UNIVERSITY OF ABERDEEN

SCHOOL OF ENGINEERING
EG2002
Process Engineering
Continuous Assessment
Diusion Laboratory
1. Introduction
Mass transfer by molecular collision is known as diusion and described by Ficks rst
law. For a binary mixture this is:
N
A
= D
AB
dc
A
dy
(1)
The resistance to mass transfer of species A in species B is characterised by the diusivity
where 1/resistance=D
AB
; the driving force is the concentration gradient dc
A
/dy; and
the mass ux is N
A
. The measurement of D
AB
is necessary for specic systems as the
diusivity is a function of the molecular forces involved in the collisions between A and B
and changes with temperature and pressure. In this laboratory exercise you will be asked
to measure the diusion of a volatile substance in air using the Winklemann method.
2. Background Theory
The Winklemann method measures the diusivity of material in air using an apparatus
similar to that shown in Figure(1). The diagram shows a t-shaped capillary tube partly
lled with a liquid. A gas is then owed through the horizontal region of the tube under
laminar ow conditions. At equilibrium, a saturated vapour exists directly over the
surface of the liquid. The owing gas at the top of the tube ensures that a concentration
gradient of the liquid species exists across the distance labeled L; diusion occurs as a
result. In evapouration of A from a free surface through a bulk gas B, the equation for
the mass ux of A is represented by Stefans law
1
:
1
See Chapter 10, Mass Transfer through a stationary gas[1]
2011/12 1 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
Bulk Gas
Liquid sample of
component being
studied
L
Length over which
diffusion is
happening
Figure 1: Winkelmann diusion apparatus
N
A
= D
AB
C
T
C
B
dC
A
d
y
(2)
where C
T
is the total gas concentration in the tube; C
B
is the concentration of the bulk
gas directly above the liquid surface; and dC
A
/dy is the concentration gradient of A in
the y-dimension. Considering two points within the tube y
1
and y
2
and carrying out some
manipulation of Eqn(2) allows the working equation of the Winkelmann method to be
stated as:
N
A
=
D
AB
y
2
y
1
C
T
C
Bm
(C
A1
C
A2
) (3)
where C
Bm
is the logarithmic mean of the concentrations of B:
C
Bm
=
(C
B2
C
B1
))
ln
_
C
B2
C
B1
_ (4)
If we now consider the Winkelmann apparatus, dening the y-dimension as vertical, note
that the concentration of A at the the top of the tube is zero since the ow of gas removes
it. If the top of the tube is dened as y
2
and the liquid surface as y
1
, then C
A2
= 0, C
A1
=
the saturated concentration of A above the liquid surface and y
2
y
1
= L in which case
Eqn(3) reduces to:
N
A
=
D
AB
L
C
T
C
Bm
C
A1
(5)
2011/12 2 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
This equation can now be used with the Winkelmann apparatus to measure D
AB
exper-
imentally as follows
2
. First consider the evapouration of the liquid at the surface. The
mass ux here can be written as:
N
A
=

L
M
w
dL
dt
(6)
where
L
is the density of the liquid and M
w
is the molecular weight of A. At steady-
state, the mass ux from diusion is in balance with the mass ux from evapouration at
liquid surface we can equate Eqns(5)& (6) to give:

L
M
w
dL
dt
=
D
AB
L
C
T
C
Bm
C
A1
(7)
re-arranging and integrating across L and t:

L
M
w
_
L(t)
L
0
LdL = D
AB
C
T
C
Bm
C
A1
_
t
0
dt (8)
where L
0
is the initial level of the liquid at t = 0. This gives:

L
2M
w
(L
2
L
2
0
) = D
AB
C
T
C
A1
C
Bm
t
and hence:
(L
2
L
2
0
) =
2M
w
D
AB

L
.
C
T
C
A1
C
Bm
t (9)
Measuring the change in the liquid level since the start of the test L L
0
is an easier
measurement to use, and so the LHS can be factorised as:
(L L
0
)(L L
0
+ 2L
0
) =
2M
w
D
AB

L
.
C
T
C
A1
C
Bm
t
and rearranging gives us the following equation which takes the form of y = mx +c:
t
(L L
0
)
=
_

L
2M
w
D
AB
.
C
Bm
C
T
C
A1
_
(L L
0
) +
_

L
M
w
D
AB
.
C
Bm
C
T
C
A1
L
0
_
(10)
where y = t/(L L
0
), x = (L L
0
), the gradient m = 2M
w
D
AB
/
L
.C
T
C
A1
/C
Bm
and
c the nal term in brackets. This then provides the opportunity for the experimental
determination of D
AB
. By plotting experimental values of t/(L L
0
) vs (L L
0
) and
measuring the gradient will allow:
m =
_

L
2M
w
D
AB
.
C
Bm
C
T
C
A1
_
2
This development follows that presented in [1]
2011/12 3 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
Time Time Time (L-L0) t/(L-L0)
hr min (seconds) (ks) (mm) (ks.mm
1
)
0 0 0 0 0 0.000
12 29 44940 44.94 2.9 15.497
19 6 68760 68.76 4.2 16.371
28 8 101280 101.28 5.8 17.462
37 28 134880 134.88 7.3 18.477
50 30 181800 181.8 9.2 19.761
80 39 290340 290.34 13 22.334
100 35 362100 362.1 15.2 23.822
Table 1: Experimental Data & Calculations for diusion of n-Octane in air.
Note Time represents time since test started.
With m known from the experimental results then the above equation can be re-arranged
for D
AB
:
D
AB
=

