Phy 260

STATISTICAL MECHANICS
Statistical mechanics is the
complex art of turning the
microscopic laws of physics into
a description of Nature on a
macroscopic scale.
 Know their mass,
charge, interactions etc.
Xxxxxxxxxxxxxxxxxxxx x

Xxxxxxxxxxxxxxxxxxxx x

Number of particles far Know Newtons Laws

greater than 10 23 Know Schrodingers
equation
What can we say about some simple questions about the stuff in the
box: is it hot? If we heat the box, what happens? How to go from
microscopic world where natures laws are known to the world around
us?
How Large is Large?
What is the temperature in this room? Say 200C.
The temperature is due to the air molecules. How many air molecules
are in this room?
Estimate the size of this room, say 10m x 10m x
3m; vol = 300m3
1L = 1000cm3 ; 1m3 = 100cm x100cm x 100cm
= 1000000cm3 = 103L
Vol = 300 x103L = 3 x 105L
How Large is Large?
At STP, I mole of air (ideal gas) occupies 22.4 L.
At 200C , the number of moles of air particles (using PV = nRT) is
n = (1atm x 3x105L)/(0.0820L.atm/mol-1.K)(293.15)K
= 3x105 atm.L /(24.03 atm.L.mole-1)
= 0.125 x 105 moles
= 6.02 x 1023 x 0.125 x 105 molecules!
= 7.51 x 1027 molecules!
 Not a chance! But we assume they
move randomly and apply the laws
of probability to predict how they
behave as a whole.
Some of the properties of bulk
matter does not depend on the
details.
Example: Heat flows from hot to
cold spontaneously
 The properties of bulk matter that
does not depend on the micro-
scopic details and the principles
that generalize them comprises
thermodynamics.
Examples: Liquids boil more
readily at lower pressure.
The maximum efficiency of heat
engine is the same whether steam
or air is used.
 How to make connection between
one molecule and 10 27 ?

Do we want to understand matter

in more detail?

For this, we must take into

account the quantum behavior of
atoms and the laws of statistics.
 When we do, we can explain the
properties of materials, say metals.
We can also explain why the
principles of thermodynamics are
what they are-why heat flows
from hot to cold, for example.
This underlying explanation of
thermodynamics comes from
statistical mechanics.
 Thermodynamics is a funny subject.
The first time you go through it, you
dont understand it at all. The second
time you go through it, you think you
understand it, except for one or two
little points. The third time you go
through it, you know you dont
understand it, but by that time you are
so used to it, it does not bother you
anymore
Arnold Sommerfeld
 Thermodynamics is a funny subject.
The first time you go through it, you
dont understand it at all. The second
time you go through it, you think you
understand it, except for one or two
little points. The third time you go
through it, you know you dont
understand it, but by that time you are
so used to it, it does not bother you
anymore
Arnold Sommerfeld
 Classical Thermodynamics is the
only physical theory of universal
content which will never be
overthrown
Einstein
Statistical Mechanics (Variety of ideas)
Is the theory with which we analyze the behavior of
natural or spontaneous uctuations
provides a set of tools for understanding simple behavior
that emerges from underlying laws
provides the basic tools for analyzing the behavior of
complex systems in thermal equilibrium
involves systems with a larger number of degrees of
freedom than we can conveniently follow explicitly in
experiment, theory or simulation
Classical mechanics, atomic physics,
quantum mechanics, nuclear
physics...deal with one or two or a few
dozen particles.
Statistical mechanics treats matter in
bulk; deals with, typically, about a mole
of particles at one time.
Thermodynamics describes ordinary matter on the level
of ordinary experience. Loosely speaking, it is the theory
of the quantitative relations between volume and
pressure, temperature and heat, and how this
characterizes dierent substances in their dierent phases
as solid, uid, or gas.
Statistical mechanics is the part of physics that derives
the macroscopic properties of matter which themselves
are primarily described by thermodynamics from
microscopic principles.
Thermodynamics is a phenomenological description of
equilibrium properties of macroscopic systems.
As a phenomenological description, it is based on a
number of empirical observations which are summarized
by the laws of thermodynamics. A coherent logical and
mathematical structure is then constructed on the basis
of these observations, which leads to a variety of useful
concepts, and to testable relationships among various
quantities.
The laws of thermodynamics can only be justied by a
more fundamental (microscopic) theory of nature. For
example, statistical mechanics attempts to obtain these
laws starting from classical or quantum mechanical
equations for the evolution of collections of particles.
Here is one need of statistical mechanics to justify the
laws of thermodynamics.
Thermodynamics is based on four
laws :
0. Thermodynamic equilibrium exists and is
characterized by a temperature.
1. Energy is conserved.
2. Not all heat can be converted into work.
3. One cannot reach absolute zero
temperature
A.Why we need a Statistical Approach
To fully characterize any thermodynamic system, we would need to
know
The initial state of the system, defined by the position and
momentum vectors of every particle in the system
The detailed interaction potentials of all the particles in the system
The solution of Newtons laws or quantum mechanical laws for
each particle in the system
Therefore, we would have to approximately solve 6 coupled
equations with ( 1) interaction potentials
A precise mechanical description is too detailed to be of practical
use.
 The objective of statistical mechanics:
To develop a more detailed description of macroscopic
systems without performing a purely mechanical
treatment.
The goal of statistical mechanics is to obtain all the
equilibrium properties of macroscopic systems by :
Applying the laws of mechanics (thus, deriving
thermodynamics from more fundamental principles)
Giving mechanical meaning to thermodynamic variables
This is accomplished by combining mechanics with
general statistical principles.
B. Methodology of Statistical Mechanics
Mechanics provides the physical framework (such as
conservation
Statistics replaces the rigorous detail required by
mechanics by using statistical assumptions whose
validity is verified by experiment.
The essential methodology of statistical mechanics can
be as follows:
Specify the macrostate and accessible microstates of
the system
Choose the statistical ensemble that is appropriate for
the system
Determine the mean values and other statistical
properties of the system.
We introduced three new terms. We will come back to them later.
In this course we will only consider systems
at thermodynamic equilibrium.
This means no time or fluxes appear in our discussion.
Neither the history of reaching equilibrium nor the speed
at which the equilibrium is reached is not of focus here.

