ABSTRACT

The objective of the experiment was to determine the diffusion coefficient of a

gas by evaporation from a liquid surface. The gas sample under study was
acetone gas, and the rate of mass transfer of gaseous acetone from liquid
acetone was determined. The main apparatus used was the Gaseous Diffusion
Apparatus [Model: CER-A(ARMFIELD)] and this was done using the
Winkelmann’s method, in which a liquid is allowed to evaporate in a vertical
glass tube over the top of which a stream of vapor-free gas is passed, at a rate
such that the vapor pressure is maintained almost at zero. It was observed that
the level of liquid acetone in the capillary tube reduced with time, as liquid
acetone was gradually being evaporated at the liquid surface and carried away
by the air-stream. The rate of mass transfer was then found to be 24.79 x 10-2
m2/s.
INTRODUCTION

Mass transfer is mass in transit due to a species concentration gradient in a

mixture. A concentration gradient is a spatial difference in the abundance of a
chemical species under study.
The term diffusion (a mode of mass transfer) is used to denote the
transference of a component in a mixture from a region where its
concentration is high to a region where the concentration is lower. Diffusion
process can take place in a gas or vapor or in a liquid, and it can result from the
random velocities of the molecules (molecular diffusion) or from the
circulating or eddy currents present in a turbulent fluid (eddy diffusion).
Mass transfer is commonly described as diffusional phenomena in the
presence of convective motion. Diffusion and mass transfer play a significant
role in many materials processing operations. In metal extraction and refining,
the chemical changes are usually associated with the transport of the reactants
to the reaction sites and the transport of products away from the reaction site.
The overall rates of the processes are often mass transfer-controlled, because
the chemical kinetics tend to be fast at elevated temperatures. Diffusion and
mass transfer are also of crucial importance in affecting the structure of solid
products. Typical examples include segregation phenomena in castings and
impurity distribution in crystal growth.
Diffusion depends on:
1. Driving force
2. The distance in the direction of transfer
3. Diffusivity (diffusion coefficient), unit area per unit time

The measure of the capability of a substance to be diffused or to allow

something to pass by diffusion is termed the diffusivity or the diffusion
coefficient.
Diffusivities of vapors are most conveniently determined by the method
developed by Winkelmann in which liquid is allowed to evaporate in a vertical
glass tube over the top of which a stream of vapor-free gas is passed, at a rate
such that the vapor pressure is maintained almost at zero. If the apparatus is
maintained at a steady temperature, there will be no eddy currents in the
vertical tube and mass transfer will take place from the surface by molecular
diffusion alone.

Figure 1: Set-up of Winkelmann's Method for determining the diffusivity of a gas

The rate of evaporation can be followed by the rate of fall of the liquid surface,
and since the concentration gradient is known, the diffusivity can then be
calculated using the Fick's law by which the mass of a substance diffusing in a
period of time through a surface normal to the diffusion direction is
proportional to the concentration gradient of this substance. Hence, physically,
the diffusion coefficient implies that the mass of the substance diffuses
through a unit surface in a unit time at a concentration gradient of unity.
Other methods for determining the diffusivity of a gas are the pressure decay
method, the constant pressure dissolving gas volumes (CPDGV) method and
the low-field nuclear magnetic resonance (NMR) method.1
The diffusion of gases has many areas of application, for example, oxygen
diffuses from the air sacs in the lungs into the blood capillaries because the
concentration of oxygen is higher in the air sacs and lower in the capillary
blood.

1
Details of these methods can be found in the Appendix on page 21
THEORY

If two gases are inter-diffusing with continual supply of fresh gas and removal
of the products of diffusion, this diffusion reaches an equilibrium state with
constant concentration gradients. This is known as steady state diffusion. If
also there is no total flow in either direction of rates of diffusion of A and B. NA
and NB are equal but have opposite signs.

According to Dalton’s law the total concentration of the two components C A

and CB is constant.

