LECTURE 4 – REAL GASES

Real gases — as opposed to a perfect or ideal gas — exhibit properties that cannot be explained
entirely using the ideal gas law. To understand the behavior of real gases, the following must be taken into
account:
▪ compressibility effects;
▪ variable specific heat capacity;
▪ van der Waals forces;
▪ non-equilibrium thermodynamic effects;
▪ issues with molecular dissociation and elementary reactions with variable composition.
Real gases have very different behavior from ideal gases, notably in cases of high pressure or near
the condensation point - a number of additional interactions must be considered.
Real gases do not obey the perfect gas law exactly. 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.
Gases that deviate from ideality are known as Real Gases, which originate from two factors:
1. The theory assumes that as pressure increases, the volume of a gas becomes very small and
approaches zero. While it does approach a small number, it will not be zero because molecules do occupy
space (i.e. have volume) and cannot be compressed.
2. Intermolecular forces do exist in gases. These become increasingly important in low
temperatures, when translational molecular motion slows down, almost to a halt. However, at high
temperatures, or even normal, everyday temperatures, the intermolecular forces are very small and tend to
be considered negligible.
For most applications, such a detailed analysis is unnecessary, and the ideal gas approximation can
be used with reasonable accuracy. On the other hand, real-gas models have to be used near
the condensation point of gases, near critical points, at very high pressures, and in other less usual cases.

4.1.MOLECULAR INTERACTIONS

Repulsive forces
- assist expansion of gas
- significant when molecules are close to one another
- operative at high pressures, when intermolecular distances are
near a single molecular diameter
Attractive forces
- assist compression of gas
- can have influence over a long distance (close but not touching)
- operative at moderate pressures

RVMLecture Manual: Physical Chemistry 1 25

 (A.) COMPRESSION FACTOR
𝑉
The compression factor, Z, of a gas is the ratio of its measured molar volume V m= , to the molar
𝑛
volume of a perfect gas, V˚m, at the same pressure and temperature:
𝑉𝑚
𝑍= ̊
𝑉𝑜𝑚
In general, deviations from ideal behavior become more significant the closer a gas is to a phase
change, the lower the temperature or the larger the pressure. Compressibility factor values are usually
obtained by calculation from equations of state (EOS), such as the virial equation which take compound
specific empirical constants as input. Alternatively, the compressibility factor for specific gases can be read
from generalized compressibility chartsthat plot Z as a function of pressure at constant temperature.

The figure above shows the deviation of nitrogen and argon from the expected behavior of an ideal gas
under particular isothermal (constant pressure) conditions.
For real gases Z may be less or more than one. If Z<1, then the gas is less compressible and it is called
positive deviation. It is observed that the deviations are low at low pressures. At high pressures, the deviations
depend on the nature of the gas.
For H2 and He, Z is greater than one while for N2, CH4 and CO2, Z is less than one. This means that these
gases are more compressible at low pressures and less compressible at high pressures than expected from
ideal behavior.
For an ideal gas the compressibility factor is Z =
1 per definition. In many real world applications
requirements for accuracy demand that deviations from
ideal gas behavior, i.e. real gas behavior, is taken into
account. The value of Z generally increases with pressure
and decreases with temperature. At high pressures
molecules are colliding more often. This allows repulsive
forces between molecules to have a noticeable effect,
making the volume of the real gas (Vreal) greater than the
volume of an ideal gas (Videal) which causes Z to increase
above one.[3] When pressures are lower, the molecules
are more free to move. In this case attractive forces
dominate, making Z < 1. The closer the gas is to
its critical point or its boiling point, the more Z deviates
from the ideal case.

EXAMPLE PROBLEM
A gas at 250K and 15atm has a molar volume 12% smaller than that calculated for the equation of
state of an ideal gas. Hence calculate:

RVMLecture Manual: Physical Chemistry 1 26

 (A) The molar volume of the gas
(B) The compressibility factor (Z) for this temp and pressure

