24.

1
Assume: 1) Ideal gas mixture, 2) constant , 3 constant c (total molar concentration).
Given

with

with M " "

and

# $ "

" " "

# #
# " "
" "
#% " # #

# # #

24-1
24.2

a. Prove &

'

' & '

Thus,

&

&
b. Prove #( #) &
From part (a),

&
[# " ]

# #
Then

&
" "

$ $ ]
*
+
[&

# # 1
· $ $
" "
" ]
# # $ $
[

" " " "

Thus,

# # $ $

$ $ ]
*
.
[$

# # $

24-2
c. Prove / / 0

/
So

/ /

1 0
Thus

/ / ·0 ·0 0

24-3
24.3

Given
6

3 54 51
1 1 4
2 14
47*,481

i =A, j = B, and n = 2 (species A and B)

95 5 ,: ;
2 ,:

5 ,: 5 ,:

⁄ 5 ,: ⁄ 5 ,:

5 ,: 5 ,:

= ,: 1 = ,:

So,

= = =
2 ,: ,: ,:

9= ,: = ,: ; = ,:

Thus,

= 9= = ,: ;
,:
2 ,:

24-4
24.4

NA = 5.0 > 10-5 kgmole A/m2·s

NB = 0 kgmole B/m2·s

= 0.005 kgmole/m3

= 0.036 kgmole/m3

Find 5 , 5 , and V

NA = 5

= 5.0 > 10AB kgmole A/mK · s

5 0.010 m/s
0.005 kgmole/mM

NB = 5 =0

Thus, vB = 0 m/s
1 1 = =
N 5 5 = =

5.0 > 10AB kgmole A/ mK · s

0.0012 m/s
0.005 kgmole/mM 0.036 kgmole/mM

24-5
24.5

P = 6.1 > 10AM bar

T = 210 K

QRS 0.9532, US 0.027, W 0.016, RS 0.0013, QR 0.0008

A = CO2

a. Find Y for CO2

10B Pa
Y Z 0.9532 6.1 > 10AM bar ^ ` 581 Pa
1 bar

b. Find for CO2

Y 581 Pa
0.333 gmole⁄mM
ab 8.314 mM · Pa⁄gmole · K 210 K

c. Find c for the Martian atmosphere

Z 610 Pa
0.349 gmole⁄mM
ab 8.314 mM · Pa⁄gmole · K 210 K

d. Find ρ for the Martian atmosphere

"efg QRS "QRS US "US W" W RS "RS QR "QR

g g g
"efg 0.9532 · 44.01 0.027 · 28.00 0.016 · 39.95
gmole gmole gmole
g g g
0.0013 · 32.00 0.0008 · 28.01 43.41
gmole gmole gmole
Thus,

"efg · c 43.41 ijklm · 0.349 15.2

i ijklm i
jn jn

24-6
24.6

A = benzene solute (C6H6) in B = liquid ethanol solvent (C2H5OH)

= 0.0050
T = 293 K

= 789 kg/m3

" 78.11 ijklm, " 46.07 46.07

i i oi
ijklm oijklm

Estimate
The solution is dilute with respect to A
kg
789 kmole
p mM 17.1
" kg mM
46.07
kgmole

1
1 1q 0.0050 0.9950
0.0050
g
78.11
" gmole
r 0.0030
0.0050 0.9950
" " g g
78.11 46.07
gmole gmole

r 0.0030 17.1 kgmole⁄mM 0.051 kgmole⁄mM 51 gmole⁄mM

24-7
24.7

a. Estimate for stK in air

A = stK and B = air

" 44.01 ," 28.97

i i
ijklm ijklm

T = 310 K
1atm
Z 1.5 > 10B Pa u v 1.49 atm
1.01 > 10B Pa
Hirschfelder Equation:

1 1 *⁄K
0.001858 b M⁄K w x
" "
Zy K Ω{

From Appendix K, Table K.2: y 3.996 Å, y 3.617 Å, 190 K, 97 K .

} }
~ ~

y y 3.996 Å 3.617 Å
y 3.807 Å
2 2
•b • • */K 1 1 *⁄K
u · v b u · v · 310 K 2.28
€ € € 190 K 97 K
From Table K.1, interpolate to find ΩD = 1.029.
*/K
1 1
0.001858 · 310 K M/K • g g ‚
44.01 28.97
gmole gmole
0.109 cmK ⁄s
1.49 atm 93.807 Å; 1.029
K

b. Estimate DAB for ethanol in air

A = ethanol and B = air

" 46.07 ," 28.97

i i
ijklm ijklm

T = 325 K
1atm
Z 2.0 > 10B Pa u v 1.98 atm
1.01 > 10B Pa
From Appendix K, Table K.2: y 4.455 Å, y 3.617 Å, 391 ƒ, 97 ƒ .
} }
~ ~

24-8
 y y 4.455 Å 3.617 Å
y 4.036 Å
2 2
•b • • */K 1 1 *⁄K
u · v b u · v · 325 K 1.67
€ € € 391K 97K
From Table K.1, interpolate to find ΩD = 1.148.
*/K
1 1
0.001858 · 325 ƒ M/K • g g ‚
46.07 28.97
gmole gmole
0.0697 cmK ⁄s
1.98 atm 94.036 Å; 1.148
K

c. Estimate DAB for CCl4 in air

A = CCl4 and B = air

" 153.82 ," 28.97

i i
ijklm ijklm

T = 298 K
1atm
Z 1.913 > 10B Pa u v 1.894 atm
1.01 > 10B Pa
From Appendix K, Table K.2, y 5.881 Å, y 3.617 Å, 327 K, 97 K .
} }
~ ~

y y 5.881 Å 3.617 Å
y 4.749 Å
2 2
•b • • */K 1 1 *⁄K
u · v b u · v · 298 K 1.67
€ € € 327K 97K
From Table K.1, ΩD = 1.148.
*/K
1 1
0.001858 · 298 K M/K • g g ‚
153.82 28.97
gmole gmole
0.0395 cmK ⁄s
1.894 atm 94.749 Å; 1.148
K

