International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

Mathematical Method for Evaluating Heat

Capacity Ratio and Joule-Thompson
Coefficient for Real Gases
Wordu, A. A, Ojong, O. E
Department of Chemical/Petrochemical Engineering
University of Science and Technology
Nkpolu, Port Harcourt, Nigeria.

ABSTRACT properties of real gases are an essential tool for

Mathematical procedure for estimating Joule- proper design of equipment such as compressors,
Thompson coefficient η, heat capacity ratio γ and piping systems, reactors, refrigeration systems
Shaft work done WS using CV, CP, z, R as precursor [Reid, Prausnitz, and Poling, 1987].
parameters for calculation is presented. The Many engineers prefer to look up physical–
research significance lies on its applications as a property data in tables. However, some commonly
quick check for these parameters by design needed properties of real gases, such as heat
engineers during design of some process plant capacity ratio, r, and the joule-Thomson
units’ i.e compressors, reactors, refrigeration coefficient, n, are frequently not available in the
system, power plant and utilities, piping systems tables. Consequently engineers require alternative
etc. The method gave acceptable deviation that can procedures of determining these properties. Hence,
be applied in process designs. They are shaft work research focuses on mathematical procedure for
done 10.6%, heat capacity ratio 1.42% and Joule- evaluating two real gases properties and further
Thompson coefficient 2.05%. replicates the research for engineering practice. The
significance of this research is to provide a
Keywords: Mathematics, Joule-Thompson theoretical and/or analytical pathway for estimating
coefficient, heat capacity ratio, Shaft work done, physical properties of real gases.
derivative-compressibility, real gases.
2. MATERIALS
1. INTRODUCTION
The necessary materials for evaluating real gases
A gas is a collection of particles in a constant, rapid physical properties comprises of various
and random motion. It is one of the four states of thermodynamic and hydraulic equations obtained
matter which includes; solid, liquid, gas and from literatures [Perry and Green, 2008], [Reid and
plasma. Gases can be subdivided into ideal gas and Sherwood, 1977]. Compressibility factor z, Mollier
real gas. Real gases are made up of atoms or chart, Pitzer Accentric factor, Critical point,
molecules that actually take up some space (i.e. Critical pressure, Critical temperature, Reduced
they have volume) no matter how small, there exist temperature, and Heat capacity are utilized [Perry
forces of attraction between their particles, there and Green, 2008], [Reid and Sherwood, 1977].
collisions are inelastic and they do not obey the
ideal gas law. 3. METHOD
Real gases approximate ideal gases at low
temperature (298K) and pressure (1bar). However,
The derivational process of the heat capacity ratio,
at higher pressures, there exists a wide variation in
Joule-Thompson coefficient, shaft work done and
behavior of real gases with respect to ideal gas.
compressibility are elucidated from known
Consequently, accurate determination of real gases
thermodynamic principles or laws.
physical properties can be achieved by accounting
for the deviation from ideality. Some physical
3.1 Heat capacity ratio
properties of interest for real gases includes;
temperature, pressure, viscosity, heat-capacity
ratio, joule-Thomson coefficient. Typically, when working with flows of
Physical properties of real gases enables engineers compressible fluids, design engineers need a value
to know the state of a system, monitor operational for γ [Smith and Van Ness, 1992]
performance of process equipment and streams,
determine operational efficiency etc. Physical

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

(1)

The real–gas heat capacity at constant pressure Cp is obtained from equation (2) below as given by [Lee and
Kessler 1999].

(2)

(3)

(4)

The real – gases heat capacity at constant volumes, , are not as readily available. To derive , use is made of
the concept of derivative compressibility factors [Reid and Sherwood, 1977] gave the definitions for these
quantities and provide tables as calculated by [Reid and Valbert, 1962].

(5)

(6)

To get an expression for , we start with the Bridgman table of differentials as given by [Reid and Valbert,
1962].

(7)

(8)

By definition:

Hence is obtained explicitly by dividing (7) by (8).

Hence

(9)

From ideal gas,

(10)

By comparing the expression for in (9) to the ideal–gas expression for in equation (10), may be said to
provide a correction from non – ideality.

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

Can be expressed from non ideality of and the Lee–kesler departure function, by substituting
equation (3) into equation (9):

(11)

Is usually calculated from an empirical polynomial in terms of absolute Temperature:

(12)

Where A, B, C and D are constants that are specific for different substances. Hence, an explicit expression for
real–gas heat capacity is:

(13)

This is obtained when equations (12) and (4) are substituted into equation (3). Combing equations (13) and (9)
results in an explicit expression for :

(14)

By substituting equations (14) and (13) into equation (1), an explicit expression for γ is obtained.

(15)

can now be calculated in terms of intensive variables and known or tabulated constants and functions.

Like the departure functions for heat capacity and other important thermodynamic functions, the derivative-
compressibility have been tabulated in a two – term format, where the first term gives the simple (ideal) fluid
function and the second term gives the departure from the simple fluid:

(16)

(17)

For reference:

(18)

Equations (16) and (17) are obtained from equation(18) compressibility z converting ideal to real gases.

