MOLECULAR DIFFUSION
IN GASES
Case 1: Equimolar counterdiffusion
pA1 pA2
pB1 pB2
P P
J*A
J*B
Constant total pressure P
Stirring keeps the concentration in each chamber uniform
Partial pressure pA1 > pA2 and pB2 > pB1
Molecules of A diffuse to the right and B to the left
Net moles of A diffusing to the right equals to the net moles of B to the
left
J * Az = − J * Bz
dc B
J * B = − D BA
dz
c = c A + cB
dc A = − dc B
dc A dc B
J * A = − D AB = − J * B = − ( − ) D BA
dz dz
D AB = D BA
For a binary gas mixture of A and B, the diffusivity coefficient DAB
for A diffusing into B is the same as DBA for B diffusing into A
Example 2
Ammonia gas is diffusing through a uniform tube
0.1m long containing N2 gas at 1.01325 x 105 Pa
pressure and 298 K. pA1 = 1.01325 x 104 Pa and pA2 =
0.507 x 104 Pa. DAB = 0.230 x 10-4 m2/s. Calculate
J*A and J*B
Tutorial (Q1)
A gas of CH4 and He is contained in a tube at 101.32
kPa pressure and 298K. At one point, the partial
pressure of methane is pA1 = 60.79 kPa, and at a point
0.02 m distance away, pA2 = 20.26 kPa. If the total
pressure is constant throughout the tube, calculate the
flux of CH4 at steady state for equimolar
counterdiffusion.
Case 2: Diffusion plus Convection
Flux can be converted to a velocity of diffusion of A
to the right by
J * A ( kgmol A / s.m 2 ) = Ad c A ( m / s )( kgmol A / m 3 )
where υAd is the diffusion velocity of A in m/s.
Conditions:
The whole fluid is moving in bulk or convective flow to the
right
Molar average velocity of the whole fluid relative to a
stationary point is υM m/s
Component A is still diffusing to the right but now its diffusion
velocity υAd is measured relative to the moving fluid
Velocity of A relative to the stationary point is the
sum of the diffusion velocity and the average or
convective velocity
A = Ad + M
A
Ad M
dx A c A
N A = − cD AB + (N A + NB )
dz c
Case 3: A diffusing through stagnant,
nondiffusing B
One boundary at the end of the diffusion path is impermeable
to component B, so it cannot pass through
2 DAB P
pA2 (pA1 - pA2 )
NA =
RT(z2 – z1) pBM
z2 – z1 (pA1 – pA2 )
NA pBM =
ln[(P - pA2 )/ (P - pA1 )]
1 p
A1
Example 3
Water in the bottom of a narrow metal tube is held at a
constant temperature of 293 K. The total pressure of air
(assumed to be dry) is 1 atm and the temperature is 293 K.
Water evaporates and diffuses through the air in the tube,
and the diffusion path is 0.1524 m long. Calculate the rate
of evaporation at steady state. The diffusivity of water vapor
at 1 atm and 293 K is 0.250 x 10-4 m2/s. Assume that the
vapor pressure of water at 293 K is 0.0231 atm.
√ √
DAB P √ √ (pA1 – pA2 )
NA = (pA1 - pA2 ) pBM =
RT(z2 – z1) pBM ln[(P - pA2 )/ (P - pA1 )]
√√ √
Tutorial (Q2)
Ammonia gas is diffusing through N2 under steady-state
conditions with N2 nondiffusing since it is insoluble in one
boundary. The total pressure is 1.013 x 105 Pa and the
temperature is 298 K. The partial pressure of NH3 at one
point is 1.333 x 104 Pa and at the other point 20 mm away it is
6.666 x 103 Pa. The DAB for the mixture at 1.013 x 105 Pa and
298 K is 2.30 x 10-5 m2/s.
(a) Calculate the flux of NH3 in kgmol/s.m2
(b) Do the same as (a) but assume that N2 also diffuses (both
boundaries are permeable to both gases and the flux is
equimolar counterdiffusion)
GASEOUS DIFFUSIVITY
Experimental diffusivity data (1 atm, 298K)
Table 6.2.1 Diffusion Coefficients of Gases at 101.32 kPa
System Diffusivity (cm2/s)
H2-NH3 0.783
H2-CH4 0.726
Ar-CH4 0.202
He-CH4 0.675
He-N2 0.687
Air-H2O 0.260
Air-C2H5OH 0.135
Air-benzene 0.0962
Prediction of gaseous diffusivity
1
D AB = u
3
1/ 2
aT 1
3/ 2
1
D AB = +
P AB M A M B
2
1/ 2
bT 1.75
1 1
D AB = +
P (v A )
1/ 3
+ (v B )
1/ 3 2
MA MB
Binary
Example 4
Normal butanol (A) is diffusing through air (B) at 1
atm abs. Using the Fuller method, estimate the
diffusivity DAB for the following temperature and
compare with the experimental data:
a) For 0°C
b) For 25.9°C
c) For 0° and 2.0 atm abs
Eperimental data:
(a) 7.03 x 10-6 m2/s (b) 8.70 x 10-6 m2/s
Tutorial (Q3)
For a mixture of ethanol (CH3CH2OH) vapor and
methane (CH4), predict the diffusivity at 1.0132 x 105
Pa and 298 K using the method of Fuller et al.
For the same mixture as above, predict the diffusivity
at 330 K and 2 atm.
