Technological Institute of the Philippines – Manila
CHE – 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017
Experiment No. 1
DIFFUSION OF LIQUIDS THROUGH STAGNANT NON-DIFFUSING AIR
Submitted by:
JAMES LAURENCE D. RAVIZ
Abstract – The experiment aims to determine the
diffusivity of vapor A through a stagnant non-diffusing
B using several known methods specifically the
Capillary Tube Method and Chapman-Enskog
Method. We have defined diffusion as the movement
under the influence of physical stimulus of an
individual component through a mixture in which the
driving force is concentration gradient of the diffusing
component.
This experiment focuses also on the temperature
dependence of diffusivity and thus the rate of diffusion
of liquids through stagnant non-diffusing air.
I.INTRODUCTION
Diffusion involves the mass transfer of a volatile
component A through a non-diffusing stagnant B. The
most common cause diffusion is concentration
gradient of the diffusing components. A concentration
gradient tends to move the component in such a
direction as to equalize concentration and destroy the
gradient while the gradient is maintained by constantly
supplying the diffusing component to the high
concentration end of the gradient and removing it at
low-concentration end. There is steady state reflux of
the diffusing component. This is characteristics of
many mass transfer operations.
Diffusion is not restricted to molecular transfer
through stagnant layers of solid or fluid. It also takes
place when fluids of different compositions are mixed.
The first step in mixing is often mass transfer called by
eddy motion characteristics of turbulent flow. This is
called eddy diffusion. The second step is molecular
diffusion between and inside the very small eddies.
Sometimes the diffusion process is accompanied by
bulk flow of the mixture in a direction parallel to the
direction of diffusion.
Diffusivity is a proportionality constant between
the mass flux due to molecular diffusion and the
gradient in the concentration of the species. It should
be apparent that the rate of molecular diffusion in
liquids is considerably slower in gasses. The
molecules in liquid are very close toether compared to
1
a gas. Hence, the molecules of the diffusing solute A
will collide with molecules of liquid B more often and
diffuse more slowly that in gases. In general, the
diffusion coefficient in a gas will be in order of
magnitude of about 105 times greater than in liquid.
A number of different experimental methods have
been used to determine the molecular diffusivity for
binary gas mixtures. One method is through the
capillary tube method. It is to evaporate a pure liquid
in a narrow tube with a gas passed over the top. The
fall in liquid level is measure with time and the
diffusivity is calculated from:
𝜌𝐴 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧02
𝐷𝐴𝐵 = ( )
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
where:
ρA - density of liquid A at temperature T
PBM – logarithmic mean pressure
R – universal gas constant
T – absolute temperature
t – time during which the meniscus fall from zo to zf
P – ambient atmospheric pressure
MA – molecular weight of liquid
PA1 – vapor pressure of liquid A at temperature T
PA2 – partial pressure of vapor A at the mouth of
capillary
zf – distance from the mouth of the capillary to the
meniscus at t=t
zo – distance from the mouth of the capillary to the
meniscus at t=0
A more accurate and rigorous treatment must be
considered which is the intermolecular forces of
attraction and repulsion between molecules as well as
the different sizes of molecules A and B. Chapman
and Enskog solved the Boltzmann equation, which
uses a distribution function instead of the mean free
path.
The final relation for predicting the diffusivity of
binary gas pair A and B molecule is:
 Diffusion of Liquids Through Stagnant Non-Diffusing Air

1.8583 𝑥 10−7 )(𝑇 1.5 ) 1 1 0.5 X

𝐷𝐴𝐵 = 2 ( + )
𝑃𝜎𝐴𝐵 𝛺 𝑀𝐴 𝑀𝐵

where:
DAB – diffusivity
T – absolute temperature Close the other end of the
capillary tube and fill it with
MA – molecular weight of gas A
pure volatile liquid
MB – molecular weight of stagnant B
P – absolute pressure
σ – average collision
Ω – collision integral
Measure the initial height of the
liquid
II. EQUIPMENT AND APPARATUS

Apparatus: Constant Water Bath Provide gentle stream of air using

Thermometers a fan
Iron Stand
Iron Clamp
Cork
Capillary Tube Provide gentle stream of air using
Vernier Caliper a fan
Portable Electric Fan
Stopwatch

Materials: Ethanol Measure the height of the

Methanol remaining liquid in the capillary
tube after 10 and 15 minutes
Acetone

Repeat procedure 2-4 for 2 trials

III. PROCEDURE/ METHODOLOGY having 65˚C and 80 ˚C as the
temperature respectively

START
Compare the result with those
obtained using Chapmann-Enskog
and other empirical formula

