Diffusion of Liquids through Stagnant,

Non-diffusing Air

by

CABIGUNDA, Bryan Christian G.

201310715

MIFA, Jeryl Dane

201310476

QUION, Lorraine
201412995

ROYALES, Cleryse Anne C. Royales

201420019

TORLAO, Julius C.
201410615

Submitted to
Engr. Pinky Joy A. Janaban
Unit Operations Laboratory 2

Chemical Engineering Department

College of Engineering
Adamson University

2nd Semester 2019-2020

 Diffusion of Liquids through Stagnant, Non-diffusing air

Abstract

The experiment aimed to determine the diffusivity of volatile organic liquids in air at
different temperature using the capillary tube method and to be able to compare the
experimental diffusivity with the empirical equation like Lenner-Jones, Gilliland and the
values available from the books. The book used in obtaining the diffusivity is the
Chemical Engineering Handbook. Due to difficulty of calculating the values of Collision
Integral of Lenner-Jones formula, Fuller, Schetter and Gittings Equation is used as
substitute. Ethanol, Acetone, Ethyl Acetate, N-heptane and Methanol are the 5 volatile
compounds used in the experiment. The temperature used in calibration of hot plate for
water bath are 50°C, 65°C and 80°C. The duration of immersing the capillary tube filled
with volatile organic solvent is 10 minutes. The result showed that the value from
Chemical Engineering Handbook and Fuller et al deviate less from the experimental
diffusivity as to compare with Gilliland Equation. It is also proved that the relationship of
temperature with diffusivity is directly proportional. Hence, an increase in temperature,
there’s an increase in diffusivity. Among all the other empirical equation and data
available, only the Chemical Engineering Handbook and the value obtained from Fuller
et al is more accurate. Furthermore, in using Fuller et al, it is very to use it because of
the availability of its constant. Some values needed for Fuller et al also obtained from
Chemical Engineering Handbook.
Contents

Introduction 1

Experimental Procedure 1

Theory 1

Results 5

Discussions 6

Conclusions and Recommendations 7

References 7

List of Figures
Figure 3.1 Diffusion of A through stagnant, non-diffusing B 3

List of Tables
Table 4.1 Mass Diffusivity in Air at 50°C and 1 atm 5
Table 4.2 Mass Diffusivity in Air at 65°C and 1 atm 6
Table 4.3 Mass Diffusivity in Air at 80°C and 1 atm 6
Table A1.1 Water Bath at 50°C and 1 atm 8
Table A1.2 Water Bath at 65°C and 1 atm 8
Table A1.3 Water Bath at 80°C and 1 atm 8
Table A2.1 Density and Vapor Pressure at 50°C 9
Table A2.2 Density and Vapor Pressure at 65°C 9
Table A2.3 Density and Vapor Pressure at 80°C 9
Table A3.1 Diffusivity available from Ch.E Handbook 10

Appendices
Appendix 1. Experimental Data 8
Appendix 2. Density and Vapor Pressure from Ch.E Handbook 9
Appendix 3. Available Data for Diffusivity from Ch.E. Handbook 10
Appendix 4. Sample Calculation 11
I. Introduction

The experiment aims to determine the mass diffusivities of volatile

organic liquids in air at different temperatures using the capillary tube method
and to compare the results with those obtained from empirical equations
(Lennard-Jones and Gilliland Equations) and available data from books.
Instead of comparing the experimental diffusivity with Lennard – Jones, the
students will replace it with Fuller, Schetter and Gittings correlation due to the
fact that Lennard – Jones’ Collision Integral is hard to find and calculate.
Capillary tube method is one of the simple device that can be used
in determining the diffusivity of a compound. In these experiment, 5 volatile
compounds were used to determine the change of height of liquid once
immersed in a water bath for 10 minutes.

