capacitance analysis, Eq. 5.6.

(c) The time, to, required for the material to reach a concentration twice that of the limiting value, CA (To) = 2 CA,f, can be calculated from Eq. (5).

IJ 1.5 m / h t o b2 1g 16 kmol / m3 = expFG b320 -16g kmol / m3 H 0.003 m 160 kmol / m3 atm 8.205 102 m3 atm / kmol K 555 K K
t o = 42.9 h

<

PROBLEM 14.52
KNOWN: Hydrogen-removal process described in Problem 14.51, but under conditions for which -11 2 the mass diffusivity of hydrogen gas (A) in the sheet (B) is DAB = 1.8 10 m /s (instead of -8 2 2.6 10 m /s). With a smaller DAB, a uniform concentration condition may no longer be assumed to exist in the material during the removal process. FIND: (a) The final mass density of hydrogen in the material if the sheet is exposed to the air stream for a very long time, A,f, (b) Identify and evaluate the parameters that describe the transient mass transfer process in the sheet; Hint: this situation is analogous to that of transient heat conduction in a plane wall; (c) Assuming a uniform concentration in the sheet at any time during the removal process, determine the time required to reach twice the limiting mass density calculated in part (a); (d) Using the analogy developed in part (b), determine the time required to reduce the hydrogen concentration to twice the limiting value calculated in part (a); Compare the result with that from part (c). SCHEMATIC:

ASSUMPTIONS: (1) One-dimensional diffusion, (2) Stationary medium, (3) Constant properties, (4) Uniform temperature in air stream and material, and (5) Ideal gas behavior. ANALYSIS: (a) The final content of H2 in the material will depend upon the solubility of H2 (A) in the material (B) at its partial pressure in the free stream. From Eq. 14.62,

CA,f = SAB p A, = 160 kmol / m3 atm 0.1 atm = 16 kmol / m3

f = M A CA,f = 2 kg / kmol 16 kmol / m3 = 32 kg / m3

(b) For the plane wall shown in the schematic below, the heat and mass transfer conservation equations and their initial and boundary conditions are
Heat transfer T 2T Mass (Species A) transfer CA 2 CA = D AB 2

<

T x,0 = Ti

b g T b0, tg = 0 x

x2

CA x,0 = CA,i

b g CA b0, tg = 0 x

T L, t = h T L, t T x

b g

b g

D AB

CA hm CA ( x,t ) Cf ( L,t ) = SAB R T x

Continued

PROBLEM 14.52 (Cont.)

The derivation for the species transport surface boundary condition is developed in the solution for Problem 14.51. The solution to the mass transfer problem is identical to the analogous heat transfer problem provided the transport coefficients are represented as
h /S R T h <=> m AB k D AB (1)

(c) The uniform concentration transient diffusion process is analogous to the heat transfer lumpedcapacitance process. From the solution of Problem 14.51, the time to reach twice the limiting concentration, CA (to) = 2 CA,f, can be calculated as
CA ( t o ) C A,f CA,i CA,f hm to = exp L SAB R T

(2)

t o = 42.9 hour
For the present situation, the mass transfer Biot number is
Bi m = hm L SAB R T D AB

<

Bi m =

. b15 m / h / 3600 s / hg 0.003 m 160 kmol / m3 atm 8.205 10-2 m3 atm / kmol K 555 K 1.8 10-11 m2 / s

Bi m = 9.5 >> 0.1

and hence the concentration of A within B is not uniform (d) Invoking the analogy with the heat transfer situation, we can use the one-term series solution, Eq. 5.43, with Bi m <=> Bi and

Fo m <=> Fo

Fo m =

D AB t L2
Continued

(3)

PROBLEM 14.52 (Cont.)

With Bim = 9.5, find 1 = 1.4219 rad and C1 = 1.2609 from Table 5.1, so that Eq. 5.44 becomes

CA t o CA,f 2 = C1 exp 1 Fo m CA,i CA,f

b g

b2 1g 16 kmol / m3 = 12609 expe1.42192 Fo m j . b320 16gkmol / m3

Fo m = 18 1011 m2 / s t o .

b0.003 mg2

= 1571 .

t o = 218 h

<

COMMENTS: (1) Since Bim = 9.5, the uniform concentration assumption is not valid, and we expect the analysis to provide a longer time estimate to reach CA(to) = 2 CA,f.

(2) Note that the uniform concentration analysis model of part (c) does not include DAB. Why is this so?

PROBLEM 14.53 KNOWN: Dimensions of polymer sheet. Temperature and relative humidity of environment.
Increase in mass of sheet over 24 and 48 hour periods.

FIND: Solubility and mass diffusivity of water vapor in polymer, assuming mass diffusivity is
greater than 7 10-13 m2/s.

