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FULL REPORT ON

EXERCISE NO. 3
JOULE-THOMSON COEFFICIENT

GUBANTES, GERRY MARK S.


CHEM 111.1 5L
2ND SEMESTER A.Y. 2016 2017

Date Performed: February 23, 2017


Date Submitted: March 09, 2017

Laboratory Instructor:
Rochelle Ibabao
I. Introduction

In the kinetic theory of molecular gases, one of the underlying assumptions is


the absence
of interaction between ideal gas molecules. However, in reality, real gases do
interact with each other. Thus, there is a deviation between ideal and real gases.
There are several means to measure the deviation of a real gas from ideality. These
are the compressibility factor (Z), fugacity coefficient () and the Joule-Thomson
coefficient (JT) (Castellan, 1983).
Joule-Thomson coefficient (JT)is a measure of deviation from ideality through
the isenthalpic cooling of gas. The Joule-Thomson coefficient was first done by
James Joule and William Thomson (Lord Kelvin). As shown in Figure 3.1., a gas was
allowed to expand adiabatically from one container to the other through a porous
barrier, while noting the changes in temperature during the process. Due to the
obstruction in A, changes in pressure were observed in gauges M and M. Thus, the
Joule-Thomson coefficient can now be defined as the ratio between the change in
temperature and the change in pressure at constant enthalpy as show below(Atkins
and de Paula, 2010; Castellan, 1983).
T

P H
JT =
JT Joule-Thomson Coefficient
T change in temperature
P change in pressure
H constant enthalphy

Figure 3.1. The Joule-Thomson Experiment


(Castellan, G.W. 1983. Physical Chemistry 3rd Edition. New York: Addison-Wesley)
For an ideal gas, the JT = 0. Meanwhile, for the van der Waal EOS, the Joule-
Thomson coefficient is derived as:
2a
b
RT
JT =
Cp
On the other hand, for the Berthelot EOS, the Joule-Thomson coefficient is equal to:
3a
2
b
RT
JT =
Cp
At normal conditions, the Joule-Thomson coefficient is positive which means that the
gas cools as it expands because (2a/RT > b). However, there is a temperature
wherein the JT coefficient becomes negative. This is called the inversion
temperature. The inversion temperature formula for the van der Waals and
Berthelot EOS are shown below (Castellan 1983).
van der Waals EOS:
2a
Ti=
Rb

Berthelot EOS:

Ti=
3a
Rb

In this exercise, the objective is to determine the Joule-Thomson coefficient of


CO2 at 25 C; and calculate the inversion temperature using the van der Waals and
Berthelot EOS.
II. Methodology

In this exercise, the Joule-Thomson coefficient of CO 2 will be determined.


Initially, the Joule-Thomson apparatus was setup. The JT apparatus is composed of
the regulated CO2 in the tank, styrofoam insulation, the water bath, sintered glass
disc and the coiled copper tubing. The 100-ft coiled copper tubing (with an outer
diameter of 0.25 inch that is wounded into 50 coils) is contained in the water-bath.
The water-bath served as the insulator in this setup to prevent or minimize the
changes in the temperature maintaining it at RT. The coil is then connected to a
porous plug, a fitted glass disk sealed in a 30-mm glass tube.
Meanwhile, at the other end of the coil, it is connected to a gas supple at a
pressure of 1 atm. To measure the change in pressure, an open-tube manometer is
used. The upper end of the tube (above the fritted disk) is insulated with a
polystyrene, and it is always maintained at the room atmospheric pressure. On the
other hand, the change in temperature is measure with the T meter, which
between the fritted disk and the water bath. At the beginning of the experiment, it
is important to note whether there are leaks in the copper tubing.
For the experiment proper, the needle bulb was opened very slowly with an
approximate rate of 5 cm Hg per minute until about -40 cm Hg. The temperature
difference was recorded over a 10-minute period. Then, very slowly again the
pressure was dropped to -35 cm Hg taking at least 1.5 min. Then, the change in
temp. was again recorded after achieving equilibrium. The procedure was repeated
until 0 cm Hg.
For the data treatment, the change in temp was plotted against the change in
pressure, and the JT coefficient was evaluated using the slope in K/atm. The
theoretical JT coeff. using the van der Waals and Berthelot was also calculated, and
the %error relative to the experimental value was also noted. Finally, the inversion
temp. of CO2 using the two EOS was also calculated.
III. Results and Discussion