24-9
24.8
Estimate for NH3 in air
A = NH3, B = air

" 17.03 ," 28.97

i i
ijklm ijklm

P = 1.0 atm, T = 373 K, „… 1.46 debye, Nˆ 25.8 , bˆ 239.7 K

+‰n
g‰Š‹Œ

Brokaw equation

1.94 > 10M „… K

1.94 > 10M 1.46 debye K
• 0.669
Nˆ bˆ ŽM
25.8 239.7 K
•Ž•‘
€
1.1891 1.3• K ; bˆ 1.18 1 1.3 0.669 K
239.7 K 447 K
•

ŽM
*/M

1.585 Nˆ 1.585 25.8

•Ž•‘
*/M
y ^ K` ’ “ 2.957 Å
1 1.3• 1 1.3 0.669 K

Since the air doesn’t have a dipole, δB = 0. Thus, δAB = 0.

97 K .
}
~
From Appendix K, Table K.2,

From Table 24.4 of Ch.24, Nˆ

+‰ n
g‰Š‹Œ
= 29.9 .

ŽM
*/M

1.585 Nˆ 1.585 29.9

•Ž•‘
*/M
y ^ K` ’ “ 3.619 Å
1 1.3• 1 1.3 0 K

y y y */K
2.957 Å · 3.619 Å */K
3.271 Å

•b • • */K 1 1 *⁄K
b ”
u · v b u · v · 373 K 1.79
€ € € 447K 97K
– s ™ ›
Ω{ Ω{,•
b” exp b” exp šb ” exp œb ”
1.06036 0.19300 1.03587 1.76474
1.79 •.*B•*• exp 0.47635 · 1.79 exp 1.52996 · 1.79 exp 3.89411 · 1.79
1.12

24-10
Hirschfelder Equation

1 1 *⁄K
0.001858 b M⁄K w x
" "
Zy K Ω{
*/K
1 1
0.001858 · 373 K M/K • g g ‚
17.03 28.97
gmole gmole
0.341 cmK ⁄s
1.0 atm 93.271 Å; 1.12
K

+‰S ež‰
Ÿ
For comparison, from Appendix J, Table J.1, DABP = 0.198 at T1 = 273 K.

ŽK Ž
Z 0.198 ŽK
s 0.198
,*
Z 1.0 atm s
•b • • */K 1 1 *⁄K
b ”
u · v b u · v · 273 K 1.31
€ € € 447K 97K
– s ™ ›
Ω{,K
b” exp b” exp šb ” exp œb ”
1.06036 0.19300 1.03587 1.76474
1.27
1.31 •.*B•*• exp 0.47635 · 1.31 exp 1.52996 · 1.31 exp 3.89411 · 1.31
+‰S
Ÿ
Table J.1: DAB = 0.198 at T = 273 K and P = 1.0 atm

Z* bK M/K Ω{,* ŽK 1 atm 373 K M⁄K 1.12 ŽK

u vu v ^0.198 `u vu v 0.279
,K ,*
ZK b* Ω{,K s 1 atm 273 K 1.27 s

The Brokaw Equation diffusion coefficient is different than that of Table J.1.
+‰ S
Ÿ
Brokaw equation, scaled to 373K and 1.0 atm, DAB = 0.279

24-11
24.9
T = 1073 K
1atm
Z 1.5 > 10B Pa u v 1.49 atm
1.01 > 10B Pa
a. Estimate DAB for SiCl4 in H2
A = SiCl4 and B = H2

" 169.9 ," 2.02

g g
g‰Š‹Œ g‰Š‹Œ

From Appendix K, Table K.2, y 5.08 Å, y 2.968 Å, 358 K, 33.3 K .

} }
~ ~

y y 5.08 Å 2.968 Å
y 4.02 Å
2 2
•b • • */K 1 1 *⁄K
u · v b u · v · 1073 K 9.83
€ € € 358K 33.3K
From Table K.1, interpolate to find ΩD = 0.7448

1 1 *⁄K
0.001858 b w M⁄K
x
" "
Zy K Ω{
*/K
1 1
0.001858 · 1073 K M/K • • • ‚
169.9 2.02 ŽK
•Ž•‘ •Ž•‘
2.58
1.49 atm 94.02 Å; 0.7448
K s

b. Estimate DA-m for SiCl4 in mixture gas

Find DAC for SiCl4 in HCl
A = SiCl4 , B = H2, C = HCl

" 169.9 , "Q 36.46

g g
g‰Š‹Œ g‰Š‹Œ

From Appendix K, Table K.2, y 5.08 Å, yQ 3.305 Å, 358 K, 360 K .

} }¡
~ ~

y yQ 5.08 Å 3.305 Å
y 4.19 Å
Q
2 2

24-12
•b • • */K 1 1 *⁄K
u · v b u · v · 1073 K 2.99
€Q € €Q 358K 360K
From Table K.1, interpolate to find ΩD = 0.9499

1 1 *⁄K
0.001858 b M⁄K w" "Q x
Q
Zy Q
KΩ
{

*/K
1 1
0.001858 1073K M/K
• • • ‚
169.90 36.46 ŽK
•Ž•‘ •Ž•‘
0.480
1.49 atm 94.19 Å; 0.9499
K s

0.4, 0.4, Q 0.2

1 1
, ¢ , ¢Q , ta
Q Q
A
¢ ¢Q 1 1 A‰ Q
Q

0.667 , 0.333
£ •.¤ £ •.K
*A•.¤ Q *A•.¤

1 ŽK
1.05
A 0.667 0.333 s
ŽK ŽK
2.58 0.480
s s

24-13
24.10

A = H2S, B = N2, C = SO2

" 34.08 ," 28.01 , "Q 64.07

g g g
g‰Š‹Œ g‰Š‹Œ g‰Š‹Œ
.

