Thermal equilibrium

The quantity with which thermodynamics concerns itself especially and uniquely is temperature. This quantity has meaning only for large systems, where by large we mean having a large number of degrees of freedom. The number of degrees of freedom in a system is directly related to the number of fundamental constituents in the systemin general, the number of moleculesthat make it up. We will usually be talking about systems with 1023 molecules in them, which makes them truly large. Temperature is an average property of a system. In a nite system we can reasonably expect there to be uctuations in the temperature, just as there were uctuations in the number of molecules in the top or bottom half of the box that we looked at in the previous lecture. These uctuations will be small for a large system, just as the uctuations in the box were, in a percentage sense. The temperature will have uctuations that are, in a percentage sense, on the order of 1/ N , where N is the number of degrees of freedom in our system. That is, if we say that the temperature of a system with N degrees of freedom is T0 , what that means is that at any given point in time the temperature will be T0 [1 A/ N ], where A is a xed number. We have an intuitive notion of what temperature is. It measures how hot something is: the higher the temperature, the hotter the object. Temperature thus has a relative meaning. It also has an absolute meaning, in that we can quantify the temperature of an object. That is, we can assign a number to the temperature, and we can use that number to characterize not only how hot that object is, but also how hot any object is that happens to be at that temperature. Note that such a quantication is possible only if equality of temperature has some of the properties of an equivalence relation. In fact, it has all the properties of an equivalence relation. To see that this is so, lets devise, for our temporary use, a symbol to denote temperature equality. T T Here it is: =. Sothe mathematical statement A = B means system A is at the same temperature as system B. Temperature equality has the following three properties: 1. Reexivity: A = A. A system is at the same temperature as itself. 2. Symmetry: If A = B then B = A. If system A is at the same temperature as system B, then system B is at the same temperature as system A. 12
T T T

3. Transitivity: If A = B and B = C, then A = C. If systems A and B are at the same temperature, and systems B and C are also at the same temperature, then systems A and C are at the same temperature. Now, the notion of temperature is one that applies in equilibrium only. In particular, it applies when there is thermal equilibrium. An iron rod that is red-hot at one end and ice-cold at the other is not in thermal equilibrium, and cannot be said to be at a single temperature. If left alone, and suciently isolated from its environment, the rod will eventually settle into a state in which it is at a uniform temperature throughout. We think of thermal equilibrium as a state that is spontaneously achieved by a system left to itself. It is also achieved by a pair of system left alone but allowed to interact appropriately. The appropriate form of interaction occurs when the systems are in thermal contact. Basically, this means that they are touching, or are close enough to each other that they can exchange heat. The notion of heat plays a fundamental role in thermodynamics. In the early development of this eld, heat was thought of as some kind of a uid (called caloric) which contained hotness. Nowadays we recognize heat as a kind of energy. What takes place between two systems in thermal contact is energy exchange. Energy ows from the hotter systemthe system at higher temperatureto the colder system. This ow continues until they are at the same temperature. The properties of temperature and the notion of thermal equilibrium as a state in which everything is at the same temperature and as a state to which systems naturally tend constitutes the zeroth law of thermodynamics. The rst law of thermodynamics can be understood in two ways. First, we can think of it as the law of conservation of energy. Second, we can think of this law as a denition of heat. It applies to a system that has undergone some change in which (a) some heat has owed into or out of the system, (b) some work was performed by or on the system and (c) the systems internal energy has changed. If we let d Q be the amount of heat that has owed into the system, d W equal the amount of work performed by the system and dU equal the change in the internal energy of the system, the rst law presents us with the equality dU = d Q d W (41) Note the lines throught the ds in d Q and d W . This is to distinguish between these two quantities and dU . Lets take a little time to discuss this distinction. 13

State variables
A state variable is a quantity that characterizes some aspect of a system in thermal equilibrium. Temperature is just such a quantity. Another one is volume; pressure is a third. A system at thermal equilibrium is at some specic temperature, occupies a certain volume and is subject to a welldened pressure. These state variables take on values that are determined by the current state of a system in thermal equilibrium. They are indepenedent of the history of the system. The internal energy of a system is a state variable. Although energy is uniquely dened only to within an additive constant, once we have established a zero for energy a system can be said o have a perfectly well-dened energy in thermal equilibrium. The change in energy in the rst law as written above appeard in the form dU . This is to signify that what we are representing is the dierence between two values of a variable that takes on a denite value in the equilibrium state of a system. By contrast, the two other terms, d Q and d W are not representable as dierences between two state variables. A state in thermal equilibrium does not have a certain amount of heat or a certain amount of work in it. We can imagine performing the following procedure on a container of liquid:

Rotating this shaft stirs theliquid, which heats up

Heat is drawn off through the walls

Figure 3: The Joule paddle experiment. If the amount of heat energy that is drawn out of the liquid equals the amount of work performed in stirring the liquid, then we can continue allowing the process pictured above to operate for an arbitrarily long time, performing an arbitrarily large amount of work on the liquid and siphoning o an arbitrarily large amount of heatin the end, not having changed the liquids internal 14

energy, or, indeed, any other aspect of the system. Thus, neither work nor heat satises the criteria for a state variable. There is a state variable related to heat. We will need to go into the second law of thermodynamics before we can develop it. First, lets discuss a simple thermodynamic system.

The ideal gas

Ideal gases satisfy two laws: P V = N kB T U = N f (T ) Here, P is the pressure under which the gas is kept. V is the volume it occupies. N is the number of molecules in the gas. T is the temperature of the gas. U is the internal energy of the gas, and kB is a constant (actually a conversion factor) called the Boltzmann constant. In the case of the monatomic ideal gas, 3 f (T ) = kB T 2 (44) (42) (43)

The ideal gas law (42) implies a temperature scale. We will adopt this scale without further discussion, at least for the time being. As we will see when we get into a deeper discussion of the second law there is a natural scale for temperatures. This scale turns out to be the same as the scale implied by (42) and (44). Let us see how the rst law operates when applied to a simple process involving a cylinder of an ideal gas. Suppose the gas were to push the piston up by a short distance x. The amount of work, d W , performed by the gas

15

Figure 4: A cylinder of gas that is compressed or allowed to expand, through the action of a movable piston. equals the force it exerts on the piston times the displacement of the piston, x. Thus d W = P A x = P [Ax]

(45)

Now, Ax is the amount of extra volume occupied by the gas now that the piston has been moved outwards. Thus, we also have in this case d W = P dV . As it turn out, this formula holds when the volume of the gas changes in more complicated ways. Thus, we may write for the rst law as applied to a simple process involving a volume change of the gas dU = d Q P dV (46)

Note that in order for this expression to apply, the force exerted by the gas on the piston must be the force the gas applies to its container in thermal equilibrium. In other words, the expansion has to take place reasonably slowly. If the expansion is too rapid, there are complications. Lets now consider two ways in which the gas can expand from an initial volume, Va , to a nal volume, Vb . The two kinds of expansion that we will look at are isothermal and adiabatic.

16

Isothermal expansion If the temperature of the gas in the container is held constant and the gas is allowed to expand slowly, we have nkB T dV (47) d W = P dV = V so the total amount of work performed in the expansion is Vb nk T Vb B P dV = dV V Va Va Vb dV = N kB T Va V Vb = N kB T ln (48) Va Because the temperature of the gas does not change, the internal energy of the gas remains constant, which means that, by the rst law, there is a ow of heat into the cylinder that compensates for the energy loss due to work performed by the gas on the piston. In other words 3 dU = d N KB T 2 = 0 = d Q P dV (49) So d Q = P dV = nkB T dV /V , and the total amount of heat that ows into the system is equal to N kB T Vb dV = N kB T ln (50) V Va Va Conversely, we can imagine an isothermal compression of the gas from a volume Vb to a volume Va in which the work done on the piston by the gas is Va Vb N kB T ln = N kB T ln (51) Vb Va and in which the net heat ow out of the gas and into the environment is N kB T ln(Vb /Va ). A slow istothermal expansion from Va to Vb followed by a slow isothermal compression back to Va leaves everythingthe gas, its container and the surrounding environmentsexactly as it started. In other words, a slow isothermal expansion, or a slow isothermal compression, can be entirely undone. Both are reversible processes. 17
Vb

Adiabatic expansion An adiabatic process involves no heat transfer between the gas and its environment. That is, d Q will equal zero in this process. Once again, we will consider only slow processes. Imagine, now, a slow expansion by a thermally isolated cylinder of ideal gas, from a volume Va to a volume Vb . From the rst law, we have dU = P dV (d Q = 0) (52) We also have dU = d = so, 3 N kB dT = P dV 2 N kB T dV = V or si that 3 T dT = dV 2 V 3 N kB T 2 (53)

3 N kB dT 2

(54)

(55)

dT 2 dV = T 3 V If we integrate both sides of this equation, we obtain ln or 2 V T = ln T0 3 V0

(56)

(57)

T V 2/3 = (58) T0 V0 Since V0 , the initial volume, is Va , and the nal volume is Vb , we have Tb = Ta Va Vb
2/3

(59)

As the volume increases, the temperature drops, which is to be expected, as the internal energy of the gas, which performs work on the piston, also drops. 18

The total amount of work performed by the gas in expanding is the difference between the initial and the nal internal energy, there being no heat exchange to contribute to the right hand side of the rst law. This mean sthat the total work done is given by Va 3 3 3 N kB Ta N kB Tb = Ta 1 2 2 2 Vb The pressure at Vb is given by Pb Vb = N kB Tb = N kB Ta This means that Pb = N kB Ta Va2/3 Vb
5/3 2/3 2/3

(60)

Va Vb

(61)

(62)

Instead of falling o like 1/Vb , as it did in the case of isothermal expansion, 5/3 the pressure falls o like Vb . On the basis of this consideration alone we can infer that the gas does less work in expanding adiabatically from Va to Vb than in expanding between the same two volumes isothermally. Like the slow isothermal process, the adiabatic process discussed above can be performed in reverse, and, hence, undone. It is also reversible.