SOLUTION:
𝑎𝑡𝑚𝐿
𝑍𝑅𝑇 (1)( 0.08206 )( 250𝐾 ) 𝐿
𝑚𝑜𝑙 𝐾
𝑉𝑚 (𝑖𝑑𝑒𝑎𝑙) = = = 1.3677
𝑃 15 𝑎𝑡𝑚 𝑚𝑜𝑙
𝑉𝑖𝑑𝑒𝑎𝑙 – 𝑉𝑚
(a) Z =
𝑉𝑖𝑑𝑒𝑎𝑙
𝐿
( 1.3677 )− 𝑉𝑚
𝑚𝑜𝑙
0.12 = 𝐿
( 1.3677 )
𝑚𝑜𝑙
𝐿
𝑉𝑚 = 1.2036
𝑚𝑜𝑙
𝐿
𝑉𝑚 1.2036
𝑚𝑜𝑙
(b) Z = = 𝐿
𝑉𝑖𝑑𝑒𝑎𝑙 1.3677
𝑚𝑜𝑙
𝑍 = 0.88

(B.) CRITICAL CONSTANTS

The 31.04º C isotherm for CO2:
If compression takes place at the so-called criticaltemperature,
Tc,the surface separating the gas and liquid phases does not appear, and
horizontal parts of the isotherm merge at thecritical point - liquid phase
does not form above the critical temperature.
The critical temperature, molar volume and pressure, Tc,Vcand
pc,are called the critical constants, which are unique to each substance
Certain substances have a very dense phase which can fill an
entire volume at T >Tc,and these are referred to as supercriticalfluids.
NOTE: For the critical constants of organic and inorganic
compounds, see page 2-138 of Perry’s Chemical Engineering Handbook.

(C.) SUPERCRITICAL FLUIDS

A SCF is defined as a substance above its critical temperature (TC) and critical pressure (PC). The
critical point represents the highest temperature and pressure at which the substance can exist as a vapor
and liquid and equilibrium. The phenomenon can be easily explained with reference to the phase diagram for
pure carbon dioxide as shown in the figure below.

RVMLecture Manual: Physical Chemistry 1 27

 This shows the areas where carbon dioxide exists as a gas, liquid, solid or as a SCF. The curves
represent the temperatures and pressures where two phases coexist in equilibrium (at triple point, the three
phases coexist). The gas-liquid coexistence curve is known as the boiling curve. If move upwards along the
boiling curve, increasing both pressure and temperature, then the liquid becomes less dense due to thermal
expansion and the gas becomes denser as the pressure rises. The critical point for carbon dioxide occurs at a
pressure of 73.8 bar and a temperature of 31.1°C. These parameters make equipment design and reaction set-
up relatively simple.

4.2. VAN DER WAALS EQUATION

Johannes Diderik van der Waals (1837-1923), a Dutch physicist, won the 1910 Nobel Prize in Physics
for his work on the equation ofstate for gases and liquids.
The van der Waals equation is written as:
𝑛𝑅𝑇 𝑎𝑛2 𝑅𝑇 𝑎
𝑃= − 2 = −
𝑉 − 𝑛𝑏 𝑉 𝑉𝑚 − 𝑏 𝑉𝑚2
wherea and b are van der Waals coefficients, specific to
each gas
Term a is adjusted to represent the attractive forces of the
molecules, without giving any specific physical origin to these
forces; V - nb, not V, nowrepresents the volume in which molecules
can move.
The Van der Waals equation shows one feature
which does not have physical significance. If the equation is plotted
as a function of pressure against volume, then all P-V isotherms below a critical temperature display loops,
within which the volume of the gas apparently decreases with increasing pressure. These Van der Waals
loops are part of a two – phase region within which gas and liquid coexist, a proportion of the gas having
condensed to a liquid phase. To represent physical reality, a horizontal line replaces the loops. Along this line,
varying proportions of gas and liquid coexist, with the right hand end representing pure gas and the left –
hand end pure liquid.

NOTE: See equation 4-100 on page 4-11 of Perry’s Chemical Engineering handbook for the Van der
Waals Equation.

SAMPLE PROBLEM
12.0 moles of gas are in a 5.00 L tank at 24.0℃. Calculate the difference in pressure between methane
and an ideal gas under these conditions. The van der Waals constants for methane are a = 2.300
(L^2)(atm)/(mol^2) and b = 0.0430 L/mol.

