Heat capacity ratio

Heat capacity ratio for

various gases[1][2]

Gas Temp. [°C] γ

−181 1.597

−76 1.453

20 1.410

H2 100 1.404

400 1.387

1000 1.358

2000 1.318

He 20 1.66

−180 1.760
Ar
20 1.670

−181 1.450

−76 1.415

20 1.400
O2
100 1.399

200 1.397

400 1.394

N2 −181 1.470

Cl2 20 1.340

Ne 19 1.640

Xe 19 1.660

Kr 19 1.680

Hg 360 1.670

H 2O 20 1.330

100 1.324
Gas Temp. [°C] γ

200 1.310

0 1.310

20 1.300

CO2 100 1.281

400 1.235

1000 1.195

CO 20 1.400

NO 20 1.400

N 2O 20 1.310

−115 1.410

CH4 −74 1.350

20 1.320

NH3 15 1.310

SO2 15 1.290

C 2H 6 15 1.220

C 3H 8 16 1.130

-15 1.404

0 1.403

20 1.400
Dry air
200 1.398

400 1.393

1000 1.365

In thermal physics and thermodynamics,

the heat capacity ratio, also known as the
adiabatic index, the ratio of specific heats,
or Laplace's coefficient, is the ratio of the
heat capacity at constant pressure (CP) to
heat capacity at constant volume (CV). It is
sometimes also known as the isentropic
expansion factor and is denoted by γ
(gamma) for an ideal gas[note 1] or κ
(kappa), the isentropic exponent for a real
gas. The symbol γ is used by aerospace
and chemical engineers.

where C is the heat capacity, the molar

heat capacity (heat capacity per mole),
and c the specific heat capacity (heat
capacity per unit mass) of a gas. The
suffixes P and V refer to constant-pressure
and constant-volume conditions
respectively.

The heat capacity ratio is important for its

applications in thermodynamical
reversible processes, especially involving
ideal gases; the speed of sound depends
on this factor.

Thought experiment
To understand this relation, consider the
following thought experiment. A closed
pneumatic cylinder contains air. The piston
is locked. The pressure inside is equal to
atmospheric pressure. This cylinder is
heated to a certain target temperature.
Since the piston cannot move, the volume
is constant. The temperature and pressure
will rise. When the target temperature is
reached, the heating is stopped. The
amount of energy added equals CV ΔT,
with ΔT representing the change in
temperature.

The piston is now freed and moves

outwards, stopping as the pressure inside
the chamber reaches atmospheric
pressure. We assume the expansion
occurs without exchange of heat
(adiabatic expansion). Doing this work, air
inside the cylinder will cool to below the
target temperature.

To return to the target temperature (still

with a free piston), the air must be heated,
but is no longer under constant volume,
since the piston is free to move as the gas
is reheated. This extra heat amounts to
about 40% more than the previous amount
added. In this example, the amount of heat
added with a locked piston is proportional
to CV, whereas the total amount of heat
added is proportional to CP. Therefore, the
heat capacity ratio in this example is 1.4.
Another way of understanding the
difference between CP and CV is that CP
applies if work is done to the system,
which causes a change in volume (such as
by moving a piston so as to compress the
contents of a cylinder), or if work is done
by the system, which changes its
temperature (such as heating the gas in a
cylinder to cause a piston to move). CV
applies only if , that is, no work
is done. Consider the difference between
adding heat to the gas with a locked piston
and adding heat with a piston free to
move, so that pressure remains constant.
In the second case, the gas will both heat
and expand, causing the piston to do
mechanical work on the atmosphere. The
heat that is added to the gas goes only
partly into heating the gas, while the rest is
transformed into the mechanical work
performed by the piston.

In the first, constant-volume case (locked

piston), there is no external motion, and
thus no mechanical work is done on the
atmosphere; CV is used. In the second
case, additional work is done as the
volume changes, so the amount of heat
required to raise the gas temperature (the
specific heat capacity) is higher for this
constant-pressure case.