The two specic heats of an ideal gas, cV and cP

The specic heat of a substance tells us how much heat must be fed under certain circumstances to raise the temperature a xed amount of that substance a given number of degrees. Well start with a more general quantity, the heat capacity. This quantity is dened, generically as the following ratio C= dQ dT (63)

The right hand side of (63) is the ratio of the heat fed in to the temperature increase. Referring, again, to our cylinder of ideal gas, we can imagine feeding the heat into the container under one of two conditions: 1. The container is kept at constant volume. 19

2. The container is kept under a constant presssure. In the rst case, we may dene a heat capacity at constant volume, CV , by CV = dQ dT (64)
V

In the second case, the heat capacity at constant pressure is given by CP = dQ dT (65)
P

Let us see what these ratios are equal to for the ideal gas Constant volume We have dU = d Q or d 3 N kB T 2 3 N kB dT 2 = dQ = 3 = N kB 2 (P dV = 0) (66)

(67)

so

dQ dT

(68)

The heat capacity of a set of N molecules of monatomic ideal gas in a container kept at xed volume is 3 N kB . 2 Constant pressure At constant pressure, the rst law tells us that dU = P dV + d Q which means that d Q is given by d Q = dU + P dV (70) (69)

20

Since P V = N kB T , we have for a system at constant pressure, P , P dV = N kB dT Furthermore, dU = d = so 3 N kB dt + N kB dT dQ = 2 5 N kB dT = 2 and CP = dQ dT 3 N kB T 2 (72) (71)

3 N kB dT 2

(73)

5 N kB T = 2 Notice that CP > CV , and that both are positive.

(74)

An irreversible expansion
Suppose we were to allow the gas in the cylinder to expand as follows: In step a in Figure 5, a partition slides in immediately below the piston. In step b, the piston is raised. No work is done on it because there is no gas below it. We are assuming that the environment is a perfect vacuum, so there is no gas outside the container pushing the piston down. Finally, in step c, the partition is removed, and the gas lls the volume below the raised piston. Because the partition is innitesimally thin (an assumption here) no work is required to push it in, nor is there any work done by the gas when it is removed. Finally, we assume that there is no heat exchange with the environment during this process. Thus, both d W and d Q are equal to zerowhich means that the internal energ, and hence, the temperature of the gasis unchanged. If we want to return the volume of the gas to its 21

Figure 5: A three-step irreversible expansion in a container of ideal gas original value, we can try slow compressionseither isothermal or adiabatic, and see what is involved. Lets assume that the original volume of the gas was Va and that it expanded in the above process to a volume Vb . In an adiabatic compression we will have had to perform an amount of work given by 3 Vb 3 nkB T0 + N kB T0 2 2 Va
2/3

3 = N kB T0 2

Vb Va

2/3

(75)

Here, T0 is the temperature of the expanded gas. Furthermore, the temperature of the gas will have increased as the result of the adiabatic compression. The increase is from T0 to T0 (Vb /Va )2/3 . Thus, in compressing the gas, we have heated it up at the expense of externally supplied energy. In an isothermal compression, the temperature of the gas has remained constant, which means that its internal energy has not changed. We have had to perform work to eect the reversal of the free expansion. The net amount of this work is Va Va dV P dV = N kB T0 V Vb Vb Vb (76) = N kB T0 ln Va 22

Because dU = 0 in this process and d W is not, there must have been a heat ow out of the gas. From the rst law (with dU = 0) we have dQ = dW Vb Va (77)

= N kB T0 ln

The right hand side of Eq. (77) is the amount of heat ow into the gas. Thus, an amount of heat equal to N kB T0 ln(Vb /Va ) has owed out of the gas and into its environment. In an isothermal re-compression we have had to perform work on the gas cylinder, and the energy we have put into the system in this process has gone into heat that was taken up by the cylinders environment.

23

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Entropy, at last
Here is where we get to the denition of entropy. We imagine a system, such as the container of ideal gas, undergoing a set of changes. Some of those changes are accompanied by transfer of heat to or from thermal reservoirs. Some of them involve no heat exchange. We will number the reservoirs from 1 to n. The ith reservoir is at a temperature Ti . The heat extracted by our system from the ith reservoir will be denoted by Qi . Finally, we will imagine that the net eect of all these changes on our system is to return it to its initial state. In other words, there is no net eect of this set of changes on the state of the system. For this reason, we will call this set of changes a cycle. A central assertion We now make the following assertion: The cycle described above will always have the following property: Qi 0 i=1 Ti
n

(104)

Eq. (104) holds as an equality for a reversible cycle. In fact, if the cycle is reversible the equality must hold. We can show that Eq. (104) holds by assuming that it does not, and then by showing that the second law is violated. What we do is imagine an n + 1st reservoir at a temperature T0 . After completing the cycle for which the inequality n Qii > 0 holds does not hold, we run a set of n reversible i=1 T cycles between each of the n reservoirs and the new one. In the ith of these cycles we extract an amount of heat equal to Q(i) from the new reservoir and deposit an amount Qi in the ith one. That is, we restore to each of the original n reserviors the amount of heat extracted from it. Since these cycles are all reversible, we have Q(i) Qi = (105) T0 Ti This means that 1 T0
n i=1

Q(i) =

Qi i=1 Ti > 0

(106)

34

The net heat extracted from the new reservoir is greater than zero. The end eect of all these cycles is that 1. All working components end up in their initial state. 2. All the reservoirs except one end up in their initial states. 3. The single reservoir that is not in its initial state has had a non-zero amount of heat extracted from it. 4. By the rst law of thermodynamics this heat can only have gone into work. The second law of thermodynamics has thus been violated. For any cycle of the kind described here, the inequality n Qii > 0 is, i=1 T thus, not allowed. In the case of a cycle that is reversible, we cannot have the opposite absolute inequality, n Qii < 0, because the cycle would violate i=1 T (104) when run in reverse. To recapitulate 1. For any cycle, Qi 0 i=1 Ti 2. For a reversible cycle, Qi =0 i=1 Ti
n n

(107)

(108)

On the basis of the equality (108) we can dene a state variable for a system at equilibrium. Actually, this state variable is, for the time being, dened only in terms of dierences. We will establish an absolute reference value for it when we get to a discussion of the third law of thermodynamics. Consider a system in a state A. This is a state of thermal equilibrium, by assumption. We assign to this system a state variable, SA , which we call its entropy when in state A. The dierence between SA and SB , the entropy of the system when in state B, is given by S B SA =
i

Qi Ti

(109)

35

Where Qi is the heat absorbed from a reservoir at temperature Ti during one of a set of reversible steps that takes the system from state A to state B. We can also write the right hand side of Eq. (109) in dierential form as follows:
B

S B SA =

dQ T

(110)

Strictly speaking, I should have put a line through the d in dQ. For convenience only, I will leave that line out. However, you should always keep in mind that the innitesimal dQ is not the dierence between two well-dened variables, but rather an increment of transferred heat. The denominator, T , in the integrand on the right hand side of (110) corresponds to the temperature of the reservoir with which the system exchanges the innitesimal amount of heat energy, dQ. By the Clausius version of the second law, and the requirement that the process taking the system from state A to state B be reversible, we can infer that T must also be the temperature of the system itself at the time of the heat transfer. Otherwise the heat transfer, and the process itself, would be irreversible. Note that it does not matter what particular set of reversible steps we B choose to take the system from state A to state B. The integral A dQ/T will be independent of our choice. If it were dierent for the two dierent set of steps, then we could take the system from state A to state B along one of them and from state B back to state A along the other one run in reverse, and in the process construct a reversible cycle for which i Qi /Ti = 0, which we now know cannot be. The dierence SB SA depends on the two states A and B and not how the system is taken between those two states. The quantities SA and SB are, thus, true state variablesto within additive constants, at least. Lets get specic and calculate the entropy dierence between an ideal gas at a temperature TA and a volume VA and the same set of molecules at a temperature TB and volume VB . First, we will calculate S(TA , VB ) S(TA , VA ). To take a gas from a volume VA to a volume VB at the same temperature, we subject it to an isothermal expansion or compression. The heat extracted from the environment by the ideal gas compensates for the work performed on it, as the internal energy of the ideal gas does not change in the process of isothermal expansion or compression. We then nd 1 Q = TA TA
VB

P dV
VA

36

N kB TA dV V VA VB = N kB ln VA = S(TA , VB ) S(TA , VA ) =

1 TA

VB

(111)

As the volume of the gas increases, so does its entropy. To take our container of gas reversibly from a volume VB and temperature TA to the same volume and a temperature TB , we can put it into thermal contact with a succession of dierent reservoirs, each at a temperature so close to the changing temperature of the gas that the heat transfer is essentially reversible. If we imagine an innite succession of these reservoirs, each contributing an innitesimal amount of heat to the process, the net change in the entropy of the gas will be
TB TA

dQ = T =

TB TA TB TA

1 dQ dT T dT V =VB 1 CV dT T

(112)

where, recall, CV is the heat capacity of the gas at constant volume. We have already calculated this heat capacity at 3N kB /2. Thus S(TB , VB ) S(TA , VA ) = dT 3 N kB T TA 2 3 TB = N kB ln 2 TA
TB

(113)