SOLUTION:
𝑛𝑅𝑇 𝑎𝑛2 12 𝑚𝑜𝑙 𝑥 0.08206 𝐿 𝑎𝑡𝑚 𝑥 297 𝐾 (12 𝑚𝑜𝑙)2 𝑥 (2.30 𝐿)2
𝑃= − = 𝐿 − =51.87 atm.
𝑉−𝑛𝑏 𝑉2 5 𝐿−(12 𝑚𝑜𝑙 𝑥 0.0430 ) (5 𝐿)2
𝑚𝑜𝑙

SUMMARY OF THE VAN DER WAALS EQUATIONS

1. Perfectgasisothermsareobtainedathightemperaturesandlargemolar
volumes:
• at highT, thefirst termmaybemuchgreaterthanthesecond
• if V ishigh,thenVm-b = Vm, P=RT/Vm
m
2. Liquidsandgasesexistwhencohesiveanddispersiveforcesarebalanced:

• first termfromKE andrepulsion,secondtermfromattraction

3. Criticalconstantsarerelatedto thevanderWaalscoefficients:

RVMLecture Manual: Physical Chemistry 1 28

 • forT <Tccalculatedisothermsoscillate,passingthrougha
minimumfollowedbyamaximum,convergingas T →Tc
• at theflat inflection, the1stand2ndderivativesarezero:
𝑑𝑃 𝑅𝑇 2𝑎
= 2
+ 3=0
𝑑𝑉𝑚 (𝑉𝑚 − 𝑏) 𝑉𝑚
𝑑2𝑃 2𝑅𝑇 6𝑎
= − =0
𝑑𝑉𝑚2 (𝑉𝑚 − 𝑏)3 𝑉𝑚4
Solvethetwoequationsintwounknowns: VmandT, thenfindpwiththeequationof state: Thisgives:
𝑎 8𝑎
Vc = 3b Pc = Tc =
27𝑏 2 27𝑅𝑏
At thispoint,thecriticalcompressionfactor,
𝑃𝑐 𝑉𝑐 3
𝑍𝑐 = =
𝑅𝑇𝐶 8

4.3. PRINCIPLES OF CORRESPONDING STATES

According to Van der Waals, the theorem of corresponding states (or principles of corresponding
states) indicates that “all fluids, when compared at the same reduced temperature and reduced pressure,
have approximately the same compressibility factor and deviate from ideal gas behavior to about the same
degree.”
Inmanyareasofscienceit isusefulto compareafundamentalpropertyof
differentobjectsonarelativescaleforpurposesof comparison.Fordifferent gases,weuse reducedvariables:
𝑃 𝑉𝑚 𝑇
𝑃𝑟 = 𝑉𝑟 = 𝑇𝑟 =
𝑃𝑐 𝑉𝑐 𝑇𝑐
The observation that real gases at the same reduced volume and reduced temperature exert the same
reduced pressure is called the principle of corresponding states. The principle is only an approximation. It
works best for gases composed of spherical molecules; it fails, sometimes badly, when the molecules are non-
spherical or polar.
The Van der Waals equation sheds some light on the principle. This equation can be expressed in
terms of reduced variable, which gives
𝑅𝑇𝑟 𝑇𝑐 𝑎
𝑃𝑟 𝑃𝑐 = − 2 2
𝑉𝑟 𝑉𝑐 𝑉𝑟 𝑉𝑐
Then the critical constants can be expressed in terms oof a and b by the equation
𝑎𝑃𝑟 8𝑇𝑟 𝑎
2
= −
27𝑏 27𝑏 (3𝑏𝑉𝑟 − 𝑏) 9𝑏 2 𝑉𝑟2
Which can be recognized to
8𝑇𝑟 3
𝑃𝑟 = − 2
3𝑉𝑟 − 1 3𝑟
This equation has the same form as the original, but the coefficients a and b, which differ from gas to
gas, have disappeared. It follows that if the isotherms are plotted in terms of reduced variables, then the same
curves are obtained whatever the gas. This is precisely the content of the principle of corresponding states, so
the Van der Waals equation is compatible with it.

4.4. COMPRESSIBILITY FACTOR EQUATION

- It is a measure of deviation from ideal – gas behavior.
- The compressibility factor Z depends not only on temperature, but also the pressure.
𝑃𝑉
Compressibility Factor, Z 𝑍=
𝑅𝑇
Ideal Gas: Z=1
Real Gases: Z>1
Z<1
Engineering calculations often require a tradeoff between ease of use and accuracy. The ideal gas
equation is very easy to use, but of questionable accuracy for many cases. Virial and cubic equations of state
are accurate, but not particularly convenient. A good compromise is a generalized compressibility factor
equation.

