Name: Seduco, Rhett Adrian C.

Date Performed: 08/24/2017

Ubas, Johnziel G. Group No. 11

Experiment No. 1
PV Isotherms of Real Gases

I. Background

In the presence of repulsive forces, when a gas is compressed, the individual

molecules begin to get in each other's way, giving rise to a very strong repulsive force acts to
oppose any further volume decrease. It is therefore expected that the PV vs. P line would
curve upward at high pressure, and this is in fact what is observed for all gases at sufficiently
high pressures. With attractive forces at very close distances, all molecules repel each other
as their electron clouds come into contact. At greater distances, however, brief statistical
fluctuations in the distribution these electron clouds give rise to a universal attractive force
between all molecules. The more electrons in the molecule (and thus the greater the
molecular weight), the greater is this attractive force. As long as the energy of thermal
motion dominates this attractive force, the substance remains in the gaseous state, but at
sufficiently low temperatures the attractions dominate and the substance condenses to a
liquid or solid.
Intermolecular attractions, which generally increase with molecular weight, cause
the PV product to decrease as higher pressures bring the molecules closer together and thus
within the range of these attractive forces; the effect is to cause the volume to decrease more
rapidly than it otherwise would. The repulsive forces always eventually win out. However, as
the molecules begin to intrude on each other’s territory, the stronger repulsive forces cause
the curve to bend upward. At higher temperatures, increased thermal motions overcome the
effects of intermolecular attractions which normally dominate at lower pressures. So, all
gases behave more ideally at higher temperatures. For any gas, there is a special temperature
(the Boyle temperature) at which attractive and repulsive forces exactly balance each other at
zero pressure (Lower and Emiritus, 2017).
The objectives of the experiment are to define what real gases are, use critical
phenomena, select two real gases (polar and nonpolar) to observe, plot the graphs of sample
polar and nonpolar substances below, above and at their critical temperatures (Tc) using the
six equations of state, namely Ideal Gas, Van der Waals, Berthelot, Modified Berthelot,
Redlich-Kwong and Peng-Robinson Equations and interpret these graphs.
II. Results

Equation of State HCl (Polar) Ar (Nonpolar)

Ideal Gas Equation

Van der Waals

Berthelot

Modified Berthelot
 Redlich-Kwong

Peng-Robinson

III. Discussion

Gas is the simplest state of matter that fills any container it occupies. It has indefinite
volume and shape. Gas differs significantly from solids and liquids in several respects. For
example, a gas expands spontaneously to fill its container. Consequently, the volume of a gas
equals the volume of its container. Gases also are highly compressible: when pressure is
applied to a gas, its volume readily decreases. Solids and liquids, on the other hand, do not
expand to fill their containers and are not readily compressible. The characteristic properties
of gases––expanding to fill a container, being highly compressible, forming homogeneous
mixtures––arise because the molecules are relatively far apart.

Initially, a gas is pictured to behave approximately as if they were ideal at ordinary

working temperatures and pressures. This idea, the perfect (or ideal) gas theory, is
supplemented by the Kinetic Theory having the following assumptions: 1) Gases are made
up of molecules which are in constant random motion in straight lines; 2) The molecules
behave as rigid spheres; 3) Pressure is due to collisions between the molecules and the walls
of the container; 4) All collisions, both between the molecules themselves, and between the
molecules and the walls of the container, are perfectly elastic; and, 5) The temperature of the
gas is proportional to the average kinetic energy of the molecules (Clark, 2017). An ideal gas
is a hypothetical gas whose pressure, volume, and temperature relationships are described
completely by the ideal-gas equation: PV=nRT (Brown, et. al., 2012). But in reality, there is
no such thing as perfect gas because the behavior of gases only conforms to the ideal-gas
equation at relatively high temperature and low pressure. Thus, the assumptions made in the
kinetic-molecular model break down at high pressure and/or low temperature.

Real gases do not exactly obey the perfect gas law. Deviations from the law are
particularly important at high pressures and low temperatures, especially when a gas is on the
point of condensing to liquid. They show deviations from the perfect gas law because
molecules interact with one another. Repulsive forces between molecules assist expansion
and attractive forces assist compression (Atkins and de Paula, 2006). Due to this deviation,
the corrected ideal-gas equation was formulated and is known as the van der Waals equation:
𝑛2 𝑎
(𝑃 + ) (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
𝑉2

In this experiment, six equations of state were used to graph the PV isotherm of two
real gases below, above, and at their respective critical temperatures (Tc). In this case, HCl
(polar) and Ar (nonpolar) were used as the samples. An equation of state is a thermodynamic
equation relating state variables which describes the state of matter under a given set of
physical conditions (Perrot, 1998). The six equations of state that were used were Ideal Gas,
Van der Waals, Berthelot, Modified Berthelot, Redlich-Kwong and Peng-Robinson
Equations. These aforementioned equations predict the behavior of real gases. The reliability
of the equation is determined by comparing the isotherms it predicts with the experimental
isotherms.