What this means is that S(TB , VB ) S(TA , VA ) = [S(TB , VB ) S(TA , VB )] + [S(TA , VB ) S(TA , VA )] 3 TB VB = N kB ln + N kB ln 2 TA VA 3/2 VB TB = N kB ln (114) VA TA Choosing our arbitrary reference system to have a temperature and a volume equal to unity, we can write S(TA , VA ) = N kB ln VA TA
3/2 3/2

(115) (116)

S(TB , VB ) = N kB ln VB TB 37

That is, in general S(T, V ) = N kB ln(V T 3/2 ), to within additive constants. Note that the entropy is a monotonically increasing function of temperature. Recall, now, the free expansion of the ideal gas from its initial volume to a greater one. According to our results for entropy, the gas under free expansion increases its entropy by an amount N kB ln(Vnal /Vinitial ). The free adiabatic compression of the ideal gas, the process that we would have had to wait essentially forever to carry out, would have involved a net decrase in the gass entropy. According to the second law of thermodynamics, this free compression cannot occur. Thermodynamics says it is impossible. Detailed investigation reveals that it is possible, but only in the mathematical sense. One will never succeed in actually carrying it out. We can now state another version of the second law; a system in thermal isolation will never decrease its entropy. To see that this is so, imagine that we had a system in thermal isolation that we have succeeded in taking from a state A to a state B with a consequent decrease in entropy. We then allow the system to establish thermal contact with various reservoirs and take it reversibly from state B to state A. In this process the entropy changes, and the change in the entropy satises A dQ = SA SB > 0 (117) B T The cycle consisting of the change in the system from state A to state B while in thermal isolation followed by the reversible undoing of this change violates the rule dQ/T 0. The second law is thus violated if the entropy of a system in thermal isolation decreases. We can extend this conclusion; any change in a system in thermal isolation that involves an increase in the systems entropy is irreversible. After all, if such a change were reversible, we could run it backards and violate the second law by reducing the entropy of a system in thermal isolation. We now have another rule; any change in a system that can be reversed leaves the entropy of the system unaltered. In the case of the monatomic ideal gas, we have S = N kB ln V T 3/2 (118) If a container of such a gas is reversibly expanded in thermal isolation, then, in order that the entropy does not change, the temperature and volume must be related via T V 2/3 . This is our previously-derived result for the relationship between T and V in adiabatic expansion or compression. 38

The rst law in terms of exact dierentials

Lets return to the rst law and consider small changes involving reversible processes. The rst law is dU = d Q d W (119)

In a reversible process d Q/T = dS, where dS is the innitesimal change in the entropy of the system. Thuse, we have dU = T dS d W For the ideal gas, dU = T dS P dV (121) Now, everything is in terms of exact dierentials. What this last formula tells us is that in any reversible change of our cylinder of gas in which the number of molecules remains constant, the change in the internal energy is expressed entirely in terms of the change in the entropy of the gas and the change in the voume of the cylinder. From this, we conclude that the temperature is not an independent state variable, nor is pressure. We can express the internal energy entirely in terms of the entropy an the volumeor U = U (S, V ). Since dU (S, V ) = we have T = U S (123)
V

(120)

U S

dS +
V

U V

dV
S

(122)

P =

U V

(124)
S

The temperature and the pressure are (plus or minus) partial derivatives of the internal energy with respect to the entropy and the volume of the system. In order to complete our specication of the independent state variables we must also consider the eect on the internal energy of the system of a change in the number of molecules that it contains. This eect is easy to assess in a simple case. Imagine that we increase the number of molecules 39

by attaching a smaller container of the gas that is at the same temperature and pressure. The number of molecules in the smaller container is N , the volume of this container is V = (V /N )N , the internal energy of this container is U = (U/N )N , and the entropy in this container is equal to S = (S/N )N . Note that there is a strong assumption here. We are assuming that the entropy of a system increases linearly with the number of molecules in it. If you check back to our current expression for the entropy, you will see that this assumption is violated by that expression. Well return to this point shortly. Under the assumption that the internal energy can be written as U (S, V, N ), we have the general result U = U N N U U = S + S V,N V

V +
S,N

U N

N
S,V

(125)

From this, we infer U N =

S,V

U U N S

V,N

S U N V

S,N

V N (126)

U S V = T +P N N N

We call the quantity on the left hand side of Eq. (126) , also known as the chemical potential. This means that we have = or U = T S + N P V (128) U S V T +P N N N (127)

40

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The Helmholtz free energy of the monatomic ideal gas

Lets now construct the Helmholtz free energy of the monatomic ideal gas. We can accomplish this by integrating up the equations of state PV = N kB T 3 U = N kB T 2 (179) (180)

The two equations of state can reframed in terms of derivatives of the Helmholtz free energy. For example, Eq. (179) takes the form F (T, V, N ) = P (T, V, N ) V N kB T = V N kB T dV V = N kB T ln V + f (T, N )

(181)

Integrating up F =

(182)

The function f (T, N ) is an integration constant. In the case of the equation of state, Eq. (180), the relationship is U (T, V, N ) = F (T, V, N ) + T S(T, V, N ) F (T, V, N ) = F (T, V, N ) T T F (T, V, N ) = T 2 T T Thus, T 2 Integrating this up F (T, V, N ) = T 3 N kB dT 2 T (185) T F (T, V, N ) T 3 = N KB T 2 (184)

(183)

3 = N kB T ln T + T g(V, N ) 2 53

Combining (182) and (185), we nd F (T, V, N ) = N kB T ln V T 3/2 + T h(N ) (186)

where h(N ) represents the remaining integration constant. We will shortly argue that the free energy must be extensive. This means that h(N ) = N kB ln N + CN which means, at last, that F (T, V, N ) = N kB T ln V 3/2 T + CT N N (188) (187)

The constant C in (187) and (188) cannot be determined in the absence of further information with regard to the thermodynamic behavior of the ideal gas. That the ideal gas equations of state are obtained from the expression (188) for the Helmholtz free energy by dierentiation is eectively obvious, given that we obtained that expression by integrating up those equations of state. Instead of taking derivatives explicitly to show that this is the case, lets perform a Legender transformation to construct the internal energy as a function of S, V and N . We have U (S, V, N ) = F (T (S, V, N ), V, N ) + T (S, V, N )S where T (S, V, N ) is obtained by inverting S= Making use of (188), we obtain S = N kB ln V 3/2 3 T + ( kB C)N N 2 (191) F (T, V, N ) T (190) (189)

If you recall our previous results for the entropy of the ideal gas, you will note that the last term on the right hand side of (191) is new. This last term is a new additive pieces that do not aect any of the calculations we have already carried out, as we have been assessing entropy changes in which N , the number of molecules in a system remains a constant. Again, we are 54

confronted with the fact that entropy is properly dened only to within an additive constant. Lets set the coecient of N in the last term on the right hand side of Eq. (191) equal to kB D. Then, solving that equation for T , we nd N NS D 2/3 T = e kB (192) V Inserting this solution into the equation (189), we obtain for the internal energy of the ideal gas 3 N NS D U (S, V, N ) = N kB e kB 2 V
2/3

(193)

If we take the derivative of this equation with respect to S and set it equal to T , we end up with the relationship (192).

Extensive and intensive quantities

There are two kinds of variables in thermodynamics. The rst kind, extenstive variables grow linearly with the size of the system. Examples of extensive variables are entropy, volume and number of molecules. When the size of the system doubles, so does each extensive variable. The other kind of variable is intensive. An intensive variable stays the same as the size of the system increases. Examples of intensive variables are temperature, pressure and chemical potential. Note that the internal energy is extensive, as is the Helmholtz free energy.

Conjugate variables
Thermodynamic variables come in pairs. Each pair contains one extensive variable and one intensive variable. Each variable in the pair is a conjugate of the other one. Here is the three pairs in the case of the ideal gas: S T , V P , N . Recall the form that we had for the internal energy: U = T S P V + N . The internal energy is equal to the sum of (plus or minus) the product of conjugate variables. This is not the only relationship involving conjugate variables. The partial derivative of a thermodynamic potential (two examples of which are the internal energy and Helmholtz free energy) with respect to one of the appropriate independent variables yields

55

(plus or minus) its conjugate variable. That is, F (T, V, N ) = S T U (S, V, N ) = T S (194) (195)

Thermodynamic potentials in general

The Legendre transformation can be utilized to construct other quantities derived from the internal energy. These quantities are known in general as thermodynamic potentials. Here are a few examples of thermodynamic potentials, and the relationship between those thermodynamic potential and the quantities with which we have already been dealing. The Gibbs free energy The Gibbs free energy is properly expressed in terms of the temperature, pressure and number of molecules. Its relation to the Helmholtz free energy is G(T, P, N ) = F + P V (196) where V is expressed as a function of P , T and N via the inversion of the relationship F P = (197) V The enthalpy The enthalpy is properly expressed in terms of the entropy, pressure and number of molecules. Its relation to the internal energy is H(S, V, N ) = U + P V where V is expressed as a function of S, P and N via the inversion of P = U V (199) (198)

56

The grand potential The grand potential is properly expressed in terms of the temperature, volume and chemical potential. Its relation to the Helmholtz free energy is = F N where N is expressed in terms of T , V and via the inversion of = F N (201) (200)

The general form of thermodynamic potentials

Because U = T S P V + N , we also know that F G H = = = = P V + N N T S + N P V (202) (203) (204) (205)

The list above clearly does not exhaust the list of all possible thermodynamic potentials. The potential that will turn out to be most useful will clearly depend on the situation. As noted earlier, the appropriate choice is controlled by the variables that are most natural in a given situation. There is one set that cannot be used, and, that is one consisting only of intensive quantities. For the ideal gas, there is no meaningful thermodynamic potential constructed out of the temperature, pressure and chemical potential. For one thing, if one asks what is left after subtracting N from the Gibbs thermodynamic potential to perform a Legendre transformation to a thermodynamic potential in terms of T , P and , we end up with zero. That there is no well-dened thermodynamic potential expressed entirely in terms of intensive quantities is obvious if one realizes that in specifying the temperature, pressure and chemical potential, one has no information with respect to the size of a system.