0.03, 0.92, Q 0.05

T = 350 K, P = 1.0 atm.
a. Determine c, cA, and ρA
Z 1.0 atm gmole
34.8
ab mM · atm mM
u8.206 > 10AB v 350 K
gmole · K
gmole gmole
0.03 u34.8 v 1.04
mM mM
g
" u1.04 v u34.08 v 35.4
gmole
gmole g
m3 m3
b. Estimate DAB for H2S in N2

b+ 373.2K, N+ 98.5 ijklm.

¥jn

cmM
y 0.841 NQ */M
0.841 98.5 */M
3.884 Å
gmole
€
0.77 bQ 0.77 373.2K 287.4K
•
From Appendix K, Table K.2, y 3.681 Å, 91.5 K .
}
~

y y 3.884 Å 3.681 Å
y 3.78 Å
2 2
•b • • */K 1 1 *⁄K
u · v b u · v · 350 K 2.16
€ € € 287.4K 91.5K
From Table K.1, interpolate to get ΩD = 1.047.

1 1 *⁄K
0.001858 b M⁄K w x
" "
Zy K Ω{

24-14
 */K
1 1
0.001858 · 350 K M/K • g g ‚
34.08 28.01
gmole gmole
0.207 cmK ⁄s
1.0 atm 93.78 Å; 1.047
K

c. Estimate DA-m for H2S in mixture gas

Find DAC for H2S in SO2

From Appendix K, Table K.2, yQ 4.290 Å, 252 K

}¡
~

y yQ 3.884 Å 4.290 Å
y 4.09 Å
Q
2 2
•b • • */K 1 1 *⁄K
u · v b u · v · 350 K 1.30
€Q € €Q 287.4K 252K
From Table K.1, ΩD = 1.273.

1 1 *⁄K
0.001858 b M⁄K w x
" "Q
Q
Zy Q K Ω{

1 1 */K
0.001858 · 350 K M/K u v
34.08 g/gmole 64.07 g/gmole
0.12 cmK ⁄s
1.0 atm 94.09 Å; 1.273
K

0.03, 0.92, Q 0.05

1 1
, ¢ , ¢Q , •¦
Q Q
A
¢ ¢Q 1 1 A‰ Q
Q

1 0.03 0.92 0.05 ŽK

, § 0.20
A 0.21 cmK ⁄s 0.12 cmK ⁄s A
s
This diffusion coefficient is slightly different than that of H2S-N2 because H2S diffuses with N2
and SO2 in the mixture gas. But, since N2 gas dominates, the diffusion coefficient is very similar.

24-15
24.11

A = CO, B = H2

y¨ 0.01, y© 0.99

dªk«m 15 > 10A¬ cm, ε 0.30, T = 673 K, P = 5.0 atm

M¨ 28.01 , M© 2.02
i i
ijklm ijklm

a. Estimate cA

y¨ P 0.01 · 5.0 atm mol

c¨ y¨ c 9.054 > 10A¬
RT cmM · atm cmM
82.06 · 673 K
mol · K

b. Estimate molecular diffusion coefficient, DAB

*
1 1 K
Hirschfelder Equation
M
0.001858 ·w · TK x
M¨ M©
D¨©
P · σK¨© Ω²

ε¨ ε© ε¨© ε¨ ε© κT
110 K, 33.3 K, ´ · 60.52 K, 11.12
κ κ κ κ κ 娩

Use Appendix K. 1 and interpolate for Ω² 0.7336

σ¨ σ© 3.590 ¸ 2.968 ¸
σ¨© 3.279 ¸
2 2
*
K
M 1 1
0.001858 · 673 K K · • g g ‚
28.01 2.02 cmK
gmole gmole
D¨© 0.599
5.0 atm · 3.279 ¸ · 0.7336
K s

c. Estimate Knudsen diffusion and effective diffusion coefficient

T 673 cmK
D¹¨ 4850 · dªk«m · º 4850 · 15 > 10A¬ · º 0.0357
M¨ 28.01 s

24-16
 w x ^ `
* * * * *
²»¼ ²»½ ²¾» ÀÁS ÀÁS
•.B¿¿ .•MB¬
 Â

D¨m 0.0337
¥jS
Ÿ

€ K D¨m 0.3 w0.0337 x 3.03 x 10AM

£ K ¥jS ¥jS
Œ Ÿ Ÿ

Knudsen diffusion is important at current conditions. D¨m p D¹¨

When D¹¨ D¨© , P ?

*
K
*
1 M 1 K
1 0.001858 · ·w
M¨
TK
M©
x
D¹¨ ·
2 P · σ¨© Ω²
K
*
K
M 1 1
0.001858 · 673 K K · • g g ‚
1 28.01 2.02 cmK
mol mol
· 0.0357
2 P · 3.279 ¸ 0.7336
K· s

§ P 42.0 atm

24-17
24.12

A = H2S, B = CH4

y¨ 0.01, y© 0.99

ε 0.50, dªk«m 20 > 10A¬ cm, T = 303 K, P = 15.0 atm

g g
M¨ 34.08 , M© 16.05
gmole gmole

a. Determine cA

y¨ P 0.01 · 15.0 atm mol

c¨ y¨ c 6.033 > 10A•
RT cmM · atm cmM
82.06 · 303 K
mol · K

b. Estimate molecular diffusion coefficient, DAB

Hirschfelder Equation

301.1 K, 136.5 , ´ ~» · 202.7 K, 1.495

Æ» ƽ Æ»½ Æ Æ½ ~Ç
~ ~ ~ ~ Æ»½

Use Appendix K. 1, Ω² 1.198

σ¨ 3.623 ¸, σ© 3.822 ¸, σ¨© 3.723 ¸

Ȼ Ƚ
K
*
K
M 1 1
0.001858 · 303 K K · • g ‚
*
M1 1 K g
0.001858 · TK
· wM 34.08 16.05
M© x gmole gmole
D¨© ¨
P · σK¨© Ω² 15.0 atm · 3.723 ¸K 1.198

cmK
D¨© 0.0119
s

Fuller Schettler Giddings Equation

Σv ¨ 2 · 1.98 17.0 20.96

Σv © 16.5 4 · 1.98 24.42

24-18
 *
K
1 1
0.001 · 303 K*.¬B · • g ‚
*
1 1 K g
0.001 · T *.¬B
·w x 34.08 16.05
M¨ M© gmole gmole
D¨©
* * K * * K
P · ^ Σv M
Σv M
` 15.0 atm · u20.96M 24.42M v
¨ ©

cmK
D¨© 0.0138
s

Results are similar.

