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== Thermodynamic Expressions ==
== Thermodynamic Expressions ==


Values based on approximations (particularly <math>C_p - C_v = R</math>) are in many cases not sufficiently accurate for practical engineering calculations such as flow rates through pipes and valves. An experimental value should be used rather than one based on this approximation, where possible. A rigorous value for the ratio <math>\frac{C_p}{C_v}</math> can also be calculated by determining <math>C_v</math> from the residual properties expressed as:
Values based on approximations (particularly <math>C_p - C_v = R</math>) are in many cases not sufficiently accurate for practical engineering calculations such as flow rates through pipes and valves. An experimental value should be used rather than one based on this approximation, where possible. A rigorous value for the ratio <math>\frac{C_p}{C_v}</math> can also be calculated by determining <math>C_v</math> from the residual properties expressed as:<ref>{{cite book|author=Jamal M. Saleh|title=Fluid Flow Handbook|edition=First Edition|publisher=McGraw-Hill|pages=pages 3.5-3.9|year=2002|id=ISBN 0-07-136372-6}}</ref>


:<math> C_p - C_v \ = \ -T \frac{{\left( {\frac{\part V}{\part T}} \right)_P^2 }} {\left(\frac{\part V}{\part P}\right)_T} \ = \ -T \frac{{ \left( {\frac{\part P}{\part T}} \right) }^2} {\frac{\part P}{\part V}} </math>
:<math> C_p - C_v \ = \ -T \frac{{\left( {\frac{\part V}{\part T}} \right)_P^2 }} {\left(\frac{\part V}{\part P}\right)_T} \ = \ -T \frac{{ \left( {\frac{\part P}{\part T}} \right) }^2} {\frac{\part P}{\part V}} </math>

Revision as of 02:23, 1 July 2008

Heat Capacity Ratio of various gases[1][2][3]
Gas °C k   Gas °C k
H2 −181 1.597 Dry
Air
20 1.40
−76 1.453 100 1.401
20 1.41 200 1.398
100 1.404 400 1.393
400 1.387 CO2 0 1.310
1000 1.358 20 1.30
2000 1.318 100 1.281
He 20 1.66 400 1.235
N2 −181 1.47 NH3 15 1.310
15 1.404 CO 20 1.40
Cl2 20 1.34 O2 −181 1.45
Ar −180 1.76 −76 1.415
20 1.67 20 1.40
CH4 −115 1.41 100 1.399
−74 1.35 200 1.397
20 1.32 400 1.394

The heat capacity ratio of a gas is the ratio of the heat capacity at constant pressure, , to the heat capacity at constant volume, . It is also often referred to as the adiabatic index or the ratio of specific heats or the isentropic expansion factor.

Either (Roman letter k), (gamma) or (kappa) may be used to denote the heat capacity ratio:

where:

= the heat capacity or specific heat of a gas
= the suffix referring to constant pressure conditions
= the suffix referring to constant volume conditions

Ideal gas relations

For an ideal gas, the heat capacity is constant with temperature. Accordingly we can express the enthalpy as and the internal energy as . Thus, it can also be said that the heat capacity ratio of an ideal gas is the ratio between the enthalpy to the internal energy:[3]

The heat capacities at constant pressure, , of various gases are relatively easy to find in the technical literature. However, it can be difficult to find values of the heat capacities at constant volume, . When needed, given , the following equation can be used to determine  :[3]

where is the molar gas constant (also known as the Universal gas constant). This equation can be re-arranged to obtain:


Relation with degrees of freedom

The heat capacity ratio ( ) for an ideal gas can be related to the degrees of freedom ( ) of a molecule by:

Thus for a monatomic gas, with three degrees of freedom:

and for a diatomic gas, with five degrees of freedom (at room temperature):

.

Earth's atmospheric air is primarily made up of diatomic gases with a composition of ~78% nitrogen (N2) and ~21% oxygen (O2). At 20 °C and an absolute pressure of 101.325 kPa, the atmospheric air can be considered to be an ideal gas. A diatomic molecule has five degrees of freedom (three translational and two rotational degrees of freedom, the vibrational degree of freedom is not involved except at high temperatures). This results in a value of:

which is consistent with the value of 1.40 listed for oxygen in the above table.

Real gas relations

As temperature increases, higher energy rotational and vibrational states become accessible to molecular gases, thus increasing the number of degrees of freedom and lowering . For a real gas, and usually increase with increasing temperature and decreases. Some correlations exist to provide values of as a function of the temperature.

Thermodynamic Expressions

Values based on approximations (particularly ) are in many cases not sufficiently accurate for practical engineering calculations such as flow rates through pipes and valves. An experimental value should be used rather than one based on this approximation, where possible. A rigorous value for the ratio can also be calculated by determining from the residual properties expressed as:[4]

Values for are readily available and recorded, but values for need to be determined via relations such as these. See here for the derviation of the thermodynamic relations between the heat capacities.

The above definition is the approach used to develop rigorous expressions from equations of state (such as Peng-Robinson), which match experimental values so closely that there is little need to develop a database of ratios or values. Values can also be determined through numerical derivatives (peturb T and P (independently!) and calculate and ).

Isentropic process

The heat capacity ratio also provides an important relation for an isentropic process of an ideal gas (i.e., a process that occurs at constant entropy):[3]

where, is the pressure and is the volume. The subscripts 1 and 2 refer to conditions before and after the process, or at any time during that process.

See also

References

  1. Frank M. White (1999). Fluid Mechanics, Fourth Edition. McGraw-Hill. ISBN 0-07-0697167. 
  2. Norbert A. Lange (Editor) (1969). Lange's Handbook of Chemistry, 10th Edition. McGraw-Hill, page 1524. 
  3. 3.0 3.1 3.2 3.3 Stephan R. Turns (2006). Thermodynamics: Concepts and Application, First Edition. Cambridge University Press. ISBN 0-521-85042-8. 
  4. Jamal M. Saleh (2002). Fluid Flow Handbook, First Edition. McGraw-Hill, pages 3.5-3.9. ISBN 0-07-136372-6.