Diffusion Coefficient or Diffusivity of Gases

Course: Mass Transfer (Th)

Batch: 2019/Fall
Prepared by: Semester: 4th
Engr. Amna Anjum
Lecturer
Department of Chemical Engineering
Dawood University of Engineering & Technology
Factors Affecting Gas Phase Diffusivity

Temperature of the system

Pressure of the system

Other factors
a) Presence of other components
b) Intra-molecular forces in the mixture
c) number of collisions of the diffusing molecules with
other molecules present in the system
 Diffusivity in terms of kinetic theory of
gases 𝜆𝑢
𝐷𝐴𝐵 =
2
where,
𝜆 is the mean free path of the diffusing molecules
𝑢 is their mean speed.
• Higher the temperature, higher is the mean speed (𝑢) and thus DAB increases which
generally varies with the absolute temperature (T) raised to the power 1.50 to 1.75.
𝐷𝐴𝐵 𝛼𝑇 1.5→1.75
• On the other hand, higher the pressure, lower is the mean free path of the molecules,
which increases the number of collisions and thus DAB reduces which varies inversely
to the total pressure up to a pressure of about 10 atm.
1
𝐷𝐴𝐵 𝛼
𝑃
Dimension of Diffusivity
𝐿 𝐿
𝐷𝐴𝐵 =
𝜃
𝐿2
𝐷𝐴𝐵 =
𝜃
Equivalence of Diffusivity
𝑫𝑨𝑩 = 𝑫𝑩𝑨
Determination of Gas Phase
Diffusivity
1. Data available in literature
Table 2.1 Diffusivities of Some Common Gas Pairs at 1 atm Pressure
2. Prediction from available Equations
a) For Binary Gas Mixtures (Gilliland Equation)
𝟎.𝟓
𝐓 𝟏.𝟓 𝟏 𝟏
𝐃𝐀𝐁 = 𝟒𝟑𝟓. 𝟕 +
𝟏/𝟑 𝟏/𝟑 𝟐 𝐌𝐀 𝐌𝐁
𝐏 𝐕𝐀 + 𝐕𝐁
Where,
DAB = diffusivity of components A in B, cm2/s
T = temperature, K
P = total pressure, N/m2
VA and VB = molar volumes of A and B respectively, m3/kmol
MA and MB = molecular weights of A and B, respectively.
Molar volumes of compounds may be estimated from Kopp’s law of additive
volumes.
b) For Binary Gas Mixtures up to moderate pressures (Fuller et al.
Equation)
𝟎.𝟓
𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = 𝟎. 𝟎𝟎𝟏𝟎𝟎 𝟐
+
𝐏 σ 𝝑𝑨 𝟏/𝟑 + σ 𝝑𝑩 𝟏/𝟑 𝐌𝐀 𝐌𝐁
Where,
DAB = diffusivity of components A in B, cm2/s
T = temperature, K
P = total pressure, atm
σ 𝝑𝑨
andσ 𝝑𝑩 = sum of atomic diffusion volumes of A and B respectively
MA and MB = molecular weights of A and B, respectively.
This equation is simple but quite reliable. In most cases, the error is
within ±5%.
b) For Binary Gas Mixtures up to moderate pressures (Fuller et al. Equation)
Table 2.2: Atomic diffusion volumes for use in Fuller et al. Equation
Atomic and Structural diffusion volume Diffusion volumes of simple molecules, Su
increments, u
c) For Binary Gas Mixtures using binary interaction parameters of the
two components (Chapman and Enskog Equation)
𝟎.𝟓
𝟏. 𝟖𝟓𝟖 × 𝟏𝟎−𝟕 𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = 𝟐 +
𝐏𝛔 𝑨𝑩 𝛀 𝐌𝐀 𝐌 𝐁
It gives fairly reliable values of DAB. The diffusivity strongly depends
upon binary interaction parameters of the two components.
Where,
DAB = diffusivity of components A in B, m2/s
T = temperature, K
P = total pressure, atm
MA and MB = molecular weights of A and B, respectively.
