have simple forms: dU dH dA dG = = = = T dS P dV T dS + V dP SdT P dV SdT + V dP.

(1) (2) (3) (4)

0.2

Maxwell Relations
U S =T
V

The rst equation implies that (5)

and

U V

= P.
S

(6)

The second derivatives are equal, however: 2U 2U = , SV V S so T V T P S V and S P =

S

(7)

P S V S P T V T

.
V

(8)

In a similar way, we nd =
S

,
P

(9) (10)

=
T

.
V

=
T

.
P

(11)

from the dierential equations for the other three potentials. These four equations are called the Maxwell relations. From them we can deduce immediately some interesting facts. For example, for most (but not all) systems V increases on heating at constant pressure: (V /T )P 0. This means that (S/P )T 0. So the entropy normally decreases on compression at constant temperature, not nearly so obvious as the rst statement. A second example relates to the specic heat at constant volume, Cv . Cv = Hence dQ dT =
V

U T S V 2

=T
V

S T

.
V

(12)

Cv |T = T V

= T
T

2P T 2

.
V

(13)

The right-hand-side depends only on the equation of state of the system. Once this is known, then the volume dependence of the specic heat is known. More complicated examples of uses of the Maxwell relations abound. One of the most often encountered is the equation relating the specic heat at constant volume Cv = T (S/T )v (which is easily calculated) to the specic heat at constant pressure Cp = T (S/T )P (which is easily measured). This requires a short digression into the subject of Jacobians. Consider two functions w(y, z ) and x(y, z ). The area dw dx in the w x plane is related to the area dy dz in the y z plane by dw dx = where (w, x) = (y, z )
w y z x y z w z y x z y

(w, x) dy dz, (y, z )

(14)

= J.

(15)

J is the Jacobian of the transformation from w, x to y, z . The straight brackets indicate the determinant. Note that J = J (y, z ). A special case is (w, x) = (y, x) w y .
x

(16)

In case there is yet a third set of variables s, t, the Jacobian satises a product rule (w, x) (w, x) (s, t) = . (y, z ) (s, t) (y, z ) (17)

S is expressed in terms of We wish to make a change of variables. Cv = T T V temperature and volume. We wish to transform to temperature and pressure. Write

Cv = T

(S, V ) (S, V ) (T, P ) =T (T, V ) (T, P ) (T, V ) V S S = T T P P T P T S T T

P

(18) V T P V P V (19)
T

= T

S P

V T

(20)
T 1 V V T

Now for any substance, we dene the thermal expansion coecient

1 V fractional change in volume per degree and T V = isothermal compressP T ibility. Both depend only on the equation of state. Putting these results together with the Maxwell relation V S = , (21) P T T P

we nd Cv = T S T +T
P

V T

P V

.
T

(22)

Substituting the denitions above gives Cv = C p T V or, as is more often seen, Cp C v = T V 2 , T (24) 2 , T (23)

Since T > 0,(as we shall see below), Cp > Cv . For an ideal gas = and T = 1 V 1 V V T =
P

1 V

N kT Nk 1 = = , P PV T

(25)

V P

=
T

N kT 1 N kT = 2 = 1/P. V P P P V

(26)

Hence Cp Cv = T V T 2 P = P V /T = N k . In the dimensionless heat capacities per particle cp = Cp /N k and cv = Cv /N k , we have cp cv = 1. For solids, it is almost always the case that the volume changes little in, say, doubling the temperature at constant pressure. (Think of the metal grill in an oven). Hence (T /V )(V /T ) P << 1 and cp cv .

0.3

The Third Law

This law of nature is not as rmly based or as universal as the rst two laws of thermodynamics. It states that the entropy of any system at zero temperature is zero: S (T = 0) = 0. We will discuss the conditions of validity of this law later on. For now, let us just mention some of the consequences of the law. Consider heating a substance at constant volume starting at T = 0 and ending up in some nal state at temperature Tf . The nal entropy is S (T ) =
0 Tf

CV dT. T

Now if CV = a + bT + cT 2 + ..., then the third law implies that a = 0. The same holds true for a process at constant pressure. All heat capacities must vanish at T = 0. This is not consistent with the relation we just deduced for ideal gases that cp cv = 1. At very low temperatures, ideal gases cannot exist. Indeed, gases do not exist at very low temperatures, as experiment has shown. The lowest boiling point for any substance at atmospheric pressure is 4.2K for helium. Near absolute zero, only helium even remains liquid; all other substances solidify. For liquids and perfectly 4