A system at a steady state (a state that is not

changing in time) is not necessarily at thermodynamic
equilibrium since there may be a ux imposed by boundary
conditions.
We are not studying these systems either.
Thermodynamic Equilibrium: is
an axiomatic concept of thermodynamics. It is an
internal state of a single thermodynamic system,
or a relation between several thermodynamic
systems connected by more or less permeable or
impermeable walls. In thermodynamic
equilibrium there are no net macroscopic flows
of matter or of energy, either within a system or
between systems..
A system under study is said to be in equilibrium when
its properties do not change appreciably with time over
the intervals of interest (observation times). The
dependence on the observation time makes the concept
of equilibrium subjective. For example, window
glass is in equilibrium as a solid over many decades, but
ows like a uid over time scales of millennia. At the
other extreme, it is perfectly legitimate to consider the
equilibrium between matter and radiation in the early
universe during the rst minutes of the big bang.
Systems in mutual thermodynamic equilibrium are
simultaneously in
mutual thermal, mechanical, chemical,
and radiative equilibria. Systems can be in one kind
of mutual equilibrium, though not in others. In
thermodynamic equilibrium, all kinds of equilibrium
hold at once and indefinitely, until disturbed by
a thermodynamic operation.
A collection of matter may be entirely isolated from
its surroundings. If it has been left undisturbed for an
indefinitely long time, classical thermodynamics
postulates that it is in a state in which no changes
occur within it, and there are no flows within it. This
is a thermodynamic state of internal equilibrium.
In a system in its own state of internal thermodynamic
equilibrium, no macroscopic changes occur. At
thermodynamic equilibrium, thermodynamic parameters
do not change with time.
Thermodynamic variables are the quantities like
pressure, volume and temperature, which help us
to study the macroscopic behavior of a
thermodynamic system. There are some other
thermodynamic variables such as entropy,
internal energy, etc., but these thermodynamic
variables can be expressed in terms of pressure,
volume and temperature
The equilibrium state is then characterized by a set of
variables like:
Pressure, p; volume, V ; electric polarization, P
magetization, M ;particle numbers, Ni of particles of type i
etc.
This implies that it is irrelevant what the previous volume,
magnetization etc. of the system were. The equilibrium
has no memory!
If a function of variables does not
depend on the way these variables have
been changed it can conveniently
written as a total differential like dV or
dNi etc.
Typically a system at thermodynamic equilibrium is
homogeneous since gradients usually produce uxes
(e.g., gradients of temperature produce a heat ux). If
we exchange one small volume in the system with
another, no gradients are there.
Zeroth law:
If two system are brought into contact such that energy
can flow from one system to the other. Experiment tells
us that after sufficiently long time they will be in
equilibrium with each other. Then they are said to have
the same temperature. If for example system A is in
equilibrium with system B and with system C, it holds
that B and C are also in equilibrium with each other.
Thus, the temperature is the class index of the
equivalence class of the thermodynamic equilibrium
From this it may be shown to follow that the
condition for thermal equilibrium between several
assemblies is the equality of a certain single-valued
function of the thermodynamic states of the
assemblies, which may be called the
temperature T, any one of the assemblies being
used as a thermometer reading the
temperature t on a suitable scale. This postulate of
the existence of temperature could with advantage
be known as the zeroth law of thermodynamics.