VAB = molecular separation at collision = (VA + VB)/2
VA and VB = molecular diameters of A and B, respectively, Å
Ω = collision integral, function of (kT/fAB), where k is the Boltzmann’s constant
fAB = energy of molecular attraction between molecules of A and B = Ö
Remarks
• Prediction of the diffusivity using Chapman and Enskog Equation gives rise to
values within 6% for nonpolar gas pairs at low density, if the collision
constants are available from viscosity data. However, the error increases to
about 10% if the Lennard-Jones parameters are estimated from
thermodynamic data.
• The Chapman-Enskog theory fails to predict a variation in the diffusion
coefficient with concentration. For example, diffusivity in some binary gas
mixtures such as chloroform-air may vary as much as 9% with concentration,
whereas in other systems like methanol-air, the diffusivity is independent of
the concentration.
• The Chapman-Enskog Equation for the transport coefficients is valid for the
range 200-1000 K. Below 200 K, quantum effects become important, and
above 1000 K the Lennard-Jones potential function is no longer applicable. If
the force constants are derived from diffusion data instead of the usual
viscosity data, the equations may be extended to 1200 K. Above 1200 K, the
force constants should be evaluated from molecular beam scattering
experiments.
• The equations were developed for dilute gases composed of nonpolar,
spherical, monoatomic molecules. Empirical functions and correlations, i.e.
the Lennard-Jones potential must be used, with the net result that the
equations are remarkable for their ability to predict diffusivity for many gas
mixtures. Agreement in nonpolar gas mixtures is excellent, even for
polyatomic molecules. For polar-nonpolar gas mixtures the same equations
are used with different combining laws
Table 2.3: Values of V and f for some common substances (Lennard-Jones potential for some
common substances)
Table 2.4: Values of collision integral, Ω
• If values of v and f are not available, the same may be estimated from
the properties of the fluid at the critical point (c), the liquid at the
normal boiling point (b), or the solid at the melting point (m), by
following very approximate relations:
1/3
𝑓 1/3 𝑇𝑐
= 0.77𝑇𝑐 𝑎𝑛𝑑 𝑉𝑐 = 0.841𝑉𝑐 , 𝑜𝑟 𝑉 = 2.44
𝑘 𝑃𝑐
𝑓
= 1.15𝑇𝑏 𝑎𝑛𝑑 𝑉 = 1.166𝑉𝑏 1/3
𝑘
𝑓
= 1.92𝑇𝑚 𝑎𝑛𝑑 𝑉 = 1.222𝑉𝑚 1/3
𝑘
• where, f/k and T are in K, v is in Å, V is in cm3/gmol, and Pc is in atm.
 Example 2.8: (Estimation of diffusivity in
gases using Gilliland equation)
Estimate the diffusivity of ammonia in air at standard atmospheric pressure and 0°C
by using Gilliland equation.
Given: Molecular volume of ammonia and air are 25.8 and 29.9, respectively.
Data
T = 273 K
P = 1.013x105 N/m2
For ammonia:
MA = 17, VA = 25.8
For air:
MB = 29, VB = 29.9
DAB=?
 Example 2.8: (Cont..)
For Binary Gas Mixtures (Gilliland Equation)
𝟎.𝟓
𝐓 𝟏.𝟓 𝟏 𝟏
𝐃𝐀𝐁 = 𝟒𝟑𝟓. 𝟕 𝟐
+
𝐏 𝐕𝐀 𝟏/𝟑 + 𝐕𝐁 𝟏/𝟑 𝐌𝐀 𝐌𝐁
Substituting values:
1.5 0.5
273 1 1
DAB = 435.7 × 10−4 +
1.013 × 105 25.81/3 + 29.91/3 2 17 29
𝐃𝐀𝐁 = 𝟏. 𝟔𝟏𝟓 × 10−5 𝑚2 Τ𝑠
Note: × 10−4 is used for conversion from cm2/s to m2/s
 Example 2.9: (Estimation of diffusivity in
gases using Fuller et al. equation)
Using Equation of Fuller et al., estimate the diffusivity of naphthalene vapour in air at
a temperature of 0°C and a total pressure of 1 atm.