Prepare the constant Water Bath

and Set it to

END

2
 Technological Institute of the Philippines – Manila
CHE – 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017

Methanol 0.00016 0.000098

IV. DATA AND RESULTS Acetone 0.000022 -

Table 4.1 Height of liquid in the capillary

Trial 1 CALCULATIONS
T=50˚C
Liquid ho T,C h10 T,C h15 T,C TRIAL 1
Ethanol 59mm - 58mm 30 57mm 38
Methanol 58mm - 57mm 30 56mm 38 ETHANOL
Acetone 53mm - 52mm 30 51mm 38
For 10 minutes:
Table 4.2 Height of liquid in the capillary (𝑃 − 𝑃𝐴1 ) − (𝑃 − 𝑃𝐴2 )
𝑃𝐵𝑀 =
𝑃−𝑃
Trial 2 ln (𝑃 − 𝑃𝐴1 )
𝐴2
T=65˚C
Liquid ho T,C h10 T,C h15 T,C
Ethanol 59mm - 57mm 48 53mm 58 (101.325 − 19.53) − (101.325)
𝑃𝐵𝑀 =
Methanol 55mm - 53mm 48 52.5 58 101.325 − 19.53
ln ( )
Acetone 55mm - 54mm 48 53mm 58 101.325

A. CAPILLARY TUBE METHOD 𝑃𝐵𝑀 = 95.98 𝑘𝑃𝑎

Table 4.3 Properties from Perry’s ChE Handbook

Liquid Density, kg/m3 Vapor Pressure, 𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2
kPa 𝐷𝐴𝐵 = ( )
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
Ethanol 781.36 775.34 10.53 16.23
Methanol 784.74 776.90 21.76 32.18 𝐷𝐴𝐵
Acetone 780.58 800.33 37.95 52.30 (781.36)(95.98)(8.314)(303.15) 0.0592 − 0.0582
= ( )
(600)(46)(101.325)(10.53) 2
Table 4.4 Diffusivities Computed for Trial 1
Liquid Diffusivity
DAB, m2/s 𝒎𝟐
𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟑𝟔𝟕
10 minutes 15 minutes 𝒔
T=30˚C T=38˚C
Ethanol 0.000367 0.000318
For 15 minutes
Methanol 0.000241 0.000205
(𝑃 − 𝑃𝐴1 ) − (𝑃 − 𝑃𝐴2 )
Acetone 6.24X10-5 8.09 X10-5 𝑃𝐵𝑀 =
𝑃−𝑃
ln (𝑃 − 𝑃𝐴1 )
𝐴2

Table 4.5 Properties from Perry’s ChE Handbook

Liquid Density, kg/m3 Vapor Pressure, (101.325 − 16.22) − (101.325)
MPa 𝑃𝐵𝑀 =
101.325 − 16.22
Ethanol 763.68 754.69 26.871 42.793 ln (
101.325
)
Methanol 766.89 756.61 50.866 77.897
Acetone 759.74 747.53 76.11 107.945
𝑃𝐵𝑀 = 93.01 𝑘𝑃𝑎
Table 4.6 Diffusivities Computed for Trial 2
Liquid Diffusivity
DAB, m2/s
10 minutes 15 minutes
T=48˚C T=58˚C
Ethanol 0.00027 0.00045

3
 Diffusion of Liquids Through Stagnant Non-Diffusing Air

𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2 𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2

𝐷𝐴𝐵 = ( ) 𝐷𝐴𝐵 = ( )
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2 𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2

𝐷𝐴𝐵
(775.34)(93.01)(8.314)(311.15) 0.0592 − 0.0572 𝐷𝐴𝐵
= ( ) (776.90)(84.21)(8.314)(311.15) 0.0582 − 0.0562
(900)(46)(101.325)(16.22) 2 = ( )
(900)(32)(101.325)(32.18) 2
𝒎𝟐
𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟑𝟏𝟖
𝒔
𝒎𝟐
𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟐𝟎𝟓
𝒔

METHANOL
ACETONE
For 10 minutes
For 10 minutes
(𝑃 − 𝑃𝐴1 ) − (𝑃 − 𝑃𝐴2 )
𝑃𝐵𝑀 = (𝑃 − 𝑃𝐴1 ) − (𝑃 − 𝑃𝐴2 )
𝑃 − 𝑃𝐴1
ln ( ) 𝑃𝐵𝑀 =
𝑃 − 𝑃𝐴2 𝑃 − 𝑃𝐴1
ln ( )
𝑃 − 𝑃𝐴2

(101.325 − 21.76) − (101.325)