Ideal-gas relations
For an ideal gas, the molar heat capacity is
at most a function of temperature, since
the internal energy is solely a function of
temperature for a closed system, i.e.,
, where n is the amount of
substance in moles. In thermodynamic
terms, this is a consequence of the fact
that the internal pressure of an ideal gas
vanishes.

Mayer's relation allows us to deduce the

value of CV from the more easily measured
(and more commonly tabulated) value of
CP:

This relation may be used to show the

heat capacities may be expressed in terms
of the heat capacity ratio (γ) and the gas
constant (R):

Relation with degrees of freedom

The classical equipartition theorem

predicts that the heat capacity ratio (γ) for
an ideal gas can be related to the
thermally accessible degrees of freedom
(f) of a molecule by

Thus we observe that for a monatomic

gas, with 3 translational degrees of
freedom per atom:

As an example of this behavior, at 273 K

(0 °C) the noble gases He, Ne, and Ar all
have nearly the same value of γ, equal to
1.664.
For a diatomic gas, often 5 degrees of
freedom are assumed to contribute at
room temperature since each molecule
has 3 translational and 2 rotational
degrees of freedom, and the single
vibrational degree of freedom is often not
included since vibrations are often not
thermally active except at high
temperatures, as predicted by quantum
statistical mechanics. Thus we have

For example, terrestrial air is primarily

made up of diatomic gases (around 78%
nitrogen, N2, and 21% oxygen, O2), and at
standard conditions it can be considered
to be an ideal gas. The above value of 1.4
is highly consistent with the measured
adiabatic indices for dry air within a
temperature range of 0–200 °C, exhibiting
a deviation of only 0.2% (see tabulation
above).

For a linear triatomic molecule such as

CO2, there are only 5 degrees of freedom
(3 translations and 2 rotations), assuming
vibrational modes are not excited.
However, as mass increases and the
frequency of vibrational modes decreases,
vibrational degrees of freedom start to
enter into the equation at far lower
temperatures than is typically the case for
diatomic molecules. For example, it
requires a far larger temperature to excite
the single vibrational mode for H2, for
which one quantum of vibration is a fairly
large amount of energy, than for the
bending or stretching vibrations of CO2.

For a non-linear triatomic gas, such as

water vapor, which has 3 translational and
3 rotational degrees of freedom, this
model predicts
Real-gas relations
As noted above, as temperature increases,
higher-energy vibrational states become
accessible to molecular gases, thus
increasing the number of degrees of
freedom and lowering γ. Conversely, as
the temperature is lowered, rotational
degrees of freedom may become
unequally partitioned as well. As a result,
both CP and CV increase with increasing
temperature.

Despite this, if the density is fairly low and

intermolecular forces are negligible, the
two heat capacities may still continue to
differ from each other by a fixed constant
(as above, CP = CV + nR), which reflects
the relatively constant PV difference in
work done during expansion for constant
pressure vs. constant volume conditions.
Thus, the ratio of the two values, γ,
decreases with increasing temperature.

However, when the gas density is

sufficiently high and intermolecular forces
are important, thermodynamic
expressions may sometimes be used to
accurately describe the relationship
between the two heat capacities, as
explained below. Unfortunately the
situation can become considerably more
complex if the temperature is sufficiently
high for molecules to dissociate or carry
out other chemical reactions, in which
case thermodynamic expressions arising
from simple equations of state may not be
adequate.

Thermodynamic expressions

Values based on approximations

(particularly CP − CV = nR) are in many
cases not sufficiently accurate for
practical engineering calculations, such as
flow rates through pipes and valves at
moderate to high pressures. An
experimental value should be used rather
than one based on this approximation,
where possible. A rigorous value for the
CP
ratio C can also be calculated by
V
determining CV from the residual
properties expressed as

Values for CP are readily available and

recorded, but values for CV need to be
determined via relations such as these.
See relations between specific heats for
the derivation 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 CV values.
Values can also be determined through
finite-difference approximation.

Adiabatic process
This ratio gives the important relation for
an isentropic (quasistatic, reversible,
adiabatic process) process of a simple
compressible calorically-perfect ideal gas:

is constant
Using the ideal gas law, :

is constant
is constant

where P is the pressure of the gas, V is the

volume, and T is the thermodynamic
temperature.