Data
T = 273 K
P = 1 atm
DAB=?
Solution:
Let,
A=naphthalene (C10H8)
B=air.
Hence, MA = 128.16, MB = 29.
 Example 2.9: (Cont..)
From Table 2.2, atomic diffusion volume increments are as follows:
෍ 𝜗𝐴 = 10 × 16.5 + 8 × 1.98 − 2 × 20.2

෍ 𝝑𝑨 = 𝟏𝟒𝟎. 𝟒𝟒

෍ 𝝑𝑩 = 𝟐𝟎. 𝟏
𝟎.𝟓
𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = 𝟎. 𝟎𝟎𝟏𝟎𝟎 +
𝐏 σ 𝝑𝑨 𝟏/𝟑 + σ 𝝑𝑩 𝟏/𝟑 𝟐 𝐌𝐀 𝐌𝐁
Substituting values
1.75 0.5
273 1 1
DAB = 0.00100 2 +
1 140.44 1/3 + 20.1 1/3 128.16 29
𝑫𝑨𝑩 = 𝟎. 𝟎𝟔𝟎𝟓 𝒄𝒎𝟐 Τ𝒔
 Example 2.10: (Estimation of binary gas
diffusivity using Chapman-Enskog equation)
Estimate the diffusivity of sulphur dioxide in air at standard atmospheric pressure and
400°C by using Equation of Chapman-Enskog.
Data
T = 673 K
P = 1 atm
DAB=?
Solution:
Let,
A=SO2
B=Air
 Example 2.10: (Cont…)
From Table 2.3,
For air:
• fA/kB = 78.6 K, VA = 3.711 Å = 3.711X10-10 m = 0.3711 nm
For SO2:
fB/kB = 335.4 K, VB = 4.112 Å = 4.112 X10-10 m = 0.4112 nm
For the system:
𝑉𝐴 +𝑉𝐵
𝜎𝐴𝐵 = 𝑉𝐴𝐵 =
2
3.711 + 4.112 × 10−10
𝜎𝐴𝐵 = 𝑉𝐴𝐵 =
2
𝝈𝑨𝑩 = 𝑽𝑨𝑩 = 𝟑. 𝟗𝟏𝟏𝟓𝑨°
𝝈𝑨𝑩 = 𝑽𝑨𝑩 = 𝟎. 𝟑𝟗𝟏𝟏𝟓𝒏𝒎
 Example 2.10: (Cont…)
𝑓𝐴𝐵 = 𝑘𝐵 𝑓𝐴 . 𝑓𝐵
𝑓𝐴𝐵 = 𝑘𝐵 78.6 × 335.4 1/2
𝑘𝐵 𝑇 𝑘𝐵 673
=
𝜀𝐴𝐵 𝑘𝐵 78.6 × 335.4 1/2
𝑘𝐵 𝑇
= 4.14
𝜀𝐴𝐵
From Table 2.4, Ω = 0.88
Using Chapman-Enskog Equation:
𝟎.𝟓
𝟏. 𝟖𝟓𝟖 × 𝟏𝟎−𝟕 𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = +
𝐏𝛔𝟐 𝑨𝑩 𝛀 𝐌 𝐀 𝐌𝐁
0.5
1.858 ×10−7 673 1.75
1 1
DAB = +
1 3.9115 2 0.88 64 28.9
Example 2.10: (Cont…)
𝐃𝐀𝐁 = 𝟓. 𝟒 × 𝟏𝟎−𝟓 𝒎𝟐 Τ𝒔
𝐃𝐀𝐁 = 𝟎. 𝟓𝟒 𝒄𝒎𝟐 Τ𝒔
 Example 2.11: (Rate of diffusion of a gas
through the pores of a catalyst):
A nickel catalyst for the hydrogenation of ethylene has a mean pore diameter of 100
Å. Calculate the diffusivities of hydrogen for this catalyst at (i) temperature 100°C,
pressure 1 atm and (ii) temperatrue 100 °C, pressure 10 atm in a hydrogen-ethane
mixture.