𝑃𝐵𝑀 = (101.325 − 37.95) − (101.325)
101.325 − 21.76
ln ( ) 𝑃𝐵𝑀 =
101.325 101.325 − 37.95
ln ( )
101.325

𝑃𝐵𝑀 = 89.99 𝑘𝑃𝑎

𝑃𝐵𝑀 = 80.87 𝑘𝑃𝑎

𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2

𝐷𝐴𝐵 = ( ) 𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2 𝐷𝐴𝐵 = ( )
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2

𝐷𝐴𝐵
(784.74)(89.99)(8.314)(303.15) 0.0582 − 0.0572 𝐷𝐴𝐵
= ( ) (780.58)(80.87)(8.314)(303.15) 0.0532 − 0.0522
(600)(32)(101.325)(21.76) 2 = ( )
(600)(58.08)(101.325)(37.95) 2

𝒎𝟐
𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟐𝟒𝟏 𝒎𝟐
𝒔 𝑫𝑨𝑩 = 𝟔. 𝟐𝟒 𝑿 𝟏𝟎−𝟓
𝒔

For 15 minutes: For 15 minutes:

(𝑃 − 𝑃𝐴1 ) − (𝑃 − 𝑃𝐴2 ) (𝑃 − 𝑃𝐴1 ) − (𝑃 − 𝑃𝐴2 )

𝑃𝐵𝑀 = 𝑃𝐵𝑀 =
𝑃 − 𝑃𝐴1 𝑃 − 𝑃𝐴1
ln ( ) ln ( )
𝑃 − 𝑃𝐴2 𝑃 − 𝑃𝐴2

(101.325 − 32.18) − (101.325) (101.325 − 52.3) − (101.325)

𝑃𝐵𝑀 = 𝑃𝐵𝑀 =
101.325 − 32.18 101.325 − 52.3
ln ( ) ln ( )
101.325 101.325

𝑃𝐵𝑀 = 84.21 𝑘𝑃𝑎 𝑃𝐵𝑀 = 72.04 𝑘𝑃𝑎

4
 Technological Institute of the Philippines – Manila
CHE – 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017

𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2 METHANOL

𝐷𝐴𝐵 = ( )
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
For 10 minutes

𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2

𝐷𝐴𝐵 = ( )
𝐷𝐴𝐵 𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
(800.33)(72.04)(8.314)(311.15) 0.0532 − 0.0512
= ( )
(900)(58.08)(101.325)(52.3) 2
𝐷𝐴𝐵
(766.89)(72.964)(8.314)(321.15) 0.0582 − 0.0572
= ( )
𝒎𝟐 (600)(32)(101.325)(50.87) 2
𝑫𝑨𝑩 = 𝟖. 𝟎𝟗 𝑿 𝟏𝟎−𝟓
𝒔

𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟏𝟔

TRIAL 2

ETHANOL
For 15 minutes
For 10 minutes
𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2
𝐷𝐴𝐵 = ( ) 𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2 𝐷𝐴𝐵 = ( )
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
𝐷𝐴𝐵
(763.68)(87.2)(8.314)(321.15) 0.0592 − 0.0572
= ( )
(600)(46)(101.325)(26.87) 2
𝐷𝐴𝐵
(756.61)(72.964)(8.314)(331.15) 0.0582 − 0.0562
= ( )
𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟐𝟕 (900)(32)(101.325)(77.897) 2

For 15 minutes 𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟎𝟗𝟖

𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2

𝐷𝐴𝐵 = ( ) ACETONE
𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
For 10 minutes
𝐷𝐴𝐵
𝜌𝐴𝐵 𝑃𝐵𝑀 𝑅𝑇 𝑧𝑓2 − 𝑧𝑜2
(753.09)(77.87)(8.314)(331.15) 0.0592 − 0.0532 𝐷𝐴𝐵 = ( )
= ( ) 𝑡𝑃𝑀𝐴 (𝑃𝐴1 − 𝑃𝐴2 ) 2
(900)(46)(101.325)(42.97) 2

𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟒
𝐷𝐴𝐵
(759.74)(72.965)(8.314)(321.15) 0.0582 − 0.0562
= ( )
(600)(58.08)(101.325)(76.11) 2

𝑫𝑨𝑩 = 𝟎. 𝟎𝟎𝟎𝟎𝟐𝟐

5
 Diffusion of Liquids Through Stagnant Non-Diffusing Air

B. CHAPMAN-ENSKOG METHOD For 15 minutes

Table 4.7 Properties of Volatile Liquid from Perry’s (1.8583 𝑥 10−7 )(311.151.5 ) 1 1 0.5
Chemical Engineer’s Handbook 8th Ed. 𝐷𝐴𝐵 = ( + )
(1)(4.40)(1.63) 32.08 29
Property Methanol Ethanol Acetone
Tb,K 336.71 351.52 329.05 𝒎𝟐
𝑫𝑨𝑩 = 𝟖. 𝟐𝟖 𝒙 𝟏𝟎−𝟔
/k 387.22 404.25 387.22 𝒔
σAB, Ǻ 4.40 3.36 5.70
ETHANOL
MW, 32.08 46 58.08
kg/kmol For 10 minutes