L
2M
w
m
.
C
Bm
C
T
C
A1
(11)
The next section will set out an example to show how the approach is applied.
3. Example - Determination of Diusivity of n-Octane in Air
An Winkelmann apparatus is used to measure the change in level of n-Octane with air as
the bulk gas at 298K and 1atm. The molecular weight of n-Octane is 114.231g.mol
1
; its
vapour pressure and liquid density at the temperature and pressure of the experiment are
1850.575N.m
2
and 699.32kg.m
3
respectively. The data gained from the Winkelmann
experiment is shown in Table(1) and plotted in Figure(2). The line tted to the points
shows that m = 0.6768ks.mm
2
or 67.6810
7
s.m
2
. The total concentration C
T
is found
from the ideal gas law:
n
V
= C
T
=
P
RT
=
101325(N.m
2
)
8314(J.kmol
1
K
1
) 298(K)
= 0.040897kmol.m
3
2011/12 4 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
y = 0.6768x + 13.535
R
2
= 1
0.0
5.0
10.0
15.0
20.0
25.0
30.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
(L-L
0
) [mm]
t
/
(
L
-
L
0
)


[
k
s
.
m
m
-
1
]
Figure 2: Experimental values for t/(L L
0
vs (L L
0
)
The concentration of n-Octane directly above the free liquid surface at 298K and 1atm
C
A1
is given by:
C
A
=
P
A
P
.C
T
=
1850.575
101325
0.040897 = 0.0007469kmol.m
3
The concentrations of air C
B1
and C
B2
are needed to calculate C
Bm
. C
B2
= C
T
(since
there is no n-Octane at the top of the tube). The concentration of air at the liquid
interface is:
C
B1
=
P
B
P
C
T
=
P P
A
P
C
T
=
101325 1850.575
101325
0.040897 = 0.04015kmol.m
3
and hence the logarithmic mean:
C
Bm
=
(C
B2
C
B1
)
ln
_
C
B2
C
B1
_ =
(0.040897 0.04015
ln
_
0.040897
0.04015
= 0.040522kmol.m
3
All of the necessary data is now available to calculate the diusivity D
AB
using Eqn(11):
D
AB
=

L
2M
w
m
.
C
Bm
C
T
C
A
=
_
699.32
2 114.231 67.68E07
_

_
0.040522
0.040897 0.0007469
_
= 6.0E6 m
2
s
1
2011/12 5 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
4. Experimental Method
In this exercise, you have been asked to calculate the diusivity of the volatile uid
provided using the Winkelmann diusion apparatus at 1atm and 298K. The vapour pres-
sure; molecular weights; and densities of the various uids used in the laboratory exercise
should be found by the student using a recognised reference for physical properties (e.g.
www.wolframalpha.com
3
or [1]). Follow the following steps:
1. Attend the lab brieng to start the test o on the Monday for your lab group.
2. Record the uid you are working with (this will be chosen by demonstrator).
3. Take the level reading using the telescopic eye piece and the level gauge.
4. Record the date, time, and level reading on the test sheet infront of the aparatus.
5. Also upload your level reading to the group blog on MyAberdeen, or create an excel
spreadsheet you can all access and update.
6. Complete two measurements during the course of the week when the room is empty.
7. Last measurement to be taken by Friday at 4pm.
8. Ensure that readings are taken every day during the week and a minimum of 1hr
apart. If someone has been before you, wait until an hour has past since the last
reading.
Using your measurement of time and height of the liquid, calculate t/(L L
0
) and plot
against (LL
0
) to gain the gradient. Use the same methodology presented in the example
to gain your experimental measurement of the diusivity of methanol in air at 1atm and
298K. A reminder that the t used in the calculations is time since experiment started;
L
0
is the initial level of the liquid at the start of the test; and, L is the level of the liquid
at time t.
3
As an example, type in vapour pressure of benzene at 298K 1atm - let it have more time if the
computation engine asks for it.
2011/12 6 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
5. Report
You are asked to write a short experimental report that addresses the following:
Write a short introduction describing the nature of the test and the key points of
background theory that support it.
Give a brief description of the experimetal methodology and any relevant observa-
tions of conditions during the week of the test.
Present your experimental results in both a table, as per Table(1) in this report,
and as a graph from Excel as per Figure(2).
Set out your calculated results for the uids diusivity D
AB
.
Compare your experimental result for D
AB
at room temperature with a value
sourced from the literature and mention any possible sources of error in your mea-
sured value.
If you have identied errors, suggest ways the result could be improved.
6. Submission
Please read the following instructions and comply with them for submission:
1. An electronic copy of your report can be submitted anytime after the completion of
the study via the Turnitin service. Given the actual diusion lectures do not occur
until w/b 28th November, the deadline for all reports is the 12th Dec 2011.
2. A link to the Turnitin exercise for your lab group will be provided in the relevant
continuous assessment folder.
3. While collaboration and discussion between memebers of the same lab grouop is
welcomed and encouraged - you are all asked to complete your own analysis and
write your own report. Turnitin identies copied work automatically. Information
2011/12 7 Dr.N.C.Renton
UNIVERSITY OF ABERDEEN
SCHOOL OF ENGINEERING
EG2002
Process Engineering
on plagiarism and how to avoid it is available for all students here http://www.
abdn.ac.uk/sls/plagiarism/.
References
[1] J. M. Coulson and J. F. Richardson. Coulson and Richardsons Chemical Engineering
Vol. 1: Fluid Flow, Heat Transfer and Mass Transfer. Butterworth-Heinemann, 1999.
2011/12 8 Dr.N.C.Renton