b. Estimate effective diffusion coefficient

D¹¨ 4850 · dªk«m · ´Ë 4850 · 20 > 10A¬ cm · ´ 0.0289

Ç M•M ¹ ¥jS
Í
» M¤.•Ì Ÿ
ÍÁÎϼ

1 1 1 1 1
u v • ‚
D¨m D¨© D¹¨ cmK cmK
0.0138 0.0289
s s

D¨m 9.37 > 10AM

¥jS
Ÿ

cmK cmK
D¢¨m εK D¨m 0.050K · 9.37 > 10AM 2.34 x 10AB
s s

24-19
24.13

A = SiH4, B = He

y¨ = 0.01, y© = 0.99

dªk«m 10 > 10A¤ cm, T = 900 K

M¨ 32.12 , M© 4.00
i i
ijklm ijklm

κ 1.38 > 10A*• ergs/K

g
0.01 · 32.12
a. Determine wA
y¨ · M¨ gmole
w¨ g g 0.750
y¨ · M¨ y© · M© 0.01 · 32.12 0.99 · 4.00
gmole gmole

b. Estimate DAB at P = 1.0 atm and P = 100 Pa, T = 900 K

P = 1.0 atm

207.6 K, 10.22 K , ´ ~» · 46.06 K, 19.54

Æ» ƽ Æ»½ Æ Æ½ ~Ç
~ ~ ~ ~ Æ»½

Using Appendix K. 1, interpolate to get Ω² 0.6676

σ¨ 4.08 ¸, σ© 2.576 ¸, σ¨© 3.328 ¸

Ȼ Ƚ
K
*
K
M 1 1
0.001858 · 900 K K · • g ‚
*
1M 1 g
0.001858 · TK
· wM 32.12 4.00
M© x
K
gmole gmole
D¨© ¨
P · σ¨© Ω²
K
1.0 atm · 3.328 ¸ · 0.6676
K

cmK
3.60
s

P = 100 Pa · 9.87 > 10A¤ atm

* ÐÑj
*•*MKB ÒÐ

24-20
 *
K
M 1 1
0.001858 · 900 K K · • g ‚
*
1
M 1 K g
0.001858 · ·wTK x 32.12 4.00
M¨ M© gmole gmole
D¨©
P · σ¨© Ω²
K
9.87 > 10 atm · 3.328 ¸ · 0.6676
A¤ K

cmK
3645
s

This value is large because at pressures this low, the gas mixture is very dilute, and the two gases
basically act independently of one another.

c. Assess importance of Knudsen Diffusion

J
κT 1.38 > 10AKM K · 900 K
Pressure = 1.0 atm

λ 1.66 > 10A¬ cm

√2πσ¨ K P √2π · 4.08 > 10A*• m K 101325 Pa

Kn 1.66 > 10A¤ Þ 1, Knudsen diffusion is not important.

× •.¬•>*•ÛÜ ¥j
ØÙÎÚ¼ *•>*•ÛÝ ¥j

Pressure = 100 Pa
J
κT 1.38 > 10AKM K · 900 K
λ 1.68 > 10A¤ cm
√2πσ¨ KP √2π · 4.08 > 10A*• m K 100 Pa

λ 1.68 > 10A¤ cm

Kn 0.168, Knudsen diffusion plays moderate role
dªk«m 10 > 10A¤ cm

d. Gas velocity for Pe = 5.0 x 10-4

D¹¨ 4850 · dªk«m · ´ 4850 · 10 > 10A¤ cm · ´ 25.67

Ç ¿•• ¹ ¥jS
Í
Ë» MK.*M Ÿ
ÍÁÎϼ

Pressure = 1 atm:

1 1 1 1 1
u v • ‚
D¨m D¨© D¹¨ cmK cmK
3.60 25.67
s s

cmK
D¨m 3.157
s

24-21
 vß·ØÙÎÚ¼
Pe 5 > 10A¤
D¨m
cm
vß 1.58
s
πdK cm cmM
Vá vß 1.58 · π · 5 > 10A¤ cm K
1.24 > 10A•
4 s s

Pressure = 100 Pa:

w x , § D¨m 25.49 cmK /s

* * *
²»¼ ²»½ ²¾»
vß·ØÙÎÚ¼
Pe 5 > 10A¤
D¨m
cm
§ vß 12.75
s
cm π cmM
Vá 12.75 · · 10 > 10A¤ cm K
1.00 > 10 AB
s 4 s

24-22
24.14

A = O2, B = N2

P = 1.0 atm, T = 293 K

D¨© 0.181
¥jS
Ÿ
at T = 273 K, P = 1.0 atm

cmK 293 K cmK

*.B
D¨© 0.181 u v 0.201
s 273 K s
g g
M¨ 32.00 ,M 28.01
gmole © gmole

dªk«m 10 > 10A• cm

a. Effective diffusion coefficient for straight 10 nm pores in parallel array

T 293 K
D¹¨ 4850 · dªk«m · º 4850 · 10 > 10A• cm · â g 0.147 cmK /s
M¨ 32.00
gmole

1 1 1 1 1
u v u v
D¨m D¨© D¹¨ 0.201 cmK /s 0.147 cmK /s

D¨m 0.085 cmK /s

ε 0.40
b. Effective diffusion coefficient for random pores of 10 nm diameter with void fraction of

See part (a)

cmK cmK
D¢¨m εK D¨m 0.40K · 0.085 0.0136
s s

24-23
c. Effective diffusion coefficient for random pores of 1.0 µm diameter with void fraction of
ε 0.40

dªk«m 1 > 10A¤ cm

T 293 K cmK
D¹¨ 4850 · dªk«m · º 4850 · 1 > 10A¤ cm · â g 1.468
M¨ 32.00 s
gmole
1 1 1 1 1
u v u v
D¨m D¨© D¹¨ 0.201 cmK /s 1.47 cmK /s

D¨m 0.177 cmK /s

cmK cmK
D¢¨m εK D¨m 0.40K · 0.177 0.0283
s s

24-24
24.15

A = CH4, B = H2O

T = 673 K, dªk«m 5 > 10AM cm, vß 4.0 cm/s

M¨ 16.04 , M© 18.02
i i
ijklm ijklm

vß dªk«m
Pe 2
D¨m

a. Knudsen diffusion coefficient for CH4

D¹¨ 4850 · dªk«m · ´Ë 4850 · 5 > 10AM cm · ´ 157 cmK /s

Ç •¬M ¹
Í
» *•.•¤
ÍÁÎϼ

D¨© will dominate the D¨m equation.

