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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 nondiffusing 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.

molecules in liquid are very close toether compared


to 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:

This experiment focuses also on the


temperature dependence of diffusivity and thus the
rate of diffusion of liquids through stagnant nondiffusing 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.

A PBM RT
z 2f z 20
D AB=
2
tP M A ( P A 1P A 2 )

where:
A - 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 z o 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

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.

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.

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

The final relation for predicting the diffusivity of


binary gas pair A and B molecule is:
1

Diffusion of Liquids Through Stagnant Non-Diffusing Air

1.8583 x 107
1
1
D AB= (T 1.5 ) 2
+
P AB M A M B

0.5

where:
DAB diffusivity
T absolute temperature
MA molecular weight of gas A
MB molecular weight of stagnant B
P absolute pressure
average collision
collision integral

Close the other end of the capillary tube


and fill it with pure volatile liquid

Measure the initial height of the


liquid

II. EQUIPMENT AND APPARATUS


Provide gentle stream of air using
a fan

Apparatus: Constant Water Bath


Thermometers
Iron Stand
Iron Clamp
Cork
Capillary Tube
Vernier Caliper
Portable Electric Fan
Stopwatch

Provide gentle stream of air using


a fan

Materials: Ethanol
Methanol
Acetone

Measure the height of the


remaining liquid in the capillary
tube after 10 and 15 minutes

Repeat procedure 2-4 for 2 trials


having 65C and 80 C as the
temperature respectively

III. PROCEDURE/ METHODOLOGY


START

Compare the result with those


obtained using Chapmann-Enskog
and other empirical formula
Prepare the constant Water Bath
and Set it to
END
X

Technological Institute of the Philippines Manila


CHE 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017

IV. DATA AND RESULTS


Table 4.1 Height of liquid in the capillary
Trial 1
T=50C
Liquid
ho
T,C
h10
T,C
h15
Ethanol
Methanol
Acetone

59mm
58mm
53mm

58mm
57mm
52mm

30
30
30

Liquid

ho

Ethanol
Methanol
Acetone

59mm
55mm
55mm

57mm
53mm
54mm

T=58C
0.00045
0.000098
-

CALCULATIONS
TRIAL 1

T,C

57mm
56mm
51mm

38
38
38

ETHANOL
For 10 minutes:

Table 4.2 Height of liquid in the capillary


Trial 2
T=65C
T,C
h10

T=48C
0.00027
0.00016
0.000022

Ethanol
Methanol
Acetone

PBM =

( PP A 1 )(PP A 2)
ln

T,C

h15

T,C

48
48
48

53mm
52.5
53mm

58
58
58

PBM =

PP A 1
PP A 2

( 101.32519.53 )(101.325)
101.32519.53
ln
101.325

A. CAPILLARY TUBE METHOD

Table 4.3 Properties from Perrys ChE Handbook


Liquid
Ethanol
Methanol
Acetone

Density, kg/m3
781.36
784.74
780.58

775.34
776.90
800.33

PBM =95.98 kPa

Vapor Pressure,
kPa
10.53
16.23
21.76
32.18
37.95
52.30

Table 4.4 Diffusivities Computed for Trial 1


Liquid

Ethanol

Diffusivity
DAB, m2/s
10 minutes
15 minutes
T=30C
T=38C
0.000367
0.000318

Methanol

0.000241

0.000205

Acetone

6.24X10-5

8.09 X10-5

Ethanol
Methanol
Acetone

Density, kg/m3
763.68
766.89
759.74

754.69
756.61
747.53

D AB=

( 781.36 ) ( 95.98 ) ( 8.314 ) ( 303.15 ) 0.0592 0.0582


( 600 )(46) ( 101.325 )( 10.53 )
2

)
(

For 15 minutes

PBM =

( PP A 1 )(PP A 2)
ln

Vapor Pressure,
MPa
26.871
42.793
50.866
77.897
76.11
107.945

PBM =

Table 4.6 Diffusivities Computed for Trial 2


Liquid

AB PBM RT
z 2f z 2o
2
tP M A ( P A 1P A 2 )

m2
D AB=0. 000367
s

Table 4.5 Properties from Perrys ChE Handbook


Liquid

D AB=

Diffusivity
DAB, m2/s
10 minutes
15 minutes

PP A 1
PP A 2

( 101.32516.22 ) (101.325)
101.32516.22
ln
101.325

PBM =93.01kPa
3

)
)

