Estimation of Diffusivity Coefficient

OBJECTIVE:
1. To determine the diffusivity of the liquid vapour in air.
2. To study the effect of different temperatures on the diffusivity.

APPARATUS/MATERIALS:
Gas Diffusion Apparatus including glass T-tube, constant water bath, air pump and scale for measurement

Sample (CCl4), Microscope, Syringe, Stop watch.

THEORY:
Gas B A+B
Stefan tube:

pA2 = 0
pA1 = vapour pressure of liquid A

dx

Volatile liquid A

Fig. 1 A representation of the Stefan tube

1
The Stefan tube is a simple device used for measuring diffusion coefficients in binary vapours. At the bottom of the tube is a pool of
mixture. The vapour that evaporates from this pool diffuses to the top of the tube, where a stream of air, flowing across the top the tube,
keeps the mole fraction of diffusing vapour there to be zero. The mole fraction of vapour above the liquid interface is at equilibrium.
Because there is no horizontal flux inside the tube, one can analyse the problem using a 1-D model. The system composition of acetone,
methanol and air has been extensively investigated.

In the method of diffusion, the Stefan tube under which the set of experiments occur, one of the components assuming A is available as
a volatile liquid and other component B is a gas which is insoluble in A. Stefan tube consists of a vertical glass tube sealed at the bottom
is joined to a larger diameter horizontal tube to form a ‘T’ shaped structure.

The liquid A is taken in the narrow vertical tube and the gas B is ejected to the horizontal tube. Evaporated A diffused through mixture
of A and B in the vertical tube, flow towards the top and swept away by the flowing stream of B. As B is not soluble in A, it will not
diffuse and the statement is confirmed to be “Diffusion of A through non-diffusing B”. The liquid tube level will gradually drop slowly
and pseudo-steady state assumption is reached.

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 sign.

According to Dalton’s law the total concentration of the two components CA and CB is constant.

dC A dC
 B (1)
dx dx

Then using the integration form of the Ficks’s Diffusion equation with appropriate constant:

2
 dC A
NA = DAB (2)
dx

dCB
NB = DBA (3)
dx

where DAB = DBA, Diffusivity coefficient DAB for A diffusing in B is the same as DAB for B diffusing into A.

Molar concentration of a perfect gas CA is related to partial pressure pA by the gas law:

pA
CA = (4)
RT

Then,

DAB dp A
NA = (5)
RT dx

Integration of Eq. (5) yields,

DAB
NA =  pA2  pA1  (6)
RTx

DAB
Similarly, NB =  pB 2  pB1  (7)
RTx

Where pA1 and pA2 are the partial pressures of A at the boundaries of the zone of diffusion and x is the distance over which diffusion
occurs.

3
In case where gas A is diffusing through stagnant gas non-diffusing B, the flow carries both components in proportions to their partial
N p N p 
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.

DAB dp A p A
NA     N A  0 (8)
RT dx P

Or

DAB dpB  p 
NA   N A 1  B  (9)
RT dx  P 

Or

x P
D P B 2 dp
N A  dx   AB  B (10)
0
RT PB1 PB

And

DAB P pB 2
NA  ln (11)
RTx pB1

Equation 11 is the expression used for the determination of vapour diffusion coefficients in gases by evaporation from surface of liquid
in a thinner bore tube and measuring the level of the falling liquid surface.

4
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 x.

In case there is some change of level, the value of x is determined by integration between the initial and final readings of level.

Thus, the observed diffusion flux causes the liquid level to decrease in the capillary that has a cross sectional area AT,

D P p   dx
N A AT   AB ln B 2  AT  A AT (12)
 RTx pB1  MA d

where

MA = Molecular weight of evaporating liquid

A = density of evaporating liquid

Integration of this expression yields:


DAB P  pB 2  M A
x
2

RT
ln   
 pB1   A 0
d   xdx
x1
(13)

DAB P  pB 2  M A x22  x12

ln    (14)
RT  pB1   A 2

Therefore,

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 RT  A x22  x12
DAB  (15)
P ln B 2 M A 2
p
pB1

 is the time of evaporation.

Other form of equation which is convenient to use is:

DAB 
 A RTpBM x 2
 xo2  1
(16)
M A P  p A1  p A2  2 

In concentration terms the expression for DAB is:

2 M A DAB C ACT
x 2  x02  (17)
 ACBM

CB1  CB 2
CBM  (18)
C 
ln  B1 
 CB 2 

Usually, xo will not be measured accurately nor is the effective distance for diffusion, x at time. Accurate value of (x  xo) is available.

