Title: Gaseous Diffusion Coefficient

Objective: To determine gas diffusion coefficient of acetone

Introduction:

The knowledge of physical and chemical properties of certain materials is important because
very often process engineering deal with the transformation and distribution of these
materials in bulk. One such property is diffusivity. Diffusion is a process where molecules
move from an area of high concentration to an area of low concentration until equilibrium is
achieved. Mass transfer by diffusion takes place when there is a concentration gradient of the
diffusing component. Naturally, the diffusion in gas phase is much faster than the diffusion in
liquid phase due to the small spaces between the molecules that hinder other molecule
movement. Other factors that will affect the diffusion are temperature, density, concentration
and other external factors. 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.

When a concentration gradient exists within a fluid consisting of two or more

components, there is a tendency for each constituent to flow in such a direction as to reduce
the concentration gradient. This is called mass transfer.

The experiment to determine the diffusivity of gaseous is based on the Winkelmann’s

method. In this method, the volatile liquid is allowed to evaporate in a vertical glass tube over
the top of which a stream of vapour-free gas is passed. A water bath is provided for
maintaining a steady temperature so that there is no eddy current in the vertical tube and mass
transfer takes place from the surface by molecular diffusion alone. By monitoring the
evaporation rate, which is the rate of fall of liquid surface, and with the knowledge of
concentration gradient, the diffusivity can be calculated.

The rate of mass transfer is given by:

CA CT
NA= D( )( )
L CBm

m2
Where, D = diffusivity ( )
s
 kmol
CA = saturation concentration at interface ( )
m3

L = effective distance of mass transfer (m)

kmol
CT =total molar concentration ( )
m3

kmol
CBm =logarithmic mean value of CB ( )
m3

Considering the evaporation of the liquid:

ρL dL
NA = ( )
M dt

kg
Where, ρL = density of liquid (m3)

kg
M = molecular weight (kmol)

From the Equation (1) and (2), the diffusivity of acetone, D can be calculated as:

ρL CBm
D=
2MCA CT s

t
Where, s is the slop of the plot L+L against (L-Lo).
o

Procedure:

1. The water bath is filled with distilled water to approximately 20mm from the top.
2. The main power is switched on from the control panel.
3. The set point on the temperature controller is adjusted to 50°C.
4. The heater is switched on. The water temperature heat up to 50°C is observed and
remains constant.
5. The capillary tube is partially filled with acetone to a depth of about 15mm.
6. The capillary tube is inserted carefully through the fitting on top of the water bath
cover.
7. The initial level of acetone is observed through the telescope. The level of acetone is
recorded.
 8. The flexible tubing is connected from the air pump line to one end of the capillary
tube. The air pump is switched on. The level of acetone for every 15 minutes are
observed and recorded in the following table.

Results:

Table 1: Raw Material and Calculated Data Table for Gaseous Diffusion Experiment

Time, t Level of acetone, L

Point (ks) (mm) L+Lo, dL (mm) t/(L+Lo)(ks/mm) L-Lo
1 0.00 72.000 144.00 0.00 0.00
2 0.90 72.200 144.20 0.01 0.20
3 1.80 73.400 145.40 0.01 1.40
4 2.70 73.800 145.80 0.02 1.80
5 3.60 74.650 146.65 0.02 2.65
6 4.50 75.400 147.40 0.03 3.40
7 5.40 76.100 148.10 0.04 4.10

0.04
0.04
0.03 y = 0.0091x
0.03
t/(L+Lo)

0.02
0.02
0.01
0.01
0.00
0.00 1.00 2.00 3.00 4.00 5.00
L-Lo

Figure 2: Graph of t/dL versus dL

s
Based upon the graph above, it has stated that the slope value is 7 x 106m2 and from the result
m2
given, the value obtained for gas diffusivity is equal to 1.5097 x 10-5 . While for the partial
s

pressure of acetone, using Antoine equation is 612.694mm Hg which is 0.8062 atm.

 Calculation:

1. Molecular weight of Acetone:

𝑘𝑔
M = 58.08 𝑘𝑚𝑜𝑙

2. Temperature was converted to Kelvin,𝑘

1𝑘
T=(50℃ × ) + 273𝑘 = 323𝑘
1℃

3. Pressure 𝑃𝑎 is a atmospheric pressure:

101.3𝑘𝑃𝑎

4. Density of Acetone:

760.0 𝑚𝑘𝑔3

5. Vapour Pressure was calculated by Antoine Equation:

𝐵
𝑃𝑎 = 10𝐴−𝐶+𝑇

Where A, B and C is a constant values for the acetone from -64℃ to 70℃.