RVMLecture Manual: Physical Chemistry 1 29

 The “compressibility factor”, z, is defined so that
𝑃𝑉
𝑍=
𝑅𝑇
Consequently, Z = 1 for an ideal gas. There are a wide variety of ways to obtain Z – it is a function of T
and P and can be determined from any of the equations of state.
Most gas properties depend on composition, but according to the “Law of Corresponding States”
a few properties are the same for all gases when expressed in terms of deviation from the critical point. We
do this by using the “reduced temperature” and “reduced pressure”.
𝑃 𝑇
𝑃𝑟 = 𝑇𝑟 =
𝑃𝑐 𝑇𝑐
Correlations and charts that take advantage of corresponding states to provide data for many gases
are called “generalized”. Thus, a “generalized compressibility factor chart” can be used to get Z once we have
the reduced temperature and pressure. There are typically several different views of the chart, depending on
the pressure range.

4.5. EQUATIONS OF STATE

An equation of state is a relation between state variables.More specifically, an equation of state is a
thermodynamic describing the state of matter under a given set of physical conditions. It is a constitutive
equation which provides a mathematical relationship between two or more state functions associated with
the matter, such as its temperature, pressure, volume, or internal. Equations of state are useful in describing
the properties of fluids, mixtures of fluids, solids, and even the interior of stars.
The most prominent use of an equation of state is to predict the state of gases and liquids. One of the
simplest equations of state for this purpose is the ideal gas law, which is roughly accurate for gases at low
pressures and moderate temperatures. However, this equation becomes increasingly inaccurate at higher
pressures and lower temperatures, and fails to predict condensation from a gas to a liquid. Therefore, a
number of much more accurate equations of state have been developed for gases and liquids. At present,
there is no single equation of state that accurately predicts the properties of all substances under all
conditions.

4.6. VIRIAL EQUATION

• Virial: derived from the Latin word for “force”
• In 1901, H. Kamerlingh – Omnes proposed an equation of state for real gases in Z as a power series in
terms of 1⁄𝑉 for a pure gas:
𝑚
• B and C: the second and third virialcoeffcients, and both are temperature dependent, but not on the
pressure.
Virial equations are a family of equation of state of the general form:
𝑃𝑉𝑛 𝐵 𝐶 𝐷 𝑐 (𝑇)
= 1+ + 2+ 3+⋯= ∑
𝑅𝑇 𝑉𝑛 𝑉𝑛 𝑉𝑛 𝑉𝑣
𝑖=0
The parameters in the equation (B, C, D = ci) are called “virial coefficients”. If ci = 0 for i > 0, the
virial equation reduced to the ideal gas equation. Just as with the ideal gas equation, the temperatures and
pressures used must be absolute.
The accuracy required determines the number of terms that are kept – more terms make the
equation more accurate, but also more complicated to work with. Virial coefficients are different for each gas,
but other than that are functions of temperature only.
Coefficients are normally obtained by making measurements P, V, and T, and the fitting the equation.
These values are then published so that others may use them.
Many forms of the virial equation exist. Often, we will truncate the virial equation to
𝑃𝑉𝑛 𝐵
=1+
𝑅𝑇 𝑉

RVMLecture Manual: Physical Chemistry 1 30

VIRIAL COEFFICIENTS
For a real gas with large molar volumes and higher temperatures, the isotherms are almost identical
to those of an ideal gas. However, there are some small differences which suggest that the perfect gas law is
only the first term in apower series:
2 𝐵 𝐶
𝑃𝑉𝑚 = 𝑅𝑇 ( 1 + 𝐵′ 𝑃 + 𝐶 ′𝑃 + ⋯ ) = 𝑅𝑇 (1 + + 2 + ⋯)
𝑉 𝑚 𝑉𝑚
These are the virial equations of state, where coefficientsB and C have to be evaluated at each
temperature
P → 0: Close to ideal gas law, but not exact
P increases: B contributes, linear relation between Z andP
P higher: C and higher order terms contribute, deviation from linearity
Virial: comes from that Latin wordvis,viris, meaning force - the coefficients in the virial
equationdepend on the forces of interaction between molecules of the gas

4.7. CUBIC EQUATIONS OF STATE

Virial equations cannot represent thermodynamic systems where both liquid and vapor are present.
A “cubic” is need to do this.