II. Experimental Procedure

The students prepared first the necessary apparatus and reagents

needed in conducting the experiment. There are 5 reagents that were used in
the experiment as prescribed by the laboratory manual. These reagents are
Ethanol, Acetone, Ethyl Acetate, N-heptane and Methanol. On the
experimental procedure, the students prepared a water bath via 1000 mL
beaker and tap water in it heated by an adjustable hot plate. Temperatures at
50°C, 65°C and 80°C were used in water bath and was monitored by a
thermometer. Each capillary tube was filled with the said volatile organic
solvents. Then, the other end of the capillary tube were sealed by a piece of
pencil eraser for clay is not available. Pencil eraser acts as the receptacles.
These capillary tubes can also be sealed using heat but with the use of blue
flame. In sealing the end of the capillary tube, Heat from Yellow flame and
Hot plate is not efficient for it to bend and be sealed. After filling and sealing
the capillary tube with solvent, the initial height of the solvent where recorded
and the sealed portion of capillary tube was immersed in water bath for 10
minutes. After 10 minutes, the height was then again measured and recorded.

III. Theory

3.1 Diffussion

Molecular diffusion or molecular transport is defined as the transfer

or movement of individual molecules through a fluid by means of the random,
individual movements of the molecules. It is also the thermal motion of
molecules at temperatures above absolute zero (Levitus, 2019). Rate of this
motion depends on temperature, viscosity of the fluid and the size and shape
of the particles. Diffusion occurs because of the so-called driving force
(Motinsky, 2019). Driving forces such as Concentration gradient, Pressure
gradient, temperature, External forced fields (forced diffusion) affect the rate
of diffusion of molecules. Diffusion also explains the net molecular flux from a

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higher concentration region to a lower concentration region. The word
“diffusion” is generally used to express the flux of other physical quantities
(Geankoplis, 2003).

Fick’s Law of Diffusion is a mathematical expression that describes

the rate of mass transfer of molecules from a particular portion to another. It
was derived by Adolf Fick in 1856. It assumes that the diffusive flux to the
concentration is under steady state condition. It is often used when the two
component diffuse against each other via equimolar counter diffusion

NA d CA (1)
J Az= =−D AB
A dz

On the other hand, if Gas A diffuses through stagnant Gas B. The

formula to be used is:

D AB P P− p A 2 (2)
N A=
RT ( z 2−z 1 )
ln ( P− p A 1 )
Or

D AB P
N A= ( p A 1− p A 2 ) (3)
RT ( z 2−z 1 ) pBM

Where PBM:

p A 1− p A 2
pBM =
P− p A 2
ln
( P− p A 1 )
III.2Diffusivity

In 1879, A. Stefan devised the capillary tube method, a convenient

way of calculating the diffusivity DAB of vapor A through stagnant gas B
experimentally (Geankoplis, 2003). An example of stagnant gas B is air
wherein it does not diffuse because of its infinite concentration compare to
vapor A. If the volatile substance A (e.g. ethyl ether or ethanol) is placed in
the lower part of a vertical capillary, then liquid A will evaporate and, by the
mechanism of diffusion, travel to the end of the capillary. Maintaining the
mouth of the capillary at a given composition automatically establishes the
concentration gradient in the capillary, and the falling rate of the meniscus in
the capillary provides the rate of transport.

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 Figure 3.1 Diffusion of A through stagnant, non-diffusing B

Diffusivity (DAB) is a measure of the capability of a substance or

energy to be diffused or to allow something to pass by diffusion. It 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) (Welty, et. al, 2001). Diffusivity depends on pressure, temperature
and composition of the system. Diffusivity of gases at low density are almost
composition independent. It increases with temperature and varies inversely
with pressure.

In order to determine the diffusivity of the given data obtained from

experiment, we need to use the derived formula of equation (1) wherein it
considers the time of diffusion and the height change of the capillary express
by equation (4).

ρ A ( z f 2 −z 02 ) RT pBM
D AB= (4)
2 M A t f P( p A 1− p A 2 )

Where:
D AB = Experimental Diffusivity
ρA = density of component diffusing A
zf = final height of liquid
z0 = initial height of liquid
R = universal gas constant
T = temperature of the system
pBM = log mean pressure of inert B
MA = molecular weight of component A
tf = duration of diffusion
P = pressure of the system
pA1 = vapor pressure of component A in the capillary tube
pA2 = pressure of component A outside of the capillary tube/

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 In calculating the density and vapor pressure of liquid, the following
formula from Chemical Engineering Handbook will be used. Formula of
density was obtained from Table 2-32 while vapor pressure was from Table 2-
8.