A= 7.02447

B= 1161

C=224

1210.5951161
𝑃𝑎 = 107.02447− 224+50 = 612.6941 𝑚𝑚𝐻𝑔

Converted to 𝑘𝑃𝑎.

101.325 𝑘𝑃𝑎
621.6941𝑚𝑚𝐻𝑔 × = 82.8857𝑘𝑃𝑎.
760𝑚𝑚𝐻𝑔

6. From the graph gradient:

s
Slope, s =7 x 106m2

7. Total molar concentration, 𝐶𝑇 (𝑘𝑚𝑜𝑙⁄𝑚3 )

 𝑃 101.3 𝑘𝑃𝑎
𝐶𝑇 = 𝑅𝑇 = 𝑚3 ×𝑘𝑃𝑎
= 0.03773 𝑘𝑚𝑜𝑙
𝑚3
8.314( )(323 𝐾)
𝑘𝑔×𝑚𝑜𝑙×𝐾

8. Logarithmic mean value, 𝐶𝐵𝑚 (𝑘𝑚𝑜𝑙⁄𝑚3 )

𝐶𝐵1 = 𝐶𝑇 = 0.03773 𝑘𝑚𝑜𝑙

𝑚3

101.3𝑘𝑃𝑎−82.8857 𝑘𝑃𝑎 𝑘𝑚𝑜𝑙

𝐶𝐵2 = (𝑃𝑎𝑃−𝑎𝑃𝑣) 𝐶𝑇 = ( )0.03773 𝑘𝑚𝑜𝑙
𝑚3
= 6.8586× 10−3
101.3𝑘𝑃𝑎 𝑚3

Solve for 𝐶𝐵𝑚

𝐶𝐵1 −𝐶𝐵2 0.03773−0.0068586

𝐶𝐵𝑚 = 𝐶 =( 0.03773 ) = 0.01811 𝑘𝑚𝑜𝑙
𝑚3
ln( 𝐵1 ) ln(
0.0068586
)
𝐶𝐵2

9. Saturation concentration at interface (𝑘𝑚𝑜𝑙⁄𝑚3 )

82.8857𝑘𝑃𝑎 𝑘𝑚𝑜𝑙
𝐶𝐴 = ( 𝑃𝑃𝑎𝑣) 𝐶𝑇 = ( ) 0.03773 𝑘𝑚𝑜𝑙
𝑚3
= 0.03087
101.3𝑘𝑃𝑎 𝑚3

10. Diffusivity, D

kg 𝑘𝑚𝑜𝑙
𝜌 𝐶𝐵𝑀 (760 3 )(0.01811 3 ) 𝑚2
D = 2𝑀𝐶𝐿 = kg
𝑚
𝑘𝑚𝑜𝑙
𝑚
𝑘𝑚𝑜𝑙 𝑠 =1.4533 x 10-5
𝐴 𝐶𝑇 s 2(58.08 )(0.03087 3 )(0.03773 3 )(7 x 106 2 ) 𝑠
mol 𝑚 𝑚 𝑚

Discussion:

The objective of this experiment is to determine the gas diffusion coefficient of acetone using
the Winkelmann’s method. In this experiment, the volatile liquid which is acetone is heated
until it evaporated into free air stream. The rate of diffusion can be observed by the rate of
decreasing of acetone level in the tube by using a telescope. Based on the result obtained, the
level of acetone was decreased when the time was increased. This is because diffusion takes
place where it is process that involves the movement of component or molecules from one
location to another location due to existing of concentration gradient. The movement of
molecules are from high concentration region to less concentration region. Acetone has the
higher concentration while air has lower thus acetone diffuse into the air.

In the experiment, the diffusion concept can be observed by the decreasing of acetone
level in the capillary tube. The boiling process of water was generated heat and the heat was
transferred to the acetone. This process was increased the movement of molecules in the
acetone until it creates body that has high concentration compare to surrounding. Besides that,
due to some driving forces and existing of concentration gradient, the molecule was move
from inside the capillary tube to the surrounding air that has less concentration.

