Abstract:

A molecular diffusion experiment was conducted for determining the diffusion coefficient of
acetone into air. This acetone was placed in a Stefan tube and was allowed to diffuse into non-
diffusing air. At first, this experiment was done at room temperature. There was a centrifugal pump
to pass over fresh air stream over the top of the tube. The flow rate of air was constant for all
temperature. By molecular diffusion, acetone diffused from tube to the non diffusing air. Then the
time for diffusion of 5 mm height of acetone in tube was determined. The experiment was repeated
by changing temperature to 43.5oC and50oC.The tube was kept at water bath to get desired
temperature. The diffusivity of acetone at two different temperatures is determined through
calculation. The diffusivity of acetone at temperature of room temperature, 43.5oC and 50oC are
4.3406*10-3m2/s, 3.9688*10-8m2/s and 2.4712*10-8m2/s respectively. By this experiment, the
diffusivity of acetone was measured at three different temperatures.

Introduction:
Molecular diffusion is the transfer or movement of individual molecules through a fluid by random
molecular movements . In the diffusion process, the molecules of interest flow from regions of
high concentration to low concentration. Molecular diffusion can occur in both directions with the
system. Many chemical engineering processes involve mass transfer by diffusion, in which
concentration gradient is the driving force. For example, evaporation of a liquid into air, transfer of
nutrient and oxygen to microorganism fermentation process, transfer of reactants to the catalyst
surface in catalytic reaction. The diffusivity coefficient characterizes the rate of a process, and is
the basic parameter in the modeling and prediction of a diffusion process.

Objective:
 To determine the diffusivity
 To calculate the evaporation rate of acetone at a given temperature under the experimental
conditions
 To study the temperature effect on evaporation and diffusion and to check water the
diffusion rate
 To calculate the enthalpy of evaporation

Theory:
For liquids of high volatility, A. Stefan (1879) devised a convenient means of measuring the
diffusivity DAB of their vapor A through a stagnant gas B. if the volatile substance A (e.g. Acetone)
is placed in the lower part of a vertical capillary, then liquid A will evaporate and, by the
mechanism of diffusion, travel to the end of capillary. Maintaining the mouth of the capillary at a
given composition automatically establishes the concentration gradient in the capillary, and the
falling rate of the meniscus in the capillary provides the rate of transport.
The capillary is placed in an envelope through which air is passed. At the meniscus the gaseous
phase composition is specified by the vapor pressure of liquid A, the diffusing constituent.at the
mouth of the capillary. The gaseous phase is essentially air. The gradient in the capillary is thus
obtained by circulating sufficient air to reduce the substance A concentration at the mouth to a
negligible quantity. The air rate should be low, constant and not turbulent. The falling rate of the
meniscus can be observed remotely with a cathetometer.

Gas B (air)
PA2 z=0

PA1 z = z1 at t=0

z = zt at t

pure liquid A

Figure: Diffusion cell with moving liquid surface

If the length of the diffusion path changes a small amount over a long period of time, a pseudo-
steady state assumption may be used. Diffusion flux is described by Fick’s Law and for the general
case of transport of gas A through another gas B by diffusion plus convection. The following
equation is:
𝑐𝑎
𝑁𝑎 = 𝐽𝑎 + (𝑁𝑎 + 𝑁𝑏) … … … … (1)
𝑐
Here,
Na and Nb is the total molar flux of A and B respectively.
Ja is the diffusion flux of A.
ca is the concentration of A and c is the total concentration.
Fick’s Law and that of ideal gas the following equation should be,
𝑑𝑥 𝑃
𝐽𝑎 = −𝑐𝐷 ,𝑐 = , 𝑐 = 𝑥𝑐, 𝑃𝑎 = 𝑋𝑎𝑃, 𝑃𝑎 + 𝑃𝑏 = 𝑃 … … … … (2)
𝑑𝑧 𝑅𝑇 𝑎
Ja is the diffusion flux of A, DAB is the diffusivity of A in the medium B. XA is the mole fraction
of A, R is the universal gas constant. Pa is the partial pressure of A.
If B is stagnant Nb=0. Combining 1 and 2 we get:
𝐷𝐴𝐵 𝑑𝑝 𝑃𝑎
𝑁𝑎 = − 𝑁𝑎 … … … … (3)
𝑅𝑇 𝑑𝑧 𝑃
The rearrangement gives:
𝐷𝐴𝐵 1 𝑑𝑃𝐴
𝑁𝐴 = − … … … … (4)
𝑅𝑇 1 − 𝑃𝐴 𝑑𝑧
𝑃
Under steady state flow condition Z=Z1, PA=PA1 and Z=Z2, PA=PA2 then we get,
𝐷𝐴𝐵 𝑃 𝑃 − 𝑃𝑎2
𝑁𝑎 = 𝑙𝑛 … … … … (5)
𝑅𝑇(𝑍2 − 𝑍1 ) 𝑃 − 𝑃𝑎1
Application of equation (5) to the measurement of diffusivity of acetone.

Acetone is contained in a graduated tube and an air flow is maintained at the top of the tube by a
blower. At time t=0 the liquid level Z=0. At the liquids evaporates from the surface, the liquid
level gradually drops down. At the given moment its position indicates by Z. Here Z is a variable.
At any moment, whenever might be the position of the liquid level Z, Pa at the liquid gas interface
assumes to be equal to the saturated vapor pressure Ps, and the top of the tube PA2=0. Assume the
pseudo steady state we can say:
𝐷𝐴𝐵 𝑃 𝑃
𝑁𝑎 = 𝑙𝑛 … … … … (6)
𝑅𝑇(𝑍2 − 𝑍1 ) 𝑃 − 𝑃𝑠
Denoting the length measure from the top of the tube (position 2) to the liquid surface L, equation
6 assumes the following form:
𝐷𝐴𝐵 𝑃 𝑃
𝑁𝑎 = 𝑙𝑛 … … … … (7)
𝑅𝑇𝐿 𝑃 − 𝑃𝑠
A is the cross-sectional area of the tube with liquid. A flux can be related to the change of the
liquid volume. We can write,
𝜌 𝑑(𝐴𝐿)
𝑁𝑎𝐴 = … … … … (8)
𝑀𝑎 𝑑𝑡
ρA and MA are the density and molar mass of the liquid. Now substituting the equation (8) and (7)
we can write,
𝐿 𝑙
𝐷𝑎𝑏 𝑀𝑎 𝑃 𝑃
∫ 𝐿𝑑𝑙 = 𝑙𝑛 ∫ 𝑑𝑡 … … … … (9)
𝐿0 𝜌𝑅𝑇 𝑃 − 𝑃𝑥 𝑟

Here, tr is the reference time and Lr is the length. Solving equation (9) we have,
𝐷𝐴𝐵 𝑀𝐴 𝑃 𝑃
𝐿2 − 𝐿2𝑟 = 𝑙𝑛 (𝑡 − 𝑡𝑟 ) … … … … (10)
𝜌𝑅𝑇 𝑃 − 𝑃𝑠

Materials:
1. Stefan tube
2. Acetone
3. Air pump

Procedure:
1) A Stefan tube was taken and the dried and cleaned and attached to a stand.
2) Acetone was taken in the vertical section up to a certain height of the tube.
3) An air pump was connected to the horizontal section of the Stefan tube and a flow rate was
set at which fresh air flow at a constant rate.
4) Time and changes of heights of acetone were measured for 7 times at definite intervals and
those collected data were noted down for further calculation.