SCHEMATIC:

`A = (100 mm)2

Polymer sheet

m = 0.012 mg, t = 24 hr m = 0.016 mg, t = 48 hr T = 300 K i = 0, = 0.95, t > 0

2L = 1 mm

ASSUMPTIONS: (1) Constant properties, (2) One-dimensional mass diffusion, (3) Mass gain
is solely due to water vapor diffusing into the sheet. PROPERTIES: Table A.6, saturated water (T = 300 K), pA,sat = 0.03531 bars, MA = 18 kg/kmol.

ANALYSIS: The process of diffusion of water vapor (A) in the polymer (B) sheet is governed
by Eq. 14.77 with boundary and initial conditions given by Eqs. 14.78 through 14.80. These equations can be cast in nondimensional form as in Eqs. 14.83 through 14.86, and the analogy with Eqs. 5.37 through 5.40 is apparent (for Bi ), with the analogous quantities defined in Table 14.2. Since the mass gained by the polymer sheet is known, it is more convenient to work the problem in mass terms. Making use of Eq. 14.1, we recognize that * defined in Eq. 14.81 can be written in the alternative form,

* =

CA CA,s CA,i CA,s

A A,s A,i A,s

(1)

Here A,i = 0 since the sheet is initially dry, and A,s = M ACA,s = M ASp A, , or

A,s = M ASpA,sat
where S is the solubility (see Eq. 14.62).

(2)

The mass gained by the polymer sheet is then analogous to the energy transfer, Q, in the heat transfer problem. Specifically, for the mass loss, we can write a sequence of equations analogous to Eqs. 5.46 through 5.48, Continued

PROBLEM 14.53 (Cont.)

Mass loss = M A = [M A (t) M A (0)] = [ A (x, t) A,i ]dV

M A,o V( A,i A,s )
and

[ A (x, t) A,i ] dV 1 M A = = (1 *)dV M A,o A,i A,s V V

If Fom > 0.2, the solution can be approximated by the first term in the series, and the result for the mass loss would be analogous to Eq. 5.49. To determine if the first term approximation can be used, we estimate the mass transfer Fourier number with knowledge that the mass diffusivity is greater than 7 10-13 m2/s, Fom = DABt/L2, Fom > 7 10-13 m2/s 24 h 3600 s/h / (0.0005 m)2 = 0.24

Thus the one-term approximation is valid and by analogy to Eqs. 5.49 and 5.44, the nondimensional mass loss is given by

M A sin 1 2 = 1 C1 exp( 1 Fo m ) M A,o 1

or

(3)

M A sin 1 2D = 1 C1 exp( 1 AB t) A,sV 1 L2

(4)

From Table 5.1 for Bi , we find 1 = 1.5707 = / 2 and C1 = 1.2733 . The quantity M A is the mass gain at the two stated times. The unknowns to be determined are DAB and S, which appears in A,s (see Eq. (2)). From Eq. (4) evaluated at the two times, we have two simultaneous equations which can be solved for the unknowns DAB and A,s, namely

0.012 10-6 kg A,s 105 kg / m3

= 1

sin / 2 2 D AB 1.2733exp( 24 h 3600 s/h) /2 4 (0.0005 m)2

0.016 106 kg A,s 105 kg / m3

= 1

sin / 2 2 D AB 1.2733exp( 48 h 3600 s/h) /2 4 (0.0005 m)2

There are two solutions to these two equations, DAB = 1.92 10-13 m2/s, A,s = 0.003848 kg/m3 or DAB = 8.5 10-13 m2/s, A,s = 0.001976 kg/m3

Continued

PROBLEM 14.53 (Cont.)

Since we expect DAB to be greater than 7 10-13 m2/s, we choose the second solution. Thus, DAB = 8.5 10-13 m2/s

< <

S = A,s / M A p A,sat = 0.001976 kg / m3 /(18 kg/kmol 0.95 0.03531 bars)

S = 3.3 103 kmol / m3 bar

diffusivity less than 7 10-13 m2/s, and is therefore rejected. That solution also has Fom < 0.2, so the solution is not valid. It does raise the question of whether there is another solution for which Fom < 0.2. If the problem is solved correctly for Fom < 0.2, it can be determined that there is no other solution.

COMMENTS: The system of equations has two solutions, but one of them would yield a mass

PROBLEM 14.54 KNOWN: Diameter of optical fiber sensor in a hydrogen chamber. Pressure of hydrogen
(species A) in environment. Mass diffusivity and solubility for hydrogen in glass fiber (species B).

