CP302 Separation Process Principles

Mass Transfer / Set 1

(Worked) Examples in Mass Transfer by Diffusion in Binary Systems
Example 1: Diffusion through a stagnant gas film
Oxygen is diffusing in a mixture of oxygen-nitrogen at 1 std atm, 25C. Concentration of oxygen
at planes 2 mm apart are 10 and 20 volume % respectively. Nitrogen is non-diffusing.
(a) Derive the appropriate expression to calculate the flux oxygen. Define units of each
term clearly.
(b) Calculate the flux of oxygen. Diffusivity of oxygen in nitrogen = 1.89x10 –5 m 2/sec.

Solution: Let us denote oxygen as A and nitrogen as B. Flux of A (= N A) is made up of two

components, namely that resulting from the bulk motion of A (= Nx A) and that resulting from
molecular diffusion J A:
N A  Nx A  J A (1.1)
dCA
From Fick’s law of diffusion, J A   D AB (1.2)
dz
dCA
Substituting (1.2) in (1.1), we get N A  Nx A  D AB (1.3)
dz
CA dCA
Since N = N A + N B and x A = C A / C, (1.3) becomes N A   N A  N B   D AB
C dz
Rearranging the terms and integrating between the planes between 1 and 2,

dz C dC A
 CD 
A2

N AC  C A  N A  N B 
C
(1.4)
A1
AB

Since B is non-diffusing N B = 0. Also, the total concentration C remains constant. Therefore,

(1.4) becomes
z C dC A 1 C  C A2
  
A2
ln
CD AB C N AC  N AC A
A1 NA C  C A1
Therefore,
CD AB C  C A2
NA  ln (1.5)
z C  C A1
Replacing concentration in terms of pressures using Ideal Gas law, (1.5) becomes

D AB Pt Pt  p A2
NA  ln
RTz Pt  p A1
(1.6)
where
DAB = molecular diffusivity of A in B
Pt = total pressure of system
R = universal gas constant
T = temperature of system in absolute scale
z = distance between two planes across the direction of diffusion
pA1 = partial pressure of A at plane 1, and
pA2 = partial pressure of A at plane 2

Given are DAB = 1.89x10 –5 m2/sec; Pt = 1 atm = 1.01325x105 N/m2; T = 25C = 298 K;
z = 2 mm = 0.002 m; pA1 = 0.2x1 = 0.2 atm; pA2 = 0.1x1 = 0.1 atm

Substituting these in (1.6), we get,

1
NA 
1.89 *10 1.01325 *10  ln  1  0.1 
5 5

= 4.55x10 –5 kmol/m 2.sec

 8314  298  0.002  1  0.2 

Example 2: Equimolar counter diffusion

Obtain the expression describing the molar flux for steady-state equimolar counter diffusion and
its concentration profile.

Solution: The molar flux NA, for a binary system at constant temperature and pressure is
described by
CA dCA
N A  N A  N B   D AB (2.1)
C dz
Equimolar counter diffusion is given by NA = - NB, which reduces (2.1) to
d CA
N A   D AB
dz
(2.2)
For steady state diffusion, (2.2) may be integrated, using the boundary conditions as
Z2 C A2

NA  dz
Z1
 D AB  dC
C A1
A

D AB
which gives NA  (C A1  C A2 ) (2.3)
z 2  z1
nA pA
For ideal gases, C A  
V RT
D AB
Therefore, (2.3) becomes N A  ( PA1  PA2 ) (2.4)
R T ( z 2  z1 )
(2.3) and (2.4) are equations describing the molar flux for steady-state equimolar counter
diffusion.

Concentration profile in the equimolar counter diffusion may be obtained from

d
(N A )  0 (Since NA is constant over the diffusion path).
d z
d CA
From (2.2), N A   D AB
dz
d  d CA  d 2 CA
Therefore,   D AB   0 or  0.
dz  d z  dz2

This equation may be solved using the boundary conditions to give

C A  C A1 zz1
 (2.5)
C A1  C A2 z1  z 2
(2.5) indicates a linear concentration profile for equimolar counter diffusion.