Fowler and Guggenheim

The concept of temperature. As
a natural generalization of
experience we introduce the
postulate: if two assemblies are
each in thermal equilibrium with
a third assembly, they are in
thermal equilibrium with each
other.
 How to get this single-valued
function of the thermodynamic
states?
Consider three systems A, B and C.
Let PA, PB ,PC, VA, VB, and VC be their
mechanical variables. P =
pressure, V = molar volume.
If A and C are in thermal contact
across a rigid wall and in equili-
brium, not all four variables are
independent.
 The variables are connected by an
equation of state. This can be
written as (PA, VA ; PC, VC ) = 0 or
PC = 1 (VA , VC ; PA ).
Similarly, when B and C are in
equilibrium, as (PB, VB ; PC, VC ) =
0 or PC = 2 (VB , VC ; PB ).
By Zeroeth law, A and B are in
thermal equilibrium.
This requires that
(PA, VA ; PB, VB ) = 0 Eqn (1)
implying that PA, VA , PB and VB are
interdependent.
We also know that
PC = 1 (VA , VC ; PA )
= 2 (VB , VC ; PB ) implying a
functional relationship exits
between PA, PB , VA, VB, and VC
Implying (PA, VA ; PB, VB; VC ) = 0. (Eqn 2.)
How to reconcile the two functions and
, one implying that PA, VA ; PB, VB; are
interdependent but not dependent on
VC and the other that they are
dependent on VC ?)
To Summarize:
1. PC = 1 (VA , VC ; PA )
2. PC = 2 (VB , VC ; PB )
3. (PA, VA ; PB, VB; VC ) = 0.
The problem is VC
How to develop a function that
depends on VC but also satisfies 1 and 2
that does not involve VC ? Make the
dependence on VC a product type and the
same for 1 and 2 . This way when we
write 1 = 2 the common function that
depends on VC gets factored out and the
dependence on VC gets eliminated.
In addition, we can also add a common
function of VC to 1 and 2 that also gets
eliminated when we write 1 = 2 .

This is possible if the functions 1 and 2

are of this form:
1 (VA , VC ; PA ) = 1 (VA , PA ) (VC ) + (VC
)

and
2 (VB , VC ; PB ) = 2 (VB , PB ) (VC )
+ (VC )