Diffusion of Liquids Through Stagnant Non-Diffusing Air

PBM =
AB PBM RT
z 2f z 2o
D AB=
2
tP M A ( P A 1P A 2 )

D AB=

( 101.32532.18 )(101.325)
101.32532.18
ln
101.325

PBM =84.21kPa

2
2
( 775.34 ) ( 93.01 ) ( 8.314 ) ( 311.15 ) 0.05920.057 2
AB PBM RT
z f z o
D
=
AB
( 900 )(46) (101.325 )( 16.22 )
2
2
tP M A ( P A 1P A 2 )

D AB=0.000318

m
s

D AB=

( 776.90 ) ( 84.21 )( 8.314 )( 311.15 ) 0.0582 0.0562


( 900 )( 32) ( 101.325 )( 32.18 )
2

METHANOL

D AB=0. 000205

For 10 minutes

PBM =

PBM =

( PP A 1 )( PP A 2)
PP A 1
ln
PP A 2

m2
s

For 10 minutes

PBM =

( 101.32521.76 )(101.325)
101.32521.76
ln
101.325

PBM =

AB PBM RT
z 2f z 2o
2
tP M A ( P A 1P A 2 )

( PP A 1 )(PP A 2)
ln

PP A 1
PP A 2

( 101.32537.95 )(101.325)
101.32537.95
ln
101.325

PBM =80.87 kPa

( 784.74 ) ( 89.99 ) ( 8.314 ) ( 303.15 ) 0.058 20.0572


AB PBM RT
z 2f z 2o
D AB=
D AB=
( 600 ) (32) ( 101.325 ) ( 21.76 )
2
2
tP M A ( P A 1P A 2 )

D AB=0. 000241

m2
s

D AB=

D AB=6.24 X 1 05

( PP A 1 )( PP A 2)
ln

PP A 1
PP A 2

For 15 minutes:

( 780.58 ) ( 80.87 ) ( 8.314 ) ( 303.15 ) 0.0532 0.0522


( 600 ) (58.08) ( 101.325 ) ( 37.95 )
2

For 15 minutes:

PBM =

ACETONE

PBM =89.99 kPa

D AB=

m2
s

Technological Institute of the Philippines Manila


CHE 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017

PBM =

( PP A 1 )( PP A 2)
ln

PBM =

PP A 1
PP A 2

( 753.09 )( 77.87 )( 8.314 )( 33 1.15 ) 0.05920.05 32


D AB=
( 9 00 ) ( 46) ( 101.325 ) ( 42.97 )
2

D AB=0.0004

( 101.32552.3 )(101.325)
101.32552.3
ln
101.325

PBM =72.04 kPa


AB PBM RT
z 2f z 2o
D AB=
2
tP M A ( P A 1P A 2 )

METHANOL

For 10 minutes

( 800.33 ) ( 72.04 ) ( 8.314 ) ( 311.15 ) 0.05320.0512


D AB=
( 900 ) (58.08) ( 101.325 ) ( 52.3 )
2

D AB=

AB PBM RT
z 2f z 2o
2
tP M A ( P A 1P A 2 )

D AB=

( 766.89 )( 72.96 4 ) ( 8.314 )( 3 21.15 ) 0.05 820.05


( 6 00 ) (32) ( 101.325 ) ( 50.87 )
2

m2
D AB=8.09 X 1 0
s

)
(

D AB=0.00016
TRIAL 2
ETHANOL

For 15 minutes

For 10 minutes

AB PBM RT
z 2f z 2o
D AB=
2
tP M A ( P A 1P A 2 )

AB PBM RT
z 2f z 2o
D AB=
2
tP M A ( P A 1P A 2 )