FIND: (a) Average hydrogen concentration in fiber after 100 hours of operation. Change in refractive index, given that n = (1.6 10-3 m3/kmol) C . (b) Average hydrogen concentration
and change in refractive index after 1 and 10 hours of operation.

SCHEMATIC: D = 100 m
`

Hydrogen, pA = 20 bars

ASSUMPTIONS: (1) Constant properties, (2) One-dimensional mass diffusion.

10-3 kmol/m3bar.

PROPERTIES: Hydrogen in vitreous silica fiber (given): DAB = 2.88 10-15 m2/s, S = 4.15 ANALYSIS: (a) This is a problem of transient mass diffusion in a cylinder, analogous to
transient conduction in a cylinder. We begin by calculating the mass transfer Fourier number,

2 Fo m = D ABt / ro = 2.88 1015 m2 / s 100 h 3600 s / h (50 106 m)2 = 0.415

With Fom > 0.2, we can use the first-term approximation to the series solution. The average hydrogen concentration can be found by analogy with the nondimensional energy transfer Q/Qo defined in Eq. 5.48, with reference to Table 14.3 for the analogous quantities. We define

(CA (x, t) CA,i ) dV 1 M A = (1 *)dV M A,o CA,i CA,s V V

(1)

Here the surface concentration, CA,s, is used in place of the environment temperature, T, because this is a problem of specified surface concentration, modeled by allowing Bim. By analogy with Eq. 5.54,

M A 2 * = 1 o J1( 1) M A,o 1
where from Eq. 5.52c, the centerline value of the nondimensional molar concentration is 2 * = C1 exp( 1 Fom ) . From Table 5.1, 1 = 2.4050, C1 = 1.6018 , so * = 0.145 . From o o Table B.4, J1(2.4050) 0.52 . Thus, Continued

PROBLEM 14.54 (Cont.) M A 2 0.145 = 1 0.52 = 0.937 2.4050 M A,o

Referring back to Eq. (1), we can determine the average hydrogen concentration,

CA = CA (x, t)

dV M A (CA,s CA,i ) = CA,i + V M A,o

where CA,i = 0 since the fiber initially contains no hydrogen, and CA,s = SpA = 4.15 10-3 kmol/m3bar 20 bars = 0.0830 kmol/m3. Thus,

CA = 0 + 0.937(.0830 kmol / m3 0) = 0.0778 kmol / m3

The change in refractive index is then

<

n = 1.6 103 m3 / kmol 0.0778 kmol / m3 = 1.24 104

(b) For the shorter times, the Fourier number is no longer larger than 0.2, and we must use a different approach. We could use the exact infinite series solution, but it is easier to use the solutions provided in Table 5.2a, which are appropriate for uniform surface concentration. For an infinite cylinder, with Lc = ro,

q* = qro / k(Ts Ti ) s
The analogous quantity is

N* = N ro / D AB (CA,s CA,i ) A A,s

With knowledge of the molar flux at the surface, N , the average hydrogen concentration can A,s be found as follows. We multiply the flux by the surface area and integrate over time to find how much hydrogen has entered the fiber. Then we divide by the volume to find the average concentration. That is,

CA = N dt 0 A,s

2ro
2 ro

2 t N dt A,s ro 0

Now from Table 5.2a for the interior case, infinite cylinder, with Fom < 0.2,

N* = N ro / D AB (CA,s CA,i ) = A A,s

Thus, we have

1 0.50 0.65Fom Fom

Continued

PROBLEM 14.54 (Cont.)

CA = 2 t N dt = A,s ro 0 t 1 0.50 0.65Fom dt D AB (CA,s CA,i ) 2 0 Fo ro m 2 Fom 1 0.50 0.65Fom dFom Fo 0 m

= 2(CA,s CA,i )

2Fo1/ 2 m 0.50Fo 0.65 Fo2 = 2(CA,s CA,i ) m m 2

At 1 hour and 10 hours, Fom = 0.00415 and 0.0415, respectively. Then with CA,s = 0.0830 kmol/m3 and CA,i = 0, we find, For t = 1 hr, C A = 0.0117 kmol / m3, For t = 10 hr, C A = 0.0346 kmol / m3,

n = 1.9 105 n = 5.5 105

< <

COMMENTS: (1) Hydrogen diffusion into glass optical fibers is highly undesirable because of
CA (0, t) CA,s hours, * = = 0.145 . This tells us that the centerline concentration is within o CA,i CA,s 14.5% of reaching the surface concentration. At the same time, the average molar concentration is 93.7% of the surface concentration, i.e. within 6.3% of reaching the surface concentration. This is because of the radial geometry, which has greater volume near the surface than near the centerline.
the effects described in the problem statement. Hermetic coatings are typically applied to the fibers to prevent diffusion of hydrogen and other unwanted species into the glass. (2) At t = 100

PROBLEM 14.55 KNOWN: Diameters of glass optical fiber and acrylate polymer coating. Mass diffusivity of
water vapor in the acrylate.

