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YASSER ASHOUR

diffusivity

NOVEMBER 2, 2017
127978
Abstract
The objective of this experiment is to measure the rate of diffusivity for 2M Nacl at different time
interval and different temperatures. Moreover, to find up a relationship between both temperature,
diffusivity and between concentration and diffusivity using special procedures and materials such as
the u-tube, stop watch, conductivity meter, mechanical stirrer and diffusion cell. Finally, after different
three temperature changes different concentration reading have been recorded at different time
intervals to be used for the calculation of diffusivity coefficient of 2M Nacl in distilled water.
Contents
Abstract ................................................................................................................................................... 0
Introduction ............................................................................................................................................ 3
Temperature dependence of the diffusion coefficient ...................................................................... 3
Solids ............................................................................................................................................... 3
Liquids ............................................................................................................................................. 4
Gases ............................................................................................................................................... 4
Pressure dependence of the diffusion coefficient .............................................................................. 4
Mechanism of diffusion in solids and its application .......................................................................... 5
Diffusion in porous solids ................................................................................................................ 5
Diffusion inside pore ....................................................................................................................... 5
Surface diffusion ............................................................................................................................. 6
Diffusion through polymers ............................................................................................................ 6
Effective diffusivity in porous media .................................................................................................. 6
Results ..................................................................................................................................................... 7
Discussion.............................................................................................................................................. 10
Procedures ............................................................................................................................................ 10
Material used .................................................................................................................................... 10
Sources of errors and its solution ......................................................................................................... 11
Conclusions ........................................................................................................................................... 12
References ............................................................................................................................................ 13
Introduction

Diffusivity or diffusion coefficient is a proportionality constant between the molar flux due to
molecular diffusion and the gradient in the concentration of the species (or the driving force for
diffusion). Diffusivity is encountered in Fick's law which is defined as:

where D is the dissemination coefficient, Ci is the convergence of segment I, and is the concentration
gradient in the z-heading. The negative sign shows the stream of transport is from locale of higher
concentration to district of lower concentration.

The diffusivity is generally prescribed for a given pair of species and pairwise for a multi-species
system. The higher the diffusivity (of one substance with respect to another), the faster they diffuse
into each other. Typically, a compound's diffusion coefficient is ~10,000 as great in air as in water.
Carbon dioxide in air has a diffusion coefficient of 16 mm2/s, and in water its diffusion coefficient is
0.0016 mm2/s. Diffusivity has an SI unit of m2/s (length2 / time). In CGS units it is given in cm2/s.

(treybal, 1981)

Temperature dependence of the diffusion coefficient

Solids
The diffusion coefficient in solids at different temperatures is generally found to be well predicted by
the Arrhenius equation:

where

D is the diffusion coefficient (m2/s),

D0 is the maximal diffusion coefficient (at infinite temperature; m2/s),

EA is the activation energy for diffusion in dimensions of (J/atom),

T is the absolute temperature (K),

k is the Boltzmann constant.


(geankoplis, 2005)

Liquids
An approximate dependence of the diffusion coefficient on temperature in liquids can often be
found using StokesEinstein equation, which predicts that

where

D is the diffusion coefficient,

T1 and T2 are the corresponding absolute temperatures,

is the dynamic viscosity of the solvent

(b.k, 2007)

Gases
The dependence of the diffusion coefficient on temperature for gases can be expressed using
ChapmanEnskog theory:

where

D is the diffusion coefficient (cm2/s),

1 and 2 index the two kinds of molecules present in the gaseous mixture,

T is the absolute temperature (K),

M is the molar mass (g/mol),

p is the pressure (atm),

(b.k, 2007)

Pressure dependence of the diffusion coefficient


For self-diffusion in gases at two different pressures (but the same temperature), the following
empirical equation has been suggested:
where

D is the diffusion coefficient,

is the gas mass density,

P1 and P2 are the corresponding pressures.

(ashton, 2008)

Mechanism of diffusion in solids and its application


The diffusion of solutes through the solids plays an important role in many processes such as
heterogeneous catalytic reactions. The structure of solid and interaction with the solutes are
important for the rate of diffusion.

(staff, 2007)

Diffusion in porous solids


The solid sometimes may act as porous barrier or as porous catalyst pellets and is normally surrounded
by a single body of fluid. The inward or outward movement of the solutes through the pores of the
solid is mainly by diffusion. This movement may occur inside the pore or at the surface of the adsorbed
solute.