Data
Mean Pore Dia of a nickel catalyst = 100 Å
i) P = 1 atm, T= 100°C=373K, DAB=?
ii) P = 10 atm, T= 100°C=373K, DAB=?
Solution:
Let, A=Hydrogen and B=Ethane
 Example 2.11: (Cont…)
From Table 2.3,
For Hydrogen (H2) (A):
• fA/kB = 59.7 K, VA = 2.827 Å = 2.827 X10-10 m = 0. 2827 nm
For C2H6 (B):
fB/kB = 215.7 K, VB = 4.443 Å = 4.443 X10-10 m = 0. 4443 nm
For the system:
𝑉𝐴 +𝑉𝐵
𝜎𝐴𝐵 = 𝑉𝐴𝐵 =
2
2.827 + 4.443
𝜎𝐴𝐵 = 𝑉𝐴𝐵 =
2
𝝈𝑨𝑩 = 𝑽𝑨𝑩 = 𝟑. 𝟔𝟑𝟓𝑨°
𝝈𝑨𝑩 = 𝑽𝑨𝑩 = 𝟎. 𝟑𝟔𝟑𝟓𝒏𝒎
 Example 2.11: (Cont…)
𝑓𝐴𝐵 = 𝑘𝐵 𝑓𝐴 . 𝑓𝐵
𝑓𝐴𝐵 = 𝑘𝐵 59.7 × 215.7 1/2
𝑘𝐵 𝑇 𝑘𝐵 373
=
𝜀𝐴𝐵 𝑘𝐵 59.7 × 215.7 1/2
𝑘𝐵 𝑇
= 3.287
𝜀𝐴𝐵
From Table 2.4, Ω = 0.92
Using Chapman-Enskog Equation:
𝟎.𝟓
𝟏. 𝟖𝟓𝟖 × 𝟏𝟎−𝟕 𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = +
𝐏𝛔𝟐 𝑨𝑩 𝛀 𝐌 𝐀 𝐌𝐁
0.5
1.858 × 10−7373 1.75
1 1
DAB = +
P 3.635 2 0.92 2.016 30.05
Example 2.11: (Cont…)
−7 1.75 0.5
1.858 × 10 373 1 1
DAB = +
P 3.635 2 0.92 2.016 30.05
When P=1atm
0.5
1.858 × 10−7 373 1.75 1 1
DAB = 2
+
1 3.635 0.92 2.016 30.05
𝐃𝐀𝐁 = 𝟖. 𝟎𝟏 × 𝟏𝟎−𝟓 𝒎𝟐 Τ𝒔
𝐃𝐀𝐁 = 𝟎. 𝟖𝟎𝟏 𝒄𝒎𝟐 Τ𝒔
When P=10atm
0.5
1.858 × 10−7 373 1.75 1 1
DAB = 2
+
10 3.635 0.92 2.016 30.05
𝐃𝐀𝐁 = 𝟖. 𝟎𝟏 × 𝟏𝟎−𝟔 𝒎𝟐 Τ𝒔
𝐃𝐀𝐁 = 𝟎. 𝟎𝟖𝟎𝟏 𝒄𝒎𝟐 Τ𝒔
 Example 2.12: (From the value of gas phase
diffusivity at a given temperature, prediction of
diffusivity for the system at another
-5
temperature)
The diffusion coefficient of H -N system is 7.84 x10 m /s at 1 atm and 298 K.
2 2 2
(i) Find out the diffusivity at 350 K and 500 K using Chapman-Enskog equation.
(ii) Using equation D = D0 (P0/P)(T/T0)n, find the diffusion coefficients at the above
temperatures assuming n = 1.75 and 1.5.
