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Determining the Joule-Thomson Coefficient for N2, and CO2

Marvin Moreland, Alex Dunsmoor,


An investigation of the isothermal and isenthalpic Joule-Thomson effect and isothermal and adiabatic JouleThomson coefficient for gas mixtures has been performed. The experimental results for these topics of interest are
in keeping with qualitative results from the: van der Waals, Beattie-Bridgeman and Lennard-Jones equations of
state. This study helps to relate the difference between an ideal gas and real gas by displaying small temperature
differences as real gases expand freely.
Washington State University, Department of Chemistry, Physical Chemistry Lab 333, Section 1
1. Introduction
The Joule-Thomson(JT) effect has been replicated and
studied in depth since its first investigation in 18521wikipedia. This
effect has been critical to theoretical studies and practical
application. This effect is a way to measure deviations from ideal
gas conditions, because an ideal gas JT coefficient is zero. The JT
effect is the cooling of a gas as it passes from a high pressure and
expanding through a nozzle to a lower pressure. On a molecular
scale this can be visualized by gas molecules converting kinetic
energy to potential energy as molecules in a dense gas change the
amount of space they take up during adiabatic expansion. The JT
expansion provides a basis for liquefaction and separation of
gases. The ratio of temperature change to pressure change is
known as the JT coefficient.
For real gases this ratio can be significant at large
pressures. Predicted values obtained for these ratios depend
largely on the equation of state and assumptions used during the
calculations. The purpose of this lab will be to compare
experimental values with that of the equations of state.

Drastic changes in pressure normally would incur a


temperature change for real gases, however due to the
infinitesimal amount of time the gas spends inside the nozzle
there is negligible heat transfer. This experiment used a gas
flowing continuously through a porous plug under adiabatic
conditions. This continuous flow allowed for thermal equilibrium
conditions of the surroundings and system, thus making the heat
capacity of the equipment negligible.
Most of these coefficients are positive and as seen in this
experiment N2 and CO2 are no exceptions. Few gases, He and H2,
have negative JT coefficients, but do change signs at certain
temperatures. For the remaining ideal gases; two conditions must
be followed, Boyles law where pressure and volume are a
function of temperature, and internal energy is independent of
volume and pressure. The independence of pressure and volume
can be seen as the lack of molecular interactions. This also makes
enthalpy a function of temperature only. With these assumptions
the following processes were used for developing this experiment
and calculating the JT coefficients for the four different methods.
Starting with developing the experimental determination the
following steps provide a simple process to get to the temperature
and pressure ratio at constant enthalpy.

H
dP
P T
H
dT +
T P
dH =

P T
T
+
P H
H

T P
H
=
P

[2]

H P
H

P T
T
=
P H
JT =

Because

cannot be zero thus

[1]

[3]

H P is the inverse of heat capacity and

P T is zero for an ideal gas. This is

where the deviation from an ideal gas is measured experimentally.


Knowing this information and given a conversion term() for
voltage reading to temperature, the JT coefficient can be
estimated from experimental data.

T P
H
=V T
P P

[4]

V TC
V
= T where ; =40.6

T V

V T

V
=
T p

RT 1
P=

[6]

][ ( ) ] ( )

c
b
V +B 0 1
6
V
VT
V

A0 1

a
V

[7]

( ){

]}

2 A 0 4 c 2 B0 b 3 A 0 a 5 B 0 c
1
= ~ B0 +
+ +

+
p
RT T 3
RT
Cp
( RT )2 R T 4

[8]
After experimentally determining the JT coefficient this
value was compared against van der Waals equation of state
predicted values. Van der Waals, Beattie-Bridgeman and
Leonnard-Jones using constants from given the data in table 1.

2a
b
(
[
RT ) ]
=
~
Cp

(vdW)

[5]
The Beattie-Bridgeman equation of state comes
from taking equation four and using the triple
product rule of partial volume partial temperature
and substituting to make equation six. Using
equation seven and taking partials with respect to
temperature and then with respect to volume and
substituting back into the JT coefficient. Finally
substitute the coefficients for BB and this results in
equation eight.

V T
1
=
Cp

The last equation of state is the Leonard-Jones(LJ). To


develop the Leonard-Jones the virial equation is truncated to the
second term, which can be done because B2 and B3 only depend
on temperature and are determined by two and three-body
interactions between molecules, respectively2. Our assumption is
below 10 bar the B3 term is negligibly small. Thus our virial
equation simplifies to equation nine.

B (T )
P~
V
=1+ 2~
RT
V

[9]

Relating equations three and four to equation nine with


respect to B2 results in equation 10. Following the same method
as for vdW the partials can be taken for B2.

T
1
=
Cp

[10]

B2 2 PV V
V
=

T
RT T
T

( )

The second virial coefficient, B2 cannot be explicitly


solved for with equation [10] and thus statistical mechanics 3 was
used to get equation [11]. The function U(r) is the so-called
LeonardJones 6-12 potential. With and in table one, a

plot(see Figure 1) of a potential energy plot vs r equation allows


for solving the integral of equation 11. By solving for where y=0
on the U(r) plot then that time constant() value can be used to
solve the area under the curves. This area allows us to integrate
11 into three functions as seen in equation 13. The first bound is
an impulse delta dirac function and the second is a first order
transfer function with a step as an input.

] r dr
B (T )=2 N [ 1e

U (r )
kT

[11]

[( ) ( ) ]

r
U ( r )=4

12

Equipment used followed that of the Experiments in


Physical Chemistry 8th Ed except for a brass fitting was used
instead of a stainless steel fitting. See figure 1 for a generic
diagram of the setup used. Gas flows from the tank, through
tygon tubing into the copper tubing, which is in the water bath.
The heat exchange occurs here and by using continuous flow a
steady state value allows for measurement of deviations in
temperature via voltage, and pressure.

[12]

r<
( r )= < r <
0 r>

B 2 (T )=2 N 0 [ 01 ] r dr 2 N 0 [ e
2

which indicates that the pressure should first be increased to four


bars. Pressure readings were not taken every thirty seconds to
dictate when a steady pressure had been reached, instead the
readings were carefully monitored until both the voltmeter and
digital barometer readings were stabilized. A range of voltage
values were taken and an average of the range was used for
analysis. The behaviors of only two gases were measured in this
lab, CO2 and N2. The temperature of the water bath was 25
degrees Celsius and the atmospheric pressure in the lab was 70.55
cmHg. After increasing pressure, pressure was decreased and
three random points were extracted from the decreasing pressure
values to compare to the slope of the increasing pressures.

/kT

1 ] r dr2 N 0 [ e 01 ] r 2 dr
2

[13]

U(r) vs r
U(r)
Linear ()

f(x) = 0x - 0
R = 0.99
3. Results and Data Analysis:
Thus having B2 solved for; next equation nine can be rearranged
and taken a derivative to solve for Bs/T. Finally the JouleThomson coefficient can be solved for using equation 10. This
creates three different methods to solve for the jewel Thomson
coefficient. Comparing each of the four solving methods allowed
for a gauge to what assumptions and conditions match best of the
four different models.

2. Methods
There were several alterations to the procedure for this lab found
on page 103 of Experiments in Physical Chemistry. The pressure
was increased throughout the majority of the lab unlike the
procedure where the majority of data was collected as pressure
decreased. Pressure never exceeded two bars unlike the procedure

3J.O.Hirschfelder,C.F.Curtiss,andR.B.
Bird,MolecularTheoryofGasesandLiquids,
chap.3andtableIA,Wiley,NewYork(1964).

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