School of Physics and Astronomy: File Topic09 PDF

School of Physics and Astronomy
Junior Honours Thermodynamics
GJA 2013-2014
Lecture TOPIC 9 1 (Finn: 5.6, 5.8, 5.9, 5.10)

Synopsis: The Second Law of Thermodynamics (review) and the Central Equation of Thermodynamics.
Entropy of an ideal gas. Entropy, probability and disorder.
The Principle of Increasing Entropy: corollary
Imagine the system of interest plus surroundings to be enclosed by an adiabatic wall (eg a wall enclosing some large volume of surroundings providing a practical realisation of a reservoir). Then for the
ensemble dq = 0 S 0.
The entropy of a thermally isolated ensemble comprising the system plus surroundings can never decrease.
This will be used later to examine conditions for equilibrium under different sets of circumstances.
The Central Equation of Thermodynamics
This combines the first and second laws for infinitesimal reversible processes in differential form:
dU = dQ + dW
dU = TdS - PdV
This equation involves only state variables. It can therefore always be integrated to relate changes
of state variables independent of the path of integration, even when those changes occur via irreversible
processes. It effectively replaces an irreversible path with an equivalent reversible path along which
the integrals can be done. Owing to its usefulness and generality it is called the central equation of
thermodynamics and is also usefully written:
T dS = dU + PdV
If applied to a system which is not a simple fluid, the equation has to be augmented to allow for other
variables. For electric charge (denoted by Z) driven through a system by an emf E , the equation becomes
dU = T dS PdV + E dZ. For a one dimensional system like a rubber band under tension F , changes in
length L dominate, so the the equation becomes dU = T dS + F dL.
Entropy of an ideal gas
For an Ideal gas U = U(T ), so that dU = Cv dT . The central equation for dS, or, more conveniently, for
the molar entropy ds then gives:
dT
dv
ds = cv
+R
T
v
where the Ideal gas equation has been used to re-express the second term. Integrating the above expression gives:
s = cv ln T + R ln v + s0
with s0 the constant of integration. In a Joule, or free expansion of an ideal gas, U does not change,
nor therefore does T . However, because v changes, there must be a change in entropy s. For 1 mole of
ideal gas, the change in entropy during a free expansion is:
s f si = cv ln T f + R ln v f + s0 (cv ln Ti + R ln vi + s0 ) = R ln
1 file
topic09.pdf
vf
vi
An example, heating water on a stove

Question: Calculate the change in entropy of water heated from 20o C to 100o C on a stove.
method 1: as per topic 08. A reversible path is constructed involving a series of heat baths between
initial and final temperatures Ti and T f with the water brought into contact with each bath in turn. The
thermodynamic definition of entropy relates changes of entropy to reversible heat transfers, which can
be applied along this alternative path between Ti and T f :
S =
Z Tf
dqR
Ti
Z Tf
Cp dT
Ti
The change of entropy of the water is the same as in the irreversible process that actually occurs since
entropy is a state function and the initial and final equilibrium states match.
method 2: Brute force solution applying the central equation:
S =
Z f
dU
i
Z f
p
i
dV
We know only Ti and T f and pi = p f , but not Ui and U f or Vi and V f . Therefore we need to expand dU
and dV in terms of {p,T}.

U
Z f U
Z f h
dT
+
V
i
T p
p Tdp
p V
S =
+
dT +
dp
T
T p
p T
i
i T
pot is open to atmosphere, so the natural choice of path is p = const = pi = p f for which d p = 0.

(U+pV )
V
H
Z T f U
Z
Z
Z Tf
+
p
Tf
Tf
T p
T p
T
T p
Cp
p
S =
dT =
dT =
dT =
dT
T
T
T
Ti
Ti
Ti
Ti T
method 3: The water is heated at constant pressure so it is likely to be more convenient to work with
H=U+PV rather than U, which combined with the central equation gives
dH = dU + pdV +V d p = (T dS pdV ) + pdV +V d p = T dS +V d p
dH = T dS +V d p
The above is an equivalent form of the central equation. We can integrate this choosing the path p =const
to get
Z
Z
dH
dS =
p=const
p=const T

Writing H = H(T, P) dH = HT dT + Hp d p = Cp dT + Hp d p. Thus along the path p =const
p
dH| p = Cp dT
S =
Z Tf
Cp
Ti
as found previously.
dT
In methods (2) & (3) we have not to had to think explicitly about an equivalent reversible path for the
irreversible process as done in method (1). The central equation deals with this implicitly.
Another example, electrical work
Consider an emf E driving a current I through a resistor R. The power delivered is E I = I 2 R. Suppose
the resistor, regarded as the system, completely fills a box with adiabatic walls. The power is dissipated
irreversibly in the resistor, which therefore heats up.
2
From the 1st law the change in internal energy of the system in time interval t is U = (q = 0)+w =
I 2 Rt (assuming the volume is fixed so that no mechanical work is done). We can relate changes of
U to changes of temperature for a constant volume process with dU = CV dT |V const . The change in
temperature is then:
Z
I 2 Rt =
Tf
CV dT = CV T
Ti
where the last equality follows if CV can be approximated as constant (independent of temperature)
T = I 2 Rt/CV .
What is the change of entropy?
method 2 The change of entropy can be calculated with the central equation dS = dU/T |V const dS =
RT
CV dT /T |V const S = Ti f CTV dT with T f calculated above.
method 1 The same answer can be found by thinking of a reversible process leading to the same change
of state variables between the initial and final equilibrium states, in this case a change of temperature
T . This could be achieved by putting the resistor successively in thermal contact with a sequence of
heat reservoirs, starting with one at Ti and ending with one at T f giving:
Z Tf
S =
Z Tf
dqR /T =
Ti
Cv dT /T
Ti
ie we have considered an alternative process where heat enters the system reversibly but no work of any
kind is done.
The connection between Entropy, Counting, and Probability

a preview of subject matter to be developed in next terms statistical mechanics course
The Second Law shows that the total entropy of an isopartition
lated system must increase and is maximised at equilibrium.
In statistical physics we expect a system to change from a
less probable initial state to a more probable final state. This