Data
DH2-N2= 7.84 x10-5 m2/s
P=1atm
T=298K
i) T=350K, T= 500K, DAB=?
ii) T=350K, T= 500K, DAB=? using equation D = D0 (P0/P)(T/T0)n assuming n = 1.75 and 1.5
 Example 2.12: (Cont…)
Solution:
Let, A=H2 and B=N2
i) From Table 2.3,
For Hydrogen (H2) (A):
• fA/kB = 59.7 K, VA = 2.827 Å = 2.827 X10-10 m = 0. 2827 nm, MA=2.016
For N2(B):
fB/kB = 71.4 K, VB = 3.798 Å = 3.798 X10-10 m = 0. 3798 nm, MB=28.0134
For the system:
𝑉𝐴 +𝑉𝐵
𝜎𝐴𝐵 = 𝑉𝐴𝐵 =
2
2.827 + 3.798
𝜎𝐴𝐵 = 𝑉𝐴𝐵 =
2
𝝈𝑨𝑩 = 𝑽𝑨𝑩 = 𝟑. 𝟑𝟏𝟐𝟓𝑨°
 Example 2.12: (Cont…)
𝑓𝐴𝐵 = 𝑘𝐵 𝑓𝐴 . 𝑓𝐵 1/2
𝑓𝐴𝐵 = 𝑘𝐵 59.7 × 71.4 1/2
𝑘𝐵 𝑇 𝑘𝐵 350
=
𝜀𝐴𝐵 𝑘𝐵 59.7 × 71.4 1/2
𝑘𝐵 𝑇
= 5.36
𝜀𝐴𝐵
From Table 2.4,Ω= 0.8314
Using Chapman-Enskog Equation:
𝟎.𝟓
𝟏. 𝟖𝟓𝟖 × 𝟏𝟎−𝟕 𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = +
𝐏𝛔𝟐 𝑨𝑩 𝛀 𝐌 𝐀 𝐌𝐁
0.5
1.858 × 10−7 350 1.75 1 1
DAB = 2
+
1 3.3125 0.8314 2.016 28.0134
 Example 2.12: (Cont…)
𝐃𝐀𝐁 = 𝟗. 𝟕𝟐𝟒 × 𝟏𝟎−𝟓 𝒎𝟐 Τ𝒔
Similarly at 500K
kBT
= 7.66
fAB
From Table 2.4,Ω= 0.7775
Using Chapman-Enskog Equation:
𝟎.𝟓
𝟏. 𝟖𝟓𝟖 × 𝟏𝟎−𝟕 𝐓 𝟏.𝟕𝟓 𝟏 𝟏
𝐃𝐀𝐁 = 𝟐 +
𝐏𝛔 𝐀𝐁 𝛀 𝐌 𝐀 𝐌𝐁
𝐃𝐀𝐁 = 𝟏𝟕. 𝟕𝟔 × 𝟏𝟎−𝟓 𝐦𝟐 Τ𝐬
 Example 2.12: (Cont…)
ii) T=350K, T= 500K, D =? using equation D = D (P0/P)(T/T0)n assuming n = 1.75 and 1.5
AB 0
𝐧
𝑷𝟎 𝑻
𝐃𝐓 = 𝑫𝟎
𝐏 𝑻𝟎
1.75
𝑃298 𝑇
D350 = 𝐷298
P 𝑇298
1.75
1 350
D350 = 𝐷298
1 298
𝐃𝟑𝟓𝟎 = 𝟏𝟎. 𝟑𝟖𝟖 × 𝟏𝟎−𝟓 𝐦𝟐 Τ𝐬
1.75
𝑃298 𝑇
D500 = 𝐷298
P 𝑇298
1.75
1 500
D500 = 𝐷298
1 298
𝐃𝟓𝟎𝟎 = 𝟏𝟗. 𝟑𝟗𝟐 × 𝟏𝟎−𝟓 𝐦𝟐 Τ𝐬
 Example 2.12: (Cont…) 1.5
𝑃298 𝑇
D350 = 𝐷298
P 𝑇298
1.5
1 350
D350 = 𝐷298
1 298
𝐃𝟑𝟓𝟎 = 𝟗. 𝟗𝟕𝟗 × 𝟏𝟎−𝟓 𝐦𝟐 Τ𝐬
1.5
𝑃298 𝑇
D500 = 𝐷298
P 𝑇298
1.5
1 500
D500 = 𝐷298
1 298
𝐃𝟓𝟎𝟎 = 𝟏𝟕. 𝟎𝟑𝟗 × 𝟏𝟎−𝟓 𝐦𝟐 Τ𝐬
• Comparison of the computed values using different methods as above, shows that
the diffusivity values obtained assuming n = 1.5 are in good agreement with those
obtained from Chapman-Enskog Equation.