1 = 2 implies the validity of

equation 1. Looking at the right
hand side, it is seen that

1 (VA , PA ) = 2 (VB , PB ) =
 We call this empirical temperature.
Thus, for every system, it is possible to
find a function of mechanical variables
P and V such that when the systems are
in equilibrium, they have the same value
of .
 Does it make sense to say that one
object is twice as hot as another?
In the Celsius or Fahrenheit scales,
it makes no sense since the zero is
arbitrary. Is 20C twice as hot as
10C? But in using the kelvin scale,
it makes perfect sense. 2K is twice
as hot as 1K.
The ideal gas temperature scale: The zeroth law merely
states the presence of isotherms. In order to set up a
practical temperature scale at this stage, a reference
system is necessary. The ideal gas occupies an
important place in thermodynamics and provides the
necessary reference. Empirical observations indicate
that the product of pressure and volume is constant
along the isotherms of any gas that is suciently dilute.
The ideal gas refers to this dilute limit of real gases, and
the ideal gas temperature is proportional to the
product.
The constant of proportionality is determined by
reference to the temperature of the triple point of the
icewatergas system, which was set to 273.16 degrees
Kelvin (0K) by the 10th General Conference on Weights
and Measures in 1954. Using a dilute gas (i.e. as P 0)
as thermometer, the temperature of a system can be
obtained from
State Functions and Equation of state:
In thermodynamics, a state function is a function
defined for a system relating several state
variables or state quantities that depends only on
the current equilibrium state of the system. State
functions do not depend on the path by which
the system arrived at its present state. A state
function describes the equilibrium state of
a system
For example, internal energy, enthalpy,
and entropy are state quantities because they
describe quantitatively an equilibrium state of
a thermodynamic system, irrespective of how the
system arrived in that state. In contrast, mechanical
work and heat are process quantities or path
functions, because their values depend on the
specific transition or path between two equilibrium
states.
Commonly used parameters include: pressure, P, and
volume, V tension, and length, L magnetic eld, H
and magnetization, M. These parameters appear in pairs,
the rst being a generalized force and the second a
generalized displacement, with the product of the pair
having the dimensions of energy. All these parameters
are well-dened by mechanics and are readily measured
mechanically.
An additional thermodynamic parameter, temperature,
T, is not a mechanical parameter
The following are considered to be state functions
in thermodynamics:

In thermodynamics, the exergy (in older usage, available work and/or availability) of a system is the maximum
useful work possible during a process that brings the system into equilibrium with a heat reservoir
In physics and thermodynamics, an equation of
state is a thermodynamic equation relating state
variables which describes the state of matter under
a given set of physical conditions. It is an
equation which provides a mathematical relationship
between two or more state functions associated with
the matter, such as
its temperature, pressure, volume, or internal
energy. Equations of state are useful in describing
the properties of fluids, mixtures of fluids, solids, and
the interior of stars.
For a given amount of substance contained in a
system, the temperature, volume, and pressure are
not independent quantities; they are connected by a
relationship of the general form:
Although usually not the most convenient equation of state, the virial equation is important because it can be
derived directly from statistical mechanics.
First law: The first law is essentially just energy
conservation. The total energy is called the internal
energy U (some books use E instead of U). U is nothing
else but the expectation value of the Hamilton operator.
Changes, dU of U occur only by causing the system to do
work, W, or by changing the heat content, Q. To do work
or change heat is a process and not an equilibrium state
and the amount of work depends of course on the
process (path). Nevertheless, the sum of these two
contributions is a total differential.
Call U(V,T) the internal energy of our system. One way
that the energy can change is if the system does
mechanical work. The work done by a system in going
from state A to B is,

since Work = Force Distance = (Force/Area)

(DistanceArea) = (Pressure) (Volume). Graphically, the
work done is the area under the path travelled in going
from A to B as shown in Fig.
Path from points A to B in pressure-volume diagram
By conservation of energy,

where QAB is the non-mechanical energy change in

going from A to B. We call QAB the heat added to the
system in going from A to B. If A and B are
innitesimally close,
dU = dQdW = dQPdV 1.1
where dU is an exact dierential though dQ and dW
are not. This is the rst law of thermodynamics, which
simply states that total energy is conserved.
Example: For n moles of an ideal gas held at constant
temperature T0 nd the work done in going from volume
VA to VB.
Solution: The number of molecules in n moles is N = n NA
where NA = 6.2051023 is Avogadros number. The ideal
gas equation of state is