(19)

Equation (19) is Peng-Robinson cubic equation for evaluating compressibility zT [Peng and Robinson, 1976].

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

3.2 Joule–Thompson Coefficient ( )

, reflects the change in temperature of a gas as pressure changes, while enthalpy remains constant. It is defined
as:

(19)

To calculate this quantity, we refer to the Bridgman tables:

(20)

(21)

To get an explicit expression for divide equation (20) by equation (21):

(22)

By combining equation (22) with the relations for Cpo in equation (12), and heat–capacity departure from (3)
and (4), η is in terms of tabulated values and extensive variables:

(23)

Summarily,

Basic steps for evaluating γ and η are as outlined below:

1. Having values for w, Tc and Pc, get , ,Z P(0)and from the attached tables.
2. Calculate ZT using the equation (16) above.
3. Calculate ZP using the equation (17) above.
4. Look up values for and from the appropriate texts (e.g Reid, Prausnitz, and Poling).
5. Look up values for A, B, C and D for use in the heat capacity equation (12) above.
6. Calculate γ from the equation (15) or η from the equation (23) above.
Specific calculations showing how to derive a value for γ and η, as well as their uses in process calculations is as
demonstrated below:

Problem Statement: Assuming adiabatic operation and a constant value of γ , estimate the power required to
compress 50 lb/min of nitrous oxide (N2O) from 80°F (288.667k) and 250Psia (17.237bars) to 800Psia
(55.158bars). Also, calculate the outlet temperature using the mollier diagram in Perry’s Handbook, the enthalpy
change is approximately 2.97 Btu/lb, yielding a requirement of 35.0hp.

Solution stepwise
Substance: Nitrous Oxide (N2O):

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

Molecular Weight: 44.013

Critical Temperature, Tc = 310K
Critical Pressure, Pc = 12.40bars
Accentric Factor, w = 0.165
Gas Constant, R = 8.314 J/gmolK

Inlet conditions: Outlet conditions:

Temperature = 80°F = 299.667K Pressure = 800Psia = 55.158bars
Pressure = 250Psia = 17.237bars Reduced pressure, Pr = 0.762
Reduced Temperature, Tr = 0.968
Reduced pressure, Pr = 0.238
Initially, we evaluate the physical properties, and hence γ, at the inlet conditions. Then, once a first value of T 2
is available, calculate a mean temperature and pressure and re-evaluate γ and continue, until successive values
of T2 converge.
The ideal–gas heat capacity is usually expressed as a polynomial of the absolute temperature:
(24)
Constants shown are from Reid, Prausnitz and Poling, using T in Kelvin.
A = 21.620 e+00, B = 72.810e-03, C = -57.780e-06, D = 1.830e-09, J/gmolk
Using the Reid and Valbert tables, interpolate to get the derivative compressibility functions at the desired
(reduced) temperature and pressure
Given:

Using these values, interpolate to find

And

Therefore

For ;
Given:

Using these values, interpolation gives

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

For ZT:
Given:

Using these values, interpolate to find

Given:

Using these values, interpolating gives

From,

For

Given:

Using these values, interpolation gives

For

Given

Using these values, interpolation gives

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

By using equation (4), γ = 1.419

Calculate the Exit Temperature
We use equation [25] thermodynamic function

(25)

From which, T2 = 410.919k

Shaft work, ws; we use the equation;

(26)

From equation [26] shaft work done can be calculated as,

3361.81 J/gmol N2O
=76.4J/g N2O =76.4 KJ/Kg N2O
W, mass flow = 22.7 Kg/min
Therefore P, power required = 1734.28 KJ/min = 38.72hp
Power required from Mollier chart = 35.0hp approx.
Deviation = 10.62% or 0.106

3.3 Determining Joule–Thomson Coefficient η

Estimate the final temperature when refrigerant 12 (dichlorodifluoromethane: CCl2F2) expands through a nozzle
from 300 psia (20.684 bars) and 180°F (355.2k) to 125 psia (8.618 bars). The enthalpy–pressure chart in Perry’s
handbook shows a final temperature of -144°F (175k)
Solutions Techniques
Declaration of industrial and literature data for estimating γ and η
Substance: Refrigerant 12(CCl2F2)
Molecular Weight = 120.913, Critical Temperature Tc = 385.0k, Critical Pressure Pc = 41.40 bars, Accentric
Factor, w = 0.304, Gas Constant, R = 8.314 J/gmol K
Inlet conditions: Outlet conditions:
Temperature = 355.2k Pressure = 8.618 bars
Pressure = 20.684 bars Reduced Pressure, Pr = 0.208
Reduced Temperature, Tr = 0.923
Reduced Pressure Pr = 0.500
The ideal–gas heat capacity is usually expressed as a polynomial in terms of the absolute temperature:

Constants shown here are from Reids, Pravsnitz and Poling, with temperature in Kelvin.
A = 31.60 e+00, B = 178.20e-03, C = -150.90e-06, D = 43.420e-09, = 77.806 J/gmol K
Using the Reid–Valbert table and interpolate to get the derivative- compressibility functions at the desired
(reduced) temperature and pressure. Since the inlet and outlet pressure are known, using the geometric mean of
these two values as a reference point for interpolation.
Given:

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

Using these values and interpolating, we get

Given:

Using these values, interpolating gives

From

For ZT:
Given:

Using these values, interpolating gives

From tables after interpolation, at Pr = 0.354 and Tr =0.932 = 1.521

From

For

Given:

Using these values, interpolation gives

For
Given

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

Using these values, interpolation gives

The compressibility z is evaluated by solving the Peng–Robinson cubic equation of state given by;

Where

a = 11.93e+06, b = 60.155, A* = 0.183, B* = 0.027, Z = 0.829

With a value of Z at hand as well as ZT, the ideal–gas heat capacity and the heat capacity deviation, η can be
calculated using equation (23) to get
η = 1.616 k/bars
The outlet temperature may be estimated assuming this value of η is an average value over the entire process.
Then:

From which
Outlet Temperature = 335.876K
From Pressure–enthalpy diagram, the outlet temperature for this change is 334.26K.
Thus, deviation = 2.05%

4. RESULTS AND DISCUSSION A* = Parameter in cubic equation of state.

The scarce nature of these physical properties for B = Parameter in cubic equation of state.
gases data has propelled the essence of embarking B = Empirical constant in ideal gas heat capacity
on alternative method of estimation. Hence, the polynomial.
mathematical method has been devised. The B* = Parameter in cubic equation of state.
method actually gave good deviations for C = Empirical constant in ideal gas heat capacity
engineering design applications. polynomial.
CP = Real gas heat capacity (at constant pressure),
5. CONCLUSION J/gmol.
This work demonstrates the mathematical = Ideal gas heat capacity (at constant
procedures for obtaining Joule-Thomson pressure), J/gmol.
coefficient η, heat capacity ratio γ and shaft work Cv = Real gas heat capacity (at constant volume),
done Ws using appropriate thermodynamic relations J/gmol.
in situations where they are not readily available
= Residual heat capacity (at constant
for design process.
pressure), J/gmol.
= Simple fluid contribution to residual heat
Nomenclature
a = Parameter in cubic equation of state. capacity (at constant pressure), J/gmol .

A = Empirical constant in ideal gas heat capacity = Departure contribution to residual heat
polynomial. capacity (at constant pressure), J/gmol.

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 International Journal of Engineering Trends and Technology (IJETT) – Volume 36 Number 8 - June 2016

D = Empirical constant in ideal gas heat capacity 7) Reid, R. C, Prausnitz, J. M, and Sherwood, T. K [1977]
The Properties of Gases and Liquids,3rd edition. McGraw-
polynomial. Hill, New York.
8) Reid, R. C, Prausnitz, J. M and Poling, B. E. [1987] The
γ = Heat capacity ratio, Cp/Cv Properties of Gases and Liquids, 4rd edition. McGraw-
Hill, New York.
η = Joule–Thomson coefficient, change in 9) Perry, R. H and Green, D. W [2008] Chemical Engineers,
8th edition. McGraw-Hill, New York.
temperature with respect to pressure of constant 10) Peng, D. Y and Robinson, D. B [1976] A new two
constant equation of state. Journal of Industrial and
enthalpy, K/bar. Engineering Chemistry: Fundamentals 15: 59-64.
P = Pressure, bars (atm).
Pc = Critical Pressure, bars
Pr = Reduced Pressure, P/Pc.
T = Temperature K.
Tc = Critical Temperature K.
Tr = Reduced Temperature T/Tc
ω = Pitzer acentric factor.
Z = Compressibility.
Z(0) = Simple fluid contribution to compressibility.
Z(1) = Departure contribution to compressibility.
ZP = Derivative-compressibility with respect to
pressure.
= Simple fluid contribution to derivative-
compressibility with respect to pressure.
= Departure contribution to derivative-
compressibility with respect to pressure.
ZT = Derivative-compressibility with respect to
temperature.
= Simple fluid contribution to derivative-
compressibility with respect to Temperature.
= Departure contribution to derivative
compressibility with respect to Temperature.

REFERENCES
1) Smith J. M. and Van Ness, H. C. [1992] “Introduction to
Chemical Engineering Thermodynamics” 2nd edition P 70
2) Lee, B. I. and Kessler, M. G. [1999] AIChE Journal. 21,
510,

3) Reid R. C. and Sherwood, T. K. [1966] The Properties of

Gases and Liquids, 2nd edition P 272.

4) Reid R. C. and Valbert J. R.[ 1962]. Industrial Engineering

Chemistry Fundamentals. P 292.

5) Ikoku C. U. [1984]. “Natural Gas Production Engineering”

2nd edition p.19-37.
6) Reid R. C. and others [2012] Properties of gases and
Liquids, 6th edition. pp, 36-39

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