3. Experimental determination of gas
phase diffusivity
Stefan tube method
Assumptions

Component A (liquid) is diffusing through

the component B (stagnant gas)

Component B (stagnant gas) is

insoluble in component A (liquid)

Constant Temperature

Figure 2.6: Determination of diffusivity

Psuedo-steady state operation by Stefan’s Method
Stefan tube method (Derivation)
• Consider a narrow glass tube 5-6 mm id, sealed at
the bottom, held vertically and joined at the top
with a larger diameter horizontal tube.
• The horizontal tube is sometimes provided with
straightners to avoid turbulence.
• The vertical tube is filled with the experimental
liquid A up to a certain distance from the top
while the gas B flows through the horizontal tube.
• The molecules of evaporated A diffuses through a
mixture of A and B, reaches the top and is swept
away by the gas B. Gas B is not diffusing as its
insoluble in liquid A. Hence, this is a case of
diffusion of one component through the stagnant Figure 2.6: Determination of diffusivity
layer of another component, i.e. gas. by Stefan’s Method
 Stefan tube method (Derivation-Cont…)
• Assuming pseudo-steady state operation, the
liquid level in the vertical tube varies very
slowly. The experiment should be continued for
a long time to reduce experimental error.
• The distances of the liquid level from the top
open end at start and end of the experiment,
and also the duration of the experiment along
with the ambient temperature and barometric
pressure are to be measured. The drop in the
liquid level should be accurately measured,
preferably with a travelling microscope.
• Let z be the distance of the liquid level from top
open end at any instant 𝜃 , then from the Figure 2.6: Determination of diffusivity
equation of diffusion through a stagnant layer), by Stefan’s Method
the diffusional flux may be expressed as:
 Stefan tube method(Derivation-Cont…)
𝐷𝐴𝐵 𝑃 𝑃𝐴1 − 𝑃𝐴2
𝑁𝐴 =
𝑅𝑇𝑧 𝑃𝐵𝑀
Equating the above flux with the drop dz in liquid level over time 𝑑𝜃,
Multiply by 𝑎𝑑𝜃
𝑎𝑑𝑧 𝜌𝐴 𝐷𝐴𝐵 𝑃 𝑃𝐴1 − 𝑃𝐴2 𝑎𝑑𝜃
= 𝑎𝑁𝐴 𝑑𝜃 =
𝑀𝐴 𝑅𝑇𝑧 𝑃𝐵𝑀
Rearranging
𝑎𝑑𝑧 𝜌𝐴 𝐷𝐴𝐵 𝑃 𝑃𝐴1 − 𝑃𝐴2 𝑎𝑑𝜃
=
𝑀𝐴 𝑅𝑇𝑧 𝑃𝐵𝑀
 Stefan tube method (Derivation-Cont…)
Integrating
𝑧2
𝜌𝐴 𝐷𝐴𝐵 𝑃 𝑃𝐴1 − 𝑃𝐴2
න 𝑧𝑑𝑧 = න 𝑑𝜃
𝑀𝐴 𝑅𝑇 𝑃𝐵𝑀
𝑧1
𝜌𝐴 2 2
𝐷𝐴𝐵 𝑃 𝑃𝐴1 − 𝑃𝐴2
𝑧 − 𝑧1 = 𝜃
2𝑀𝐴 2 𝑅𝑇 𝑃𝐵𝑀
𝜌𝐴 𝑅𝑇𝑃𝐵𝑀
𝑧2 2 − 𝑧1 2 = 𝐷𝐴𝐵
2𝑀𝐴 𝑃 𝑃𝐴1 − 𝑃𝐴2 𝜃
𝜌𝐴 𝑅𝑇𝑃𝐵𝑀
𝐷𝐴𝐵 = 𝑧2 2 − 𝑧1 2
2𝑀𝐴 𝑃 𝑃𝐴1 − 𝑃𝐴2 𝜃
where,
z1 and z2 are the distances of the liquid surface from the top at the beginning and at the
end of the experiment.