1. Redlich and Kwong Equation (RK)

𝑅𝑇 𝑎
𝑃= −
𝑉𝑚 − 𝑏 √𝑇𝑉𝑚 (𝑉𝑚 + 𝑏)
𝟎. 𝟒𝟐𝟕𝟒𝟖 𝑹𝟐 𝑻𝟐.𝟓𝒄 𝟎. 𝟎𝟖𝟔𝟔𝟐 𝑹𝑻𝒄
𝒂= 𝒃=
𝑷𝒄 𝑷𝒄
Introduced in 1949 the Redlich–Kwong equation of state was a considerable improvement
over other equations of the time. It is still of interest primarily due to its relatively simple form. While
superior to the van der Waals equation of state, it performs poorly with respect to the liquid phase
and thus cannot be used for accurately calculating vapor-liquid equilibrium. However, it can be used
in conjunction with separate liquid-phase correlations for this purpose.
The Redlich–Kwong equation is adequate for calculation of gas phase properties when the
ratio of the pressure to the critical pressure(reduced pressure) is less than about one-half of the ratio
𝑷 𝑻
of the temperature to the critical temperature (reduced temperature): < .
𝑷𝒄 𝟐𝑻𝑪

2. Soave RedlichKwong Equation (SRK)

𝑅𝑇 𝑎𝛼
𝑃= −
𝑉𝑚 − 𝑏 𝑉𝑚 (𝑉𝑚 + 𝑏)
𝟎. 𝟒𝟐𝟕𝟒𝟖 𝑹𝟐 𝑻𝟐𝒄 𝟎. 𝟎𝟖𝟔𝟔𝟒 𝑹𝑻𝒄 𝑻
𝒂= 𝒃= 𝑻𝒓 =
𝑷𝒄 𝑷𝒄 𝑻𝒄
𝜶 = (𝟏 + ( 𝟎. 𝟒𝟖𝟓𝟎𝟖 + 𝟏. 𝟓𝟓𝟏𝟕𝟏 𝝎 − 𝟎. 𝟏𝟕𝟔𝟏𝟑𝝎𝟐 )( 𝟏 − 𝑻𝒓 𝟎.𝟓 ) )𝟐
Where ω is the acentric factor for the species.
In 1972 Soave replaced the 𝟏⁄ term of the Redlich-Kwong equation with a function α
√𝑻
(T,ω) involving the temperature and the acentric factor. The 𝜶 function was devised to fit the vapor
pressure data of hydrocarbons and the equation does fairly well for these materials.
Note: This replacement changes the definition of a slightly, as the Tcis now to the second
power.

3. Peng - Robinson Equation of State

𝑹𝑻 𝒂𝜶
𝑷= −
𝑽𝒎 − 𝒃 𝑽𝟐𝒎 + 𝟐𝒃𝑽𝒎 − 𝒃𝟐

RVMLecture Manual: Physical Chemistry 1 31

 𝟎. 𝟒𝟓𝟕𝟐𝟒𝑹𝟐 𝑻𝟐𝒄 𝟎. 𝟎𝟕𝟕𝟖𝟎𝑹𝑻𝒄 𝑻
𝒂= 𝒃= 𝑻𝒓 =
𝑷𝒄 𝑷𝒄 𝑻𝒄
𝜶 = (𝟏 + ( 𝟎. 𝟑𝟕𝟒𝟔𝟒 + 𝟏. 𝟓𝟒𝟐𝟐𝟔 𝝎 − 𝟎. 𝟐𝟔𝟗𝟗𝟐𝝎𝟐 )( 𝟏 − 𝑻𝒓 𝟎.𝟓 ) )𝟐
where, ω is the acentric factor of the species and R is the universal gas constant.

The Peng-Robinson equation was developed in 1976 in order to satisfy the following goals:
1. The parameters should be expressible in terms of the critical properties and the acentric
factor.
2. The model should provide reasonable accuracy near the critical point, particularly for
calculations of the compressibility factor and liquid density.
3. The mixing rules should not employ more than a single binary interaction parameter,
which should be independent of temperature pressure and composition.
4. The equation should be applicable to all calculations of all fluid properties in natural gas
processes.
For the most part the Peng-Robinson equation exhibits performance similar to the Soave
equation, although it is generally superior in predicting the liquid densities of many materials,
especially nonpolar ones.

NOTE: See equation 4-100 on page 4-11 of Perry’s Chemical Engineering handbook for the above equations.
Use Table 4-2 on page 4-11 of Perry’s Chemical Engineering handbook for the Parameter Assignment of the
equation.

4.8. SELECTED EQUATIONS OF STATE

A varietyof equationsofstatesimilarto vanderWaalsequationhavebeen developedandappliedto
differenttypesof gases.