Rewriting Eq. (17) as,

  ACBM  ACBM
 ( x  x0 )  x0 (19)
x  x0 2M A DAB C ACT M A DAB C ACT

6
 
A graph between against (x  xo) should yield a straight line with slope
x  x0

 ACBM
S (20)
2M A DABCT C A

 ACBM 1
DAB  (21)
2M AC ACT S

If we take kilogram molecular volume of a gas as 22.4 m3, then

1 Tabs
CT  (22)
22.4 T

If the vapour pressure of evaporating liquid A is vapour pressure (kN/m2) at the operating temperature in K, then,

 (VP) A 
CA    CT (23)
 total 
P

The diffusivity obtained from literature should be corrected for the temperature and pressure of your system by the following equation:

1.75
T   P1 
DAB T1 , P1   DAB T2 , P2   1    (24)
 T2   P2 

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OBSERVATIONS:
1. Temperature = C
2. Initial height of liquid in the tube (xo) = mm

OBSERVATIONS TABLE:

Reading of the height   

Drop in the
Time of the liquid level on  
Obs. No
 (min) Vernier of time
liquid level  xo  x 
xo  x (mm) (min/mm)
x (mm)

8
CALCULATIONS:
At operating temperature = °C

MA = gm/mol
A = gm/cm3
pA1 = atm (calculate using Antoine Eq. at Given T, which is the partial pressure of A at the liquid surface)
pA2 = atm (partial pressure of A at the open mouth of the tube)

1. Experimental diffusivity of vapour DAB

DAB 
 A RTpBM  xo 2  x 2  1
M A P  p A1  p A2  2 

pA = vapour pressure of A at temperature T

pB = partial pressure of vapour A at the mouth of the capillary

R = gas constant

 = time during which the meniscus fall from xo to x

P = ambient atmospheric pressure

A = density of liquid A at T

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2. Liquid level, xo  x = mm

  
3.   = min/mm
 xo  x 

  
4. Plot the graph of   vs. xo  x
 xo  x 

5. From the graph plotted, determine

Slope of the graph, S = min/mm2

= s/m2

6. Molecular weight of the sample, MA = g/mol

= kg/kmol

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

 1   Tabs 
CT     , where Tabs = 273.15 K
 kmolVol   T 

= kmol/m3

8. Saturation concentration at interface,

p 
C A   A  CT (pA is the partial pressure exerted by the molecules on the liquid surface, i.e. PA1, see Figure
 P 
1)

10
 = kmol/m3

9. Logarithmic mean molecular concentration of vapour, CBM (kmol/m3)

CB1 = CT

CB1 = kmol/m3

 p  C   P  pA 
CB 2  1  B  CT = T = kmol/m3
 P  P

 
 
 CB1  CB 2 
CBM 
 C 
 ln  B1  
  CB 2  

= kmol/m3

10. Diffusivity, DAB (m2/s)

A = kg/m3

  C 1
DAB   A BM 
 2 MC ACT S

= m2/s

11
RESULTS:
o Diffusion coefficient
1. Experimental:
2. Theoretical:

Block Diagram:

12
UTILITIES REQUIRED:
o Electricity Supply: Single Phase, 220 V AC, 50 Hz, 5-15 Amp combined socket with
earth connection.
o Water Supply (Initial fill)
o Floor Drain Required.
o Floor Area Required: 1.5 m  0.75 m

EXPERIMENTAL PROCEDURE:
STARTING PROCEDURE:
1. The water bath temperature is set at the desired level between 25C to 60C and to wait till
the bath attains the set temperature. Start the agitator. Steady temperature of the bath is
noted down.

2. The T-tube is filled with the sample liquid to up to 2 cm of the top of capillary. The initial
height of the liquid in the capillary from the top is noted down (Lo).

3. Then the connection with the air of vacuum pump is made and a gentle current of air is
allowed to flow over the capillary.

4. The height of liquid (x) from the top of the capillary bore is recorded after every 30
minutes. Then the complete variation of x with  is recorded and the diffusivity DAB is
calculated corresponding to its bath temperature using equation (6.14).