(james, 2001)

Diffusion inside pore


At low pressure the mean free path of the molecules may be larger than the diameter of the passage
when the diffusion occurs inside the fine pores of the solid. The collision with wall becomes important
compared to collision among molecules. The diffusion of this kind is known as Knudsen diffusion. To
quantify Kundsen diffusivity a simple Equation based on kinetic theory of gases was proposed as
follows:

where rp radius of passage and v is the average velocity of the molecules due to their thermal
energy which is defined as:

Here T is the temperature in K and M is the molecular weight. The flux due to Knudsen diffusion is
similar to Ficks law:
(ashton, 2008)

Surface diffusion
The diffusion of adsorbed molecules on the surface due to concentration gradient is kwon as surface
diffusion. If the fractional coverage of the surface is less than unity, then the some of the active sites
remain empty. Adsorbed molecule having energy greater than the energy barrier tends to migrate to
an adjacent vacant site. This migration is visualized to occur by hoping mechanism.

(w.f, 2004)

Diffusion through polymers


The diffusion of solutes through polymeric solids is more like diffusion in liquids, particularly for the
permanent gases. The gas dissolves into the solid exposed to the gas and usually described by Henrys
law. The gas then diffuses from high to low pressure side. Hence, high pressure is applied to increase
gas concentrations, thus increasing respective solubility (difference in solubility is the key feature) of
gases. The polymeric chains are in a state of constant thermal motion and diffusing molecule move
from one location to the adjacent location due to the potential barrier. An Arrhenius type Equation
may be applied for the temperature dependency of the diffusion coefficient in polymers.

where HD is the energy of activation and D0 is a constant. For the permanent gases the typical
diffusivity value is in the order of 10-10 m2/s

(w.f, 2004)

Effective diffusivity in porous media


The effective diffusion coefficient describes diffusion through the pore space of porous media. It is
macroscopic in nature, because it is not individual pores but the entire pore space that needs to be
considered. The effective diffusion coefficient for transport through the pores, De, is estimated as
follows:

where

D is the diffusion coefficient in gas or liquid filling the pores,

t is the porosity available for the transport (dimensionless),


is the constrictively (dimensionless),

is the tortuosity (dimensionless).

The transport-available porosity equals the total porosity less the pores which, due to their size, are
not accessible to the diffusing particles, and less dead-end and blind pores (i.e., pores without being
connected to the rest of the pore system). The constrictively describes the slowing down of diffusion
by increasing the viscosity in narrow pores as a result of greater proximity to the average pore wall.
It is a function of pore diameter and the size of the diffusing particles.

(mendelev, 2005)

Results
For the first 80sec at 50C degree temperature

conductivity-1M-1
5
4.5
4
3.5
conductivity

3
2.5
2
1.5
1
0.5
0
0 10 20 30 40 50 60 70 80 90
time sec

From the slop we can get the diffusivity which is = 0.0001915

Cm2/sec

For temperature 51 C degree


conductivity-1M-1
4.57

4.56

4.55
conductivity

4.54

4.53

4.52

4.51

4.5
0 20 40 60 80 100 120 140 160 180
time

DIFFUSIVITY= 3.19E-05 cm2/sec

For Temp 52 C degree

conductivity-1M-1
4.545
4.54
4.535
4.53
conductivity

4.525
4.52
4.515
4.51
4.505
4.5
4.495
0 50 100 150 200 250
time

Diffusivity is = 7.98E-07 cm2/sec

For temp 54 C degree


conductivity-1M-1
4.55

4.54

4.53
conductivity

4.52

4.51

4.5

4.49

4.48
0 50 100 150 200 250 300 350 400 450
time

Diffusivity = 6.38E-06 cm2/sec

Then we have to plot the graph between Temp and diffusivity.