FIND: Whether microcracking would occur within several hot and humid days. SCHEMATIC: Di = 125 m Do = 250 m
`

Humid environment

ASSUMPTIONS: (1) One-dimensional mass diffusion. (2) Use of acrylate properties

throughout the cylinder is sufficient for estimating the diffusion process in order to answer the question.

PROPERTIES: Water vapor in acrylate polymer (given): DAB = 5.5 10-13 m2/s. ANALYSIS: We arbitrarily begin by considering a two-day period. Then the mass transfer
Fourier number is,

2 Fom = D ABt / ro = 5.5 1013 m2 / s 48 h 3600 s / h (125 106 m)2 = 6.1

Since Fom > 0.2, we can use the one-term approximation, analogous to Eq. 5.49a. Referring to Table 14.3 for the analogies,

* =

CA (r, t) CA,s CA,i CA,s

2 = C1 exp( 1 Fo m )J o (1r*)

(1)

where from Table 5.1, as Bi, 1 = 2.4050, C1 = 1.6018 . At the outer surface of the glass, r* = 0.5 and from Table B.4, J 0 (2.4050 0.5) J 0 (1.2) 0.67 . Thus

* = 1.6018exp( 2.40502 6.1) 0.67 = 5.6 1016

Referring to the definition of * in Eq. (1), we see that this very small value means that the concentration has essentially already reached the surface concentration. Therefore, careful storage of the optical fiber will not prevent microcracking, since within two days (probably much less), the water vapor has penetrated through the acrylate polymer coating.

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COMMENTS: (1) Equation 5.52 assumes uniform properties throughout the cylinder. Since
the glass is impermeable to moisture, the build-up of moisture in the coating would be even more rapid than this equation predicts. (2) The time required for the concentration to be within 5% of the surface concentration (* = 0.05) is around four hours. (3) Development of hermetic coatings for use in fiber optic and other high technology applications is an ongoing area of research.

PROBLEM 14.56

KNOWN: Mass of insect repellent applied to known area of skin. Convective mass transfer
coefficient, partition coefficient at the ingredient skin interface, mass diffusivity of the ingredient in the skin.

FIND: (a) Initial thickness of the active ingredient, (b) Duration of effective treatment, (c)
Duration of effective treatment with use of reformulated repellent with a very small partition coefficient.

SCHEMATIC:

A, nconv

hm = 5 10-3 m/s A,s,c

L(t)

DAB = 1 10-13 m2/s Repellent Skin

A = 2000 kg/m3 K = 0.05 A,s,D

ndif A,s,i

ASSUMPTIONS: (1) Constant properties and steady-state conditions, (2) Stationary medium.
(3) Skin is semi-infinite medium.

PROPERTIES: Active Ingredient, given: A = 2000 kg/m3, MA= 152 kg/kmol, pA,sat = 1.2 10-5
bars, K (active Ingredient-skin interface) = 0.05, DAB (active ingredient in skin) = 1 10-13 m2/s.

ANALYSIS:
(a) For an active ingredient volume fraction of f = 0.25, the initial thickness of the active ingredient is

L(t = 0) =

fM 0.25 10 10-3 kg = = 2.5 10-6 m = 2.5 m kg A A 2000 3 0.5 m 2 m

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(b) The duration of the effective treatment is associated with the complete depletion of the active ingredient through combined evaporation and absorption. For absorption of the ingredient into the skin, the analogy to Eq. 5.61 may be employed to provide
L(t = 0) =
t t 1 1 " n A,co nv dt + n" dt = A,dif A A 0 0

t t D AB ( A,s,D A,i )dt h m ( A,s,c A, )dt + t 0 0

Continued

PROBLEM 14.56 (Cont.)

Noting that A, = A,i = 0 and A,s,D = KA, the integrations may be carried out to yield
L(t = 0) = D AB K 1 h m ( A,s,c )t + 2 t A

The surface concentration of the active ingredient is

A,s,c = p A,sat (Ts ) (R / M A )Ts = 1.2 105 bar = 71.9 106 kg / m 3 -2 3 (8.314 10 m bar/kmol K/152 kmol/kg) (273 +32)K

Substituting the values of L(t = 0), A,s,c, and the quantities given in the problem statement, the preceding equation may be solved to yield t = 6130 s or 1.7 h (c) Setting K = 0, the preceding equation may be solved again to yield t = 13900 s or 3.9 h

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COMMENT: In part (b), convective losses are 43% of the total loss, while losses due to diffusion into the skin are 57%.