School of Chemical and Biomedical Engineering

Division of Chemical and Biomolecular Engineering

CH 2802

Measurement of
Liquid Diffusion Coefficient
C6
Location: N1.2 B4-
16

Name:
Matric number:
Group: Group 22
Date of experiment: 15 February 2023
 Grade:
Aim
The aim of this experiment is to determine the diffusion coefficient of 2M sodium
chloride solution in deionised water.

Abstract
A diffusion cell containing 2M sodium chloride solution was placed into a
magnetically stirred diffusion vessel containing deionised water, allowing for diffusion
to occur. A conductivity probe, connected to a conductivity meter, was placed in the
diffusion vessel and conductivity values were recorded at different times. Graphs of
conductivity versus time were plotted so as to determine the diffusion coefficient, D.
The values will be compared with literature values and the factors affecting the
values of the diffusion coefficient will be discussed.

Theory
When there is a concentration gradient within a fluid which consists of two or more
components, each component flows in a direction so as to reduce the concentration
gradient. This process is known as diffusion. This process is mathematically
described by Fick’s Law. For one-dimension diffusion, Fick’s Law states that the
molar flux (Ni) of each individual component (i) is:

𝑑𝐶𝑖
𝑁𝑖 = −𝐷
𝑑𝑧

Where Ni = molar flux of each individual component i

D = diffusion coefficient
Ci = concentration of each component i

The negative sign indicates that flow is from high to low concentration.

To determine the diffusion coefficient of 2M sodium chloride, a diffusion cell

containing 2M sodium chloride is placed into a 1L diffusion vessel containing
deionised water, causing the sodium chloride to diffuse into the deionised water. The
water and 2M sodium chloride are separated by a honeycomb of accurately
dimensioned capillaries. In order to restrict the diffusion to one dimension, 121
capillaries of length 5 mm and diameter 1 mm are used.

Since the concentration at the upper end of the tube is effectively zero, and the
concentration at the lower end of the tube is the molarity of the solution, the
concentration gradient can be approximated as:

𝑑𝐶 𝑀
≈−
𝑑𝑧 𝐿

Where M = molarity of solution

L = length of tube

Applying Fick’s Law, the amount of sodium chloride diffusing into the capillaries ( ṁ1)
is approximately:

𝜋𝑑2
𝑀
𝑚̇ 1 = 𝑛 (𝐷 )
4 𝐿

Where n = number of capillaries

d = diameter of capillary
L = length of capillary

On the other hand, the amount of sodium chloride entering the diffusion vessel (ṁ2)
is related to the change in the conductivity (k) of the solution with respect to time (t),
and is approximately:

𝑉 𝑑𝑘
𝑚̇ 2 =
𝐶𝑀 𝑑𝑡

Where V = volume of water in vessel

CM = conductivity change per molarity change (given as 0.41 Ω -1M-1)

Since mass balance requires that ṁ1 = ṁ2, the equations for ṁ1 and ṁ2 can be
combined to obtain the following relationship between the diffusion coefficient (D)
and conductivity (k):

4𝑉𝐿 𝑑𝑘
 𝐷 = 𝜋𝑑2𝑛𝑀𝐶𝑀 𝑑𝑡

By recording down the conductivity readings at different time intervals, conductivity

(k) can be plotted against time (t) to obtain the slope of the graph, dk
. Thus, the
diffusion dt coefficient (D) can be calculated.

Materials and Apparatus

2M NaCl solution
Deionised water
Dropper
Beaker
Syringe
1L diffusion vessel
Diffusion cell
Conductivity probe
Conductivity meter
Magnetic stirrer
Magnetic stir bar
Stopwatch

Experimental Procedure
1. The 1 L vessel was rinsed and filled deionised water.
2. The magnetic stirrer was activated with the knob at the lowest rotational
speed.
3. Readings of conductivity were recorded.
4. Diffusion cell was rinsed and filled with 2M Nacl solution. With the aid of a
syringe, air bubbles were removed from the interface of the diffusion cell. Excess
solution remaining at the top of the interface was removed with a dry towel.
5. Diffusion cell was tights fixed on cover of the diffusion vessel.
6. The diffusion cell was then gradually lowered into the vessel. The timer was
started when the interface of the cell was completely submerged into water.
7. Conductivity readings were recorded for every 200 seconds.
 8. The solution of the diffusion cell was discarded, and the vessel was rinsed.