C2
ln ( p )=C 1 +
C
+C 3 ln ( T ) +C 4 T , P∈Pascal 5
(5)
T

C1 (6)
ρ¿ C4
, ρ∈mol / L
T

C
( ( ))
1 + 1−
C3
2

The result from the experiment must also be able to compare from
Lennard-Jones Model, Gilliland Model and other constant available in books.
In terms of available diffusivity in books, Chemical Engineering Handbook will
be used. In order to relate the diffusivity from the book, Fuller et. al correlation
formula will be used.

Lennard-Jones Equation:

( 12 )( MW1 1

D AB=8.42×10−24

Where:f
(√ T3

P T J AB Ω2
A
2
+
MW B )
) (7)

D AB = Mass diffusivity, m2/s

MW A = Molecular Weight of Component A, kg/mol
MW B = Molecular Weight of Component B, kg/mol
T = absolute temperature of the system, K
PT = total pressure of the system
PT , J AB , Ω 2= Lennard – Jones Constant

Gilliland Equation:

√ ( 12 )( MW1 1
)
( )
3
T +
−7 A MW B (8)
D AB=1.38 × 10 1 1 2
( 3
PT V A +V B 3
)
Where:
D AB = Mass diffusivity, m2/s
MW A = Molecular Weight of component A, kg/mol
MW B = Molecular Weight of component B, kg/mol
T = Temperature, K
PT = Total Pressure, atm

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 VA = molar volume of component A, m3/gmol
VB = molar volume of component B, m3/gmol

Fuller, Schetter and Gittings Correlation:

D AB 2 P1 T 2 1.75
= =
D AB 1 P2 T 1 ( ) (9)

(√ MW1 + MW1 )
( )
1.75
T
−7 A B (10)
D AB=1.011× 10 1 1 2
( 3
P T V A +V B 3
)
Where:
D AB = Mass diffusivity, m2/s
MW A = Molecular Weight of component A, kg/mol
MW B = Molecular Weight of component B, kg/mol
T = Temperature, K
PT = Total Pressure, atm
VA = molar volume of component A, m3/gmol
VB = molar volume of component B, m3/gmol

Molar volumes used is obtained from Chemical Engineering

Handbook Table 5-12.

IV. Results
Results from the experiment are shown below. There are three
trials conducted in the experiment that varies with different temperature. On
each temperature, it shows different value of diffusivity from different
approach like Fuller et. al, Gilliland and available data from books. Students
obtained the available data from books using Chemical Engineering
Handbook, Table 2-325. The diffusivity there is evaluated at different
temperatures. Hence, it is required to use equation (9).

Table 4.1 Mass Diffusivity in Air at T1 = 50°C and P = 1 atm

Liquid Experimental Fuller et. al. Gilliland Available Data
2 2
(m /s) (m /s) (m2/s) From Perry
(m2/s)
Ethanol 1.7259 ×10−3 1.4357 ×10−5 3.2684 ×10−6 1.3688 ×10−5
Acetone 1.2744 ×10−4 1.2325 ×10−5 2.8058 ×10−6 1.4628 ×10−5
Ethyl Acetate 1.8295 ×10−4 1.0152× 10−5 2.3111× 10−6 9.5954 × 10−6
N-heptane 3.4271 ×10− 4 8.2066 ×10−6 1.8682× 10−6 7.7606 ×10−6

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 Methanol 2.2098 ×10−4 1.8824 ×10−5 4.2853 × 10−6 2.2098 ×10−5

Table 4.2 Mass Diffusivity in Air at T1 = 65°C and P = 1 atm

Liquid Experimental Fuller et. al. Gilliland Available Data
(m2/s) (m2/s) (m2/s) From Perry
(m2/s)
Ethanol 3.7167 ×10−5 1.5544 ×10−5 3.4986 ×10−6 1.4820 ×10−5
Acetone 7.0036 ×10−4 1.3344 ×10−5 3.0034 ×10−6 1.5837 ×10−5
Ethyl Acetate 3.3698 ×10−5 1.0991× 10−5 2.4739 ×10−6 1.0388 ×10−5
N-heptane 4.0566 × 10−5 8.8848 ×10−6 1.9998 ×10−6 8.4019 ×10−6
Methanol 2.0262 ×10−5 2.0380 ×10−5 4.5871 ×10−6 1.9178 ×10−5

