Chemical Engineering

Thermodynamics
CHE 325

1
Equation of State
(EOS) for Gases

2
 EQUATIONS OF STATE (EOS)
Any equation that relates the pressure, temperature, and specific
volume of a substance is called an Equation of State (EOS). That
is, the correlation for P-V-T is known as equation of state.

EOS is a functional equation that expresses the relationship among

P, V and T

There are several equations of state, some are simple while the
mathematical expressions of some EOS are complex.
EOS predicts the P-V-T behaviour of a gas quite accurately within
some properly selected region.
 EQUATIONS OF STATE FOR IDEAL GAS
An ideal gas is defined as a gas whose molecules are spaced far apart so that
the behaviour of a molecule is not influenced by the presence of other
molecules – a situation encountered at low densities.

A P-V-T system could be for a gas, a liquid or a solid. Indeed, if the system is a
sample of water, it could be in any of those states, depending on the particular
values of P, V and T.

• The P–V–T behaviour of an ideal gas is expressed by the simple relation

PV = RT, which is called the ideal gas equation of state.
 EQUATIONS OF STATE FOR IDEAL GAS
• When two or more ideal gases are mixed, the behaviour of a molecule
is normally not influenced by the presence of other similar or
dissimilar molecules, and therefore a non-reacting mixture of ideal
gases also behave as an ideal gas.

• For instance, Air is conveniently treated as an ideal gas in the range

where nitrogen and oxygen behave as ideal gases.

• The P–V–T behaviour of real gases is expressed by more complex

equations of state or by PV = ZRT, where Z is the compressibility
factor.
IDEAL GAS EQUATION OF STATE

where n = no. of moles, 𝜌 = density

 EQUATIONS OF STATE FOR IDEAL GAS
• The gas constant R is different for each gas, but Universal gas
ധ is the same for all gases and its values are
constant, 𝑅,

• The molar mass M can simply be defined as the mass of one mole (also
called a gram-mole, abbreviated gmol) of a substance in grams, or the
mass of one kmol (also called a kilogram-mole, abbreviated kgmol) in
kilograms.
• In English units, it is the mass of 1 lbmol in lbm.
 EQUATIONS OF STATE FOR IDEAL GAS
• Note that the molar mass of a substance has the same numerical
value in both unit systems because of the way it is defined.
• When we say the molar mass of nitrogen is 28, it simply means the
mass of 1 kmol of nitrogen is 28 kg, or the mass of 1 lbmol of
nitrogen is 28 lbm. That is, M = 28 kg/kmol = 28 lbm/lbmol.
• The mass of a system is equal to the product of its molar mass M
and the mole number n. (That is, m = nM)
• The properties of an ideal gas at two different states (1 and 2) are
related to each other using
𝐏𝟏 𝐕𝟏 𝐏𝟐 𝐕𝟐
=
𝐓𝟏 𝐓𝟐
 EQUATIONS OF STATE FOR NON IDEAL GAS (Real Gases)
• For real gases, their molecules interact if they are close enough and have a
potential energy contribution.
• Deviation from ideal gas law are particularly important at high pressures
and low temperatures.
• Real gases differs from ideal gases in that there can be interactions between
molecules in the gas phase.
• At low temperatures and high pressures, real gases do not behave ideally.

Reasons for deviation from ideality are:

• The molecules are very close to one another thus their volume is important.
• At high pressures and low temperatures, the molecules interactions are also
important.
 EQUATIONS OF STATE FOR NON IDEAL GAS
• Non ideal gas is a gas that does not obey ideal gas equation of state.
• Equations that predict the P-V-T behavior of Non ideal gases are many.