57

A couple of other systems

The van der Waals gas
The van der Waals equation of state is V P +a N
2

(V N b) = N kB T

(206)

What this equation of state tells us is that the eective pressure in increased because of interactions between the molecules. This is the source of the term a(N/V )2 . The coecient a is related to the strength of the attractive interactions. Furthermore, the eective volume decreases because of hard core repulsion between the molecules. This is the source of the term N b. The coecient b is related to the volume of a single molecule. If we assume that the heat capacity at constant volume is equal to 3 N kB 2 (207)

we can obtain the Helmholtz free energy by integration. This will be assigned as a homework problem.

The ideal paramagnet

To study the equilibrium properties of a magnetic solid, we introduce two new variables, the total magnetization of the sample, M , and the externally applied magnetic eld, H. Although both of those quantities are vectors, we will assume a direction, and deal only with amplitudes. This means that both M and H are scalar variables. In fact, they are a conjugate pair, M being the extensive one and H being intensive. The magnetic Gibbs free energy of a magnetic system is written as, G(T, H, N ). The total magnetization of this system is given by G(T, H, N ) M = (208) H Given that the Gibbs free energy is, like all thermodynamic potentials, extensive, and given that the only extensive variable in the set T, H, N is N , the number of molecules in this system, we know that the magnetic Gibbs free energy must have the form G(T, H, N ) = N g(T, H) 58 (209)

The equation of state of the ideal paramagnet is the Curie formula M = ND H T (210)

Here, D is a system-dependent constant. Note the appearance of the factor N . This is to ensure that the magnetization is extensive. To add to our knowledge of the thermodynamic properties of this system, well assume a heat capacity at zero magnetic eld given by CH = N T 3 (211)

Here, is a system-dependent coecient. This form for the heat capacity is characteristic of crystalline systems in which the low-temperature properties are controlled by vibrations of the molecules. As it turns out, the exact form is not particularly important. Now, lets obtain the magnetic Gibbs free energy by integrating up (210) and (211). Starting with Eq. (210), we obtain G = = M dH ND

H dH T 1 H2 = ND + N f (T ) 2 T

(212)

The integration constant function f (T ) is obtained by performing a double integration of the heat capacity. Since S = G/T , and CH = T S/T , we have CH = T 2 G/T 2 . Performing the requisite integrations, we nd G = N 4 g(H) T + AN + BN T + 12 T (213)

Combining (212) and (213), we nd for the magnetic Gibbs free energy G = N 4 H2 T + AN + BN T N D 12 2T (214)

The constants A and B cannot be determined from the information that we have in hand. For convenience, we will set them both equal to zero. This has no eect on the discussion that follows. 59

The entropy of the ideal paramagnet To nd the entropy of our magnetic system, lets take the derivative of the magnetic Gibbs free energy with respect to temperature. We have S(T, H, N ) = G(T, H, N ) T H2 = N D 2 + N T 3 2T 3

(215)

How does this entropy behave as T 0? First, if H = 0, we have S . This is because of the term going as 1/T 2 on the right hand side of Eq. (215). On the other hand, if H = 0, the expression for entropy consists entirely of the second term on the right hand side of (215). This term goes to zero as T 0. The entropy at T = 0 depends on whether there is a non-zero applied magnetic eld. As we will see next. This implies a possible strategy for cooling a system to the absolute zero of temperature.

60

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H=0

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Molecules in a box
Let us consider the system shown in the gure below. We will ask pertinent

Figure 1: A set of molecules in a box with an imaginary partition separating one half from the other. questions concerning the distribution of the molecules. For the time being, we will concentrate on the spatial distribution of the molecules, and we will ask simple questions with regard to the gross features of the distribution. Here is one question: If there are N molecules in the box, what is the probability, given no other information about the molecules that n of them are in the top half of the box and N n of them are in the bottom half? To simplify matters, we will assume that the molecules are non-interacting, and we will also neglect the eect of gravity. Then, suppose that N 1 of them are in the top half and the last molecule has to decide where to go. According to this assumption, it has no preference for either half of the box. The probability that it chooses the top half is 1/2, and the probability that it will end up in the bottom half is also 1/2. Each molecule thus has a 50% chance of ending up in either half of the box, regardless of where the other molecules happen to be. Lets warm up by asking an extreme version of the above question: What is the probability that all N of the molecules are in the top half of the box? If the probability that any one of the molecules is in the top half of the box is 1/2, then the probability that all N of them are is (1/2)N , or 1/2N . How small is this number? In other words, how large is 2N for characteristic 1

values of N ? Suppose we are thinking of a macroscopic box. A reasonable value for the number N would then be of the order of Avagadros number, 6 1023 . We will take N to be 1023 . 23 How big is 210 ? It is, quite obviously, a very big number, but we will nd it edifying to investigate just how large it is. Lets start by converting to powers of 10. We know that 210 = 1024 103 . Then 210
23

= =

210 103

1022 1022
22

= 10310
23

(1)

which means that 210 equals 1 followed by 3 1022 zeros. This is clearly an enormous number. It is, in fact, unimaginably huge. To see this, let us imagine that the molecules are moving around in the box quite at random and estimate the amount of time that we will have to wait for all of them to be in one half of the box. Lets take the box to be one meter per side and have the molecules move faster than they possibly can. Well assume that they move with the speed of light. This is 3 108 meters per second. For a molecule to go from one side of the box to the other takes less than 108 seconds. To be precise, it takes (1/3) 108 seconds. We can then imagine that every (1/3) 108 seconds there is a complete re-arrangement of the molecules in the box, so that every time one of these incredibly brief time interval passes the molecules have another chance to all be in the same half of the box. There are about 3 107 seconds in a year, so the number of times the molecules rearrange themselves each year is
1 3

3 107 seconds = 9 1015 rearrangements 108 seconds/rearrangement

(2)

The molecules rearrange themselves about 1016 times each year. 22 We will have to wait until there are the order of 10310 rearrangements of the molecules until we can reasonably expect to see all of the molecules in 22 one half of the box. That means that we will have to wait 10310 /1016 = 22 10310 16 years. The number 3 1022 is so much greater than 16 that we can forget about the 16 in the last exponent above. We will have to wait 22 10310 years before there will be any reasonable likelihood of seeing all the molecules in one half of the box. 2

We can expect our solar system to live a few billion years longer. Lets be generous and give it a total life-span of 100 billion years = 1011 years. We can now ask how many solar system lifetimes we will have to wait. This number is 22 10310 22 = 10310 27 (3) 16 1011 10 Again, the 3 1022 in the exponent swamps the number we are subtracting, 22 and we must conclude that it will take 10310 solar system lifetimes for this incredibly unlikely event to occur. Now, imagine that I asserted that it is a law of nature that in a box with a mole of gas in it, you will never see all of the gas molecules happen to congregate in one half. Should you take this statement seriously? Clearly, it is not rigorously true. There is a non-vanishing likelihood that such an occurrence will come about. However, if you wait around, expecting to see it, you will be wasting your time. Although it can happen, a violation of the above law is so highly unlikely that it might as well never take place. The practical dierence between this law and a law that is always obeyed is, for all practical purposes, nonexistent.

A bit more detail

Because the molecules are non-interacting, each of them might as well ip a coin to decide which half of the box it will occupy at some particular point in time. We can gure out the probability that n of the molecules are in one half of the box and N n are in the other half by performing N coin ips and asking for the probability that we have n of them turning up tails and N n of them heads. This is a problem in combinatorics. The way we calculate the probability is to divide the number of ways of having n tails and N n heads turn up in N ips by the number of ways N ips can turn out. This latter number is 2N , corresponding to the fact that there are two possibilities per toss. The numerator of our fraction is the number of ways of dividing a set of N objects into two subsets, the rst containing n and the second N n elements. This is n N = N! n!(N n)! (4)

The probability that there are n tails and N n heads in the N ips is N! 1 n!(N n)! 2N (5)

To proceed further we need a good asymptotic formula for the value of n! when n is large.

Stirlings approximation
The number n! = n(n 1)(n 2) (2)(1) can be written as an integral. We have n! = tn et dt (6)
0

To see that the integral on the right hand side of (6) is, indeed, a representation of n!, we will integrate by parts. Starting with the integral representation for 1!:
0

tet dt = et t

0 0

+
0

et dt

= 0 et = 1 If we dene F (n)
0

(7) tn et dt

(8) (9)

we have F (1) = 1 Now, what about F (n) when n > 1? Heres an integration by parts

F (n) =
0

tn et dt
0

= et tn

+n
0

tn1 et dt

= n
0

n1 t

e dt (10)

= nF (n 1)

So, F (n) = = = = nF (n 1) n(n 1)F (n 2) n(n 1)(n 2)(n 3) 3 2 F (1) n!