where R = k NA = 8.31 J/(mol K) is the universal gas

constant.
To nd the work done, we solve,

Since the temperature is xed at T0, then P(V ) =

nRT0/V or
The heat capacity gives the amount of heat energy
required to change the temperature of an object while
holding certain mechanical variables xed. We also
dene the heat capacity per unit mass, which is often
called the specic heat, and the heat capacity per
particle (e.g., cV = CV /N). For liquids and solids, since
their expansion at constant pressure is often negligible,
one nds CP CV ; this is certainly not the case for gases.
If we hold volume xed (i.e., set dV = 0) in this
expression and in Eqn. 1.1, then we obtain the result
This result is easy to understand since the change in
internal energy equals the heat added when volume is
xed since no work can be done if volume is xed. The
heat capacity is important because given the equation of
state and the heat capacity of a system, all other
thermodynamic properties can be obtained.
A quasi-static transformation is one that is performed
suciently slowly so that the system is always in
equilibrium. Thus at any stage of the process, the
thermodynamic coordinates of the system exist and can
in principle be computed. For such transformations, the
work done on the system (equal in magnitude but
opposite in sign to the work done by the system) can be
related to changes in these coordinates.
Typically one can divide the state functions {X} into a set
of generalized displacements {x}, and their conjugate
generalized forces {J}, such that for an innitesimal quasi-
static transformation
Table [1] provides some common examples of such
coordinates. Note that the displacement is usually an
extensive quantity, i.e. proportional to system size, while
the forces are intensive and independent of size.
Joules Free Expansion Experiment
Lets apply some of these results to a historically
important experiment. Take a dilute gas in an insulated
container as shown in Fig. Experimentally, one nds that
TB = TA, that is, the temperature remains constant after
the dilute gas expands to ll both sides of the containerIn
the free-expansion, the gas does no work so, WAB = 0.
The system is insulated so no heat enters or leaves, thus
QAB = 0. From rst law, the internal energy U must
remain constant.
The physical meaning of this result is that when the
particles in an ideal gas move farther apart, the energy
of the particles does not change. This means that there
is zero potential energy associated with any interaction
between the particles. In a real gas this is not exactly
true since there is a weak interaction between the
molecules. In an ideal gas we assume that the potential
energy is negligible so all the energy is kinetic energy.
Illustration of an ideal gas cooling in an adiabatic
expansion under pressure.
If CV constant then,
U(T) = CV T + constant (Ideal gas)
If we say U(T = 0) = 0 then for an ideal gas U(T) = CV T.
Later we derive these results using statistical
mechanics. Note: When a gas expands in a piston, it
does work and thus if the system is insulated, the gas
cools (see Fig.). In this case QAB = 0 as before but WAB
> 0 so UB < UA and thus TB < TA.
Example: For n moles of an ideal gas held at constant
temperature T0 nd the heat added in going from
volume VA to VB.