Example 3:
Methane diffuses at steady state through a tube containing helium. At point 1 the partial
pressure of methane is pA1 = 55 kPa and at point 2, 0.03 m apart, pA2 = 15 KPa. The total
pressure is 101.32 kPa, and the temperature is 298 K. At this pressure and temperature, the
value of diffusivity is 6.75x10 –5 m 2/sec.
(a) Calculate the flux of CH 4 at steady state for equimolar counter diffusion.
(b) Calculate the partial pressure at a point 0.02 m apart from point 1.

Solution: For steady state equimolar counter diffusion, molar flux is given by

2
 D AB
N A 
RT z
p A1  p A2  (3.1)
Therefore,
6.75  10 5 kmol
NA   55  15 kmol  3.633  10 5
m 2  sec
8.314  298  0.03 m 2  sec

And from (3.1), partial pressure at 0.02 m from point 1 is calculated as follows:
6.75  10 5
3.633  10 5 
8.314  298  0.02
55  p A 
p A = 28.33 kPa

Example 4:
In a gas mixture of hydrogen and oxygen, steady state equimolar counter diffusion is occurring
at a total pressure of 100 kPa and temperature of 20C. If the partial pressures of oxygen at two
planes 0.01 m apart, and perpendicular to the direction of diffusion are 15 kPa and 5 kPa,
respectively, and the mass diffusion flux of oxygen in the mixture is 1.6x10 –5 kmol/m 2.sec,
calculate the molecular diffusivity for the system.
D AB
Solution: For equimolar counter current diffusion, NA 
RTz
 
p A1  p A2 (4.1)
where
NA = molar flux of A (1.6x10 –5 kmol/m 2.sec)
DAB = molecular diffusivity of A in B
R = Universal gas constant (8.314 kJ/kmol.k)
T = Temperature in absolute scale (273 + 20 = 293 K)
z = distance between two measurement planes 1 and 2 (0.01 m)
PA1 = partial pressure of A at plane 1 (15 kPa); and
PA2 = partial pressure of A at plane 2 (5 kPa)
D AB
Substituting these in (4.1), we get 1.6  10 5  15  5
 8.314  293  0.01
Therefore, DAB = 3.898x10 –5 m 2/sec

Example 5:
A tube 1 cm in inside diameter that is 20 cm long is filled with CO 2 and H2 at a total pressure of
2 atm at 0C. The diffusion coefficient of the CO2 – H2 system under these conditions is 0.275
cm2/sec. If the partial pressure of CO 2 is 1.5 atm at one end of the tube and 0.5 atm at the other
end, find the rate of diffusion for the following cases:
i) steady state equimolar counter diffusion (N A = - N B)
ii) steady state counter diffusion where N B = -0.75 N A, and
iii) steady state diffusion of CO2 through stagnant H2 (NB = 0)

Answers: Denote CO2 by A and H2 by B.

i) N A  6.138x10-6 kmol/m2.sec; Rate of diffusion of A = 1.735x10–3 mol/hr
ii) N A  7.028x10-6 kmol/m2.sec; Rate of diffusion of A = 1.987x10–3 mol/hr
iii) N A  1.349x10-5 kmol/m2.sec; Rate of diffusion of A = 3.814 mol/hr

CP302 Separation Process Principles

Mass Transfer / Set 1
(Worked) Examples in Mass Transfer by Diffusion in Binary Systems
3
 continued

Example 6:
Water in the bottom of a narrow metal tube is held at T = 293 K. For air, P = 1.01325x105 Pa (=
1 atm) and T = 293 K. Water evaporates and diffuses through the air in the tube and Δz =
0.1524 m. Calculate the rate of evaporation at steady state in kmol/s.m 2. The diffusivity of water
vapour in air at 293 K and 1 atm pressure is 0.250x10 -4 m2/s. Assume that the system is
isothermal.

