EXERCISE 3

JOULE-THOMSON COEFFICIENT

Umerez, Ruth B.

I. Introduction

Consider a system of isenthalpic condition, constant enthalpy, as pressure decreases, gas

expands adiabatically. This scenario is true with ideal gas. Contrary, in real gases, there will be an
accompanying change in temperature with respect to change in pressure. The ratio of temperature
and pressure changes can be expressed in terms of the Joule-Thomson coefficient. Given the
condition for real gases, is it expected that the value for Joule-Thomson coefficient is equal to zero
and not equal to zero for real gases. This parameter, is then, a measure of the deviation of gas from
the ideal gas behavior. The Joule-Thomson coefficient can be expressed as:

Over considerable range, temperature change is linear with pressure change.

Enthalpy is a function of temperature and pressure and is equal to zero for ideal gas. The
equation is expressed as the Joule-Thomson coeffiecient by dividing the partial derivative of pressure
at constant enthalpy in each terms. Rearranging results to the equivalent Joule-Thomson coefficient
equation; however, enthalpy cannot be measured directly. Thus, thermodynamic equations were used
to expressed it in a more measurable parameters of volume and temperature. The denominator,
partial derivative of enthalpy over partial derivative of temperature, can be simply expressed as the
specific heat. The general equation is shown as follows:

The numerator in terms of enthalpy is zero for ideal gas which explains why the Joule-
Thomson coefficient value for ideal gas is zero; however, this has a value for real gases. To account
for this, equation of states are utilized to predict real gas behavior. The van der Waals equation of
state, , is expressed in terms of molar volume and differentiated with respect to
temperature. Values are subsituted to the general equation and a Joule-Thomson coefficient equation
for van der Waals results:

Positive value for Joule-Thomson coefficient means that gas is more inclined to attraction;
thus, expansion is not favored. Otherwise, the gas is more of compression favoring expansion.
Positive value also shows that gas cools upon expansion or warms upon compression and vice-versa.

Inversion temperature, in which the Joule-Thomson coefficient changes sign, for van der
Waals is also derived as:

The same process of dervation is done with Berthelot equation of state in which the
equation for Joule-Thomson coefficient and inversion temperature, respectively, are as follows:

At the end of the exercise, the students should be able to determine the Joule-Thomson
coefficient of carbon dioxide at 25 degrees Celsius through experimentation and equation of states:
namely, Van der Waals and Berthelot.

II. Materials and Methods

Figure 3.1 The Joule-Thomson apparatus.

A 100 feet of copper tubing, with an outer diameter of one-fourth inch, which was wounded
into 50 coils was connected by a short length of pressure tubing to the lower end of a 30-mm glass
tube in which a porous plug, a fritted glass disk, was sealed.The coil and the lower end of the glass
tube up to the fritted disk were submerged into a constant temperature bath at 25 degrees Celsius for
the gas to be brought to the bath temperature. A supply of gas, at a pressure of 1 atm above
atmospheric pressure, was connected to the other end of coil. The change in pressure was measured
with the open-tube mercury manometer. The upper end of the glass tube, above the fritted disk, which
was always at atmospheric pressure was thermally insulated with an outer jacket filled with a material
such as polystyrene. Change in temperature between the gas above the fritted disk and the water in
the bath was measured with a digital thermometer. Leaks in the copper tubing were checked before
the start of the experiment.

The needle bulb was opened very slowly until the pressure in the system, as indicated by
the manometer, was increased at an approximate rate of 5 cmHg per minute. The needle bulb was
adjusted continuously until a pressure change of about -60 cmHg. Pressure changes were made with
care since a change in temperature below its steady-state value will be obtained when the porous
fritted glass cooled as the initial surge of gas would not be brought to bath temperature if the gas
pressure was increased rapidly at the beginning. A steady-state was achieved in about 40 minutes.
Temperature difference, when no significant change in over a 10- minute period, was recorded with
digital thermometer. The pressure drop was reduced at approximately -55 cmHg as the needle valve
was closed very slowly which took at least 1.5 minutes. The temperature difference when a steady-
state was achieved again was recorded. The procedure was repeated in which a data of change in
pressure equal to -50, -45, -40, -35, -30, -25, -20, -15, -10, -5, and 0 in cmHg were obtained.

A change in temperature versus change in pressure was plotted. The best fit line through
these points passing through the origin was drawn. the Joule-Thomson coefficient in degrees per
atmosphere was evaluated from the slope. The Joule-Thomson coefficient in same unit and
temperature in which the Van der Waals and Berthelot equation of states were applied were
calculated. Percent error were calculated between the Joule-Thomson coefficient and calculated with
the two equation of states, and the actual value. Inversion temperatures of carbon dioxide were
computed using the two equation of states.

III. Results and Discussion

The change in temperature was corrected since the plot between change in pressure and
temperature must pass through the origin and this was done by adding 0.72 degrees Celsius to each
recorded temperature. The change in pressure was also corrected using the given equation 3. 7 with a
room temperature of 28 degrees Celsius. The Joule-Thomson coefficient can be obtained by either
simply using linear regression or plotting the data values, in Table 3.1, of change in temperature
versus change in pressure and getting the slope. The plot is shown below.