Because of the large size of the Knudsen diffusion coefficient, its effect will not be important.

b. Total system pressure for Pe = 2.0

5ß
Z
…ŠWŒ

5ß …ŠWŒ
Œ
Z
ÀÁ

D¨m 0.01
¤.• ·B>*•Ûn ¥j ¥jS
Â
K Ÿ

1 1 1 1 1 1
u v u v
D¨m cmK D¨© D¹¨ D¨© 157 cmK /s
0.01
s

D¨© 0.01
¥jS
Ÿ

Fuller, Schettler, and Giddings Equation:

1 1
0.001 · T*.¬B · */K
M¨ M©
D¨© * *
P· Σv M
¨
Σv M K
©

24-25
Σvê ¨ 16.5 4 · 1.98 24.42
Σvê © 12.7

1 1
0.001 · 673 K*.¬B · g g
*/K
16.05 18.02 cmK
gmole gmole
D¨© 0.01
* * s
P 24.42 M
12.7 M K

1 1
0.001 · 673 K*.¬B · g g
*/K
16.04 18.02
gmole gmole
P 111.6 atm
cmK
* *
0.01 · 24.42 M
12.7 M K
s

24-26
24.16

A = albumin, B = H2O

D¨© 5.94 > 10A¬ cmK /s, T = 293K, κ 1.38 > 10A*• ergs/K

kg
1 Pa · s 1
m·s

1 erg = 1 g·cm2/s2

1000 g 1m g
µ© 293 K 993 > 10A• Pa · s · u v·u v 993 > 10AB
1kg 100 cm cm · s

Stokes Einstein Equation:

κT
D¨©
6πr¨ µ©

cmK
κT 1.38 > 10A*• g · · 293K
diameter¨ r¨ · 2 2· 2· sK · K
6πD¨© µ© cmK g
6 · π · 5.94 > 10A¬ · 993 > 10AB
s cm · s
7.27 nm

This answer is close to the known value of 7.22 nm

24-27
24.17

A = O2, B = H2O

T = 310 K, V¨ 25.6 cmM /gmole, Φ© 2.6

1000 cP
µ© 7.083 > 10A¤ Pa · s · u v 0.7083 cP
1 Pa · s

M© 18.02 g/gmole

Wilke Chang Equation

* *
7.4 > 10AÌ Φ© M© K T 7.4 > 10AÌ 2.6 · 18.02 K 310
D¨© · ·
V¨ •.• µ© 25.6 •.• 0.7083

D¨© 3.17 > 10AB cmK /s

Hayduk and Laudie Equation (used for nonelectrolytes in H2O)

D¨© 13.26 > 10AB ” µ©A*.*¤ · V Ä•.BÌ¿ 13.26 > 10AB 0.7083 A*.*¤
· 25.6 A•.BÌ¿

2.91 > 10AB cmK /s

24-28
24.18

T = 288 K

Physical property information

Interpolate and convert Pa·s to cP from Appendix I to find viscosity of liquid water at 288 K:

µìKí 288 K 1.193 cP (water)

For viscosity of liquid ethanol and n-butanol, From Perry’s Chemical Engineering Handbook,
interpolate and convert to cP:

µîì¤í 288 K 0.641 cP (ethanol)

µî¤ì*•í 288 K 3.41 cP (n-butanol)

VìKí 18.9 cmM /gmole (water)

From Table 24.4 and Table 24.5

Vîì¤í 14.8 4 · 3.7 7.4 37.0 cmM /gmole (ethanol)

Vî¤ì*•í 4 · 14.8 10 · 3.7 7.4 103.6 cmM /gmole (n-butanol)

ΦìKí = 2.6 (water)

Φîì¤í = 1.9 (ethanol)
Φî¤ì*•í = 1.0 (n-butanol)

MìKí 18 g/gmole (water)

Mîì¤í 32.04 g/gmole (ethanol)
Mî¤ì*•í 74.12 g/gmole (n-butanol)

Hayduk and Laudie Equation (used for nonelectrolyte solutes in H2O water solvent)

D¨© 13.26 > 10AB µA*.*¤

© · V Ä•.BÌ¿

Wilke Chang Equation

7.4 > 10AÌ Φ© M© */K

T
D¨© ·
V¨ •.• µ©

a. Molecular diffusion coefficient for liquid methanol solute (A) in solvent H2O (B)

Appendix J.2 Value: DAB = 1.28 > 10AB cmK /s

D¨© 13.26 > 10AB µA*.*¤

© V Ä•.BÌ¿

24-29
 cmK
D¨© 13.26 > 10AB 1.193 A*.*¤
· 37.0 A•.BÌ¿
1.29 > 10AB

b. Molecular diffusion coefficient for liquid solute H2O (A) in solvent ethanol (B)

7.4 > 10AÌ Φ© M© */K

T
D¨© ·
V¨ •.• µ©

7.4 > 10AÌ 1.9 · 18 */K

288 cmK
D¨© · 4.45 > 10AB
18.9•.• 0.641 s

c. Molecular diffusion coefficient for liquid n-butanol solute (A) in solvent H2O (B)