𝑑𝐶𝐴 𝑑𝐶𝐵
= − Equation 1
𝑑𝐿 𝑑𝐿

Then using the integrated form of the Fick’s Diffusion equation with
appropriate constants:
𝑑𝐶𝐴
𝑁𝐴 = −𝐷𝐴𝐵 Equation 2a
𝑑𝐿

𝑑𝐶𝐵
𝑁𝐵 = −𝐷𝐵𝐴 Equation 2b
𝑑𝐿

Where DAB = DBA = Diffusivity coefficient of A/B.

Molar concentration of a perfect gas CA is related to partial pressure PA by the
gas law:
𝑃𝐴
𝐶𝐴 = Equation 3
𝑅𝑇

Then,
𝐷 𝑑𝑃𝐴
𝑁𝐴 = Equation 4
𝑅𝑇 𝑑𝐿
Integration of equation 4 yields,
𝐷 𝐷
𝑁𝐴 = (𝑃𝐴1 − 𝑃𝐴2) = 𝑁𝐵 = (𝑃 − 𝑃𝐵2 )
𝑅𝑇𝐿 𝑅𝑇𝐿 𝐵1 Equation 5

Where PA1 and PA2 are the partial pressures of A at the boundaries of the zone
of diffusion and L is the distance over which diffusion occurs.
In cases where gas A is diffusing through stagnant gas non-diffusing B, the flow
𝑁 𝑃 𝑁 𝑃
carries both components in proportions to their partial pressure 𝐴 𝐴 + 𝐵 𝐵
𝑃 𝑃
The total transfer of A is the sum of this proportion of the flow and the transfer
by diffusion.
𝑃𝐴 𝐷 𝑑𝑃𝐴
𝑁𝐴 = 𝑁𝐴 − Equation 6
𝑃 𝑅𝑇 𝑑𝐿

And
𝐷𝑃 𝑃𝐵2
𝑁𝐴 = 𝑙𝑛
𝑅𝑇𝐿 𝑃𝐵1 Equation 7

This is the expression used for the determination of vapour diffusion

coefficients in gases by evaporation from a surface of liquid in a thinner bore
tube and measuring the level of the falling liquid surface.
The distance of the liquid surface below the open end of the tube is measured
before and after evaporation over a particular period of time. If the change in
level is small then the arithmetic mean of these two readings is taken as the
value of L. In case there is some change of level, the value of L is determined by
integration between the initial and final readings of level.

Thus, the rate of evaporation is given by,

𝐿 𝑑𝐿
𝑁𝐴 = Equation 8
𝑀 𝑑𝑡

In terms of concentration the expression for D is:

2. 𝑀𝐴 . 𝐷𝐴𝐵 𝐶𝐴 . 𝐶𝑇
𝐿2 − 𝐿20 = 𝑡. ( ).( ) Equation 9
𝐿 𝐶𝐵𝑀
Usually, L0 will not be measured accurately nor is the effective distance for
diffusion, L at time, t. Accurate value of (L – L0) is available.
 𝑡 𝐿 . 𝐶𝐵𝑀 𝐿 . 𝐶𝐵𝑀
= = (𝐿 − 𝐿0) + 𝐿
𝐿 − 𝐿0 2𝑀𝐴 𝐷𝐴𝐵 𝐶𝐴 𝐶𝑇 𝑀𝐴 𝐷𝐴𝐵 𝐶𝐴 𝐶𝑇 0 Equation 10

𝑡
A graph between against (L – L0) should yield a straight line with slope
𝐿−𝐿2

 𝐶𝐵𝑀
𝑠 = ( 𝐿 ).( )
2. 𝑀. 𝐷 𝐶𝐴 . 𝐶𝑇 Equation 11

And the diffusivity is defined mathematically as

𝐿 . 𝐶𝐵𝑀
𝐷=( )
2. 𝑠. 𝑀. 𝐶𝐴 . 𝐶𝑇 Equation 12