Phase Equilibrium

When a gas and a liquid phase which are not thermodynamically in

equilibrium are brought into close contact, transfer of one or more
components may occur from the gas phase to the liquid or, vice versa,
by the mechanism of molecular diffusion.
Mass transfer by molecular diffusion is the basic physical
mechanism underlying many important areas of soil science,
petroleum engineering, chemical engineering, biotechnology and
nuclear engineering.
In this experiment, a method for determining diffusion coefficients
of Carbon dioxide gas in Stoddard solvent at constant volume,
pressure and temperature is developed using Integral Phase
Equilibria Unit.
Determine
diffusion coefficient,
Solubility,
Henrys Constant
The enthalpy of solution of carbon dioxide
in Stoddard solvent in the range of 18 -
35C and at 1.0 atmosphere pressure.
Objective
Introduction
Diffusion Coefficient
Measures the rate of diffusion
Time-dependent
Solubility
Measures maximum amount of gas dissolved in liquid
Time-independent
Henrys Law constant
Dissolved gas in liquid is proportional to partial pressure in
vapor phase
Heat of mixing
Correlation between Henrys Law constant and T
Determination of diffusion coefficient
from experimental data
C
Gas phase
Interface
Z Z(t) Z=0

C
av
r J Cu
t
C
v v
+ V = V +
c
. .
c
A number of mathematical models have
been proposed to determine the
diffusion coefficients from experimental
volumetime profiles, however all these
models are developed from the equation
of continuity for the solute component:
where
r = Rate of reaction (kg/m3s)
J = Mass transfer by the mechanism of
molecular diffusion (kg/m
2
s)
v = Molar volume (m
3
)
Stoddard
Solvent
V=100 CC
Referring to Fig 1&2
for a one-dimensional diffusion cell
absence of chemical reaction,
movement of the interface in the boundary conditions of
the system, in which a component in the gas phase is
absorbed into a liquid phase starting at time zero and
continuing at longer times.
Based upon a model proposed by Higbie (penetration theory)
the liquid interface is thus always at saturation, since the
molecules can diffuse in the liquid phase away from the
interface only at rates which are extremely low with respect
to the rate at which gaseous molecules can be added to the
interface.
It is also assumed that the distance between the interface
and the bottom of the cell is semi-infinite; that is, diffusion
is slow enough that the concentration at the bottom of the
cell is negligible compared to the concentration at the
interface.
According to the film theory
the gas and the liquid phases at the interface are
thermodynamically in equilibrium, i.e. the interface
concentration of the solute, C
i
remains unchanged as long as
temperature and pressure of the system are kept constant.

Ci
C(t,Z)
Z(t)
Z
Gas
V=104 CC
Thus the unsteady-state differential equation representing concentration
changes with time and position is:




Solution of Ficks 2
nd
Law using the boundary conditions described is:






Solve for the number of moles added up to a time t:





If one plots N
T
versus t
1/2
, the slope of this line is equal to


2AC
i
(D12/t)
1/2




D
12
c
2
C
cZ
2
=
cC
ct
where
C = Concentration of
dissolved CO
2
in the
liquid phase at Z and t.
Z = Distance in cm
traveled from the
liquid interface.
t = time
D
12
=Diffusion
coefficient of species 1
in 2.


C
i
C
C
i
= erf
Z
2 D
12
t
|
\


|
.
|
|
The boundary
conditions are:

Z =0 C =C
i

Z : C = 0

The initial
condition is

C =0
at t =0:


N
T
= 2AC
i
D
12
t
|
\

|
.
|
1
2
t
Solubility
Henrys Law constant

The solubility of a gas in a liquid solvent may be represented to good accuracy at
dilute concentrations of the dissolved gas by Henry's Law:

f = H X

where f is the fugacity of the gas in the gas phase in equilibrium with the liquid
phase of concentration X of dissolved gas.
H is the Henrys law constant, which is a function of temperature.
Thus, by measuring the solubility one can obtain an estimate of the Henry's law
constant.




X =
n
n + n
solvent
n = gram moles of carbon dioxide absorbed in the liquid phase

PT = corrected barometer reading
= vapor pressure of Stoddard Solvent at cell temperature

Tp = temperature at the pump

Tc = temperature of the cell (bath temperature)
= total gas volume delivered from the pump to the cell

Vcg = volume of the gas phase in the cell

Zp = compressibility factor of CO2 at pump T and PT

Zc = compressibility factor of CO2 at cell T and PT

Vd = dead volume in the system (cc)


n =
P
T
(AV
P
V
d
)
Z
p
RT
P

V
cg
(P
T
P
1
)
Z
c
RT
c
The fugacity, f, can be determined from the Lewis and Randall
Rule, which gives



f = fugacity of CO
2
in the gas phase

f
o
= fugacity of pure gaseous CO
2
at P
T
and cell T
y = mole fraction of CO
2
in gas phase




Thus



by definition:

the fugacity coefficient for pure CO
2
in the gas phase at cell T and P
T






f = f

y

y =
P
T
P
1

P
T

f =
f

P
T
|
\

|
.
|
P
T
P
1

( )

f

P
T
= |
Use Henrys Law coefficients at the three experimental temperatures to
obtain the heat of mixing:



Plotting ln(H) vs. 1/T gives a line with a slope of H
mix
/R.

H
mix
is expected to be negative, which would indicate that CO
2
and
Stoddard solvent are more energetically stable than apart (i.e., the
interactions are favorable).
Heat of Mixing

cln H
i
( )
c 1/T
( )
|
\

|
.
|
P,x
CO
2
=
AH
mix
R
Experimental: Cell Evacuation
-
Experimental: Filling Syringe
-
Experimental: Reduce to
Atmospheric Pressure
+
Experimental: Fill Cell
0

between
V4 and the
cell is 40.5
cm and the
pipe
diameter is
0.15 cm
Penetration Model
0 1 2 3 4 5 6 7 8 9 10
x 10
4
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
Time [=] Seconds
C
o
n
c
e
n
t
r
a
t
i
o
n

[
=
]

M
o
l
a
r
i
t
y
Concentration as a function of time for a given height


Concentration at bottom of tank
Concentration at middle of tank
Ending time of experiment
References
Koretsky, Milo D. Engineering and Chemical Thermodynamics.
John Wiley & Sons, Inc., 2004.
Ophardt, Charles E. Virtual Chembook. Elmhurst College, 2003.
[Online] Available at:
http://www.elmhurst.edu/~chm/vchembook/174temppres.html
http://en.wikipedia.org/wiki/Lake_Nyos

Cell information
the dimension
Diameter = 51.43 mm
Height of the lid = 21.7 mm
Diameter to the lower section = 50.4 mm
Depth of the lower section averaged = 70.5
mm
Volume of the Stoddard liquid 100ml
Volume of the space (Gas) 104 ml