Appendix J.2 Value: D¨© 7.7 > 10A• cmK /s

D¨© 13.26 > 10AB ” µ©A*.*¤ · V Ä•.BÌ¿

cmK
D¨© 13.26 > 10AB 1.193 A*.*¤
· 103.6 A•.BÌ¿
7.05 > 10A•
s

d. Molecular diffusion coefficient for liquid H2O solute (A) in solvent n-butanol (B)

7.4 > 10AÌ Φ© M© */K

T
D¨© ·
V¨•.• µ©

7.4 > 10AÌ 1.0 · 74.12 */K

288 cmK
D¨© · 9.23 > 10A•
18.9•.• 3.41 s

24-30
24.19

A = Benzene (C6H6, liquid), B = Ethanol (C2H6O, liquid)

M¨ 78.11 g/gmole, M© 46.07 g/gmole

Interpolate and convert Pa·s to cP from Appendix I to find viscosity of liquid benzene at 288K

lbj 0.45359 kg 1 ft
µ¨ 59ï 44.5 > 10AB ·u vu v 0.662 > 10AM Pa · s 0.662 cP
(59 F)

ft · s lbj 0.3048 m

From Perry’s Chemical Engineering Handbook, interpolate and convert units to cP:

µ© 288 K 1.34 cP

cmM
Using Table 24.4 and 24.5
V¨ 6 · 14.8 6 · 3.7 15 ring 96.0
gmole
cmM
V© 2 · 14.8 6 · 3.7 7.4 59.2
gmole

Φ¨ 1.0, Φ© 1.5

Wilke Chang correlation (liquid benzene in ethanol)

7.4 > 10AÌ Φ© M© */K

T
D¨© ·
V¨ •.• µ©

g
7.4 > 10AÌ 1.5 · 46.07 */K
288 K
gmole
D¨© · 8.55 > 10A• cmK /s
cmM
•.• 1.34 cP
96
gmole

Schiebel correlation (liquid benzene-solute in ethanol-solvent)

K
K T 3V© M
D¨© ·
*/M µ
,K 8.2 > 10 AÌ
· 1 u v
V © V¨
¨
K
cmM M
K 288 K ò 3 · 59.2
gmole õ
D¨© · ,K 8.2 > 10AÌ · ñ1 ’ “ ô
*
1.34 cP cmM
cmM 96.0
gmole
M
u96.0 v
gmole ð ó

24-31
D¨© 9.65 > 10A• cmK /s

Wilke Chang correlation (liquid ethanol in benzene)

7.4 > 10AÌ Φ¨ M¨ */K

T
D©¨ ·
V©•.• µ¨

7.4 > 10AÌ 1.0 · 78.11 g/mole */K

288 K cmK
D©¨ · 2.46 > 10AB
59.2 cmM /gmole•.• 0.662 cP s

Schiebel correlation (liquid ethanol-solute in benzene-solvent)

Note VB < 2VA, benzene is the solvent

D©¨ · µ ,K 18.9 > 10AÌ

¹ Ç
÷/n
ö½ »

18.9 > 10AÌ 288 K

D©¨ · ,
*
0.662 cP
cmM M
59.2
gmole

D©¨ 2.11 > 10AB cmK /s

D¨© ø D©¨ because the molecular diffusion coefficient equations are not symmetric, with
assignments to the solute and solvent. Also, unlike gases, liquid molecules do not behave
independently of each other due to the influence of intermolecular forces between them.

24-32
24.20

A = CuCl2 (an ionic solute), B = H2O

T = 298 K, ù 96,500 C/gmole

J
R 8.316
gmole · K

A · cmK
λ Cu
° K
108
V · gmole

A · cmK
λ°A ClA
76.3
V · gmole

n valence of cation 2

nA valence of anion 1

Nernst-Haskell Equation

1 1
RT
D¨© n nA
1 1
ù K
λ° λ°A
1 1 J
8.316 · 298K cmK
2 1 gmole · K
D¨© 1.78 > 10AB
1 1 s
96,500 C/gmole K
A · cmK A · cmK
108 76.3
V · gmole V · gmole

24-33
24.21

A = C6H6, B = H2O

dpore = 0.30 µm = 300 nm

a. Find cA (molar concentration of benzene)

ρA 0.100 g/L
cA = = = 0.00128 gmole A/L
MA 78 g/gmole

b. Find xA and wA

Assume dilute solution

ρB
c ≅ cB =
MB

From Appendix I, ρΒ = 996.7 kg/m3 = 996.7 g/L at 298 K

996.7 g/L
c= = 55.3 gmole/L
18.02 g/gmole

cA 0.00128 gmole/L
xA = = = 2.31×10−5 gmole A/total gmole (can be written without units)
c 55.3 gmole/L

wA =
xA M A
=
( 2.31×10−5 ) ( 78 g/gmole )
= 1.00 ×10−4 g A/total g
x A M A + xB M B ( 2.31×10 ) ( 78 g/gmole ) + ( 0.99998 )(18.02 g/gmole )
−5

c. DAB for benzene in groundwater

Wilke-Chang Equation

DAB µ B 7.4 ×10−8 (φB M B )1/2

=
T VA0.6

From Appendix I, µΒ = 9.0925×10−4 Pa ⋅ s = 0.90925 cP at 298 K, φΒ = 2.6

1.048
(
VA = 0.285Vc1.048 = 0.285 259 cm 3 gmole ) = 96.4 cm 3 gmole

24-34
DAB =
7.4 ×10−8 (2.6 × 18.02 )1/2 ( 298 ) = 1.07 ×10−5 cm 2 s
0.6
( 96.4 ) ( 0.90925 )

d,e. Effective diffusion coefficient of benzene in water-filled pore

DAe = D o AB F1 (ϕ ) F2 (ϕ )

Solving for ü of benzene

ü 0.15 Ž

ds 0.15 nm
ϕ= = = 5 ×10−4
d pore 300 nm

F1 (ϕ ) = (1 − ϕ ) 2 = (1- 5.0 x 10-4 ) 2 =0.999

3 5
F2 (ϕ ) = 1 − 2.104ϕ + 2.09ϕ 3 − 0.95ϕ 5 = 1 − 2.104 ( 5 × 10−4 ) + 2.09 ( 5 × 10−4 ) − 0.95 ( 5 ×10−4 ) = 0.999

The two correction factors, F1 (ϕ) and F2 (ϕ), are nearly 1, and so DAe ≈ D o AB .

