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The Simple Ideal Gas PDF
The Simple Ideal Gas PDF
12. T H E I D E A L G A S
The two extreme idealized thermodynamic systems are the ideal gas and the perfect crystal.
In the first the arrangement of molecules (or atoms) is completely random, in the second it
is perfectly ordered. The thermodynamic properties of an ideal g a s are particularly
instructive because of their relative simplicity. The simplest ideal gas is the m o n a t o m i c ideal
gas which will be discussed in the next chapter. Any real gas, monatomic or not, appro-
ximates the behavior of an ideal gas in the limit that T ~ oo and P ---+ O.
12.1 The Fundamental Equation of the Ideal Gas in the Entropy Representation
12.2 The Equations of State of the Ideal Gas in the Entropy Representation
12.3 Equivalence of the Complete Set of the Equations of State
with the Fundamental Equation
12.4 Empirical Ideal Gas Laws
12.5 The Primary Set of Partial Derivatives for an Ideal Gas
12.6 The Fundamental Equations of the Ideal Gas in Parametric Form
12.7 The Fundamental Equations of the Ideal Gas in Parametric Form
in Terms ofcv (T)
12.8 The Fundamental Equations of the Ideal Gas in Parametric Form
in Terms ofcp(T)
12.9 The Fundamental Equation of the Ideal Gas in the Free Energy
Representation
12.10 The Fundamental Equation of the Ideal Gas in the Free Enthalpy
Representation
12.11 The Cfibbs-Duhem Equation ofthe Ideal Gas
12.1 The Fundamental Equation of the Ideal Gas in the Entropy Representation
Although thermodynamic theory does not depend on the existence of an explicit
form of the fundamental equation (cf. w 3), it is, nevertheless, useful to learn how the theory
applies when such a fundamental equation is available. The ideal gas presents us with the
opportunity of studying the properties of a rather simple fundamental equation. The ideal
rubber offers another such opportunity (cf. w 17.15).
The fundamental equation of an ideal gas cannot be derived within phenomeno-
logical thermodynamic theory. It can be obtained, however, in the entropy representation
from a complete set of the equations of state (cf. w 12.3), and can also be derived with the
help of classical statistical mechanics and quantum mechanics. Appendix 4 gives a short
account of the derivation of the (molar) fundamental equation of the single-component ideal
gas in the entropy representation. It leads to
depends simultaneously on both u and v and thus satisfies the requiremen~ for ideal beha~4or
as formulated in w 11.2. The function f(u) is a function of u only. Its explicit form differs
from gas to gas but it will always be such that t~uo)= 0.Because ~u) is not known
explicitly in general, Eq.(12.1)1 cannot be solved for the molar fimdamental equation in the
energy representation, u = u(s, v).
In terms of the mole number, N, Eq.(12.1)l becomes
& VN.
s = u~ + m(U/N) + N R n, (12.1)2
.zvo YoN
as the general form of the fimdamental equation of a single-co~onent Meal gas in the
entropy representation. In the remainder of this chapter 'ideal gas' ~ refer to a single-
component ideal gas unless otherwise stated.
12.2 The Equations of State of the Ideal Gas in the EnWopy Representation
Because we have no expficit fimdamental equation of the idea} gas m the energy
representation, we derive the three equations of state of the ideM gas in the entropy
representation. For the first equation we find
1 OS ] -- N di~U/N) d~u)
T -- OU V,N dU -- du (IZ2)i
i cNR cR
m
(12.2)2
T U u
P OS NR R
w
~ (12.2)a
T - o V U,N V v
PV = NR_T or P v = RT (12.2h
76 I. EQUILIBRIUM THERMODYNAMICS
and has the same form for aH ideal gases including the multicomponent ideal gas
(cf. w 15.3). The second equation of state is sometimes referred to simply as THE equation
of state of the ideal gas or THE ideal gas equation o f state.
Introducing the equations U = c N R T and P V = N R T into H = U + P V it is
seen at once that the enthalpy of an ideal gas also depends only on the temperature a p ~
from the mole number, N.
To derive the third equation of state we turn to Eq.(3.I1)4.2. We find
os I
T -- - ~ON u, v = O N -~o + Nf(U/N) + N R h~ VNo
Iron
] (12.2),
i.e.,
_ Of(U/N____)) VNo o z~ N
# So flU~N)- N ON - R In VoN + N R O---N' (12.2)6
T No
so that
or
Of(U/N) df(u)
(12.2)9
O(U/N) a~ '
and this equals 1 / T by Eq.(12.2h. Equations (12.2)7 and (12.2)8 represent the third
equation of state of a single-component ideal gas.