(11)

where we made use of (9) to eliminate F (1) from the right hand side of Eq. (11). What, now, when n is large? In this case, tn is a rapidly increasing function of t, while et is a function that ultimately dies o faster than any power of t. The integrand will look like the curve in Figure 2.

tn e-t
1.210 11 110 10 810 10 610 10 410 10 210 5 10 15 20 25 30
11

Figure 2: The function tn et , with n = 15. At what value of the integration variable t is the integrand a maximum? To nd this out, we maximize tn et = en ln tt (12)

We accomplish this by maximizing the exponent on the right hand side of (12). The extremum equation is d n [n ln t t] = 1 dt t = 0 The solution of this equation is, clearly, t = n. 5

(13)

The integrand is, thus, at its maximum when t = n. At this value of t, the integrand is n n (14) nn en = e For large n this number is very large. Look at the vertical axis in Figure 2, where the integrand is plotted for n = 15. Supppose we shift the origin in the graph above to t = n. That is, we replace t by x + n, where x ranges from n to . The integral representation of n! is, then
n

(x + n)n e(n+x) dx =

en ln[n+x]nx dx

(15)

Taylor expanding the logarithm in the exponent above: x ln [n + x] = ln n + ln 1 + n x x 1 x2 +O = ln n + 2 n 2n n The integral is, then,
n
2 x 1 x2 +O n 2 n x3 n3

(16)

en ln nn e

dx =

n ln nn 1 2

x2 +O n

x3 n2

dx

(17)

2 The gaussian factor ex /2n is much less than one when x = A n, where A is a sizable, but xed, number. If n is very large, we have x3 n2 A3 n3/2 n2 3 1/2 = An 1

(18)

and over the width of the gaussian we can neglect the term of order x3 /n2 in the integrand (and higher order terms, as well). The integral we now have to perform is n n 1 2 e 2 x /n dx (19) e n The lower limit can be replaced by with the introduction of negligible error ( en ). We then have, in the limit of large n, n n 1 x2 n! e 2 n dx e n n = 2n (20) e 6

This is Stirlings approximation, and it is an excellent approximation for n! when n is greater than 10. To see how good it is, we compare ln 15! with 15 ln 15 2 15 . The results for the two are e ln 15! = 27.8993 . . . ln 15 e
15

(21) (22)

2 15

= 27.8937 . . .

Back to our problem of the molecules in the box. We can apply Stirlings formula (without the square root factors, for the time being) to the probability of having n molecules in one half of the box (say, the top) and n N in the other half. This probability is N! 1 n!(N n)! 2N = exp [lnN ! ln n! ln(N n)! N ln 2] exp N ln N n N n n ln (N n) ln N ln 2 e e e = exp [N ln N n ln n (N n) ln(N n) N ln 2] (23)

Lets write n = (N/2) + . We already know that the most probable distribution will have half of the molecules in each side of the box. Our exponent is, now N ln N N N N N + ln + ln N ln 2 (24) 2 2 2 2

We can Taylor expand the second and third terms in (24) with respect to . Given that d x ln x = ln x + 1 dx d2 d (x ln x) = (ln x + 1) 2 dx dx 1 = x we have N N N N N 1 2 + ln + = ln + + 1 + 2 2 2 2 2 2 2 N 7 (27) (25)

(26)

and N N N N 1 2 N ln = ln + 1 + ()2 2 2 2 2 2 2 N This means that our exponent is N ln N 2 N N 22 22 ln N ln 2 = 2 2 N N (29) (28)

Forgetting about the square roots in Stirlings formula, which is what weve been doing up to now, we now have for the probability that there are N/2+ molecules in one half of the box and N/2 molecules in the other e2
2 /N

(30)

Notice that this is a gaussian distribution. If we had put the square roots in and carried them along in our calculation, the result for this probability would have been 2 22 /N e (31) N The width of the probability distribution in (31) is proportional to N . > That is, the gaussian starts to fall o dramatically when N . If there 2 /N are 1023 molecules in the box, the gaussian e2 starts to fall o when > 1022 = 1011 , or when there is an excess of 1011 molecules in one half of the box. Now, imagine that I told you that it is a law of nature that, given a box containing some molecules ying around at random, one half of the box will always contain half of the molecules. How seriously should you take me? Clearly, what I said is not always true. In fact, it is in general not true at all. According to our results, th probability that exactly half of the molecules are in one half of the box is 2 2(=0)2 /N e = N 2 N (32)

When N 1023 , this probability is vanishingly small (actually it is 1011 ). On the other hand, if I were to say that half of the molecules, more or less, are in the bottom (or top) half of the box, I would be making an essentially correct statement. The percentage dierence between N/2 and N/2 N is 8

N /(N/2) 1011 (if N 1023 ), so half of the molecules are in the bottom half of the box, to within errors of a few parts per trillion. Lets be a little more quantitative and ask what the mean square deviation is from the predictedor averageconguration. We want to calculate 2 =

2 22 /N 2 e N 2 22 /N 2 e d N (33)

Gaussian integrals: a review We want to be able to evaluate

x2n eax dx

(34)

When n = 0, we have

eax dx =

a (35)

= 1/2 a1/2 If we note that x2n = (1)n we have, straightforwardly,

dn ax2 e dan

(36)

x e

2n ax2

dn ax2 dx = (1) e dx dxn dn = (1)n n 1/2 a1/2 da

n

(37)

so, for instance,

x2 eax dx =

d 1/2 1/2 a da 1 = 1/2 a3/2 2

(38)

Back to the quantity of interest Our integral is 2 N

e2

2 /N

2 d = = = N 4

2 N

ea d
3/2

a=

2 N

2 1/2 2 N N

(39)

So, 2 = N/4. The mean square deviation in the number of molecules in one half of the box is of order N . On the average, there are, then, N (40) 2 = 2 extra molecules on one side of the box or the other.

10

Principles of statistical mechanics

We will begin our discussion of statistical mechanics with a denition of entropy that is suitable for use in the consideration of the behavior of large systems. For the time being, the denition will be simply stated. The validity of this denition will be establshed through its application to a few systems.

Statistical denition of entropy

The entropy, S, of a system is dened as follows: S = kB ln {number of states available to the system} Here, kB is Boltzmanns constant. (1)

An example of the application of this denition of entropy: a spin 1/2 system

Lets assume that we have N 1023 spin 1/2 particles. The z-component of the spin of each points either up or down. The net magnetic moment in the z-direction of this collection of particles is given by
N

Mz =
i=1

si

(2)

where si = 1 for each individual spin, and is the product of the Bohr magneton and the gyromagnetic ratio. Suppose we do not specify Mz . Then, each spin can be in one of two states, and the system as a whole can be in one of 2N states. According to our denition of entropy, S = kB ln 2N = N kB ln 2

(3)

Notice that according to this denition, the entropy is extensive. Now, suppose we specify Mz . That means that we must have N+ spins with Si = +1 and N spins with Si = 1, where N+ + N = N (N+ N ) = Mz 1 (4) (5)

In other words, N+ = N Mz 1 N+ 2 1 Mz = N 2 (6) (7)

We have already worked out the number of ways of separating N objects into two piles, one containing N+ objects and the other with N objects. The combinatorial factor is N! (8) N+ !N ! Thus, S = kB ln N! N+ !N ! = kB ln N ! kB ln N+ ! kB ln N !

(9)

Making use of Stirlings formula: ln n! n ln we have S kB N ln N N+ N N+ ln N ln e e e = N ln N N+ ln N+ N ln N Mz 1 Mz 1 N+ ln N+ = N ln N 2 2 1 Mz 1 Mz N ln N 2 2 1 Mz N+ 2 1 Mz N 2 n e (10)

(11)

Using N= we have S kB = 1 Mz 1 Mz N+ ln N + N ln N 2 2 2 + (12)

1 2 1 = 2 1 = 2 1 2

Mz Mz N+ Mz N+ Mz N+ 1 = N ln 2 N 2 N+

Mz 1 Mz 1 Mz N ln N 2 2 Mz 1 Mz 1 Mz 1+ N ln 1 N 2 2 N 1 Mz 1 N ln 2 2 Mz 1 Mz Mz ln 1 + N ln 1 N 2 N Mz Mz 1 Mz Mz + ln 1 + N ln 1 N 2 N (13) ln N+

1 2 1 ln 2 1 ln 2

Notice that the entropy if this system is extensive, in that if N 2N and Mz 2Mz , then S(N, Mz ) S(2N, 2Mz ) = 2S(N, Mz ).

Entropy versus energy for this model

If there is an external eld on the syhstem of spin 1/2 magnetic moments, then the energy of interaction of the moments with the magnetic eld, also known as the Zeeman energy, is given by E = M H Mz H

(14)

That is, we assume that the magnetic eld points in the zdirection. The free energy of this system is G = U TS = Mz H kB T N ln 2 Mz Mz 1 Mz Mz 1 N+ ln 1 + N ln 1 2 N 2 N (15)

If this free energy is to be minimized with respect to the net magnetization, Mz , then G Mz = 1 Mz Mz HMz kB T N ln 2 N+ ln 1 + Mz 2 N 3

 = 0 or

1 Mz Mz N ln 1 2 N (16)

0 = H kB T

1 Mz ln 1 + N

M 1 N + z Mz 2N 1 + N

1 Mz + ln 1 N or

M 1 N z + Mz 2N 1 N

(17)

1+ H = ln KB T 1 or e Solving for Mz /N , Mz N
H/kB T

Mz N Mz N Mz N Mz N

(18)

1+ 1

(19)

eH/kB T 1 eH/kB T + 1 1 H = tanh 2 kB T = 1 H 2 kB T H 2kB T

(20)

Thus, Mz = N tanh When H is small, tanh and Mz 2 N H 2kB T 2 N H = 2kB T 1 H 2 kB T (22) (21)

(23)

The total magnetic moment in the z-direction obeys the Curie law. On the other hand, when H is large, H 1 (24) tanh 2kB T and Mz N (25) The magnetization is saturated, as all the moments are essentially perfectly lined up. If we plug our results back into the expression for the free energy, we nd H N kB T ln 2 G = N H tanh 2kB T N H H + kB T 1 + H tanh ln 1 + H tanh 2 2kB T 2kB T H N H + kB T 1 H tanh ln 1 H tanh (26) 2 2kB T 2kB T Given our statistical denition of entropy and thermodynamic approaches based on combinations of energy and entropy, we have ended up with an expression for the magnetic Gibbs free energy of a set of magnetic moments carried on spin-1/2 particles that interact with an externally imposed magnetic eld, but not with each other.