V
V
suggests there is a relationship between probability and engas
vacuum
tropy. As an example, consider the Joule expansion of a
large number of atoms, N, of an ideal gas (see figure). Imbreak
mediately after the partition is removed the gas is initially
partition
?
?
all on the left hand side of the container, whereas in the final
state the gas has an equal density everywhere. Denote the
2V
left hand side of the container by A and the right hand side
gas everywhere
by B with VA = VB = V for simplicity. A long time after the
partition has been removed and assuming the system is free
to explore all possible states available to it (respecting energy conservation), the probability that any one
molecule is in A is 1/2. The chance that all the molecules are in A is (1/2)N . This is the probability of
finding the system in its initial state a long time after the wall has been removed. Denote the total number
of possible states available with energy E and all the particles in A, to be A (N,VA , E). Denote the
total number of states with energy E, N particles, and volume VA +VB with the particles located anywhere
within volume VA +VB as A+B (N,VA+B , E). Assume that all the accessible microstates are equally
likely. Then
1 N
A
(N,V, E)
=
=
(1)
A+B (N, 2V, E)
2
Suppose that there is a relationship between the entropy and the number, , of microstates available to
the system; S = f () where f is some arbitrary function. If we consider 2 isolated systems we know
that the total entropy is the sum of the entropies of each state, S = S1 + S2 , whereas the total number of
microstates available grows much faster, as the product 1 2 . Therefore we require that,
f (1 2 ) = f (1 ) + f (2 )
(2)
Only a logarithm can achieve this Formally: differentiate EQN 2 first with respect to 1 and then with
respect 2 (eg by changing the volume of system 1 and then the volume of system 2) we have:
f 0 (1 2 )2 =
00
f 0 (1 )
f (1 2 )1 2 + f (1 2 ) = 0
00
(differentiating EQN 2 w.r.t. 1 )
(3)
(differentiating EQN 3 w.r.t. 2 )
(4)
= f (x)x + f (x) = 0
(substituting 1 2 = x in EQN 4)
0
d(x f (x))
= 0
=
dx
kB
= f 0 (x) =
(kB is an arbitrary constant at this stage)
x
= f (x) = kB log(x) + const
(5)
(6)
(7)
(8)
Thus we see that if S and are related the relationship must be of the form S = kB log() + S0 . Setting
the constant S0 to zero defines a natural zero for the entropy; if the state is unique (eg the system is in
a quantum ground state) the entropy is zero. As the temperature is increased more states are accessible
and the entropy increases (we will return to this when we discuss the 3rd law). Call S defined in this way
the statistical entropy:
S = kB log()
Definition of statistical entropy for fixed E
(9)
Taking the logarithm of our expression for an Ideal gas, EQN 1, we have:
SA+B SA = kB Nlog(2)
(10)
SA+B is the statistical entropy of the gas freely occupying the whole volume, which is the final equilibrium
state of the system. SA is the statistical entropy when the gas is restricted to be in volume VA , which
is the initial state of the system. The expression is identical to the expression for the change in the
thermodynamic entropy (page 2) if we identify kB NA = R (where NA is the number of atoms in a mole).
kB is the Boltzmann constant.
General definition of statistical entropy

It is often more convenient to work with systems at constant temperature than at constant energy. The
collection of states available is known as a canonical ensemble. A micro-canonical ensemble refers to
the collection of states with a fixed total energy. It will be proved next term that a more general statistical
definition of entropy that is also applicable to the canonical ensemble is given by:
S = kB
pi log(pi )
general statistical definition of entropy
(11)
The sum is over all microstates accessible to the system. pi is the probability that the system is in
microstate i. If we specialise to the micro-canonical ensemble where the total energy is fixed, all the
microstates have a-priori equal probability. If there are possible states, pi = 1/ is the probability of
the system being in any one of them. Substituting this into the above expression for the statistical entropy
we get the expression for the entropy of a micro-canonical ensemble given in EQN 9.
Heat and work in the statistical picture

The mean energy of a system can be written as probability of a given energy that energy: < E >=
i pi i where i is the energy of each (quantum mechanical) microstate. The differential of E is,
d < E >= d pi i + pi di
i
The first sum on the right hand side can be interpreted as heat supplied to the system and the second sum
can be interpreted as the work done. < E > corresponds to the internal energy, U (proof in Stat.Mech.).

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School of Physics and Astronomy

Junior Honours Thermodynamics

Lecture TOPIC 9 1 (Finn: 5.6, 5.8, 5.9, 5.10)

An example, heating water on a stove

The connection between Entropy, Counting, and Probability

less probable initial state to a more probable final state. This

(differentiating EQN 2 w.r.t. 1 )

(differentiating EQN 3 w.r.t. 2 )

Definition of statistical entropy for fixed E

General definition of statistical entropy

general statistical definition of entropy

Heat and work in the statistical picture

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