Example 7: Diffusion in Liquids

Calculate the rate of diffusion of butanol at 20C under unidirectional steady state conditions
through a 0.1 cm thick film of water when the concentrations of butanol at the opposite sides of
the film are 10% and 4% butanol by weight, respectively. The diffusivity of butanol in water
solution is 5.9x10–6 cm2/sec. The densities of 10% and 4% butanol solutions at 20C may be
taken as 0.971 and 0.992 g/cc, respectively. Molecular weight of butanol (C 4H9OH) is 74, and
that of water is 18.

Solution:
Equation derived for diffusion in gases equally applies to diffusion in liquids with some
modifications. Mole fraction in liquid phases is normally written as xA = CA/C and the
  
concentration term, C, is replaced by average molar density,   .
 M  av
a) For steady state equimolar counter diffusion, N A = - N B = const
 C A1  C A2   AB C  x A1  x A2   D AB     x A1  x A 2 
D AB D
NA
z z z  M  av
(7.1)
b) For steady state diffusion of A through non diffusive B, N A = constant and N B = 0
D AB   
NA    x A1  x A2  (7.2)
z x B ,lm  M  av
x B 2  x B1
x B ,lm 
where z = z2 – z1, the length of diffusion path; and x  (7.3)
ln  B 2 
 x B1 

To calculate the rate of diffusion of A (butanol) under steady state unidirectional diffusion, use
(7.2).

Conversions from weight fraction the mole fraction give the following:
x A1 
 0.1 74   0.026 and
 0.1 74  0.9 18
x A2 
 0.04 74   0.010
 0.04 74  0.96 18
Average molecular weight at 1 & 2 are given by the following:
1
M1   19.47 kg kmol and
 0.1 74  0.9 18
1
M2   18.56 kg kmol
 0.04 74  0.96 18

     1 M 1   2 M 2  0.971 19.47  0.992 18.56

   
 M  av 2 2
 0.0517 mol cm 3  51.7 k mol m 3

4
(7.3) gives,

x B ,lm 
x B 2  x B1

1  x A2   1  x A1  1  0.01   1  0.026 

ln  x B 2 x B1   1  x A2   1  0.01 
ln   ln  
 1  x A1   1  0.026 
0.016
  0.982
0.0163

D AB     x A1  x A2 
Therefore N A   
2  M  avg x B , lm
5.9  10 6  10 4  51.7  0.026  0.010
 
0.1  10  2 0.982
kmol gmol  1.789  74 g
 4.97  10 7  1.789 2
m 2  sec m  hr m 2
 hr
g
 132.4
m  hr
2

Example 8: Diffusion through a stagnant air film (past paper question)

A circular tank 6 m in diameter contains benzene at 22 oC, which is exposed the atmosphere for
6 hours per working day in such manner that the liquid is covered with a stagnant air film
estimated to be 5 mm thick. The concentration of benzene beyond the stagnant air film is
negligible. The vapour pressure of benzene at 22 oC is 100 mm Hg. if a litre of benzene costs
Rs 1500/=, estimate the daily loss due to evaporation of benzene. The specific gravity and
diffusivity of benzene at storage conditions are 0.88 and 0.299x2.581x10 -5 m2/s, respectively.
Molecular weight of benzene is 78 kg/kmol. Universal gas constant is 8.314 kJ/kmol.K. The
atmospheric pressure may be taken as 1.013 bar. (1 bar = 100 kN/m2 = 750 mm Hg)

Example 9: Diffusion through a stagnant air film (past paper question)

A pool of water 1 mm in depth lies on a horizontal surface in contact with dry air at 20 oC and 1
atm. Evaporation takes place and can be treated as molecular diffusion through a 5 mm thick
film of moist air immediately above the water surface. Above this gas film, water vapour is
assumed to be perfectly mixed with the surrounding (with the zero partial pressure). Assuming
that evaporation does not affect the temperature of water, calculate (i) the molar flux of water
vapour from the surface, and (ii) the time taken for complete evaporation of the liquid. Diffusivity
of water in air can be taken as 2.6x10 -5 m2/s, saturated vapour pressure of water at 20oC as
2340 N/m2 and gas constant as 8314 J/kmol.K.