Solution: Since U(T) for an ideal gas, if T is xed, then so

is the internal energy. The rst law says, UB UA = WAB
QAB since UB = UA, then QAB = WAB, so the heat
added equals the work done for an isothermal path
The Second Law
The rst law rules out so called perpetual motion
machines of the rst kind, i.e. engines that produce
work without consuming any energy. However, the
conservation of energy is not violated by an engine that
produces work by converting water to ice. Such a
perpetual motion machine of the second kind would
certainly solve the worlds energy problems, but is
ruled out by the second law of thermodynamics.
Perpetual motion machine of the second kind is a
machine which produces work from a single heat
source. In this kind of perpetual motion machine,
there is only one heat reservoir, and it is being
spontaneously cooled generating work without
heat transfer to a cooler reservoir. The prototype
machine of this kind was the ammonia motor
(called zeromotor) proposed in 1880s by John
Gamgee. In ammonia motor, the heat reservoir is
filled with ammonia.
Ammonia boils at -33 C. It would be vaporized under
ambient temperature, producing a vapor pressure of 4
atm that would drive a piston. As the vapor expanded it
would also cool, condense and return to the reservoir
for the next cycle. This kind of machine is impossible,
since it violates the Second law of thermodynamics.
Heat cannot be transferred from a colder to a hotter
body. Therefore, it must be cooled by refrigeration for
the ammonia to be condensed, which requires more
energy than the energy produced by engine.
It was a tempting prospect and Gamgees enthusiasm
was such that he persuaded the Chief Engineer of the US
Navy and President Garfield to support the design.
However, even US Presidents cant break the Second
Law of Thermodynamics. The fatal flaw in Gamgees plan
was failing to understand that condensing ammonia
vapour would require cooling it to well below ambient
temperature, to -33C, something which would require
more energy than was obtained from the piston stroke.
Too bad, a shame for the man who saved the British cattle
industry and brought us New Zealand lamb and ice skating.
A device that extracts heat from a source and then converts
this heat completely into other forms of energy; it violates the
second law of thermodynamics. The signature of a perpetual
motion machine of the second kind is that there is only one
heat reservoir involved, which is being spontaneously cooled
without involving a transfer of heat to a cooler reservoir. This
conversion of heat into useful work, without any side effect, is
impossible, according to the second law of thermodynamics.
The observation that the natural direction for the ow of
heat is from hotter to colder bodies is the content of the
second law of thermodynamics. There are a number of
dierent formulations of the second law, such as the
following two statements.
Kelvins Statement: No process is possible whose sole
result is the complete conversion of heat into work.
Clausiuss Statement: No process is possible whose sole
result is the transfer of heat from a colder to a hotter
body.
A perfect engine is ruled out by the rst statement, a
perfect refrigerator by the second. In fact the two
statements are equivalent as shown below. Proof of the
equivalence of the Kelvin and Clausius statements
proceeds by showing that if one is violated so is the other.
(a) Let us assume that there is a machine that violates
Clausiuss statement by taking heat Q from a cooler
temperature TC to a higher temperature TH. Now consider
an engine operating between these two temperature,
taking heat QH from TH and dumping QC at TC.
The combined system takes QH Q from TH, produces
work equal to QH QC and dumps QC Q at TC. If we
adjust the engine output such that QC = Q, the net result
is a 100% ecient engine, in violation of Kelvins
statement.
(b) Alternatively, assume a machine that violates Kelvins
law by taking heat Q and converting it completely to
work. The work output of this machine can be used to
run a refrigerator, with the net outcome of transferring
heat from a colder to a hotter body, in violation of
Clausiuss statement. Although these statements may
appear as rather trivial and qualitative descriptions,
they have important quantitative implications as we will
see later.
I
Entropy
The rst law of thermodynamics may be written as: dU
= dQdW We have an expression for work in terms of
thermodynamic parameters: dW = PdV or
WAB =

where WAB is the work done by the system in going

from state (TA,VA) to (TB,VB) along some given path.
We now introduce a similar result for heat:

where QAB is the heat added to the system.

Unfortunately, the entropy, S, is not as easily measured
as other thermodynamic variables. We can write:

The differential dS is exact (like dU and dV ) so if we

select a path between A and B such that T = T0 is fixed,
then:
By experimentally measuring QAB, we obtain S.

Here is a valid question: Q we know is not an exact

differential. How by dividing by T we make it an exact
differential?
Here we will give a simple answer after a
mathematical digression.
But what if we cannot get from A to B along an
isothermal path? Along an adiabatic path (no heat
added or removed) dQ = 0 so dS = 0. In general, we can
build a path between any two points A and B by
combining isothermal and adiabatic paths and thus
calculate SB SA. The entropy is important in that given
S(U,V ) for a physical system, all other thermodynamic
properties may be computed. We derive and use this
result when we develop statistical mechanics.
 A Mathematical Digression
Let's think, for the moment, in terms of functions of the
variables x and y and consider the differential,
df = 2xy3 dx + 3x2y2dy
Is there a function f = f(x, y) such that
df = (f/x)y dx + (f/ y)x dy
Comparing the two equations, we want
(f/x)y = 2xy3 and (f/ y)x = 3x2y2
If such a function f = f(x, y) exists, it should satisfy
Eulers relationship:
 (2f / x y) = (2f / y x)
Carrying out the second differentiation, we have

(/ y)(f/x)y = (/ y)(2xy3 ) = 6 xy2

(/ x)(f/y)x = (/ x)(3x2y2 ) = 6 xy2
The mixed second derivatives are equal. So we
conclude that there exists a function, f(x,y). Doing
the double integration, we find the function to be
Equal to f(x,y) = x2y3 .