More on entropy
Recall our denition of entropy, (1). Suppose the system of interest consists of n1 type 1 components that can be in one of f1 states, n2 type 2 components that can be in one of f2 states, . . . nm type m components that can be in one of fm states. The total number of states available to the n n n system as a whole is then f1 1 f2 2 fmm , which means that the entropy of this system is
m n n n kB ln f1 1 f2 2 fmm = kB i=1

ni ln fi

(27)

In the case originally considered, there was only one type of component, a magnetic moment with spin 1/2. This moment could exist in one of two states, so the entropy of a system consisting of N of these moments is kB ln 2N = N kB ln 2 5 (28)

Additivity of the statistically dened entropy

Suppose we split our system into two subsystems as follows: We place n1a of the n1 type 1 components into system a and the remaining n1b of those components into system b, and so on. This means that the total number of n n n states available to system a is f1 1a f2 2a fmma , while the number of states n n n available to system b is f1 1b f2 2b fmmb . The entropies of the two systems are given by
m

Sa = kB
i=1 m

nia ln fi nib ln fi
i=1

(29) (30)

S b = kB

Notice that the total entropy of the combined system is

m

S = kB
i=1 m

ni ln fi (nia + nib ) ln fi
i=1

= kB

= Sa + Sb

(31)

The entropy of the combined system is equal to the sum of the entropies of the two subsystems. In this case, at least, entropy is additive.

The eects of a constraint on the entropy

Suppose there is a constraint on the states that the system can occupy. Suppose, for example, that ths system, because it is energetically isolated from the rest of the universe, can only exist in states that have a total energy E. Suppose, furthermore, that the system is made up of N identical components (i.e. n1 = N and there is no other kind of component). Furthermore, let us assume that each component can exist in one of two states, and that the energy of one of those states is zero, while the energy of the other state is . Thus, we are considering a system made up of a set of two-level components. The total number of states available to this system is just equal to the number of ways of having m components in the energy equal level and N m components in the energy equal to zero level, where m = E. We 6

have solved this sort of problem beforein fact just a few pages agousing combinatorial factors and Stirlings approximation. We will now solve it in a dierent way. . . one that will allow us to look at much more complex systems. We start by noting that the number of states that the system can occupy subject to the above condition is just equal to the coecient of em in [1 + e ] [1 + e ] [1 + e ] = [1 + e ]N (32)

That is, the number of states that are available to the system is equal to the coecient of eE (since E = m ) in [1 + e ]N . There are a number of tricks for nding that coecient. That one that we will use starts with the replacement of e with ei . We are then interested in the coecient of eim = eiE/ in [1 + ei ]N . We are going to obtain that coecient by multiplying [1 + ei ]N by eiE/ , and then integrating over from to . This picks out the coecient of eim , since, when k is an integer eik d = 0 (33)

unless k = 0, when we have

eik d =

= 2 The quantity of interest is 1 2

(34)

1 + ei

eE/ d ==

1 2

i eN ln[1+e ] eiE/ d

(35)

Now, we will be interested in the case in which E/ = O(N ). If this is true, then both the real and the imaginary parts of the exponent will be very rapidly varying as a function of the integration variable . The rapid phase variations in the integrand will give rise to essentially complete cancellation, except where the phase is at an extremum, or, when 0 = d E N ln 1 + ei i d N iei E = i i 1+e

(36)

or, where ei E (37) = i 1+e N This extremum equation is satised only when is imaginary. Let = i. Then, e E (38) = 1+e N Solving for : E/N e = (39) 1 E/N or 1 E/N (40) = ln E/N The integral is essentially equal to the integrand at this extremum point. Recall our discussion of Stirlings approimation, as derived from the integral representation of the factorial. The entropy is, then, given by S = kB ln 1 N ln[1+ei ]iE/ e d 2 1 kB ln + kB ln eN ln[1+e ]+E/ 2 E 1 + kB ln 1 + e + = kB ln 2 1 1 E 1 E/N + N kB ln + kB ln = kB ln 2 1 E/N E/N

(41)

If we are to carry through on our identication of this quantity with entropy we ought to identify the temperature, T , with E/S, or 1 T S E 1 = N kB ln E 1 E/N =

+ kB

ln

1 E/N E/N

(42)

Carrying out the algebra, we end up with the result 1 kB 1 E/N = ln T E/N 8 (43)

This means that e /kB T = or, solving for E,

1 E/N E/N

(44)

N 1 + e /kB T Lets use this result to construct the free energy of our system E= F = E TS we have S = N kB ln 1 1 E/N + kB E ln 1 E/N E/N + kB ln 1 2

(45)

(46)

(47)

The last term on the right hand side of Eq. (47) is negligible compared to the rst two and will be dropped from now on. Substituting for E, we nd E T S = N kB T ln 1 + e /kB T e /kB T = N kB T ln 1 + e /kB T

(48)

We have thus derived from our statistical denition of entropy and a mathematical trick a quantity that contains all the thermodynamic information for a set of N two-level components at a temperature, T . The next question is, of course, why we ought to believe the physical premises on which the above calculation was based.

The two-level system and the canonical ensemble

Before we talk about the foundations of statistical mechanicswhich will be necessary, just to establish a bit of condence in the approach that we will be takinglet us work a little on what we have obtained, to extract some new results.

Extensivity of the entropy

In our calculation based on combinatorial factors and the use of Stirlings formula we found for the entropy of a two-level system S = N kB ln = Ns E N 1 1 E/N + E 1 E/N ln N E/N (49)

In the above expression, terms that do not grow as fast as N have been neglected. This means that the number of congurations available to our set of N two-level components, subject to the restriction that the total energy is E, is given by N (E) = eN s(E/N )/kB (50) We expect this to he a general property of large systems. It is essential to the development that follows. Now, lets use this result to nd the probability that a given two-level component is in the excited state. If the component is excited, the amount of energy available to the remaining N 1 components is E . The number of states available to them is e(N 1)s((E )/(N 1))/kB We can write (N 1)s((E )/(N 1)) as (N 1)s E N 1 N 1 = (N 1)s E E + s N 1 N 1 2 E s + (52) + N 1 N 1 (51)

10

The rst term on the right hand side of (52) is O(N ), the second term is O(1), and the remaining terms are O(1/N ) and smaller. We will neglect those remaining terms. Now, S E N 1 E (N 1)s E N 1 = S(E, N 1) E 1 = TN 1 =

(53)

Assume that we can neglect the dierence between the temperature, so dened, for an N 1 component system and the temperature for an N component system. Then, if the component of interest is in the excited state, there are e(N 1)s(E/(N 1))/kB e /kB T (54) congurations available to the other N 1 components. If the component of interest is in the ground state, there are clearly e(N 1)s(E/(N 1))/kB (55)

congurations available. We assume that the system visits indiscriminately and with equal weight all the congurations available to it. This means that the probability of nding the component of interest in its excited state is equal to the ratio [# of congurations available when the component is in its excited state] [# of excited state congurations] [# of ground state congurations] e(N 1)s(E/(N 1))/kB /kB T = (N 1)s(E/(N 1))/k /k T B B e + e(N 1)s(E/(N 1))/kB e /kB T = /k T (56) B e +1 Alternatively, the probability that the component is in its ground state is 1 e /kB T + 1 (57)

11

How the energy is shared in general

Let us consider two systems that share a total amount of energy E. Lets suppose that the rst system has an energy E1 and the second system has an energy E2 . The total number of congurations available to the two systems with this division of energy is eS1 (E1 )/kB eS2 (EE1 )/kB (58)

Here the rst term in the product is the number of congurations available to the rst system, while the second term in the product is the number of congurations available to the second. If we want to sum over all possible ways of sharing the energy, we have for the total number of congurations eS1 (E1 )/kB eS2 (EE1 )/kB dE1 (59)

Now, both exponents in the above expressions are very large. We will be able to show that the integral above is dominated by contributions from the region in the immediate vicinity of the value of E1 that maximizes the integrandor, equivalently, that maximizes S1 (E1 ) + S2 (E E1 ) To nd the energy, E1 , that does this, take the derivative d (S1 (E1 ) + S2 (E E1 )) dE1 and set it equal to zero. That is, 0 = d (S1 (E1 ) + S2 (E E1 )) dE1 = S1 (E1 ) S2 (E E1 ) 1 1 = T1 T2 (61) (60)

(62)

The dominant contributions to the congurations is from the immediate vicinity of the energies for which the temperatures of the two subsystems are equal.