For the determination of the Joule-Thomson Coefficient of CO 2, the gas was


allowed to expand at 25.7 C using the Joule-Thomson apparatus. The pressure was
adjusted accordingly, and the changes of temperature was noted. The data are
shown in Table 3.1.
Table 3.1. Data on the determination of the Joule-Thomson Coefficient of
CO2
P 40 35 30 25 20 15 10 5 0
(cm Hg)

correcte 39.81496 34.8380 9.9537 29.8612 24.8843 14.930 9.95374 4.97687 0


d P 9 4 2 5 61
(cm Hg)
ave T -2.268 -1.886 -1.797 -1.578 -1.524 -1.454 -1.408 -1.299 -1.081
(K)

correcte -1.187 -0.805 -0.716 -0.497 -0.443 -0.373 -0.327 -0.218 0


d T
(K)
slope 0.049237773 0.0248181 3.742070 1.8861787 R2 0.96337 0.9246226959
94 42 K/cm 82 96 K/atm 89766
K/cm Hg Hg K/atm
y- 0.121244444 -0.00140000
intercep 4K K
t
Determination of the Joule-Thomson Coefficient
2.5
2
f(x) = 0.05x + 0.12
1.5 R = 0.96
1
T 0.5
0
0 f(x) =
5 0.02x
10- 1 15 20 25 30 35 40 45
-0.5 R = 0.92
-1
-1.5

P
Figure 3.2. The plot
on the determination of the Joule-Thomson Coefficient of CO 2.

Table 3.3. Data summary for the determination of the JT coefficients and the
inversion temperatures of the various EOS against the
experimental value.
Experimental Lit. Value Van der Waals Berthelot

Joule- 3.742070 1.8861787 1.11 0.6871707633 -0.08691543632


Thomson 82 96
Coefficie
nt
(K/atm)
%error 237.12349 69.92601 444.561 174.4847 - -
73 77 9953 27339 4405.4156 2270.130963
76 91
Inversion Temperature 1500 2053.80554 9.80480300
(K)

The Joule-Thomson coefficient is the amount of potential energy being


converted to kinetic energy, and the other way around, in an adiabatic expansion.
As the gas pass through the porous disk, the temperature changes depending upon
the balance of the repulsive and the attractive forces. If the temperature decreases,
this means that the kinetic energy is transformed to potential energy. If the
temperature increases, the potential energy is being converted to kinetic energy
(Shoemaker et al., 2009).
Usually, the gas cools upon expansion. At normal conditions, the attractive
forces overcome the repulsive forces implying that the sign of the JT coefficient is
positive. In contrast, if the repulsive forces overcome the attractive counterpart, the
JT coefficient is negative. For the van der Waals equation, the JT coefficient is
positive when (2a /RT)> b, and negative when (2a /RT)< b (Shoemaker et al. 2009;
Atkins and de Paula., 2010).
As shown in Table 3.3. and Figure 3.2., the JT coefficient for the first setup
(increasing pressure) experiment is 3.74207082 K/atm. Relative to the Lit. value, it
has an error of 237.1234973%. Relative to the vdW EOS, it has an error of
444.5619953%. Lastly, relative to the Berthelot EOS, it has an error of
-4405.415676%. For the second setup (decreasing), the JT coefficient is
1.886178796 K/atm. Relative to the Lit. value, it has an error 69.9260177%. Relative
to the vdW EOS, it has an error of 174.484727339%. Lastly, relative to the Berthelot
EOS, it has an error of -2270.13096391%.
Based on the experiment, the JT coefficients for both setups are positive. This
means that the attractive forces dominate the repulsive forces for the CO 2 gases.
This also implies that as the gas pass through the porous disk and expands, it cools
in the process. In addition, it can also be seen that the first setup (increasing
pressure) has a higher % error than the second setup (decreasing pressure). This
may be because as the pressure is increased, it is more difficult to attain equilibrium
than when the pressure is decreased since the application of pressure to the system
makes it harder for it to settle down.
Nevertheless, the %errors for both setups are very large. The possible
sources of errors in the experiment are the inability of the mercury nanometer to
attain equilibrium due to the very high sensitivity of the knob; the improper
insulation of the porous disk; and the non-adiabaticity of the system even when
water with a high heat capacity was used.
An application of the Joule-Thomson effect is the Linde refrigerator wherein a
gas at high pressure is expanded through a throttle cooling it in the process. The
Linde technique is used in petrochemical industries to liquefy gas (Atkins and de
Paula, 2010). Other applications of the Joule-Thomson effect are the production of
liquid oxygen and liquid nitrogen in cryogens (Castellan, 1983).
Meanwhile, Pistun, Matiko and Masnyak (2015) provide another way of
determining the JT coefficient of a fluid at pressure ranges of 0.1 to 15 MPa and 250
to 350 K. This was done on nitrogen and carbon dioxide gases. The method used
parameters such as the reduced density and the reduced temperature of the gases.
The JT coefficient was then calculated as:

Where aij is based on the gas composition and the density at standard
conditions
(calculated experimentally)
is the reduced temperature
is the reduced density
The calculated results yield only a %error no greater than 1.5%, while using short
ranges of pressure and temperature unlike ordinary methods of determination
(Pistun, Matiko and Masnyak, 2015).
On the other hand, the temperature at which the sign changes is called the
inversion temperature. The inversion temperature (T I) is the temperature at which
below it the gas cools down upon expansion, and above it the gas heats up upon
expansion. For the carbon dioxide, the inversion temperature is 1500 K. Thus, above
1500 K, carbon dioxide heats up upon expansion instead of the usual cooling
process (Shoemaker et al., 2009). Meanwhile, based on the calculations, the
inversion temperatures for CO2 are 2053.80554 K and 9.80480300 K using the vdW
and Berthelot EOSs, respectively.

IV. Sample Calculations

Correction of P, cmHg:

TR = 25.7 C
Pcorr = P[11.8 104 ( T R ) ]
Pcorr =5 cmHg [ 11.8 104 (25.7 ) ]
4.97687 cmHg

Theoretical JT

VdW constants for CO2:


a = 36.490 x 10-2 Pa m6/mol2
b = 42.74 x 10-6 m3/mol
Cp = 37.11 J/mol K

2a
b
RT
JT =
Cp
Pa m6
(
2 36.490 x 102
mol2 ) 6
42.74 x 10
m3
J mol

JT =
( 8.314
K mol )
( 25+273.15 K )

J
37.11
molK
K 101325 Pa
(6.781848145 106 )( )
Pa 1atm
K
JT =0.6871707633
atm
Berthelot constants for CO2:
Pa m6
a= 8.490 x 10 3
2
K
mol
b = 31.867 x 106 m3/mol
Cp = 37.11 J /mol-K
3a
b
R T2
JT =
Cp
6

(
3 8.490 x 103
Pa m
mol
2
K ) 3 1.867 x 106
m
3

J mol

JT =
( 8.314
K mol )
( 298.15 K ) 2

J
37.11
mol K
K 101325 Pa
(8.577886634 )( )
Pa 1atm
K
JT =0.08691543632
atm

Inversion temperature

Van der Waals EOS:


Ti = 2a/Rb
Pa m 6


(
2 36.490 x 102
mol2 )
m3
( 8.314
J
K mol )(
42.74 x 106
mol )
2053.80554 K
Berthelot EOS:

T I=
3a
Rb


3 Pa m 6
3( 8.490 x 10 2
K)
mol

( 8.314 K Jmol )(42.74 10 6 3
m / mol)
= 9.80480300 K
% error:

Experimental vs Literature:

For vdW EOS


experimentalliterature
%error= x 100
literature

3.742070821.11
error = x 100
1.11

error =237.1234973

VdW EOS
experimentalTheoretical
%error= x 100
Theoretical

3.742070820.6871707633
error = x 100
0.6871707633

error =444.5619953

Berthelot EOS

experimentalTheoretical
%error= x 100
Theoretical

3.74207082(0.08691543632)
error = x 100
0.08691543632

error =4405.415676
V. Summary and Conclusion

In the experiment, CO2 gas was allowed to pass through in a porous disk
using the Joule-Thomson apparatus. As the pressure is increased and decreased
continuously, the change in temperature was measured. Through this, the slope (JT
coefficient) was then determined.
It was found out that the Joule-Thomson coefficients for the experiment were
3.74207082 K/atm and 1.886178796 K/atm for the increasing-pressure and
decreasing-pressure setups, respectively. Both experimental value yielded high
%errors. On the other hand, using the EOSs, the inversion temperatures were
calculated as 2053.80554 K and 9.80480300 K for the vDW and Berthelot EOSs,
respectively.
Overall, the experiment was successful because the Joule-Thomson coefficient of
CO2 at 25 C was determined, and the inversion temperatures using the van der
Waals and Berthelot EOS were calculated.
VI. References

Atkins, P. and de Paula, J. 2010. Physical Chemistry 9 th Ed. New York: W.H. Freeman

and Co.

Castellan, G. 1983. Physical Chemistry 3rd Ed. London: Addison-Wesley Pub. Co.

Pistun, Y., Matiko, F. and Masnyak, O. 2015. Simplified Method for Calculation of the

JouleThomson Coefficient at Natural Gas Flowrate Measurement. Energy

Engineering And Control Systems Vol. 1 No. 2.

Shoemaker, D.P., Garland, G.C., and Nibler, J. 2009. Experiments in Physical

Chemistry

New York: Addison-Wesley Pub. Co.