Suppose we have another differential

dg = 2x2y3dx + 3 x3y2dy
We will find that Eulers condition is not obeyed and
so dg is not an exact differential and no g(x,y) that
will give
dg = 2x2y3dx + 3 x3y2dy.
Both the differential df and dg can be integrated from
Initial (x1, y1) to (x2, y2): the difference is for the
exact differential there exists an integral whose
value depends only on the end points only.

df = f(x2,y2) f(x1, y1)

But the integral dg cant be so simply evaluated
without knowing the detailed function throughout
the path.
Now we come back to the question we started
with. How by dividing by T we make Q an exact
differential?
One should not be surprised that path dependence
of an integral is changed through multiplication of
the integrand by simple functions.
From the first law of thermodynamics, from Eqn
1.1

Or dQ = dU+PdV
=
The Clausius theorem (1855) states that for a
system exchanging heat with external reservoirs
and undergoing a cyclic process (i.e. a process
which ultimately returns a system to its original
state):

where Q is the amount of heat absorbed by the

system from the reservoir and T is the temperature
of the external reservoir at a particular instant.
The equality holds in the reversible case and the
inequality holds in the irreversible case. The
reversible case is used to introduce the entropy
state function. This is because in a cyclic process
the variation of a state function is zero.
That means the line integral is path independent.
So we can define a state function S, called entropy,
which satisfies
Third Law of Thermodynamics
The entropy is a function of the thermodynamic
parameters so we may write it as S(T,V ). The third law
says: S(T = 0,V ) = 0, that is, at zero Kelvin the entropy is
zero. Thus, we can nd the entropy for arbitrary T and
V by computing:

along any convenient path.