12

0 Lets expand with respect to E1 in this region. Set E1 = E1 +E1 . Then, 0 0 S1 (E1 + E1 ) + S2 (E E1 E1 ) 0 0 0 0 = S1 (E1 ) + S2 (E E1 ) + E1 S1 (E1 ) + S2 (E E1 ) 1 2 0 0 + S1 (E1 ) + S2 (E E1 ) E1 + 2 1 0 0 2 0 0 = S1 (E1 ) + S2 (E E1 ) + S1 (E1 ) + S2 (E E1 ) E1 + 2 The term proportional to E1 vanishes because of the equality of the temperatures of the two systems. Now, by assumption E1 S1 (E1 ) = N1 s1 (63) N1 which means that E1 (64) S1 (E1 ) = s1 N1 1 E1 S1 (E1 ) = (65) s1 N1 N1 and so on for higher derivatives of the entropy of system 1 with respect to the energy of that system. The same considerations apply to system 2. This means that the higher one goes in the Taylor expansion of the entropy of the two systems sharing energy, the smaller the terms are, when N1 and N2 are large. This means that our integral over energy in (59) is well-approximated by

E (S1 (E1 )+S2 (EE1 ))/kB

0 0

0 0 2 e[S1 (E1 )+S2 (EE1 )]E1 /2kB dE1

(66)

The integral is well-approximated by a gaussian integral. To see what the 2 integrand looks like in a bit more detail, well consider the coecient of E1 . Since 1 (67) S1 (E1 ) = T1 we have d 1 S1 (E1 ) = dE1 T1 1 = 2 dT1 /dE1 T1 1 1 = 2 (68) T1 dE1 /dT1 13

If we make the connection E = U , with U the systems internal energy, we have dE dU = dT dT = C where C is the appropriately dened heat capacity. Thus, S1 (E1 ) = 1 1 2 T1 C1 (70)

(69)

The extremum is a maximum only if the above term is negativeso we require C1 > 0, in line with previous arguments based on thermodynamic stability. Note that we can write C1 = N1 c1 , with c1 an intensive quantity. We have now
0 0 e[S1 (E1 )+S2 (EE1 ]/kB

1 2kB T 2

1 + N 1c N1 c1 2 2

2 E1

dE1 (71)

0 0 = e[S1 (E1 )+S2 (EE1 ]/kB

2kB T 2
1 N1 c1

1 N2 c2

The entropy of this combined system is

0 0 S1 (E1 ) + S2 (E E1 ) +

kB ln 2

2kB T 2 1 1 + N2 c2 N1 c1

(72)

The rst two terms dominate the expression in (72), since S1 N1 and S2 N2 . The third terms goes like ln (N1 , N2 ). The entropy of the combined system is essentially the sum of the entropies of the individual components with the energy shared between them in such a way tha the combined entropy is maximum. We can see what the expected uctuations are in there energy distribution. We do this by calculating
1 e 2kB T 2
1 + N 1c N1 c1 2 2 2 E1

2 E1 dE1

1 e 2kB T 2

1 + N 1c N1 c1 2 2

2 E1

dE1

= kB T 2

1 N1 c1

1 +

1 N2 c2

14

N1 N2 kB T 2 N2 + N21 c1 c (73)

= O(N1 , N2 )

The root mean square deviation in energy on either side from the maximizing amount is 1/2 1/2 2 E1 = O(N1 , N2 ) (74) This quantity is small compared to the total energy in either component, which is of order N1 , N2 . Thus, the uctuations in the amount of energy in either system are small compared to the total energy, by are not absolutely small. Furthermore, the extent of the uctuations is controlled by the heat capacities of the two systems.

Two systems sharing energy, one of which is much larger than the other
Here, we are going to look at the energy-sharing that takes place between two systems, one of which will play the role of a thermal reservoir. We will utilize the subscript B to label quantities associated with the large system. Quantities associated with the smaller system will be labeled with the subscript S. The key relationship between the two systems is NB NS . We will assume for the entropy of the thermal bath SB (EB , NB ) = NB sB EB NB (75)

and similarly for the system S. Then, we have for the total entropy of the combined system eS/kB = eSS ( )/kB eSB (E )/kB d (76)

The arguments of the previous section carry through in this case. Here, the integral is dominated by the maximum, which occurs when SS ( ) = SB (E ) or, when TS = TB 15 (78) (77)

Because the bath has so many more degrees of freedom than the system, the width of the energy distribution is dominated by the heat capacity of the smaller system, S. This is because the second derivative with respect to energy of the quantity N s(E/N ) goes as 1/N , and 1/NS 1/NB . So far, this is just a relatively simple variation on the case discussed in more generality in the preceding sections. Lets expand SB (E ) with respect to . Then, the integral over all possible partitions of energy between the system, S, and the bath, B, takes the form eSB (E)/kB eSS ( )/kB /kB T d (79)

where we have removed the subscript from the temperature of the bath, TB , in the integral. Lets remove the multiplicative factor eSB (E)/kB from (79). The integral is now eSS ( )/kB /kB T d eSS ( 0 )/kB 0 /kB T (80)

where 0 is the energy at which the integrand is a maximum. When logs are taken of both sides of the expression (80), one recovers an equality, to within terms that are small compared to the leading ones by the ratio ln N/N . Now, 0 is equal to the energy of the system, S, with the greatest likelihood. That is, the result of the integration over of eSS ( )/kB /kB T (81)

is, to within multiplicative corrections that are negligible after the taking of logarithms, eSS (US )/kB US /kB T (82) That is, the result of the summation over all partitions of the total energy between the system and the bath with which it is in contact, is eF/kB T , where F = U T S is the Helmholtz free energy of this system. Lets do a little checking. Well start with the derivative of this candidate for the Helmholtz free energy with respect to temperature: ( T
0

T S( 0 )) = S( 0 ) + 1 T = S( 0 )

S 0 (83)

The last equality follows from the fact that S/ | = 0 = 1/T . 16

Now, the quantity eSS ( )/kB is the sum over all states of the system subject to the requirement that the total energy in each of those states is equal to . That is eSS ( )/kB = (84) states with energy Multiplying the expression on the left hand side of (84) by e /kB T and the summing (or integrating) over all values of is the same as multiplying the sum on the right hand side by e /kB T and then performing an unrestricted sum over all states of the system. Putting all this together, we end up with the result eF/kB T = all states of the system The sum on the right hand side of Eq. (85) is called the partition function. eEstate /kB T (85)

17

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Modications of the ideal gas

Suppose the atoms or molecules that make up the ideal gas are in an external potential. The, the total energy of the system of N of them is
N p2 1 + U (ri ) i=1 i=1 2m N

(113)

The partition function is given by Z =

states

eEstate /kB T

1 N !h3N 1 = N !h3N

d3N pd3N re e
k 1T
B p2 2m

k 1T
B

p2 i 1 kB T i 2m

U (ri )

3N

U (r) BT

d3 r

(114)

and we have for the Helmholtz free energy F = kB T ln Z

1 = kB T ln h3N

2 e N 1 p e kB T 2m N U (r) e = N kB T ln h3 (2mkB T )3/2 e kB T N

3N

U (r) BT

d3 r

(115)

The eect of interactions between the molecules

Suppose, now, that we introduce pairwise interactions into the total energy. Dropping the external potential from the energy, we have E =
i

p2 i + u(ri rj ) 2m i>j p2 i + uij 2m i>j (116)

The partition function is now 1 1 Z= N ! h3N d

3N

rd pe

3n

p2 i i 2m

uij i>j kB T

(117)

26

A little inspection reveals that this partition function is far from trivial to evaluate. In fact, for general interaction potentials, u(r), the exact evaluation of the 6N -fold integration is impossible, at least at present. So, what can one do? Here is one trick that works if the interaction energies are small compared to other energies. First, we write euij /kB T as follows: euij /kB T = 1 + euij /kB T 1 1 + fij Then, e
i>j

(118)

uij

=
i>j

euij /kB T [1 + fij ]

i>j

(119)

If iij kB T , then euij /kB T 1, and fij is small. We can then try to expand the product in (119) with respect to the small quantities fij : [1 + fij ] = 1 +
i>j i>j

fij +

(120)

Then, the partition function is given by Z = 1 1 h3N N ! d3N pd3N re d3N pd3N re

p2 i i 2mkB T

[1 + fij ]
i>j

1 1 3N h N!

p2 i i 2mkB T

1 +
i>j

fij

(121)

The zeroth order term in the expansion above is 1 1 h3N N ! d3N pd3N re

p2 i i 2mkB T

1 VN [2mkB T ]3N/2 hN (N/e)N

(122)

which is the partition function of the noninteracting gas. The rst order term is 3N 2 1 e N p dpe 2mkB T d3N rfij (123) h3N N i>j 27

The result of the integration above will be the same for every index pair, i, j. This means that the rst order term will be equal to the result of the integrations for a given i and j, (say, i = 2, j = 1) multiplied by the number of distinct pairs. This number, the number of ways of making unordered pairs out of a set of N objects, is N (N 1)/2. The rst order term is, thus,
2 e N N (N 1) 1 p e 2mkB T dp f12 d3 r1 d3 r2 2 h3N N e N N (N 1) 1 [2mkB T ] V N 2 f12 d3 r1 d3 r2 = 3N 2 h N

3N

d3(N 2) r (124)

Now, because f12 = eu12 /kB T 1 = eu(r1 r2 ) 1 depends only on the dierence r1 r2 , we can write the integral f12 d3 r1 d3 r2 as follows: d3 r1 d3 (r1 r2 )f12 = V e
k
u(r) BT

1 d3 r (125)

V 1 (T ) Our rst order term is equal to N2 2 e N [2mkB T ]3N/2 V N 1 1 (T ) h3 N eV N NN = [2mkB T ]3N/2 1 (T ) 3N h 2 V

(126)

Adding the zeroth and rst order terms in our new expansion, we obtain eV Z= h3 N
N

[2mkB T ]3N/2 1 +

NN 1 (T ) 2 V

(127)

This means that the free energy, to rst order in our expansion, is given by F = kB T ln Z 2mkB T = kB T ln h2

3N/2

V e N

NN 1+ 1 (T ) 2 V
N

2mkB T = N kB T ln h2 kB T ln 1 +

3N/2

V e N

NN 1 (T ) 2 V 28

(128)

The next step is to perform an entirely unjustied expansion. We write ln 1 + NN NN 1 (T ) 1 (T ) 2 V 2 V (129)

This expansion is valid if (N/2)(N/V )1 (T ) 1. Clearly, as the system becomes arbitrarily large (N , V , N/V a constant) the second term in the logarithm that we have expanded overwhelms the rst one. Lets ignore that problem for the time being and continue. We now have 2mkB T F = N kB T ln h2

3/2

N eV N kB T 1 (T ) N 2V

(130)

We now have in hand the rst two terms in the virial expansion of the Helmholtz free energy. This expansion produces corrections to the ideal gas laws. The corrections are small as long as the gas is dilute and the temperature is not too low.