REDUCED CRITICAL CONSTANTS

EQUATION
FORM
PC VC TC
𝑅𝑇
Perfect gas 𝑃=
𝑉𝑚

𝑅𝑇 𝑎 8𝑇𝑟 3 𝑎 8𝑎
Van der Waals 𝑃= − 𝑃𝑟 = − 3b
𝑉𝑚 − 𝑏 𝑉𝑚2 3𝑉𝑟 − 1 𝑉𝑟2 27𝑏 2 27𝑏𝑅

1 1
𝑅𝑇 𝑎 8𝑇𝑟 3 1 2𝑎𝑅 2 2 2𝑎 2
Berthelot 𝑃= − 𝑃𝑟 = − [ ] 3b [ ]
𝑉𝑚 − 𝑏 𝑇𝑉𝑚2 3𝑉𝑟 − 1 𝑇𝑟 𝑉𝑟2 12 3𝑏 3 3 3𝑏𝑅

−𝑎 −2
𝑅𝑇𝑒 𝑅𝑇𝑉𝑚 𝑒 2 𝑇𝑟 𝑒 𝑇𝑟𝑉𝑟 𝑎 𝑎
Dieterici 𝑃= 𝑃= 2b
𝑉𝑚 − 𝑏 2𝑉𝑟 − 1 4𝑒 3 𝑏 2 4𝑅𝑏

Virial
𝑅𝑇 𝐵(𝑇) 𝐶(𝑇)
(Kammerlingh 𝑃= {1 + + + ⋯}
𝑉𝑚 𝑉𝑚 𝑉𝑚2
Onnes)

(Reference: Atkins, 2006)

RVMLecture Manual: Physical Chemistry 1 32

EXERCISES:

1. By the use of Van der Waals Equation, find the T at which 3 mol CO 2 will occupy a volume of 10L at a
pressure of 1 atm.
2. Employing the KamerlinghOnnes equation of state, find the compressibility factors or CO at -50℃ and
pressure of 10 atm.
3. Compare the reduced pressures of N2 and NH3 when each exerts a pressure of 100 atm.
4. At 0℃ and under a pressure of 100 atm, the compressibility factor of O 2 is 0.927. Calculate the weight of
O2 necessary to fill a gas cylinder of 100-liter capacity under the given conditions.
5. A particular mass of N2 occupies a volume of 1.00 L at -50℃ and 800 bar. Determine the volume occupied
by the same mass of N2 at 100℃ and 200 bar using the compressibility factor for N2. At -50℃ and 800 bar,
it is 1.95; at 100℃ and 200 bar, it is 1.10. Compare this value to that obtained from the ideal gas law.
6. At what temperature and pressure will H2 be in a corresponding state with CH4 at 500.0 K and 2.00 bar
pressure?
7. A gas obeys the Van der Waals equation with Pc = 3.040 x 106 Pa and Tc = 473 K. Calculate the value of
the Van der Waals constant b for this gas.
8. The Van der Waals constants for HCl are a = 3.67 atm-liter2/mole2, and b = 40.8 cc/mole. Find the critical
constants of this substance.
9. What is the molar volume of He gas assumed as Van der Waals gas at 1.3 atm and a temperature of 45℃.
For He gas, a = 0.034 atm-liter2/mol2 and b = 0.0237 L/mol.
10. What pressure in atm is generated when 1 lbmol of methane is stored in a volume of 2 ft 3 at 122℉? Use
Redlich Kwong equation?
11. Ethylene has a critical pressure of Pc = 61.659 atm and a critical temperature of Tc = 308.6 K. Calculate
the molar volume of the gas at T= 97.2℃ and 90.0 atm. Compare the value so found with that calculated
from the ideal gas equation.
12. The critical temperature Tc of nitrous oxide (N2O) is 36.5℃ and its critical pressure Pc is 71.7 atm.
Suppose that 1 mol of N2O is compressed to 54.0 atm at 356 K. Calculate the reduced temperature and
pressure.
13. The density of liquid benzene at 0℃ is 0.899 g/cm3 and the Van der Waals constant a is 1.824 m6/mol2 Pa.
Estimate the internal pressure and the potential energy contribution to the internal energy.
14. Cylinders of compressed gas are typically filled to a pressure of 200 bar. For oxygen, what would be the
molar volume at this pressure and 25℃ based on (a) the perfect gas equation, (b) the Van der Waals
equation?
15. At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate (a) the volume occupied by 8.2
mmol of the gas under this condition and (b) the approximate value of the second virial coefficient B at
300 K.

RVMLecture Manual: Physical Chemistry 1 33