1. Van der Waals Equation of State

It is intended to account for the volume occupied by the gas
molecules and for the attractive forces between molecules. It is
𝑹𝑻 𝒂
P= -
𝒗 −𝒃 𝒗𝟐
where 𝒂 and 𝒃 are related to the critical-point of each substance.
That is,
𝟐𝟕𝑹𝟐 𝑻𝟐𝒄 𝑹𝑻𝒄
𝒂 = and 𝒃 =
𝟔𝟒𝑷𝒄 𝟖𝑷𝒄
Table of the Critical constants of some substances
 Critical Properties of Phase-Change Fluids
Material Properties Useful for the Real Gas Model Critical-Point Properties
Substance Formula Molar Mass Temperature Pressure Volume
. . M Tcr Pcr vcr
. . kg/kmol K MPa m^3/kmol
Air -- 28.97 132.5 3.77 0.0883
Ammonia NH3 17.03 405.5 11.28 0.0724
Argon Ar 39.948 151 4.86 0.0749
Benzene C6H6 78.115 562 4.92 0.2603
n-Butane C4H10 58.124 425.2 3.8 0.2547
Carbon Dioxide CO2 44.01 304.2 7.39 0.0943
Carbon Monoxide CO 28.011 133 3.5 0.093
Carbon Tetrachloride CCl4 153.82 556.4 4.56 0.2759
Chlorine Cl2 70.906 417 7.71 0.1242
Ethane C2H6 30.07 305.5 4.48 0.148
Ethylene C2H4 28.054 282.4 5.12 0.1242
Helium He 4.003 5.3 0.23 0.0578
Hydrogen (normal) H2 2.016 33.3 1.3 0.0649
Methane CH4 16.043 191.1 4.64 0.0993
Neon Ne 20.183 44.5 2.68 0.0419
Nitrogen N2 28.013 126.2 3.39 0.0899
Oxygen O2 31.999 154.8 5.08 0.078
Propane C3H8 44.097 370 4.26 0.1998
Propylene C3H6 42.081 365 4.62 0.181
Sulfur dioxide SO2 64.063 430.7 7.88 0.1217
Tetrafluoroethane (R-134a) CF3CH2F 102.03 374.3 4.067 0.1847
Water H2O 18.015 647.1 22.064 0.0564
Table of Constants of the van der Waals Equation
 Equation of State for Non Ideal Gas

2. Redlich–Kwong Equation of State

𝑹𝑻 𝒂
P= -
𝒗 −𝒃 𝒗(𝒗 + 𝒃)𝑻𝟎.𝟓
where 𝒂 and 𝒃 constants are given as
𝑹𝟐 𝑻𝟐.𝟓
𝒄 𝑹𝑻𝒄
𝒂 = 0.4275 and 𝒃 = 0.0867
𝑷𝒄 𝑷𝒄
Table of constants of Redlich-Kwong Equation
 Equation of State for Non Ideal Gas

3. Virial Equation of State

It presents the product pv as a series expansion. The virial
equations of state include
Pv = A + BP(T) + 𝑪𝑷𝟐 (T) + 𝑫𝑷𝟑 (T) + ……

𝑹𝑻 𝑩(𝑻) 𝑪(𝑻) 𝑫(𝑻)

P= + + + +…
𝒗 𝒗𝟐 𝒗𝟑 𝒗𝟒
where 𝑨, B, C, D….. are constants and temperature dependent.
 Equation of State for Non Ideal Gas

4. Compressibility Factor (Z)

Compressibility factor (Z) is defined as
PV
Z=
RT
Compressibility factor accounts for the deviation of real gases from
ideal gas behaviour at a given temperature and pressure.
Z = 1 for all ideal gases but real gases have varied Z values different
from 1 (less or greater than 1). The farther away Z is from 1, the more
the gas deviates from ideal-gas behaviour.
 Example
Determine the mass of an ideal gas in a closed container whose dimensions
are 4 m × 5 m × 6 m at 100 kPa and 250C. (Molecular weight of the gas is 14
kPa . m3
and Universal gas constant = 20.287 ).
kg . K
Solution
ന𝑻
𝑷𝑽 = 𝒏𝑹
𝒎
𝑷𝑽 = 𝑹 ന𝑻
𝑴
𝒎
(4 x 5 x 6)100 = (𝟐𝟗𝟖 𝒙 𝟐𝟎. 𝟐𝟖𝟕)
𝟏𝟒

𝟒 𝒙 𝟓 𝒙 𝟔 𝒙 𝟏𝟎𝟎 𝒙 𝟏𝟒
m=
𝟐𝟗𝟖 𝒙 𝟐𝟎.𝟐𝟖𝟕

mass of the gas = 27.789 kg

Example:
The atmospheric surface pressure on Venus is 90 bar. The atmosphere near
the surface is composed of 96% carbon dioxide and 4% other gases. Given a
surface temperature of 730 K, what is the mass of carbon dioxide present
per cubic centimetre at the surface? Assume ideal gas behaviour.
Solution:
CO2 partial pressure is related to the proportion of CO2 present (i.e 0.96 of
the total pressure)