Modication of the equation of state

Lets see how our result for the Helmholtz free energy alters the equation of state that expresses the pressure, P , as a function of N , V and T . We have P = F V

T,N

2mkB T = N kB T ln V h2 = nkB T N 2 kB T 1 (T ) V V 2 N N 1 (T ) kB T 1 = V V 2

3/2

eV N + N kB T 1 (T ) N 2V

(131)

Notice that as N/V goes to zero, the second term in brackets on the last line of (131) will become negligible compared to the rst one. Furthermore, if kB T is suciently large and u(r) is well-behaved, 1 (T ) = eu(r)/kB T 1 d3 r u(r) 3 dr kB T 29 (132)

so dening a as follows: a we have 1 2 u(r)d3 r (133)

N 2 N kB T a (134) P = V V If the molecules attract each other, then the interaction potential u(r) will be negative and a as dened in (133) will be positive. Rearranging the terms in (134) we end up with the equation of state N P +a V
2

V = N kB T

(135)

This is almost the van der Waals equation of state. If we were to invoke the notion of impenetrable hard cores, and reduce the eective volume, V in (135) by V N b, where b is the volume displaced by each molecule, we would have the van der Waals equation of state in its entirety.

30

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Quantum statistical mechanics

Symmetric and antisymmetric wave functions
An important tenet of quantum mechanics is that the wave function of N identical particles will be either symmetric or antisymmetric with respect to interchange of two of them. For reasons having to do with relativity and locality in quantum eld theory the parity (symmetry or antisymmetry) of the wave functionis tied to the intrinsic spin of the particles that it controls. Particles with integral spin have symmetric wave functionsand obey BoseEinstein statistics. Particles with half-integral spin have wave functions that are antisymmetric with respect to particle interchange. Such particles obey Fermi-Dirac statistics. If identical particles can occupy single-particle energy levels, then the state of an N -particle system is completely specied by the number of particles that occupy each level. The issue of which particle occupies which level is meaningless in the context of a symmetric or anti-symmetric wave function. In this the key dierence between Fermi-Dirac and Bose-Einstein particles is that any number of Bose-Einstein particles can occupy a given energy level, while at most one Fermi-Dirac particle can occupy a single energy level. This is because interchange of the two particles occupying the same energy level yields the same wave function, which is impossible if the wave function is antisymmetrized. To see how statistics work out, lets calculate the grand partition function for each type of particle Bose-Einstein Let the energy of the ith level be i . The occupation number of the ith level will be denoted ni . The total energy of the system is ni
i i

(172)

and the total number of particles is ni

i

(173)

Then, eE+N = e 40
i

ni i +

ni

=
i

eni

i +ni

=
i

eni ( i )

(174)

The sum over states is a sum over all possible values of the occupations numbers, ni . Since each occupation number can take any value from 0 to , we have

e
states

Estate +Nstate

= = =
i

eni ( i )

n1 =0 n2 =0 i ni ( i ) i ni=0

1 1 e( i )

(175)

Thus, the grand partition function, , is given by = kB T ln Q = kB T ln

i

1 1 e( i ) (176)

= kB T
i

ln 1 e( i )

Now, N = = kB T

ln ln 1 e( i )
i

=
i

=
i

e( i ) 1 e( i ) 1 ( i ) e

(177)

This seems to indicate that the average occupation number per energy level will be given by 1 ni = ( i ) (178) e 1 which is, in fact, the case. 41

Fermi-Dirac Here, the grand partition function is exactly as it is in the case of BoseEinstein particles, except that the ni s take on the values of 0 and 1 only. The grand partition function is Q =
n1 =0,1

en1 ( 1 )
n2 =0,1

en2 ( 2 ) 1 + e( 2 ) (179)

= =

1 + e( 1 ) 1 + e( i )
i

and = kB T ln Q = kB T ln 1 + e( i )
i

(180)

and N = =
i

e( i ) 1 + e( i ) 1 e( i ) + 1

=
i

(181)

which seems to indicate that ni = 1 e( i ) +1 (182)

The Fermi gas

Suppose that the fermions are electrons. In particular, assume that they are the conduction electrons in a metal. According to the currently-accepted version of simple metals, the conduction electronselectrons in the outer orbitals of the constituent atomsare released and propagate freely through the metal. The ionized atoms that they leave provide a positively charged, eectively inert, background. In the following, we will neglect the charges 42

carried by the electrons, which means that we will ignore the electromagnetic interactions between them, and between the electrons and the ionic background. In light of the importance of electromagnetic interactions at the atomic level, it may seem a little unreasonable to expect our results to be very useful, but they turn out to correspond remarkably well with experimental observations in the case of a number of real metals. One of the important results of mid-twentieth-century solid state physics is a series of calculations that show why it is permissible to neglect electrostatic interactions for some purposes. Actually, what those calculations show is how some of the essential features of a non-interacting collections of electrons are preserved when the interactions are included. It also turns out that we are provided by nature with another system to which the calculations are directly relevant. That system is a uid consisting of 3 He, the two-proton-one-electron isotope of Helium. Because 3 He contains an odd number of Fermions, its total spin (internal angular momentum) is half-integral. 3 He is a uid at very low temperatures. At extremely low < temperatures, 103 K, it is a superuid. The calculations below do not apply to that exotic state of matter. However, when 3 He is a normal uid it does behave, in many respects, the way a non-interacting gas of Fermi-Dirac particles is predicted to behave. This behavior and more complex behavior that can be explained in terms of interactions, is described theoretically by a model developed by the celebrated Russian physicist Lev Landau. The model is known as the theory of normal Fermi liquids. Fermions are assumed to be conned to a rectangular box. The eigenstate of a single particle in such a box is a standing wave. If the dimensions of the box are (Lx , Ly , Lz ) then the wave-vector of the standing wave will be of the form nx ny nz , , (183) (kx , ky , kz ) = Lx Ly Lz The energy of this eigenstate is E k h2 2 2 k 2 + k y + kz 2m x h2 nx 2 ny + = 2m Lx Ly =

nz + Lz

(184)

The sum over eigenstates is accomplished as follows: 43

We know that a unit change in one of the quantum numbers, say, nx , leads to an incremental change in the corresponding component of k, kx , equal to /Lx . That is, kx = (185) Lx Furthermore, ky = /Ly , kz = /Lz . Thus, because each of the factors in brackets below is equjal to one, the product Lx L y Lz 3 (186)

is equal to one. We can turn the sum over a suciently smooth function of k into an integral with the use of the above identity f k = = V 3 f k L x Ly Lz kx ky kz 3 (187)

f k kx , ky kz

Since each ki becomes innitesimal as Lx , Ly , Lz we can replace the sum above by an integral, i. e. f k V 3 f k dkx dky dkz (188)

The integrals are over positive kx , ky , kz . If the function has the property f (kx , ky , kz ) = f (kx , ky , kz ) = , then we can replace the integral above by an integral over all ks, so that f k V (2)3 f k d3 k (189)

Finally, if we replace kx by px / , and similarly for ky and kz , h f k v (2)3 V = (2)3 = f k dpx dpy dpz f p dpx dpy dpz h (190)

In the case of Fermions, = kB T ln Q 44

= kB T
i

ln 1 + e( i )
h ln 1 + e k
2

= kB T = kB T

k2 /2mkB T +/kB T

V 2 ln 1 + ep /2mkB T +/kB T d3 p 3 (2 ) h 2 V p + = kB T 4 ln 1 + e 2mkB T kB T p2 dp (2 )3 h 0 The number of particles is given by N = 4V kB T = (2)3

0

(191)

0
2 BT

ln 1 + e
+ k T
B

p 2mk

2 BT

+ k T
B

p2 dp

V = 2 2 h3 V 2 2 h3 V = 2 2 h3 =

p 2mk

1+e

p2 2mk T B

+ k T
B

p2 dp

p2 dp e[ (p)] + 1

(192)

Here, (p) = p2 /2m, and, as always, = 1/kB T . Occupation of a single energy level Using an argument like the one that led to a result for the probability that a given two-state atom is in the excited state, we arrive at the following result for the expectation, or average, value of the occupation number of the ith single particle statein the case of Fermions. ni = 1 e( i ) +1 (193)

This result arises naturally when we consider the way in which averages are taken in the grand canonical ensemble.

45

The extra factor of two We have neglected an important property of electrons; they have two spin polarization statesspin up and spin down. That is, each spatial eigenstate each kcorresponds to two electron eigenstates, one for each spin polarization. That means that we really ought to have for the formula for the number of particles N = 2
p2 dp V 2 2 h3 0 e[ (p)] + 1 V p2 dp = 2 h3 0 e[ (p)] + 1

(194) (195)

The limit T = 0 If T = 0, then = , and the function e( ) takes on one of two values: 0 when (p) < and when (p) > . This means that, in the limit of zero temperature, 1 1 (p) < = (196) [ (p)] + 1 0 (p) > e and our expression for N has the form N = V p2 dp 2 h3 (p)< 2m V = p2 dp 2 h3 0 V = [2m]3/2 3 2 h3

(197)

The integral over p is conned to the interior of a sphere in p-space of radius [2m]1/2 . This radius is called the Fermi momentum, pF . The energy, p2 /2m = , is called the Fermi energy, F . F

46