 Stefan tube method (Derivation-Cont…)
The PA1 at the liquid surface is the vapour pressure of A at the temperature of
experiment. At the top open end of the tube, PA2 may be assumed zero since vapours of
A are swept away by B.
 Example 2.13: (Experimental determination of
diffusivity of a gas by Stefan-tube method)
A narrow vertical glass tube is filled with liquid toluene up to a depth of 2 cm from
the top open end placed in a gentle current of air. After 150 hr, the liquid level has
dropped to 4.4 cm from the top. The temperature is 25°C and the total pressure 1.013
x 105 N/m2.
At 25°C, the vapour pressure of toluene is 29.2 mm Hg and the density of liquid
toluene is 850 kg/m3. Neglecting the effects of convective currents and counter
diffusion of air, calculate the diffusivity of toluene in air at 25°C and 1.013 x 105 N/m2
pressure.
 Example 2.13: (Cont…)
Data For toluene at 25°C:
T = 25°C = 298 K Vapour pressure =PA1= 29.2 mm Hg = 3.89 x 103 N/m2
P = 1.013 x105 N/m2, Density =𝜌𝐴 = 850 kg/m3
θ = 150 hr = 150 × 3600 = PB1 =P-PA1= 101.3 x 103 - 3.89 x103 = 97.41 x 103 N/m2
5.4 × 105 s
PA2 = 0
z1 = 2cm= 0.02 m
PB2 = 101.3 x 103 N/m2
z2 = 4.4cm=0.044 m
R = 8314 Nm/(kmol)(K)
Molecular weight of toluene=MA =
92
 Example 2.13: (Cont…)
Solution
𝜌𝐴 𝑅𝑇𝑃𝐵𝑀
𝐷𝐴𝐵 = 𝑧2 2 − 𝑧1 2
2𝑀𝐴 𝑃 𝑃𝐴1 − 𝑃𝐴2 𝜃
𝑃𝐵2 − 𝑃𝐵1
𝑃𝐵𝑀 =
𝑃
𝑙𝑛 𝐵2
𝑃𝐵1
𝜌𝐴 𝑅𝑇 𝑃𝐵2 − 𝑃𝐵1
𝐷𝐴𝐵 = 𝑧2 2 − 𝑧1 2
𝑃
2𝑀𝐴 𝑃 𝑃𝐴1 − 𝑃𝐴2 𝑙𝑛 𝐵2 𝜃
𝑃𝐵1
Substituting values
850 8314 298 101.3 − 97.41 × 103
𝐷𝐴𝐵 = 0.0442 − 0.022
5 3 5 1.013 × 103
2 92 1.013 × 10 (3.89 × 10 ) − 0 5.4 × 10 𝑙𝑛
97.41 × 103
𝑫𝑨𝑩 = 𝟎. 𝟖𝟐 × 𝟏𝟎−𝟓 𝒎𝟐 Τ𝒔
 Twin Bulb Method
• This method is suitable for measuring the
diffusivities of permanent gases or of
components that are gases at least at the
conditions of the experiment.
• Consider the experimental set-up consisting of
two large bulbs of volumes V1 and V2, connected
by a narrow tube fitted with a stop cock or a plug
type valve. Let a and z be the cross sectional area
and the length of the connecting tube. Fig 2.7: The twin bulb set-up
• Before starting the experiment the valve in the
connecting tube is closed, the two bulbs are
evacuated, washed several times with the
respective gases to be filled in that bulb. Then
one bulb is filled with pure A while the other with
pure B, both being at the same pressure.
 Twin Bulb Method (Cont…)
• The experiment is then started by opening the
valve in the connecting tube. During the
experiment the contents of the two bulbs should
be constantly stirred to maintain uniform
concentration and the entire system should be
kept at constant temperature and pressure. Since
the two bulbs are large and are at equal and
constant pressure, equimolal counter-diffusion
takes place through the connecting tube.
• Concentrations (or partial pressures) of these two Fig 2.7: The twin bulb set-up
components will change only very slowly so that
pseudo-steady state conditions may be assumed.
