Heat Capacities | PNG 520: Phase Behavior of Natural Gas and Condensate Fluids

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Heat Capacities
Heat Capacities
The constant volume heat capacity is defined by:
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Course Orientation

(19.1)
Resources
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Syllabus
Academic Integrity Guide
ANGEL
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Course Outline
Introduction and Purpose
Phase Diagrams, Part I
Phase Diagrams, Part II
Phase Diagrams, Part III
Phase Diagrams, Part IV
PT Behavior and
Equations of State (EOS),
Part I
PT Behavior and
Equations of State (EOS),
Part II
PT Behavior and
Equations of State (EOS),
Part III
Cubic EOS and Their
Behavior (I)
Cubic EOS and Their
Behavior (II)
Cubic EOS and Their
Behavior (III)
Elementary Vapor-Liquid
Equilibrium (I)
Elementary Vapor-Liquid
Equilibrium (II)
Thermodynamic Tools (I)
Thermodynamic Tools (II)
Thermodynamic Tools (III)
Vapor-Liquid Equilibrium
via EOS
Properties of Natural Gas
and Condensates (I)
Properties of Natural Gas
and Condensates (II)
Heat Capacities
Joule-Thomson
Coefficient
Viscosity
Action Item
Engineering Applications
(I)
Engineering Applications
(II)

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To see the physical significance of the constant volume heat capacity, let us consider a 1 lbmol of gas within a rigid-wall
(constant volume) container. Heat is added to the system through the walls of the container and the gas temperature rises.
It is evident that the temperature rise ( ) is proportional to the amount of heat added,
(19.2)
Introducing a constant of proportionality cv,
(19.3)
In our experiment, no work was done because the boundaries (walls) of the system remained unchanged. Applying the first
law of thermodynamics to this closed system, we have:
(19.4)
Therefore, for infinitesimal changes,

(19.5)
As we have seen, constant volume heat capacity is the amount of heat required to raise the temperature of a gas by one
degree while retaining its volume.
Let us now consider the same 1 lbmol of gas confined in a piston-cylinder equipment (i.e., a system with non-rigid walls or
boundaries). When heat is added to the system, the gas temperature rises and the gas expands so that the pressure in the
system remains the same at any time. The piston displaces a volume V and the gas increases its temperature in
degrees. Again, the temperature rise ( T) is proportional to the amount of heat added, and the new constant of
proportionality we use here is cp,
(19.6)
This time, some work was done because the boundaries (walls) of the system changed from their original position. Applying
the first law of thermodynamics to this closed system, we have that:
(19.7)
If the pressure remained the same both inside and outside the container, the system made some work against the
surroundings in the amount of W=P V. Introducing (19.7) into (19.6),
(19.8)
The left hand side of this equation represents the definition of enthalpy change ( H) for a constant-pressure process.
Therefore:
(19.9)
Finally, for infinitesimal changes,

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(19.10)
The function cp is called the constant pressure heat capacity. The constant pressure heat capacity is the amount of heat
required to raise the temperature of a gas by one degree while retaining its pressure.
The units of both heat capacities are (Btu/lbmol-F) and (cal/gr-C). Their values are never equal to each other, not even for
ideal gases. In fact, the ratio cp /cv of a gas is known as k the heat capacity ratio and it is never equal to unity. This
ratio is frequently used in gas-dynamics studies.

(19.11)
Heat capacities can be calculated using equations of state. For instance, Peng and Robinson (1976) presented an
expression for the departure enthalpy of a fluid mixture, shown below:

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Heat Capacities | PNG 520: Phase Behavior of Natural Gas and Condensate Fluids

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(19.12)
The value of the enthalpy of the fluid (H) is obtained by adding up this enthalpy of departure (shown above) to the ideal gas
enthalpy (H*). Ideal enthalpies are sole functions of temperature. For hydrocarbons, Passut and Danner (1972) developed
correlations for ideal gas properties such as enthalpy, heat capacity and entropy as a function of temperature. Therefore, an
analytical relationship for cp can be derived taking the derivative of (19.12), as shown below:

(19.13)
where:
= ideal gas C P,
also found in the work of Passut and Danner (1972).
The second derivative of

with respect to temperature can be calculated through the expression:

(19.14a)

where,

(19.14b)

For the evaluation of expression (19.13), the derivative of the compressibility factor with respect to temperature is also
required. Using the cubic version of Peng-Robinson EOS, this derivative can be written as:

(19.15)
where,

cp and cv values are thermodynamically related. It can be proven that this relationship is controlled by the P-V-T behavior
of the substances through the relationship:

(19.16)
For ideal gases,

and Equation (18.28) collapses to:

(19.17)

Properties of Natural Gas and Condensates (II)

up

Joule-Thomson Coefficient

Course Author: Michael Adewumi, Professor, Petroleum & Natural Gas Engineering, The Pennsylvania State University.

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Heat Capacities | PNG 520: Phase Behavior of Natural Gas and Condensate Fluids

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