(1.8583 𝑥 10−7 )(303.151.5 ) 1 1 0.5

kT 𝐷𝐴𝐵 = ( + )
𝑇𝑜 = (1)(3.36)(1.69) 46 29

𝒎𝟐
𝑫𝑨𝑩 = 𝟏. 𝟐𝟐 𝒙 𝟏𝟎−𝟓
0.1
𝒔
𝛺 = (44.54𝑇 𝑜 −4.909 + 1.91𝑇 𝑜 −1.575 )
For 15 minutes

(1.8583 𝑥 10−7 )(311.151.5 ) 1 1 0.5

(1.8583 𝑥 10−7 )(𝑇1.5 ) 1 1 0.5 𝐷𝐴𝐵 = ( + )
𝐷𝐴𝐵 = ( + ) (1)(3.36)(1.67) 46 29
𝑃σ2AB 𝛺 𝑀𝐴 𝑀𝐵
𝒎𝟐
𝑫𝑨𝑩 = 𝟏. 𝟐𝟗 𝒙 𝟏𝟎−𝟓
𝒔

ACETONE
Methanol
Property

Acetone
Ethanol

For 10 minutes

(1.8583 𝑥 10−7 )(303.151.5 ) 1 1 0.5

Time 𝐷𝐴𝐵 = ( + )
10 15 10 15 10 15 (1)(5.70)(1.65) 58.08 29
min min min min min min
𝑇𝑜 0.78 0.80 0.75 0.77 0.78 0.80 𝒎𝟐
𝑫𝑨𝑩 = 𝟒. 𝟏𝟔 𝒙 𝟏𝟎−𝟔
𝛺 1.65 1.63 1.69 1.67 1.65 1.63 𝒔

(1.8583 𝑥 10−7 )(311.151.5 ) 1 1 0.5

𝐷𝐴𝐵 = ( + )
Diffusivities for Trial 1 (1)(5.70)(1.63) 58.08 29
Liquid Diffusivity
DAB, m2/s 𝒎𝟐
𝑫𝑨𝑩 = 𝟒. 𝟑𝟖 𝒙𝟏𝟎−𝟔
10 minutes 15 minutes 𝒔
T=48˚C T=58˚C
Ethanol 7.86 𝑥 10−6 8.28 𝑥 10−6
Methanol 1.22 𝑥 10−5 1.29 𝑥 10−5 HAZARDS
Acetone 4.16 𝑥 10−6 4.38 𝑥10−6
Among numerous hazards posed by the conduct of
this experiment, is minor chemical reagent irritation,
scalding acquired from the hot water in the constant water
TRIAL 1 bath and lacerations and wound that can be acquired if the
METHANOL glass apparatuses breaks and is mishandled.

For 10 minutes WASTE DISPOSAL

(1.8583 𝑥 10−7 )(303.151.5 ) 1 1 0.5 Hot water from the constant temperature water bath
𝐷𝐴𝐵 = ( + )
(1)(4.40)(1.65) 32.08 29 needs to be cooled first before discharging it to the
drainage system. Organic solvents used must be disposed
𝒎𝟐 in the organic waste bottle.
𝑫𝑨𝑩 = 𝟕. 𝟖𝟔 𝒙 𝟏𝟎−𝟔
𝒔

6
 Technological Institute of the Philippines – Manila
CHE – 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017

V. CONCLUSION

From this experiment it can be concluded that

diffusivity of volatile liquids can be determined using
different known methods. However poses slight
discrepancies in the results because of certain parameters.
In addition, from this experiment it can be learned that the
driving force of diffusion is the concentration gradient
between the two interfaces.

The experimental setup wherein a portable fan is used

VI. DOCUMENTATION to force air in the system

The reagents used in the experiment namely (from left

to right) Ethanol, Acetone and Methanol

Raviz, James Laurence, Chemical Engineering

Department, Technological Institute of the Philippines,
Manila, Philippines, 09179744486, (e-mail:
laurenceraviz@gmail.com).

A few of the apparatuses used in this experiment. The

iron stand and iron clamp that is used to hold the capillary
tube and thermometer in place just above the constant
temperature water bath.