2
D ' Ae = ε 2 DAe = ( 0.40 ) (1.07 ×10−5 cm 2 s ) = 1.71×10−6 cm 2 s

24-35
24.22

a. DAB for glucose in water

A = C6H12O6, B = H2O

Stokes-Einstein equation

κT
DAB =
6π rA µ B

1 1
¦ 0.86 Ž 4.3 r10AÌ Ž
2 2

From Appendix I, µΒ = 0.00826 g cm ⋅ s at 303 K

DAB =
(1.38 ×10 −16
g ⋅ cm 2 s 2 ⋅ K ) ( 303 K )
= 6.25 ×10−6 cm 2 s
6π ( 4.3 ×10 −8
cm ) ( 0.00826 g cm ⋅ s )

b. DAe of glucose through the membrane

DAe = D o AB F1 (ϕ ) F2 (ϕ )

ds 0.86 nm
ϕ= = = 0.287
d pore 3.0 nm

2
F1 (ϕ ) = (1 − ϕ ) 2 = (1 − 0.287 ) = 0.508

3 5
F2 (ϕ ) = 1 − 2.104ϕ + 2.09ϕ 3 − 0.95ϕ 5 = 1 − 2.104 ( 0.287 ) + 2.09 ( 0.287 ) − 0.95 ( 0.287 ) = 0.444

DAe = ( 6.25 × 10−6 cm 2 s ) ( 0.508 )( 0.444 ) = 1.41× 10 −6 cm 2 s

24-36
24.23

DAe for the enzyme urease in a single cylindrical pore

DAe = D o AB F1 (ϕ ) F2 (ϕ )

DoAB = 3.46 x 10-7 cm2/s

ds 12.38 nm
ϕ= = = 0.124
d pore 100 nm

2
F1 (ϕ ) = (1 − ϕ ) 2 = (1 − 0.124 ) = 0.767

3 5
F2 (ϕ ) = 1 − 2.104ϕ + 2.09ϕ 3 − 0.95ϕ 5 = 1 − 2.104 ( 0.124 ) + 2.09 ( 0.124 ) − 0.95 ( 0.124 ) = 0.743

DAe = ( 3.46 × 10 −7 cm 2 s ) ( 0.767 )( 0.743 ) = 1.97 × 10 −7 cm 2 s

24-37
24.24

Find dpore when DAe = 5.0 x 10-7 cm2/s

DAe = Do AB F1 (ϕ ) F2 (ϕ )

DoAB =DAB = 1.19 x 10-6 cm2/s (dilute solution)

DAe 5.0 ×10−7 cm 2 s

F1 (ϕ ) F2 (ϕ ) = = = 0.420
DAB 1.19 ×10−6 cm 2 s

2
0.420 = (1 − ϕ ) (1 − 2.104ϕ + 2.09ϕ 3 − 0.95ϕ 5 )

Solve for ϕ

ϕ = 0.183

ds
ϕ=
d pore

3.6 nm
d pore = = 19.7 nm
0.183

24-38
24.25

a. Determine molecular diffusion coefficients of solute A and solute B in water at 293 K

Wilke-Chang Equation

DA− H 2O µ H 2O 7.4 × 10−8 (φ M H 2O )1/2

=
T VA0.6

From Appendix I, µH2O = 9.93 x 10-4 Pa ⋅ s = 0.993 cP at 293 K

MH2O = 18.02 g/gmole

For Solute A

DA − H 2 O =
7.4 x 10-8 (2.6×18.02 g/gmole)1/2 ( 293 K ) = 5.67 x 10-6 cm 2 s
0.6
( 233.7 cm 3
gmole ) ( 0.993 cP )

DA − H 2 O = 5.67 x 10-6 cm2/s

For Solute B,

DB − H 2O =
7.4 x 10-8 (2.6×18.02 g/gmole)1/2 ( 293 K ) = 4.47 x 10-6 cm 2 s
0.6
( 347.4 cm 3
gmole ) ( 0.993 cP )

DB − H 2O = 4.47 x 10-6 cm2/s

b. Determine dpore to achieve a separation factor of α = 3

ds
ϕ=
d pore

DAe = D o A− H 2O F1 (ϕ ) F2 (ϕ )

F1 (ϕ ) = (1 − ϕ ) 2 F2 (ϕ ) = 1 − 2.104ϕ + 2.09ϕ 3 − 0.95ϕ 5

DAe DA− H2O F1 (ϕ A ) F2 (ϕ A )

α= =
DBe DB − H2O F1 (ϕ B ) F2 (ϕ B )

24-39
 2.0 nm 3.0 nm
ϕA = ϕB =
d pore dpore

2
DA− H 2O (1 − ϕ A ) (1 − 2.104ϕ A + 2.09ϕ A3 − 0.95ϕ A5 )
α= 2
DB − H 2O (1 − ϕ B ) (1 − 2.104ϕ B + 2.09ϕ B 3 − 0.95ϕ B 5 )

 2.0 nm 
2
    
3
  
5

DA − H 2 O  1 −  1 − 2.104  2.0 nm  + 2.09  2.0 nm  − 0.95  2.0 nm  

 d pore        
   d pore   d pore   d pore  
α=
 3.0 nm 
2
    
3
  
5

DB − H2O 1 −  1 − 2.104  3.0 nm  + 2.09  3.0 nm  − 0.95  3.0 nm  

 d pore    d   d   d 
   pore   pore   pore  

Trial-and-error; Guess dpore and solve for α

Guess dpore = 7.5 nm

 2.0 nm   2
 2.0 nm   2.0 nm 
3
 2.0 nm  
5

(5.67 ×10 −6
cm s )  1 −
2

 7.5 nm 
 1 − 2.104   + 2.09 
 7.5 nm 
 − 0.95 
 7.5 nm 
 
 7.5 nm  
α= 
 3.0 nm    3.0 nm  
2 3 5
 3.0 nm   3.0 nm 
( 4.47 ×10 −6
cm s )  1 −
2
 1 − 2.104 
 7.5 nm  
 + 2.09 
 7.5 nm 
 − 0.95 
 7.5 nm 
 