( 763.68 ) ( 87.2 )( 8.314 )( 321.15 ) 0.05 920.05 7 2


D AB=
( 6 00 ) ( 46) ( 101.325 ) ( 26.87 )
2

)
D AB=

D AB=0.00027

D AB=

( 756.61 )( 72.964 )( 8.314 )( 3 3 1.15 ) 0.05820.05 6


( 9 00 ) (32) ( 101.325 ) (77.897 )
2

D AB=0.000098

For 15 minutes

AB PBM RT
z f z o
2
tP M A ( P A 1P A 2 )

ACETONE
For 10 minutes

)
(

Diffusion of Liquids Through Stagnant Non-Diffusing Air

AB PBM RT
z f z o
D AB=
2
tP M A ( P A 1P A 2 )

D AB=

Methanol
Acetone

1.22 x 105
4.16 x 106

2
( 7 59.74 ) ( 72.965 )( 8.314 ) ( 321.15 ) 0.05820.056TRIAL
1
( 6 00 ) (58.08) ( 101.325 )( 76.11 )
2
METHANOL

For 10 minutes

D AB=0.000022

D AB=

( 1.8583 x 107 ) ( 303.151.5 )


(1)(4.40)(1.65)

B. CHAPMAN-ENSKOG METHOD

D AB=7.86 x 10

Table 4.7 Properties of Volatile Liquid from Perrys


Chemical Engineers Handbook 8th Ed.
Propert
Methanol
Ethanol
Acetone
y
Tb,K
336.71
351.52
329.05
387.22
404.25
387.22
/k
AB,
4.40
3.36
5.70
MW,
32.08
46
58.08
kg/kmol

D AB=

o4.909

+1.91T

D AB=

o1.575 0.1

1.5

( 1.8583 x 10 ) ( T ) 1
1
+
2
P AB

(M

MB

0.5

m2
s

15
min
0.80
1.63

10
min
0.75
1.69

15
min
0.77
1.67

10
min
0.78
1.65

15
min
0.80
1.63

m
s

(1)(3.36)(1.6 7)

0.5

( 46 29 )

m2
s

ACETONE
For 10 minutes

Diffusivities for Trial 1


Liquid

Diffusivity
DAB, m2/s
10 minutes
15 minutes
T=48C
T=58C
6

( 46 29 )

( 1.8583 x 107 ) ( 3 11.151.5 ) 1 1


+

D AB=1.29 x 105

D AB=

7.86 x 10

(1)(3.36)(1.6 9)

0.5

For 15 minutes

Acetone

Ethanol

Methanol

Property

( 1.8583 x 107 ) ( 3 03.151.5 ) 1 1


+

D AB=1.22 x 105

0.5

D AB=

Ethanol

(1)( 4.40)(1.6 3)

1
1
+
32.08 29

For 10 minutes

To

ETHANOL

=( 44.54 T

10
min
0.78
1.65

0.5

( 1.8583 x 107 ) ( 3 11 .151.5 )

D AB=8.28 x 106

kT
T =

D AB=

m
s

1
1
+
32.08 29

For 15 minutes

Time

1.29 x 105
4.38 x 106

( 1.8583 x 107 ) ( 3 03.151.5 )


(1)(5.70)(1.6 5)

D AB=4.16 x 106

8 . 28 x 10

D AB=
6

1
1
+
58.08 29

1
1
+
58.08 29

0.5

m
s

( 1.8583 x 107 ) ( 3 11.151.5 )


(1)(5.70)(1.6 3)

0.5

Technological Institute of the Philippines Manila


CHE 502 Unit Operations Laboratory 2, 1st Semester SY 2016-2017

D AB=4.38 x 106

m
s

HAZARDS
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
bath and lacerations and wound that can be acquired if
the glass apparatuses breaks and is mishandled.
WASTE DISPOSAL
Hot water from the constant temperature water
bath needs to be cooled first before discharging it to the
drainage system. Organic solvents used must be
disposed in the organic waste bottle.
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.

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.

VI. DOCUMENTATION

The experimental setup wherein a portable fan is used


to force air in the system
The reagents used in the experiment namely (from left
to right) Ethanol, Acetone and Methanol

Diffusion of Liquids Through Stagnant Non-Diffusing Air


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

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