1 P #
s = --u + - - v - -- (12.3)t
T T T'
T = u/cR (12.3)2
P = RT/v (12.3)3
and
# = - soT - T f(u) + u - R T I n v / v o + R ~ (12.3)4
into the molar form of the Euler equation in the energy representation,
u = T s - P v + #, (12.3)5
might lead to the fundamental equation in the energy representation, is not borne out.
In fact, doing so leads to
10V 1
O~pm - (12.5h
V OT p T
78 I. EQUILIBRIUM T H E R M O D Y N A M I C S
1 OV 1
KT = - ~ (12.5)2
V OP
These two relations apply to any ideal gas, thus also to the monatomic and
multicomponent ideal gases to be discussed in detail in Chapters 13 and 15.
The same cannot be said about the isochoric and the isobaric heat capacities of an
ideal gas. Differentiation of the entropy, Eq.(12.1)2, with respect to the temperature shows
that the heat capacities of an ideal gas are functions of f(u) and, therefore, generally, of the
temperature. The monatomic ideal gas is an exception (see w 13). Since flu) differs from gas
to gas for all other ideal gases, so also do Cv(T) and Cp(T). However, combining
Eq.(10.3)3, i.e., ce = cr + Tva2/tr with the equation of state, Pv = RT, gives the
molar heat capacity difference of any ideal gas as
which, for the monatomic ideal gas becomes simply c p - cv = R, and for any component
ofa multicomponent ideal gas takes the form cpi(T) - cvi(T) = R (cf. w 15.4).
du = c v ( T ) d T . (12.7)1
u = Uo + c y ( T ' ) dT ~, (12.7)2
,)
f(u)= T' dT'. (12.7)3
s = 3o +
f Tcv(T') dT" + R In V/Vo (12.7)4
To T"
Equations (12.7)2 and (12.7)4 are the molar parametric equations for a single-component
ideal gas in terms of cy (T), the molar heat capacity at constant volume.
Eq.(12.7)3 yields
or
where Po = RTo / Vo. Equations ( 12.8)t with ( 12.8)3 o r with (12.8)4 form alternative pairs
of the molar parametric equations of the single-component ideal gas in terms of cp(T), the
molar heat capacity at constant pressure.
12.9 The Fundamental Equation of the Ideal Gas in the Free Energy Representation
To derive the expression for the fundamental equation of the ideal gas in the free
energy representation, we first multiply the expressions for the molar parametric equations
written in terms of the heat capacity at constant volume, cv(T), by the number of moles,
N. This leads to
with Fo = U o - TSo, as the fundamental equation of the ideal gas in the free energy
representation
12.10 The Fundamental Equation of the Ideal Gas in the Free Enthalpy Representation
To obtain the fundamental equation of the ideal gas in the free enthalpy
representation we use the parametric equations written in terms of the heat capacity at
constant pressure, cp(T), since we need the pressure as another canonical variable m this
case. By multiplying with the number of moles, N, we obtain
12. THE IDEAL GAS 81
S = N S~ flT
No + N j7
cp(T') d T ' - N R In P / P o (12.10)2
~o T"
with Go = U o - TSo + PoVo, as the fundamental equation of the ideal gas in the free
enthalpy representation.
With the help of Eqs. (12.8)1 and (12.8)2 and the use o f P v = ~ this becomes
= v o ( T ) + P,T tn P / P o (12.11h
where
~~T" T
r e ( T ) = ~o - T~o + R-To + ~r= cp(T') dT'. (12.11)3
or, alternatively,
The function #o(T) is the standard chemical potential at the temperature T and the
standard (reference) pressure Po. The zero s-ubscript in #o(T) refers to this pressure. Thus
#o(T) is standard with respect to a standard pressure but it is a ~ c t i o n of temperature.
Equation (12.11)2 with either (12.11)3 or (I 2.11)4 provides a functional relation
between the intensive parameters T, P, and #. They thus together represent the integrated
82 I. EQUILIBRIUM T H E R M O D Y N A M I C S
form of the Gibbs-Duhem equation of the ideal gas in terms of the molar heat capackies at
constant pressure or constant volume. Behavior in accordance with Eq.(12.11)2 constitutes
a sufficient cotutition for the ideal behavior of a gas.