Results
Run 1 Run 2 Run 3

Time t Conductivity k (µΩ- Conductivity k (µΩ- Conductivity k

(seconds) 1
) 1
) (µΩ-1)

0
200

400

600

800

1000

1200

1400

1600

1800

Figure 1: Graph of conductivity against time

Graph of Conductivity (k) vs Time (t)

50
y = 0.674x + 26.42
40 R² = 0.9986

30
k (µΩ-1)

y = 0.5623x + 18.75
R² = 0.9932
20
Run 1
10 Run 2

0
0 5 10 15 20 25 30
t (min)
Based on Figure 1, there is an overall increase in the conductivity of the solution with
respect to time, with a drastic increase in the first minute. The slopes of the two best
fit lines are very similar, averaging at about 0.62 x 10 -6 Ω-1/min.

The first reading (when t=0) was omitted when plotting the graphs in Figure 1 due to
the following reasons:

1. The first reading was taken before the diffusion cell was immersed in the vessel,
so no diffusion has occurred yet.
2. If, instead, the first reading was taken the moment the diffusion cell was
immersed in the vessel, the reading would not be accurate due to the drastic
changes in conductivity during the first few seconds. The refresh rate of the
conductivity meter would be too slow for accurate readings to be obtained.

From the slopes of the graphs in Figure 1, the diffusion coefficients (D) for both runs
are calculated below:

Run 1: dk

= 0.5623 (from Figure 1)

dt

4VL dk

D1 = πd2nMCM dt
-6
0.5623×
= ×

-10
m2
= 6.01×10 s
Run 2: dk
= 0.674 (from Figure 1)
dt

4VL dk

D2 = πd2nMCM dt

0.674× -6
= ×

m
2

= 7.21×10-10
s

Discussion
Comparison with Literature Values

The literature value of the diffusion coefficient of sodium chloride in deionized water
is given as 1.52 x 10-9 m2/s (Chang & Myerson, 1985). Based on the experimental
results, the diffusion coefficient of sodium chloride in deionized water was calculated
to be 6.01 x 10-10 m2/s for Run 1. This corresponds to a difference of 9.19 x 10 -10
m2/s. For Run 2, the diffusion coefficient was calculated to be 7.21 x 10 -10 m2/s, which
corresponds to a difference of 7.99 x 10 -10 m2/s. The difference between literature
and experimental values may be due to several sources of error as well as other
factors to be discussed below.
Sources of Experimental Error

1. Although, measures were taken to remove air bubbles form the interface of the
diffusion cell, (such as using a needle syringe to release air bubbles) some air
bubbles may have formed in the honeycomb interface when the diffusion cell was
lowered into the water medium despite the careful loading and lowering of the cell
into the water. These trapped air bubbles could not be removed until the run was
complete. The presence of trapped air bubbles in the honeycomb interface would
have caused hinderance to the movement of sodium chloride particles from the
diffusion cell into the diffusion vessel. Hence the rate of diffusion of sodium
chloride particles would have decreased in magnitude as a result. Therefore, the
calculated
diffusion coefficient is lower in magnitude compared to the literature values.

2. In order to indicate the appropriate amount of water to be filled, the 1L

diffusion vessel had a mark. However, the diffusion cell had no such mark to
indicate the amount of sodium chloride solution to be filled. Hence discrepancies
in the diffusion coefficient could have arisen due to the differing amounts of
sodium chloride solution used in each run.