Table 4.3 Mass Diffusivity in Air at T1 = 80°C and P = 1 atm

Liquid Experimental Fuller et. al. Gilliland Available Data
(m2/s) (m2/s) (m2/s) From Perry
(m2/s)
Ethanol 4.3176 × 10−5 1.6771× 10−5 3.7340 ×10−6 1.5989 ×10−5
Acetone 6.0350 ×10−4 1.4397 ×10−5 3.2055 ×10−6 1.7086 ×10−5
Ethyl Acetate 3.8866 ×10−5 1.1858 ×10−5 2.6403 ×10−6 1.1208 ×10−5
N-heptane 3.2769 ×10−4 9.5860 ×10−5 2.1343 ×10−6 9.0649 ×10−6
Methanol 1.3304 ×10−4 2.1988 ×10−5 4.8957 × 10−6 2.0692 ×10−5

The data from Table 4.1 to Table 4.3 is the calculated diffusivity
evaluated from 50°C, 65°C and 80°C. Experimental diffusivity is calculated
using Equation (4). First , density and vapor pressure from different
temperature is calculated using equation (5) and (6). Plugging in all the
necessary value in the Equation (4), Experimental Diffusivity is able to
calculate. Lennard-Jones Equation is replace by Fuller et. al equation due to
the difficulty in calculating the Collision Integral of Lennard-Jones Equation.
Diffusivity using Gilliland Equation and Fuller et al are calculated using
Equation (8) and (10). The available data from Chemical Engineering
Handbook is evaluated at different temperature. Therefore, correlation
equation of Fuller et al is used using Equation (9) to convert the diffusivity to
the desired temperature.

V. Discussion
The experimental diffusivity obtained the highest value among the
other diffusivity formula. However, it can be seen that the experimental
diffusivity value is closer to the value of Fuller et al and available data from
Chemical Engineering Handbook. The deviation of experimental diffusivity
from Gilliland equation is higher compared to Fuller et al and from Chemical

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 Engineering Handbook. The discrepancy of the value obtained between Fuller
et al and Chemical Engineering Handbook is least compared to the other
value obtained from different formula. Fuller et al is the common diffusivity
formula used in approximating the theoretical diffusivity due to its accuracy
compared to the other approach and the availability of its element. The
elements of Fuller et al such as molar volume can be obtained from Chemical
Engineering Handbook.
From the results, it was found out that as temperature increases,
the diffusivity also increases which supports the characteristic of every
empirical equation. It proves the theory that diffusivity is directly dependent to
the temperature and varies inversely with pressure.

VI. Conclusions/Recommendations

It can be concluded that the value from Fuller et al and Chemical

Engineering Handbook is much more accurate because it deviate less to
experimental diffusivity compared to Gilliland Equation. Diffusivity is affected
directly with temperature and inversely with pressure.
The students would highly recommend that the experiment should
be conducted with high accuracy to be able to compare it with other empirical
formula. Human error and apparatus error could contribute a high deviation
from the true value. Furthermore, heat from hot plate must properly
distributed to obtain an optimum result. Time and temperature must be
monitored thoroughly to minimize an error.