5. Steps from 1 to 4 are repeated for different temperatures.

6. DAB at each temperature is calculated by plotting the graph of /(xxo) vs. (xxo) using Eqs.
6.18 and 6.19.

7. Compare the experimental values with the values calculated using Gilliland’s correlation.

8. Different organic liquids like toluene, benzene is used and the results were tabulated and
discussed.

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CLOSING PROCEDURE:

1. When experiment is over stop the air supply.

2. Switch OFF heater and stirrer.
3. Switch OFF the main power supply.
4. Clean the tube and drain the water bath by open the valve.

PRECAUTION & MAINTENANCE INSTRUCTIONS:

1. Please read the MSDN of chemicals before conducting experiment.
2. Don’t switch ON the heater before filling water in the bath.
3. Microscope focus should be clear, if not then adjust it.
4. Record the zero error of Vernier scale if any.

TROUBLESHOOTING:
1. If the temperature is not increasing after switch ON the heater, check the continuity of
heater.
2. If the meniscus is not clear, then adjust the focus of the lens.
3. If the movement of the microscope is not smooth put some lubricating oil on it.

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APPENDIX

Table 1 Diffusion Coefficients of Gases at 101.32 kPa Pressure

Temperature Diffusivity
System
[(m2/s)104 or cm2/s]
℃ K
Air-NH3 0 273 0.198
0 273 0.220
16.1 289.1 0.282
25 298 0.260
Air-H2O 25.9 298.9 0.258
39.6 312.6 0.277
42 315 0.288
60.2 333.2 0.305
3 276 0.142
Air-CO2 9 282 0.148
44 317 0.177
0 273 0.6110
Air-H2
9 282 0.710
Air-CH4 9 282 0.196
0 273 0.102
Air-C2H5OH 25 298 0.135
42 315 0.145
0 273 0.106
25.9 298.9 0.087
Air-CH3COOH
59 332 0.106
Air-n-Hexane 21 294 0.080
Air-Benzene 25 298 0.0962
26.1 299.1 0.074
Air-aniline
59 332 0.090

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Air-2-propanol 26.1 299.1 0.099
25.9 298.9 0.086
Air-toluene
59 333.2 0.092
0 273 0.0703
Air-n-butanol 25.9 298.9 0.087
59 332 0.104

H2-CH4 0 273 0.625

25 298 0.726
24.2 297.2 0.779
H2-N2 25 298 0.784
85 358 1.052
H2-Benzene 38.1 311.1 0.404
22.4 295.4 0.83
H2-Ar
44 317 0.902
H2-CO 22.6 295.6 0.743
H2-CO2 25.2 298.2 0.646
H2-H2O 34.1 307.1 0.915
H2-O2 43 316 0.891
H2-NH3 25 298 0.783
12.5 285.5 0.525
H2-SO2
50 323 0.61
H2-C2H5OH 67 340 0.586
H2-Ethane 25 298 0.537
H2- n-Hexane 15.7 288.7 0.290
H2-cyclohexane 15.6 288.6 0.319
H2-Xe 68.2 341.2 0.751
He-Ar 25 298 0.729
He-n-butanol 150 423 0.587
9 282 0.658
He-air
44 317 0.765
He-CH4 25 298 0.675

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 He-CO 22.6 295.6 0.702
He-CO2 25.4 298.4 0.597
H2-He 44 317 1.706
He-H2O 25.2 298.2 0.908
25 298 0.687
He-N2
44 317 0.794
He- NH3 24.1 297.1 0.842

He-O2 25 298 0.729

44 317 0.822
He-O2 (trace) 25.2 298.2 0.737
He (trace)-O2 25.2 298.2 0.718
Ar-CH4 25 298 0.202
CO2-CO 42.4 315.4 0.185
CO2-N2 25 298 0.167
0 273 0.139
CO2-O2 20 293 0.153
23 296 0.156
CO2-Propane 25.1 298.1 0.087
CO2-SO2 -10 263 0.064
N2-n-butane 25 298 0.0960
H2O-CO2 34.3 307.3 0.202
22.8 295.8 0.212
CO-N2
100 373 0.318
CO-O2 0 273 0.185
CH3Cl-SO2 30 303 0.0693
(C2H5)O-NH3 26.5 299.5 0.1078
CH4-H2O 34.7 307.7 0.292
12
CO-14CO 100 373 0.323
12
CO2-14CO2 39.8 312.8 0.125
0 273 0.181
N2-O2
43 316 0.230

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 20.2 293.2 0.220
N2-Ar 43 316 0.216
N2-NH3 25 298 0.230
N2- H2O 25.2 298.2 0.293
N2- SO2 -10 263 0.104
N2-ethane 25 298 0.148
N2-n-butane 25 298 0.096
N2-isobutane 25 298 0.090
N2-n-hexane 15.6 288.6 0.076
N2-n-octane 30.1 303.1 0.073