The total pressure (P) in the bulbs, the duration of
the experiment (𝜃), and the partial pressures of
component A in the two bulbs ( PA1 and PA2) are to
be noted.
 Twin Bulb Method (Cont…)
• If PA1 and PA2 (PA1 > PA2) be the partial pressures of
component A in bulb 1 and bulb 2 at any instant
𝜃, the steady state rate of transport of A from
bulb 1 to bulb 2 can be expressed as follows in
terms of the below equation
EQUIMOLAR COUNTER DIFFUSION
𝐷𝐴𝐵 𝑃𝐴1 − 𝑃𝐴2
𝑁𝐴 = Fig 2.7: The twin bulb set-up
𝑅𝑇𝑧
𝒂𝑫𝑨𝑩 𝑷𝑨𝟏 − 𝑷𝑨𝟐
𝒂𝑵𝑨 =
𝑹𝑻𝒛
 Twin Bulb Method (Cont…)
Since PA1 and PA2 are the instantaneous partial pressures of component A in the two bulbs,
the rates of change of partial pressures are given by
𝑉1 𝑑𝑃𝐴1
𝑎𝑁𝐴 = −
𝑅𝑇 𝑑𝜃
𝒂𝑵𝑨 𝑹𝑻 𝒅𝑷𝑨𝟏
=−
𝑽𝟏 𝒅𝜽
𝑉2 𝑑𝑃𝐴2
𝑎𝑁𝐴 =
𝑅𝑇 𝑑𝜃
𝒂𝑵𝑨 𝑹𝑻 𝒅𝑷𝑨𝟐
=
𝑽𝟐 𝒅𝜽
Combining above two equations
𝑎𝑁𝐴 𝑅𝑇 𝑎𝑁𝐴 𝑅𝑇 𝑑𝑃𝐴1 𝑑𝑃𝐴2
+ =− +
𝑉1 𝑉2 𝑑𝜃 𝑑𝜃
 Twin Bulb Method (Cont…)
𝟏 𝟏 𝒅
𝒂𝑵𝑨 𝑹𝑻 + =− 𝑷 − 𝑷𝑨𝟐
𝑽𝟏 𝑽𝟐 𝒅𝜽 𝑨𝟏
From equation
𝑎𝐷𝐴𝐵 𝑃𝐴1 − 𝑃𝐴2
𝑎𝑁𝐴 =
𝑅𝑇𝑧
𝒂𝑫𝑨𝑩 𝑷𝑨𝟏 − 𝑷𝑨𝟐
𝒂𝑵𝑨 𝑹𝑻 =
𝒛
Substitute 𝑎𝑁𝐴 𝑅𝑇 𝑖𝑛 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝐴
𝑎𝐷𝐴𝐵 𝑃𝐴1 − 𝑃𝐴2 1 1 𝑑
+ =− 𝑃𝐴1 − 𝑃𝐴2
𝑧 𝑉1 𝑉2 𝑑𝜃
𝒅 𝒂𝑫𝑨𝑩 𝑷𝑨𝟏 − 𝑷𝑨𝟐 𝟏 𝟏
− 𝑷𝑨𝟏 − 𝑷𝑨𝟐 = +
𝒅𝜽 𝒛 𝑽𝟏 𝑽𝟐
 Twin Bulb Method (Cont…)
𝒅 𝑷𝑨𝟏 − 𝑷𝑨𝟐 𝒂𝑫𝑨𝑩 𝟏 𝟏
− = + 𝒅𝜽
𝑷𝑨𝟏 − 𝑷𝑨𝟐 𝒛 𝑽 𝟏 𝑽𝟐
Integrating above equation with the following limits:
θ = 0, (PA1 - PA2) = (P - 0) = P; and θ = θ′ , (PA1 - PA2) = (PA1 - PA2) yields
𝑷 𝒂𝑫𝑨𝑩 𝟏 𝟏
𝒍𝒏 = + 𝜽′
𝑷𝑨𝟏 − 𝑷𝑨𝟐 𝒛 𝑽 𝟏 𝑽𝟐
Thank you