VII. References

Geankoplis, C.J. (2003). Principles of Transport Processes and Separation

Processes

Levitus, M. (2019). Molecular Diffusion. Retrieved from

https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_
Chemistry_Textbook_Maps/Book%3A_Mathematical_Methods_in_
Chemistry_(Levitus)/12%3A_Partial_Differential_Equations/12.04%
3A_Molecular_Diffusion

Mostinsky, I.L. (2019). Diffusion Coefficient. Retrieved from

http://www.thermopedia.com/content/696/

Wetty, James R.; Wicks, Charles E.; Wilson, Robert E.; Rorrer, Gregory
(2001). Fundamentals of Momentum, Heat and Mass Transfer

7|Page
Appendix 1. Experimental Data

Table A1.1 Water Bath at 50°C and 1 atm

Organic Solvent Initial Height (mm) Final Height (mm)
Ethanol 55.11 37.52
Acetone 53.56 46.27
Ethyl Acetate 48.24 43.99
N-heptane 60.09 55.92
Methanol 56.23 53.19

Table A1.2 Water Bath at 65°C and 1 atm

Organic Solvent Initial Height (mm) Final Height (mm)
Ethanol 57.82 57.11
Acetone 58.46 29.75
Ethyl Acetate 35.37 33.02
N-heptane 41.95 40.73
Methanol 42.32 41.01

Table A1.3 Water Bath at 80°C and 1 atm

Organic Solvent Initial Height (mm) Final Height (mm)
Ethanol 42.36 35.30
Acetone 39.04 35.36
Ethyl Acetate 45.9 40.9
N-heptane 47.2 28.24
Methanol 40.9 39

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Appendix 2. Density and Vapor Pressure from Ch.E Handbook

Table A2.1 Density and Vapor Pressure at 50°C

Organic Solvent Density (kg/m3) Vapor Pressure (atm)
Ethanol 762.8957 0.2921
Acetone 757.3545 0.8071
Ethyl Acetate 863.4103 0.3712
N-heptane 659.8775 0.1857
Methanol 764.8542 0.5480

Table A2.2 Density and Vapor Pressure at 65°C

Organic Solvent Density (kg/m3) Vapor Pressure (atm)
Ethanol 748.3119 0.5616
Acetone 739.0303 1.2615
Ethyl Acetate 844.4676 0.6525
N-heptane 646.3792 0.3099
Methanol 749.2399 0.9457

Table A2.2 Density and Vapor Pressure at 80°C

Organic Solvent Density (kg/m3) Vapor Pressure (atm)
Ethanol 733.0465 1.0076
Acetone 720.0089 1.8730
Ethyl Acetate 824.8357 1.0801
N-heptane 632.4393 0.4859
Methanol 732.9302 1.5324

9|Page
Appendix 3. Available Data for Diffusivity retrieved from Ch.E. Handbook

Table A3.1 Diffusivity available from Ch.E Handbook

Organic Solvent Temperature, °C DAB, cm2/s
Ethanol 0 0.102
Acetone 0 0.109
Ethyl Acetate 0 0.0715
N-heptane 20 0.06544
Methanol 0 0.132

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Appendix 4. Sample Calculation

A4.1 Calculation of Experimental Diffusivity of Ethanol at 50°C using Equation 4

55.11 2 37.52 2
kg L∙ atm 0.2921−0
762.8957
1000m3
m −
(( 1000 ) (
m × 0.08206
mol
2 ∙K
))× 323.15 K ×
1−0
(( )
D AB=
D AB=1.7259 ×10
−3 m
s
ln
1−0.2921 )
g 1 kg
2 × 46.07 × ×600 s ×1 atm × ( 0.2921 atm−1atm )
A4.2 Gilliland Equation Calculation
mol 1000of Ethanol
g at 50°C

√( ( 12 )× ( 46.07
1 1
D AB=1.38 × 10−7
323.153 ×
1
1 atm × (50.36 +20.1 )
3
+ )
29
1 2
3 )
=3.2684 ×10 −6 m2
s

V Ethanol =2C ( 16.5 ) +6 H ( 1.98 ) +1O (5.48 )=50.36

V Air =20.1

A4.3 Fuller et. al Equation Calculation of Ethanol at 50°C

1 1
(√ 46.07
D AB=1.011× 10 −7

( 323.151.75

(
1
1 atm× 50.36 3 +20.1 3
+ )
29
)
=1.4357 ×10
1 2
)
−5 m2
s

A4.3 Available data from Chemical Engineering Handbook

cm 2 1m 2 1.75
50℃ +273.15 m2
D AB 2=0.102
s
× 2
100 cm 2
× (
0 ℃+ 273.15 ) =1.3688 ×10
−5
s

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