Figure 3.2. Effect of Temperature on the Pressure of Carbon Dioxide

at 25 degrees Celsius

The obtained Joule-Thomson coefficient in cmHg was converted to degrees per

atmosphere, 0.4473977418. The values of Joule-Thomson coefficient using the equation of states,
van der Waals and Berthelot, are 0.6673522005 and -0.08540581749, respectively. These are
obtained through the derived formula 3.3 and 3.5 shown earlier. The value obtained from Berthelot is
less than and whose value is even negative compared to the value from van der Waals. This shows
that during an expansion where change in P is negative, cooling occurs which results to negative
change in T while during compression, change in P is positive, heating occurs which results to positive
change in T. On the other hand, the value obtained from experiment is less than the theoretical. The
room temperature used was 28 degrees Celsius, heat capacity of 37.76676065 Joule per mole Kelvin,
and gas constants, a and b values for each equation of states obtained from certain table of values.
Units were carefully considered for the cancellation. Inversion temperatures were obtained for each
equation of states, 2053.80554 and 9.804803001 in K, respectively using equations 3.4 and 3.6.
These computed values can be seen at Table 3.2. Percent error between the experimental Joule-
Thomson coefficient and theoretical or actual value is 2381.013864%, van der Waals is 49.1630686,
and Berthelot is -119.089461%. These computed values can be seen at Table 3.3.

Possible sources of experiment include limitation of measuring devices such as the digital
thermometer and open tube mercury manometer. Another is the ability of student in reading
measurements which can be subjective at times due to the intervals of measuring devices. Uncareful
changes made in pressure is a major source of error. If the gas pressure is increased rapidly at the
beginning, the coil will not be able to bring the initial surge of gas to bath temperature , and the porous
fritted glass will be cooled below its steady state value of temperature difference.

The Joule-Thomson coefficient is siginificant because the value indicates how close the
gas is to ideal behavior. In ideal gases, the value should be equal to zero; however, that is not the
case with real gases (Atkins, ) . Depending on certain conditions such as the identity of gas, and the
intermolecular forces of attraction or the magnitude of attractive or repulsive forces, the value can
deviate from zero which can either be positive or negative. When change in temperature is negative
corresponding to the negative change in pressure, a positive Joule-Thomson coefficient results. This
means that gas cools upon expansion. There are cases, however, when gases have negative value
upon heating but exhibits positive value when a temperature less than their inversion temperature was
applied. It is useful in the careful selection of refrigerants. The more negative the Joule-Thomson
coefficient value, the better the quality of the refrigerant. It is also applied when it comes to physical
interpretation and measurement of liquefaction of gases. Linde refrigerator applies the Joule-
Thomson expansion for gas liquefaction. At high pressure, the gas is expanded, cooled and allowed to
pass the incoming gases.It will be subjected to more expansion making it very low in temperature,
thus, condensing into liquid.

A recent journal article covers a new method to obtain the Joule-Thomson coefficient for
natural gases which can be beneficial in hydrocarbon production. In this study, a new correction factor
is developed as a function of gas gravity, temperature and pressure of producing gas and tested
rigorously for 20 different gas mixtures and applied to evaluate the Joule-Thomson coefficient for gas
mixtures. The newly developed correction factor take into account the Joule–Thomson effect. For each
sample, the model has been run for a wide range of temperature and pressure conditions, and the
model was rigorously verified by comparison of the results estimated throughout the study with the
results obtained Peng–Robinson equation of state. It is observed that model is very simple and robust
yet can accurately predict the Joule–Thomson effect. This is in comparison with the traditional way of
obtaining the Joule-Thomson coefficient. The process isenthalpic, constant enthalpy, expansion
whether it results to heating or cooling of the gas. The Joule-Thomson apparatus is thermally
insulated, adiabatic, in which the gas is allowed to expand in the porous barrier, as done in the
experiment. The change in temperature was monitored with respect to the change in pressure during
the expansion. Other values were obtained as well using the equation of states: van der Waals and
Berthelot.
https://link.springer.com/article/10.1007/s13202-017-0398-z
IV. Summary and Conclusions

Joule-Thomson coefficient, ratio of temperature change with respect to pressure change

when gas expands in constant enthalpy condition resulting to either heating or cooling of gas. The
Joule-Thomson apparatus is thermally insulated, adiabatic, in which the gas is allowed to expand in
the porous barrier, as done in the experiment. The change in temperature was monitored with respect
to the change in pressure during the expansion. Reals gases have a Joule-Thomson coefficient value
of 0. Deviations are observed from real gases, on the other hand. When change in temperature is
negative corresponding to the negative change in pressure, a positive Joule-Thomson coefficient
results. This means that gas cools upon expansion. When heating, change in temperature is positive
in which the coefficient value is negative.

There are four values of Joule-Thomson coefficient of carbon dioxide at 25 degrees

Celsius in the exercise. First is the theoretical or actual value. Second is obtained via experiment in
which data values of change in pressure and temperature corresponding to each other were recorded.
Using these data, a plot was made in which the slope represents the Joule-Thomson coefficient.
Linear regression can also be applied which is a much easier way. The third and fourth values are
from the equation of states, van der Waals and Berthelot. The formula for the Joule-Thomson
coefficient for each was derived. Alongside are the formula for their inversion temperature.

This concept is useful in liquefaction of gases in which the Linde refrigerant is one
application. At high pressure, the gas is expanded, cooled and allowed to pass the incoming gases.It
will be subjected to more expansion making it very low in temperature, thus, condensing into liquid.

V. Sample Calculations

(refer to the Postlab Notebook)

VI. Literature Cited