Based on the graph, the x-axis is the differences between final level of acetone and the
initial level of acetone and the y-axis is the time taken divide by the difference between the
levels of acetone. From the graph, we know that the trend of the graph is increased
proportionally. When the difference between the levels of acetone increases, the time taken
over the difference between the levels of acetone is also increases. The equation that obtained
from the graph is y=0.0091x, where the slope of the graph is 0.007 in positive value. From
the calculation and the data from the table, the value of diffusivity was determined which is
m2
1.4533 x 10-5 .
s

The Antoine equation was used in the calculation in order to determine the partial
pressure and the concentration. The relationship between the partial pressure and the
concentration is directly proportional:

𝑃
𝐶=
𝑅𝑇

Where the C is the concentration, P is partial pressure, R is gas constant and T is the
temperature. When the partial pressure of the substance is increase, the concentration of the
substance is also increasing. This is because pressure affects the movement of the molecular
particles in the solvent.

Before the experiment started, the temperature controller has been set up only at 50℃
along the experiment and it not been set beyond 70 ºC. It is because the boiling point of the
acetone is at 56 ºC. When the temperature exceeds 70 ºC, the rate of evaporation is faster
compare to temperature at the boiling point. This situation can cause the problem to the
experimenter to collect the data or difference of acetone level since acetone can volatize
easily. The molecular attraction of the particles in acetone will be unstable when the
temperature exceed 56.0 ºC and thus make it to evaporate easily. Finally, the discrepancy
from the experimental data is the value of the time divide by difference between levels of
acetone between intervals is not increased constantly due to some errors such as parallax
error and the initial value of the acetone in the capillary tube was not read accurately.

The fuller correlation extracted from Perry’s Chemical Engineers’ handbook, stated
that the diffusion coefficient of acetone in air is (1.22± 0.11) × 10−5 m²/s.
 1.4533×10−5 −1.22×10−5
Percentage of error = | | × 100%
1.22×10−5

=19.12%
The percentage of error as compare to the theoretical is 19.12% which is considered
relatively high. The deviation might due to the certain errors made during conducting the
experiment. Firstly, parallax error might be occurred during taking the reading of liquid
acetone level. This is because the meniscus of the liquid acetone in the capillary tube is not
parallel to the reference line. Next, the assumption we made. We assume the partial pressure
of the acetone as zero at the mouth of the capillary tube are the second factors that affecting
the inaccuracies in the results because the partial pressure may not exactly be zero since some
acetone vapour might not being displaced by the air flow. The fluctuating temperature of the
water is also one of the reasons that causing inaccuracies of the results.
Hence, we can make some improvements. Before the acetone was pumped, we have
to make sure that there was no air bubble inside the capillary tube. Next, the travelling
microscope that attached to the Vernier scale must be installed tightly and stable and also
parallel to the capillary tube. Moreover, when we adjust the Vernier scale, the position of the
travelling microscope should remain constant.
Temperature is also a factor that affects the rate of diffusion. Heating caused the particles
to gain more kinetic energy at higher temperature to act their way faster and collide with each
other in a not oriented path. If this happened in the experiment, it is easier to evaporate,
resulting in an increase of rate of diffusion.

Conclusion:

The diffusivity coefficient for the unimolecular acetone diffusion in air at 50°c(323K) and 1
𝑚2
atm is 1.4533 × 10−5 . The experimental value is 19.12% deviated from the actual one.
𝑠

We can conclude that diffusivity of the acetone with higher temperature will have a higher
value. Besides that, it has been theoretically proved that higher temperature causes the
molecules of substance to gain higher kinetic energy and moves randomly and freely hence
increasing the rate of diffusion.

References:

 Castells,R.C .( 2004) . Determination of gas-liquid partition coefficients by gas

 Mass Transfer and Diffusion Coefficients. (n.d.). Retrieved June 8, 2013, from
http://www.discoveramfield.co.uk/data/cer
 Determination of gaseous diffusion. (n.d.). Retrieved June 8, 2013, from
http://www.mendeley.com/.ion.diffusion.coefficient.gas

 Leonard B., Kinetic Theory of Gases, Mineola, New York: Dover Publications Inc.
 Landolt-Bornstein, Gases in Gases, Liquids and Their Mixtures, New York: Springer
Berlin Heidelberg.
 E.L. Cussler, Diffusion: Mass Transfer in Fluid Systems, 2nd ed. Cambridge, United
Kingdom : The Press Syndicate Of University Of Cambridge