 7.5 nm  

α = 3.20

Guess dpore = 7.88 nm

 2.0 nm   2
 2.0 nm   2.0 nm 
3
 2.0 nm  
5

( 5.67 ×10 −6
cm s )  1 −
2

 7.88 nm 
  1 − 2.104   + 2.09 
 7.88 nm 
 − 0.95 
 7.88 nm 
 
 7.88 nm  
α= 
3.0 nm    3.0 nm  
2 3 5
  3.0 nm   3.0 nm 
( 4.47 ×10 −6
cm s )  1 −
2
 1 − 2.104 
 7.88 nm  
 + 2.09 
 7.88 nm 
 − 0.95 
 7.88 nm 
 
 7.88 nm  

α = 3.00

To achieve a separation factor (α) of 3, dpore = 7.88 nm.

24-40
24.26

a. DAB for protein A in solution at 293 K

A = protein A, B = solvent

Stokes-Einstein Equation

κT
DAB =
6π rA µ B

µΒ = 1.0 cP = 0.01 g cm ⋅ s , rA = 12.5 nm = 1.25 x 10-6 cm

DAB =
(1.38 ×10 g ⋅ cm s ⋅ K ) ( 293 K ) = 1.72 ×10
−16 2 2
−7
cm 2 s
6π (1.25 ×10 cm ) ( 0.01 g cm ⋅ s )
−6

b. Determine DAe for protein A within a single cylindrical desired membrane material

DAe = D o AB F1 (ϕ ) F2 (ϕ )

F1 (ϕ ) = (1 − ϕ ) 2

Solve for ϕ if F1 (ϕ) = 0.64

2
0.64 = (1 − ϕ )

ϕ = 0.2

3 5
F2 (ϕ ) = 1 − 2.104ϕ + 2.09ϕ 3 − 0.95ϕ 5 = 1 − 2.104 ( 0.2 ) + 2.09 ( 0.2 ) − 0.95 ( 0.2 ) = 0.596

DAe = (1.72 ×10−7 cm 2 s ) ( 0.64 )( 0.596 ) = 6.56 ×10 −8 cm 2 s

c. Pore diameter for size exclusion of solute

All other proteins other than protein A will be “excluded” from the membrane when ϕ = 1 so that
DAe = 0 at ds = dpore. Consequently, d pore ≤ 25 nm .

24-41
24.27

A = solute, B = solvent

Find solvent viscosity to achieve a D'Ae of 1.0 x 10-7 cm2/s

DAB = 2.04 x 10-7 cm2/s

D ' Ae = ε 2 D Ae

D ' Ae 1.0 × 10 −7 cm 2 s
DAe = 2
= 2
= 2.04 × 10 −7 cm 2 s
ε ( 0.70 )
For hindered diffusion of a solute in a solvent-filled pore

DAe = D o AB F1 (ϕ ) F2 (ϕ )

Hindered diffusion of the solute within the pore can be neglected so DAe ≅ DAB

Stokes-Einstein Equation

κT
DAB =
6π rA µ B

rA = 10 nm = 1 x 10-6 cm

Rearrange to solve for µΒ

µB =
κT
=
(1.38 ×10 −16
g ⋅ cm 2 s 2 ⋅ K ) ( 303 K )
= 0.0109 g cm ⋅ s = 0.00109 Pa ⋅ s
6π DAB rA 6π (1×10−6
cm )( 2.04 ×10−7 cm 2 s )

24-42
24.28

Estimate Q from DAB at two T points by the point-slope form of the Arrhenius equation

 D (T )   1.0 x 10-12 cm 2 /s   8.314 J   1 kJ 

ln  AB 1  R ln    
 DAB (T2 )   1.0 x 10-11cm 2 /s   mol ⋅ K   1000 J 
Q= = = 386 kJ/mol
1 1 1 1
− -
T2 T1 1316 K 1408 K

Use Arrhenius equation to solve for Do

DAB
DAB = Do e −Q RT
or Do =
e −Q RT

At 1316 K, solve for Do

1.0 × 10−13 cm 2 s
Do = = 210 cm 2 s
 ( 3.86 ×10 J/gmole ) 
5

exp  −
 ( 8.314 J/gmole ⋅ K ) (1316 K) 
 

Check Do at 1408 K

1.0 ×10−12 cm 2 s
Do = = 209 cm 2 s
 ( 3.86 ×10 J/gmole ) 
5

exp  −
 ( 8.314 J/gmole ⋅ K ) (1408 K) 
 

No direct matches to Table 24.7, but Ga could possibly be a candidate for the dopant material.

24-43
24.29

A = carbon, B = solid iron

DAB for carbon diffusing into fcc iron and bcc iron at 1000 K

Arrhenius equation

 Q 
DAB = Do exp  − 
 RT 

DAB for carbon diffusing into fcc iron at 1000 K

From Table 24.8, Do = 2.5 mm2/s and Q = 144.2 kJ/gmole = 144200 J/gmole

 mm2   144200 J/gmole  −8 2 −10 2

DAB =  2.5  exp  −  = 7.34 ×10 mm / s = 7.34 ×10 cm / s
 s   ( 8.314 J/gmole ⋅ K )(1000 K ) 

DAB for carbon diffusing into bcc iron at 1000 K

From Table 24.8, Do = 2.0 mm2/s and Q = 84.1 kJ/gmole = 84100 J/gmole

 mm 2   84100 J/gmole  −5 2 −7 2
DAB =  2.0  exp  −  = 8.09 ×10 mm / s = 8.09 × 10 cm / s
 s   ( 8.314 J/gmole ⋅ K )(1000 K ) 

24-44