If mass per cubic centimetre is the density d,

where m is the mass and V is the volume. m can be expressed in terms of
the number of moles n and the molecular weight M,
The number of moles n can be determined from the ideal gas equation. Solving
the ideal gas equation for n yields

This expression for the number of moles n can be substituted into the equation
for the mass m,

Finally, this equation for the mass m can be inserted into the relation for the
density d
Now, for the Venus atmosphere, the temperature is 730 K, the pressure of
carbon dioxide is 86.4 bar, the molecular weight of CO2 is 44.0 g/mol, or
0.0440 kg/mol.
Substituting into the expression for the density, the result is
 Example
The second virial term, BIP , of 𝑍 = 1 + 𝐵𝐼 𝑃 of water vapour at 2500C and 10
− 0.01482𝑚3 −2 𝑏𝑎𝑟.𝑚3
bar is . Given that R is 8.314 𝑋 10 . Calculate the
𝑘𝑔𝑚𝑜𝑙 𝑘𝑔𝑚𝑜𝑙.𝐾
compressibility factor (Z) and the volume, V, using the virial equation truncated
at second term.
Solution
Compressibility factor, 𝑍 = 1 + 𝐵𝐼 𝑃 (truncated at second term)
= 1 + −0.01482 10 = 0.8518
To obtain volume,
𝑃𝑉
= 1 + 𝐵𝐼 𝑃
𝑅𝑇
10𝑉
−2
= 1 + −0.01482 10
8.314𝑥 10 (250 + 273)
V = 3.704 m3/kgmol
Example
A 3 L tank contains 2 gram-moles of N2 at (–150.8 K). Estimate the tank pressure
using the
(a) Ideal gas equation of state
(b) van der Waal equation of state
(c) Redlich–Kwong Equation of State
Data for N2: TC = 126.2 K, PC = 3.39 atm, R = 0.08206 L atm/mol. K

Solution
(a) Using Ideal gas equation of state
 Class work: obtain the pressure obtain (and compare the values)

(b) van der Waal equation of state

𝑹𝑻 𝒂
P= -
𝒗 −𝒃 𝒗𝟐
where 𝒂 and 𝒃 are related to the critical-point of each substance. That is,
𝟐𝟕𝑹𝟐 𝑻𝟐𝒄 𝑹𝑻𝒄
𝒂 = and 𝒃 =
𝟔𝟒𝑷𝒄 𝟖𝑷𝒄
(c) Redlich–Kwong Equation of State
𝑹𝑻 𝒂
P= -
𝒗 −𝒃 𝒗𝟐
where 𝒂 and 𝒃 constants are given as
𝑹𝟐 𝑻𝟐.𝟓
𝒄 𝑹𝑻𝒄
𝒂 = 0.4275 and 𝒃 = 0.0867
𝑷𝒄 𝟖𝑷𝒄
 Exercises
1. 1 lbmole of methane is to be stored at temperature of 1220F and a pressure of
600atm. What is the volume (in ft3) of the vessel that must be provided?
𝑓𝑡 3 𝑎𝑡𝑚.
Given that Universal gas law constant, R = 0.7302 , 1m = 3.2808ft
𝐼𝑏𝑚𝑜𝑙𝑒. 𝑜𝑅
and 0R = oF + 46.
2. Determine the mass of H2 (ideal gas) in a closed container whose dimensions
are 4m X 5m X 6m at 100 kPa and 25 0C (Universal gas constant = 0.287
kPa . m3
)
kg . K
3. Repeat Exercise 2 using van der Waals equation with a = 1.023 and b =
0.00156
 Exercises
4. Estimate the pressure of nitrogen at a temperature of 220 K and a specific
volume of 0.04 m3 /kg using
(a) Ideal gas equation
(b) the van der Waals equation
(c) the Redlich-Kwong equation

5. 10 kg of 600 0C steam is contained in a 182 liter tank. Find the pressure using
(a) Ideal gas equation
(b) the van der Waals equation
(c) the Redlich-Kwong equation
(d) the steam table