3. During the fixation of the cover of the diffusion vessel to the diffusion cell, the
position of the cover is not held fixed throughout the runs, hence the distance
between the diffusion cell and the conductivity probe is not held constant
throughout all the runs. This results in different conductivity coefficients for each
reading to be obtained. In order to reduce this error, markings can be made on
the diffusion cell hence its position relative to the probe in held constant.
Furthermore, multiple probes can be utilised to obtain multiple readings at
multiple sites in the vessel. The values can be averaged to obtain accurate
results.

4. The was non-uniform rate of stirring of the solution as the magnetic stirrer’s
size is relatively small compared to the vessel. Hence the conductivity readings
obtained are not accurate for the entire solution is the vessel. Also, the probe is
placed at a relative distance away from the interface of the diffusion cell (where
diffusion occurs). Due to the incorrect reading of diffusion coefficient at an
inappropriate site, the obtained diffusion coefficient is different from the literature
value. A small vessel relative to the stirrer size as well as a probe placed at an
appropriate position to the cell.
 5. When the sodium chloride solution was discarded after each run, some
sodium chloride may have remained inside the cell. Though the outer surface
was cleaned thoroughly, the inner surface may not have been thoroughly cleaned
of sodium chloride. This could have led to increased conductive leading to the
diffusion coefficient to increase with subsequent run and deviation from literature
values.

Discussion of Results

Based on Table 1, there was a significant increase in conductivity for both runs in the
first minute. This is because the concentration gradient is very steep at the beginning
as the vessel only contains deionized water, whereas the diffusion cell contains 2M
sodium chloride. After the first minute, conductivity increases linearly with respect to
time since the concentration gradient is not so steep and the diffusion reaches
steady state.

Although the slopes of the graphs for both runs are similar in magnitude, the graph
for Run 2 lies entirely above the graph for Run 1 because the conductivity readings
for both runs are different. This is due to the several experimental errors discussed
previously. In addition to the measures mentioned previously to reduce experimental
error, the entire experiment can also be conducted more than twice so as to obtain
more accurate data.

Further Discussion

One assumption that was made to simplify calculations was that the concentration at
one end of the capillaries was constant and is equal to the molarity of the solution,
whereas the concentration at the other end of the capillaries is effectively zero, such
that the following approximation can be made for the concentration gradient:

𝑑𝐶 𝑀
≈−
𝑑𝑧 𝐿
Due to the presence of the concentration gradient, water from the vessel can also
move into the diffusion cell. The molarity of sodium chloride at one end of the
capillary was therefore lower than 2M. This results in a higher than expected slope of
the graph. However, this effect is minimal since there were no significant changes in
the slope.

The deviations from literature values is also because the diffusion coefficient is
dependent on temperature. For liquids, the dependence of diffusion coefficient on
temperature is described using the Stokes-Einstein equation (Welty, Wicks, Wilson,
& Rorrer, 2008):

𝑘𝑇
𝐷=
6𝜋𝑟𝜇𝐵

From the equation, a lower temperature (T) leads to a lower diffusion coefficient (D).
The literature value was obtained from experiments conducted at 25°C (Chang &
Myerson, 1985). However, our experiment was conducted at 21°C based on the air
conditioner control readings. Therefore, our experimentally determined diffusion
coefficients were lower than the literature value.

Conclusion
From this experiment, the diffusion coefficient of 2M sodium chloride was determined
to be 6.01 x 10-10 m2/s and 7.21 x 10-10 m2/s for Run 1 and Run 2 respectively. There
was some deviation from the literature value due to the several sources of error
mentioned above.

References
Chang, Y., & Myerson, A. (1985). The diffusivity of potassium chloride and sodium
chloride in concentrated, saturated and supersaturated aqueous solutions. AIChE
Journal, 31, 890-894.

Welty, J. R., Wicks, C. E., Wilson, R. E., & Rorrer, G. L. (2008). Fundamentals of
Momentum, Heat, and Mass Transfer. John Wiley & Sons, Inc.