In gas dynamics we are interested in the

local relations between pressure, density
and temperature, rather than considering a
fixed quantity of gas. By considering the
density as the inverse of the
volume for a unit mass, we can take
in these relations. Since for
constant entropy, , we have , or
 , it follows
that

For an imperfect or non-ideal gas,

Chandrasekhar[3] defined three different
adiabatic indices so that the adiabatic
relations can be written in the same form
as above; these are used in the theory of
stellar structure:
All of these are equal to in the case of an
ideal gas.

See also
Relations between heat capacities
Heat capacity
Specific heat capacity
Speed of sound
 Thermodynamic equations
Thermodynamics
Volumetric heat capacity

References
1. White, Frank M. (October 1998). Fluid
Mechanics (4th ed.). New York: McGraw
Hill. ISBN 978-0-07-228192-7.

2. Lange, Norbert A. (1967). Lange's

Handbook of Chemistry (10th ed.). New
York: McGraw Hill. p. 1524. ISBN 978-0-07-
036261-1.

3. Chandrasekhar, S. (1939). An Introduction

to the Study of Stellar Structure. Chicago:
University of Chicago Press. p. 56.
ISBN 978-0-486-60413-8.
Notes
1. γ first appeared in an article by the French
mathematician, engineer, and physicist
Siméon Denis Poisson:
Poisson (1808). "Mémoire sur la
théorie du son" (https://babel.hathitrus
t.org/cgi/pt?id=mdp.39015074785588
&view=1up&seq=327) [Memoir on the
theory of sound]. Journal de l'École
Polytechnique (in French). 7 (14): 319–
392. On p. 332, Poisson defines γ
merely as a small deviation from
equilibrium which causes small
variations of the equilibrium value of
the density ρ.
In Poisson's article of 1823 –
Poisson (1823). "Sur la vitesse du son"
(https://babel.hathitrust.org/cgi/pt?id=
iau.31858046217836&view=1up&seq=
11) [On the speed of sound]. Annales
de chimie et de physique. 2nd series
(in French). 23: 5–16.
γ was expressed as a function of density D
(p. 8) or of pressure P (p. 9).
Meanwhile, in 1816 the French
mathematician and physicist Pierre-Simon
Laplace had found that the speed of sound
depends on the ratio of the specific heats.
Laplace (1816). "Sur la vitesse du son
dans l'air et dans l'eau" (https://babel.h
athitrust.org/cgi/pt?id=hvd.hx3dvc&vie
w=1up&seq=244) [On the speed of
 sound in air and in water]. Annales de
chimie et de physique. 2nd series (in
French). 3: 238–241.
However, he didn't denote the ratio as γ.
In 1825, Laplace stated that the speed of
sound is proportional to the square root of
the ratio of the specific heats:
Laplace, P.S. (1825). Traité de
mecanique celeste (https://babel.hathi
trust.org/cgi/pt?id=gri.ark:/13960/t9d5
32b05&view=1up&seq=137) [Treatise
on celestial mechanics] (in French).
Vol. 5. Paris, France: Bachelier.
pp. 127–137. On p. 127, Laplace
defines the symbols for the specific
heats, and on p. 137 (at the bottom of
the page), Laplace presents the
 equation for the speed of sound in a
perfect gas.
In 1851, the Scottish mechanical engineer
William Rankine showed that the speed of
sound is proportional to the square root of
Poisson's γ:
Rankine, William John Macquorn
(1851). "On Laplace's Theory of Sound"
(https://babel.hathitrust.org/cgi/pt?id=
umn.31951000614090i&view=1up&se
q=239) . Philosophical Magazine. 4th
series. 1 (3): 225–227.
It follows that Poisson's γ is the ratio of the
specific heats — although Rankine didn't
state that explicitly.
See also: Krehl, Peter O. K. (2009).
History of Shock Waves, Explosions
 and Impact: A Chronological and
Biographical Reference (https://books.
google.com/books?id=PmuqCHDC3p
wC&pg=PA276) . Berlin and
Heidelberg, Germany: Springer Verlag.
p. 276. ISBN 9783540304210.

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