The third law of thermodynamics is sometimes stated as
follows, regarding the properties of systems in
equilibrium at absolute zero temperature:
The entropy of a perfect crystal at absolute zero is
exactly equal to zero.
A classical formulation by Nernst (actually a
consequence of the Third Law) is:
It is impossible for any process, no matter how idealized,
to reduce the entropy of a system to its absolute-zero
value in a finite number of operations
A mathematical proof of this statement has been
developed by Oppenheim just this year!
Masanes, L. & Oppenheim, J. A general derivation
and quantification of the third law of
thermodynamics. Nat. Commun. 8, 14538 doi:
10.1038/ncomms14538 (2017).
Summary of Principles of General Systems (Callen)
Postulates:
1. There exists particular states (called equilibrium states) that,
macroscopically, are characterized completely by the
specification of the internal energy U and a set of extensive
parameters (like V) to be enumerated.
2. There exists a function (called the entropy ) of the extensive
parameters , defined for all equilibrium states. And having the
following properties. The values assumed by the extensive
parameters in the absence of a constraint are those that
maximize the entropy over the manifold of constrained
equilibrium states.
3. The entropy of a composite system is additive over the
constituent subsystem ( where the entropy of each constituent
system is a homogeneous first-order function of the extensive
parameters). The entropy is continuous and differentiable and is
a monotonically increasing function of the energy.
4. The entropy of any system vanishes in the state for which
T = (U/ S) (extensive parameters) = 0.
Theorem: Let f be a function with two variables with
continuous second order partial derivatives fxx , fyy and
fxy at a critical point (a,b). Let
D = fxx(a,b) fyy(a,b) - fxy2(a,b)
If D > 0 and fxx(a,b) > 0, then f has a relative minimum
at (a,b).
If D > 0 and fxx(a,b) < 0, then f has a relative maximum
at (a,b).
If D < 0, then f has a saddle point at (a,b).
If D = 0, then no conclusion can be drawn.
Engines and Refrigerators : A heat engine is described by
a closed cycle in a P V diagram for which the enclosed
area (i.e., the work done) is positive (contour loop is
clockwise). If the loop is counterclockwise we have a
refrigerator. Call the heat added in a cycle Q+ and the
work done W; we dene engine eciency as = W/Q+,
that is, the fraction of the heat added that is converted
into work. An important example is a Carnot engine. In a
Carnot engine the cycle consists of a pair of isothermal
paths and a pair of adiabatic paths (see Fig. ).
 Carnot engine cycle Carnot engine cycle
in P V diagram in T S diagram
Carnot Engine:
Three Characteristics:
1. Reversible
2. Operates in cycles
3. All heat input/output at two temperatures
T+ (hot) and T- (cold)
Efficiency
= W/ Q+ = (Q+ Q) /Q+ = 1(T /T+ )
Carnots Theorem: No engine operating between two
reservoirs (at temperatures T+ and T- ) is more ecient
than a Carnot engine operating between them.
Since a Carnot engine is reversible, it can be run
backward as a refrigerator. Use the non-Carnot engine
to run the Carnot engine backward.
Corollary: All reversible (Carnot) engines have the same
universal eciency (T+,T-), since each can be used to
run the other one backward.
Approach to Equilibrium and Thermodynamic Potentials
Evolution of non-equilibrium systems towards equilibrium is
governed by the second law of thermodynamics. For an
adiabatically isolated system entropy must increase in any
spontaneous change and reaches a maximum in equilibrium.
What about out of equilibrium systems that are not
adiabatically isolated and which may also be subject to
external mechanical work? It is usually possible to
dene other thermodynamic potentials that are
extremized when the system is in equilibrium
Gibbs-Duhem Equation:
Important to note that the intensive parametrs are
not all independent. For a single component
system, is a function of T and P. the existence of a
relationship among the intensive parameters is a
consequence of the homogeneous first-order
property of the fundamental relation. For a single
component system, this property permits the
fundamental relation to be written as U = U(S,V).
 The Gibbs-Duhem is a relationship among the intensive
parameters of the system. It follows that for a simple system
with r components, there will be r+1 independent parameters,
or degrees of freedom. For example, a simple system with a
single component will have two degrees of freedom, and may
be specified by only two parameters, such as pressure and
volume for example.
The commonly
known phases solid, liquid and vapor are separated
by phase boundaries, i.e. pressure-temperature
combinations where two phases can coexist. At
the triple point, all three phases can coexist.
However, the liquid-vapor boundary terminates in
an endpoint at some critical temperature
Tc and critical pressure pc. This is the critical point.
In water, the critical point occurs at around
647 K (374 C; 705 F) and 22.064 MPa
(3200 psia or 218 atm)
In the vicinity of the critical point, the physical properties
of the liquid and the vapor change dramatically, with
both phases becoming ever more similar. For instance,
liquid water under normal conditions is nearly
incompressible, has a low thermal expansion coefficient,
has a high dielectric constant, and is an excellent solvent
for electrolytes. Near the critical point, all these
properties change into the exact opposite: water
becomes compressible, expandable, a poor dielectric, a
bad solvent for electrolytes, and prefers to mix with
nonpolar gases and organic molecules.
At the critical point, only one phase exists. The heat
of vaporization is zero. There is an inflection point in
the constant-temperature line (critical isotherm) on
a PV diagram. This means that at the critical point:

Above the critical point there exists a state of matter

that is continuously connected with (can be
transformed without phase transition into) both the
liquid and the gaseous state. It is called supercritical
fluid.
 Home page for ESCI 341
Dr. Alex DeCaria

e-mail: alex.decaria@millersville.edu
Lecture Notes: These are the notes that I use to prepare and deliver my lecture
Answers to Selected
Reading
Number Topic Exercises

1 Math Review

2
Last updated: August 26, 2015
Definitions
Petty 2

First Law of Petty 5.1 - 5.2.1

3 Thermodynamics Answers

4 Ideal Gasses Answers

5 Enthalpy/Specific Heat Petty 5.2.2 - 5.3, 5.7.1 -

5.7.2
Petty 5.4.1 - 5.4.2
6 Processes Answers

Vertical Structure Petty 4

7

Stability of Dry Air Petty 8

8

Entropy Petty 6.1

9 Answers

Second Law of Petty 5.5 - 5.6

10
Thermodynamics Answers

10b Physical Explanation of

Entropy (optional)
Energy Minimum
11
Principle
12 Phase Changes Petty 7.2 - 7.3

13 Curved Droplets and

Solutions

Humidity Petty 7.1, 7.4

14

Pseudoadiabatic Petty, 7.7.1

15 Processes

16 Thermodynamic
Diagrams

17 Skew-T Diagram Use AF Skew-T Manual

(PDF) Chap. 1, 2, 4