TempVS Diffusivity
0.00025

0.0002
Diffusivity Cm2/sec

0.00015

0.0001

0.00005

0
49.5 50 50.5 51 51.5 52 52.5 53 53.5 54 54.5
TEmp C
Discussion
It is well known that a change in the temperature of a solution will result in the change of conductivity.
An increase in temperature results in an increase in conductivity. The increase that is observed is
because of several factors. Firstly, the increase in temperature can cause ionic compounds to split
resulting in an increasing number of ions in the solution. So, in this experiment the diffusivity of NaCl
in H2O, the NaCl compound will break apart resulting in Na and Cl ions surrounded by H2O molecules.
As the NaCl (in water it is classed as an electrolyte) dissolves charged ions (Na and Cl) are formed that
can carry charge. Secondly, the increasing temperature of a solution can result in a lower viscosity.
This in turn increases ion mobility throughout the H2O, which further increases the ability of the ions
to carry the charge throughout the solution and therefore increases conductivity. These two factors
highlight the significance that temperature plays in the diffusivity of a compound in a solution. Not
including the variation of temperature would certainly have affected the final value. However, as
shown in the final graph between temperature and diffusivity it is clearly shown that the relation
between temp and diffusivity is an inversely proportional relation which is not true as temp is directly
proportional to diffusivity as T have to be equal D. moreover, this may be a result of in accurate
experiment setup and high in accuracy in the devices used.

Procedures
A diffusion cell is an instrument that is used to study the diffusion of liquid or gaseous mixtures. The
diffusion cell used in this experiment consists of a honeycomb of 121 accurately dimensioned vertical
capillaries that are 5mm long and 1mm wide in diameter. This is to restrict the diffusion to a one -
dimensional diffusion.

To prepare the diffusion cell for use, a small volume of concentrated solution is first placed on one
side of the honeycomb, whilst the other side consists of a large volume of pure solvent (de-ionized
water). The concentration within the larger volume will increase gradually as diffusion of the solute
occurs. This change in concentration is monitored closely with a conductivity sensor and meter. To
ensure a uniform concentration within the larger volume, the mixture is continuously stirred with a
magnetic stirrer. The concentration at the lower end of the tube is in fact constant and is equal to the
molarity of the solution. The concentration at the upper end of the tube is effectively zero.
Honeycomb structure with capillaries Concentration of solution outside tube is zero Concentration of
solution inside tube is 2M NaCl.

Material used
Water vessel with magnetic stirrer

Diffusion cell

Conductivity meter

Stopwatch

50 ml beaker
Nacl

The one litre vessel was filled with de-ionized water up to 1cm below the graduation (black) mark. The
magnetic stirrer was set to the lowest setting. The conductivity meter was connected to the electrodes
and then switched on. The diffusion cell was filled with 2M (molarity) sodium chloride solution (116.9g
NaCl/litre). Excess solution on top of the capillaries and on the sides, was wiped off gently with a soft
tissue. The diffusion cell was clamped in its position with the top of the capillaries lying parallel with
the graduation mark on the vessel. The vessel was carefully filled to the graduation mark with the
provided de-ionized water bottle. The nozzle of the bottle was aimed away from the capillaries and
towards the wall of the vessel, so as to minimise the turbulence caused. The timer was started
immediately when the vessel was filled to the graduation mark. The reading on the conductivity was
noted down at the same time. The conductivity readings were noted down every 10 seconds till
480sec. After the end of Run 1, the solution in the vessel and diffusion cell was disposed. Both the
vessel and the diffusion were washed thoroughly with de-ionized water.

Sources of errors and its solution

1.

If the walls of the capillary tubes are wet, or if the diffusion tube is filled up too slowly or wrongly, air
bubbles may form under the capillaries in the honeycomb structure. The bubbles can significantly
impede diffusion through the capillaries, affecting the rate of diffusion.

solution

Ensure that no air bubbles are formed in or under the honeycomb structure. This can be achieved by
filling the diffusion cell slowly.

2.

Evaporation of water from the 1 litre vessel during the experiment could affect thevolume present in
the vessel and hence diffusion coefficient would be affected, since the calculation of the diffusion
coefficient involves the volume of water present in the vessel.

Solution:

The vessel could be covered with a cover or lid to minimise evaporation of water.

3.

The stopwatch should be started as close as possible to the instant when the water covers the surface
of the capillaries. This is because significant changes in concentration can occur at this point Intime
due to the steep concentration gradient between the 2 solutions. However, human reaction time will
result in some delay.

solution
Have one person to fill up the vessel until the honeycomb structure is fully submerged in water, while
another person looks from the side and starts the stopwatch once the honeycomb structure is fully
submerged. This will minimise the human reaction time.

4.