Based on the PV isotherms of both polar and nonpolar substances, the graphs at and
above the critical temperatures resemble the parabolic characteristic. On the other hand, the
graphs below the critical temperatures differ depending on the equations of state used. In
ideal gas equation, the graph is still parabolic. Modified Berthelot, on the other hand, is also
slightly parabolic but approaching linear. For Van der Waals, Berthelot, Redlich-Kwong, and
Peng-Robinson, the graphs resemble the cubic characteristic and the visibility of the curve is
increasing, respectively.

IV. Calculation

A. Equations of State
RT
Ideal Gas Equation: P=
Vm
RT a 𝑉𝑐
Van der Waals EoS: P=V − V2 𝑎 = 3𝑃𝑐 𝑉𝑐2 𝑏=
m− b m 3
RT a 8𝑃𝑐2 𝑉𝑐3 𝑉𝑐
Berthelot EoS: P=V − V2 T 𝑎= 𝑏=
m− b m 𝑅 3

RT
Modified Berthelot EoS: P = RT 9Tc 1−6Tc 2
Vm [1−( )( )( )]
Vm 128Pc T T2
 5
RT a 𝑅 2 𝑇𝑐2
Redlich-Kwong EoS: P=V − 𝑎= 3
m− b √TVm(Vm +b) 9( √2−1)𝑃𝑐

3
( √2−1)𝑅𝑇𝑐
𝑏= 3𝑃𝑐

RT a
Peng-Robinson EoS: P=V −
m −b Vm (Vm +b)+ b(Vm −b)

0.45724𝑅 2 𝑇𝑐2 2 𝑇
𝑎 = 𝐴𝛼 ; 𝐴 = ; 𝛼 = [1 + 𝛽(1 − √𝑇𝑟 )] ; 𝑇𝑟 =
𝑃𝑐 𝑇𝑐

𝛽 = 0.37464 + 1.5422𝜔 + 0.26992𝜔2 𝜔 = 𝑎𝑐𝑒𝑛𝑡𝑟𝑖𝑐 𝑓𝑎𝑐𝑡𝑜𝑟

0.07780𝑅𝑇𝑐
𝑏=
𝑃𝑐

B. Critical Constants
1) HCl (polar)
-Pc: 81.5 atm
-Vc: 0.081 mL
-Tc: 324.7 K

2) Ar (nonpolar)
-Pc: 48 atm
-Vc: 0.07525 mL
-Tc: 150.72 K

C. Other Significant Calculations (refer to attached Microsoft Excel file)

V. Conclusion

The difference between the graphs of ideal gas equation and real gas equation can be
clearly observed on PV isotherms below the critical temperature. The reliability of the
equations of state can be tested by comparing its predicted isotherms with the experimental
isotherms. It is inappropriate to expect just a single, simple expression to be the true equation
of state of all substances.

VI. References

Atkins, P., & de Paula, J. (2006). Atkins' Physical Chemistry 8th Edition. Oxford, New
York: Oxford University Press.
Brown, T. L., LeMay, H. E., Bursten, B. E., Murphy, C. J., & Woodward, P. M. (2012).
Chemistry: The Central Science 12th Edition. United States of America: Pearson Prentice
Hall.

Perrot, P. (1998). A to Z of thermodynamics. Oxford: Oxford University Press.

Clark, Jim. (2010). Ideal Gases and The Ideal Gas Law. Retrieved on August 24, 2017,
from http://www.chemguide.co.uk/physical/kt/idealgases.html

Stephen Lower, Professor Emeritus. (24 February 2017). 6.6: Real Gases and Critical
Phenomena. Retrieved on August 21, 2017 from
https://chem.libretexts.org/Textbook_Maps/General_Chemistry_Textbook_Maps/Map%3
A_Chem1_(Lower)/06._Properties_of_Gases/6.6%3A_Real_Gases_and_Critical_Pheno
mena