Chapter 4 Isolated Paramagnet Subsystems and Temperature 4.

.1 Microscopic states and thermodynamic equilibrium So far only one new concept has been introduced beyond the dynamic of the system, which is the probabiity within a set of states, or an ensemble. It is time to try and connect this new concept with thermodynamic quantities. The firs among these is the temperature. We turn therefore to the identification of the relative temperature of two systems. obviously, in order to discuss temperatur we need at least two systems, since the temperature is precisely the intensive variable, whose equality characterizes the equilibrium between them when there is no mechanical interaction. We choose, therefore, two paramagnetic systems: System with N spin and a magnetic field H , System b with Nb spin and a magnetic field Hb . We isolate both systems from the rest of the universe, but allow them to interact thermally. This means that the total energy of the two systems E, will be constant but the energies of the two systems E and Eb are unconstrained provided E + Eb = E. No forces will act between the spins, except for the tiny forces we mentioned earlier which drive the system towards thermal equilibrium namely, to uniform occurrence rates of all microscopic states of the combined isolated system, as explained in chap.3. The energy of a given state of system is E = and that of system b is Eb = E - E 4.2 and the temperature If the number of states of system with energi E is (E), then system b has (E - E) states, and the total number of states of the composite system, for which system has energy E is (2.4.2)
B

(2.4.1)

T = (E , H , N) . (Eb , Hb , Nb) = (E , H , N) . (E - E , Hb , Nb) (2.4.3)

Where we have emphasized the dependence of both factors on the number of spins of the subsystems and on the magnetic field of each of them. The rest of the argument has the following structure: When the numbers N and Nb are very large, there exists a value of E, which we denote by , for which T is maxsimal. Moreover, the maximum is extremely sharp, and the number of states in which E differs from is, relatively, very small. This will be the equilibrium state, because if the combined system visits all the states with total energy E at the same frequency, it will almost always be in a state for which E = . In this case we can identify the intensive quantity that becomes equal in the two subsystems. This quantity will be called the temperature. In order to proced, we write (2.4.3) in the form T = exp (
( ) ( )

(2.4.4)

Where for each system we have defined separately = ln The number of states attains its maximum at , which may be determined by the requirement that the derivative of the exponent with respect to E should vanish, or
( )

| =

| b ,

(2.4.5a)

Where Eb is not an independent variable but satisfies Eb = E - E and b = E - and has the dimensions of energy to the power of 1. Since is a monotonic function of S, if S has a maximum is maximal as well. In conclusion, we found an intensive quantity which characterizes the maximum of T and has the same value in the two subsystems. We called this quantity . Second, if we also find that almost all the states of the composite system satisfy E = , then this will be the systems thermal equilibrium state. 4.2 and the temperature

Before we proceed to prove the sharpness of the maximum, let us identify the quantity in our model of a paramagnet. came about from equilibrium conciderations between two systems dan b, but it is possible to define it in general for a single paramagnetic system with a given Energy E : =
( )

(2.4.5b)

The entropy S of an isolated paramagnet is given by Eq.(2.3.13) and by differentiating it be obtain = ln *( ) ( ) + (2.4.6)

Recalling the expression (2.3.7) and (2.3.8), for the probabilities for a spin to point up or down, we can write = ln * From which we obtain the interesting result
( ( ) ) ( ( ) )

(2.4.7)

(2.4.8)

Exercise 4.1 Use Eq. (2.4.8) to calculate ( Solution on page 201 Namely, if we knew that = , then (2.4.8) would be the expression for the ) and ( ). Compare to (2.3.7) and (2.3.8).

Boltzmann distribution, as in part I. That is, the ratio of the probabilities of the two states is , where = is their energy difference.

But a present we canot conclude that 1/ is proportional to an absolute temperature, only that it is an increasing function of the relative temperature since even after demonstrating the sharpness of the maximum, we will only know that is identical for systems at thermal equilibrium with each other. In order to identify as defined by Eq. (2.4.5) as an absolute temperature, we have to show that it connects the entropy change with the heat increase, or

that it may be identified from the ideal gas law. However, we may note that if S is indeed the entropy, then (2.4.5b) is the connection between the entropy and the absolute temperature. 4.3 Sharpness of the maximum In order to find the behavior of the number of states of the combined system as a function of E near its maximum, we will use the expression for (E) when N 1, i.e. Eq. (2.3.14).

Inserting it into Eq.(2.4.3) and taking for simplicity H = Hb = H , we obtain T = C Cb exp ( ) exp [
( )

],

(2.4.9)

Where C and Cb are normalization constants that depend on N and Nb. Interms of the entropy we obtain ST = ( ) = ln T = ln (C Cb) *
( )

(2.4.10)

Next we find the maximum of the entropy. Since (2.4.10) is a quadratic function of E , there is no need to diferentiate with respect to E ; it is enough to complete the expression in brackets to a square:
( ) ( )

+ ) +

= so that ST = ln (C Cb) [ (

(2.4.11)

(2.4.12)

This is quadratic function of

whose maximum is attained at = (2.4.13)

As will immediatelly be shown, T has a sharp maximum at this energy, so that this will also be the average of E. We see therefore, that the energy is distributed between the two systems in direct proportionality to their size. In order to show that the overwhelming majority of states are concentrated around E = , We return to T , and rewrite it using (2.4.12) in the form

T(E) = CT exp *

) +,

(2.4.14)

Where the constant CT includes all the factors which do not depend on E.