N2-2,2,4-trimethylpentane 30.3 303.3 0.071

N2-benzene 38.3 311.3 0.102

O2- H2O 35.1 308.1 0.282
O2-CCl4 23 296 0.075
O2-benzene 38.3 311.3 0.101
O2-n-hexane 15.6 288.6 0.075
O2-n-octane 30.1 303.1 0.071

O2-2,2,4-trimethypentane 30 303.0 0.071

Ar-Xe 30 303 0.140

Ar-Kr 56.9 329.9 0.137
Ne-Kr 0 273 0.223
Ethylene-H2O 34.8 307.8 0.204

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Table 2 Diffusion Coefficients for Dilute Liquid Solutions

Temperature
Diffusivity
Solute Solvent
oC K [(m2/s)109 or (cm2/s)105]

12 285 1.64
NH3 Water
15 288 1.77
18 291 1.98
O2 Water
25 298 2.41
CO2 Water 25 298 2.00
H2 Water 25 298 4.8
Methyl alcohol Water 15 288 1.26
10 283 0.84
Ethyl alcohol Water
25 298 1.24
n-Propyl alcohol Water 15 288 0.87
Formic acid Water 25 298 1.52
9.7 282.7 0.769
Acetic acid Water
25 298 1.26
Propionic acid Water 25 298 1.01
HCl(9gmol/liter) 10 283 3.3
Water
(2.5 g mol/liter) 10 283 2.5
Benzoic acid Water 25 298 1.21
Acetone Water 25 298 1.28
Acetic acid Benzene 25 298 2.09
Urea Ethanol 12 285 0.54
Water Ethanol 25 298 1.13
KCl Water 25 298 1.870
Ethylene
KCl 25 298 0.119
glycol

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 Table 2 Diffusion coefficients at infinite dilution in water at 25C

Solute D(10-5 cm2/sec)

Acetic acid 1.21
Acetone 1.16
Ammonia 1.64
Argon 2.00
Benzene 1.02
Benzoic acid 1.00
Bromine 1.18
Carbon dioxide 1.92
Carbon monoxide 2.03
Chlorine 1.25
Ethane 1.20
Ethanol 0.84
Ethylene 1.87
Glycine 1.06
Helium 6.28
Hemoglobin 0.0069
Hydrogen 4.50
Hydrogen sulfide 1.41
Methane 1.49
Methanol 0.84
n-Butanol 0.77
Nitrogen 1.88
Oxygen 2.10
Ovalbumin 0.078
Propane 0.97
Sucrose (0.5228-0.265c1)a
Urea (1.380-0.0782 c1 +0.00464 c12 )a
Urease 0.035
Valine 0.83
Note:“Known to very high accuracy, and so often used for calibration: c1 is in moles per liter.”

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Table 3 Diffusion coefficients at infinite dilution in non-aqueous liquids at 25oC, unless noted

Solvent Solutea D(10-5 cm2/sec)

Chloroform Acetone 2.35

Benzene 2.89
Ethyl alcohol(15oC) 2.20
Ethyl ether 2.14
Ethyl acetate 2.02
Benzene Acetic acid 2.09
Benzoic acid 1.38
Cyclohexane 2.09
Ethyl alcohol (15oC) 2.25
n-Heptane 2.10
Oxygen(29.6oC) 2.89
Toluene 1.85
Acetone Acetic acid 3.31
Benzoic acid 2.62
Nitrobenzene (20oC) 2.94
Water 4.56
n-Heptane Carbon tetrachloride 3.70
Dodecane 2.73
n-Hexane 4.21
Propane 4.87
Toluene 4.21
Ethanol Benzene 1.81
Iodine 1.32
Oxygen (29.6oC) 2.64
Water 1.24

21
 Carbon tetrachloride 1.50

n-Butanol Benzene 0.99

p-Dichlorobenzene 0.82
Propane 1.57
Water 0.56
n-Heptane Benzene 3.40
Note: “Temperature 25oC except as indicated.

Source: Adapted from

Dutta, B. K., 2006. Principle of Mass-Transfer and separation process-molecular diffusion., Prentice Hall
India Learning Private Limited

Geankoplis, C. J., 1983.Transport Processes: Momentum, Heat and Mass. 2nd ed. (revised), Allyn &
Bacon.

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