The solution may not be well-stirred enough, thus resulting in a higher concentration at the diffusion
surface than the rest of the solution.

solution

Have more than one conductivity sensor at various locations or depth along the vessel enables us to
get more accurate conductivity readings by averaging the values obtained.

6.

The vessel may not be thoroughly cleaned from previous experiment by other students, therefore
leaving sodium chloride residue at the wall of the vessel. This may add to the conductivity of the
solution during the diffusion experiment when the vessel is filled with de-ionised water and therefore
lead to an error when calculating the diffusion coefficient of sodium chloride.

solution

Clean the equipments thoroughly once more with de-ionised water to ensure that no residues are
present on the equipment.

8.

Convection occurred in the experiment is a major factor that will affect the accuracy of the
experiment. The rotation of the magnetic stirrer could introduce convection currents in the water.

solution

The addition of dye to the vessel containing water can be used to determine whether the magnetic
stirrer is causing too much convection. This should be done before the commencement of the actual
experiment to ensure minimal or no convection are present. The dye should never be used during the
commencement of the experiment as it might interfere with the diffusion rate of sodium chloride
solution.

Conclusions
The aim of the experiment was to determine the diffusion coefficient of 2M Sodium Chloride solution
in de-ionised water. The purpose of the experiment is achieved using diffusion cell and the
conductivity meter to study the change in concentration along the vessel at regular intervals. The
value of our experimental result has been detected for different temp stages, which is common for
liquid mixtures. This implies that the method of using honeycomb diffusion cell and measuring the
change in conductivity to calculate the accumulation of the sodium chloride in the de-ionized water is
appropriate for the determination of diffusion in a liquid mixture in this experiment. However, one
should be aware that the conductivity method is only applicable for solute which fully dissociates in
water. Solutes which do not dissociate in water will not give any changes in conductivity of the de-
ionized water. It was found that the diffusion coefficient determined in the experiment was totally in
correct as it shows that D=1/T not D=t. This is most likely because of lake of accuracy in the devices
used in this experiment. The effect of hydration tends to increase the rate of diffusion, and this was
the case that should have happened for sodium chloride solution. Therefore, if we were to take into
consideration the effect of hydration on the ions in our calculation of the literature values, the
diffusion coefficient calculated will be close to our experimental value. Due to the limitations of the
experiment procedure, we were unable to determine the extent in which convection affects the
experiment. Dyes could have been used to detect the presence of any significant convection currents
due to the rotation of the magnetic stirrer. This experiment has showed that it is very difficult to
calculate the actual diffusion coefficient very accurately using mathematical models and scientific
concepts that we currently have. Since the values of diffusion coefficients for liquid mixtures are very
small but the application of this value may have large implications in actual situations, such as in
chemical plants. Therefore, much effort should be utilised for future research works to accurately
determine the actual diffusion coefficients under different situations and conditions.

References

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1981

2. Geankoplis, C.J., Transport Processes and Separation Process

Principles. 4th Edition, Prentice-Hall of India, New Delhi, 2005.

3. Dutta, B.K., Principles of Mass transfer and Separation Processes.

Prentice-Hall of India, New Delhi, 2007.

4 Barron, J. and Ashton, C. (2008) 'The Effect of Temperature on Conductivity Measurement',


County Clare, Ireland.

5 Lide, D.R. and Staff, L.D.R. (2007) CRC handbook of chemistry and physics, 88th edition (Crc
handbook of chemistry and physics). 88th edn. Boca Raton, FL: CRC Press.
6 Welty, James R.; Wicks, Charles E.; Wilson, Robert E.; Rorrer, Gregory (2001). Fundamentals of
Momentum, Heat, and Mass Transfer. Wiley.

7 Smith, W. F. (2004). Foundations of Materials Science and Engineering (3rd ed.).


McGraw-Hill.

8 Berg, H. C. (1977). Random Walks in Biology. Princeton.

9 Bird, R. B.; Stewart, W. E.; Lightfoot, E. N. (1976). Transport Phenomena. John Wiley &
Sons.
10 Crank, J. (1980). The Mathematics of Diffusion. Oxford University Press.

11 Bokshtein, B. S.; Mendelev, M. I.; Srolovitz, D. J., eds. (2005). Thermodynamics and
Kinetics in Materials Science: A Short Course. Oxford: Oxford University Press. pp. 167
171.

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