Chapter two

Statistical Description of
Systems of Particles
Contents
• Specification of the state of a system
• Statistical ensemble
• Statistical postulates
• Probability calculations
• Number of stats accessible to a macroscopic system
• Distribution of energy between macroscopic systems
• Thermal equilibrium, Temperature and Heat
• Heat transfer
• Mean energy of ideal gas
• Mean pressure of ideal gas
1
 Statistical Formulation
In this chapter & the rest of the course, we’ll combine statistical ideas with the Laws
of Classical or Quantum Mechanics ≡ Statistical Mechanics
The four essential ingredients for a statistical Description of a Physical System with
many particles
1. Specification of the State (macrostate) of the system.
2. Statistical Ensemble
3. A Basic Postulate about priori Probabilities.
4. Probability calculations
Specification of the State of a System
• For a Statistical description of a physical system with many particles ,We need a detailed
method
• Specification of the State of a System State ≡ Macrostate
• These many particle systems that contain many particles will obey the laws of Quantum
+ ClassicalMechanics
• Let us take the Quantum treatment of State ≡ Macrostate,
• Specifically, the particles in that system can be described by a wave function

• Where q1,q2,….qf a set of generalized coordinates and f represents degrees of freedom

which are required to characterize the system (q needn’t be position coordinates) 2
 Quantum mechanical description
• A particular quantum state (macrostate) of the system is specified by giving values of
some set of f quantum numbers.
• Single particle quantum mechanical states are represented by a vector (or a wave
function Y). Normalization condition:
• Physical observables are represented by Hermitian operators whose eigenvectors form a
complete set
• Position: Momentum:
• Energy (Hamiltonian):
Example
 Now, lets look at some simple examples (Quantum Mechanics)
 Let a system is a single particle, fixed in position. But It has intrinsic spin ½ (intrinsic
angular momentum = ½ћ).
 In the Quantum description of this system, the state of the particle is specified by specifying
the projection m of this spin along a fixed axis (which we usually call the z-axis).
 The quantum number m can thus have 2 values:
 ½ (spin up) or -½ (spin down)
 So, there are 2 possible states of the system.

3
• When we extend that system which has N particles (non-interacting), fixed in position. Each
has intrinsic spin ½
• So each particle’s quantum number
 mi (i = 1,2,…N) can have one of the 2 values ½.
 Suppose that N is huge( N ~ ).
 The state of this system is then specified by specifying the values of each of the quantum
numbers m1,m2, .. mN.
 There are (2)N unique states of the system! With N ~ , this number is HUGE
 simple harmonic oscillator, with position coordinate x & classical frequency ω.(a single
or more) i.e
 The system which consist of one particle, of mass m, confined to a rectangular box, -----
Schrödinger Equation
 What about the classical description of the state of a System?
 Even though the quantum description is correct, it is often useful & convenient to make the
classical approximation
 It is, therefore, worth making a few comments about, the specification of the state of a system
in classical mechanics.
 How do we specify the state of the system then?
 Lets start with a very simple case: Consider a Single Particle in 1 Dimension
 In classical mechanics, it can be completely described in terms of it’s generalized
position coordinate q & it’s momentum p.
4
 Classical description
 The usual case is to consider the Hamiltonian Formulation of classical mechanics,
where we talk of generalized coordinates q & generalized momenta p,
 So q & p completely describe the particle for all time.
 Of course, the particle obeys Newton’s Law under the action of the forces on it.
 Given q, p at any initial time (say, t = 0), they can be determined at any other time t
by integrating the (Newton’s 2nd Law) Equations of Motion forward in time.
 This situation can be abstractly represented in the following geometric way:
 The plot represent the classical phase space of a single particle in one dimension
 At any time t, stating the (q, p) of the particle describes it’s state.
 Specification of the State of the Particle is done by stating which point in this
plane the particle occupies.
 As q & p change in time, according to the equation of motion, the point
representing the particle State moves in the plane
Trajectory

Phase space 5
The 2-dimensional space constructed from these 2f variables as the coordinates in the phase space of the system. Each
point in the phase space (phase point) corresponds to a microscopic state.
Therefore the microscopic states in classical statistical mechanics make a continuous set of points in phase space.

• We’d like to describe the particle

Stateclassically in a way that the number
of states are countable.
• It is convenient to subdivide the ranges of
the variables q and p arbitrarilysmall
discrete intervals. it’s coordinate lies
between q & q + q &thatit’s momentum
lies betweenp & p + p
• Then, think of this 2-d phase space as
divided into cells of equal area: State ≡ phase space cell labeled by
the (q,p) that the particle
ho ≡ small constant with units of angular occupies.
momentum.
6
 However, we can use Quantum Mechanics & the Heisenberg Uncertainty
Principle:
 It is impossible to simultaneously specify a particle’s position & momentum to a
greater accuracy than qp ≥ ½ћ
 So, the minimum value of hois clearly ½ћ.As , the classical description of the State
the quantum description becomes more & more accurate.
 Lets generalize all of this to a MANY PARTICLE SYSTEM
 1 particle in 1 dimension means we have to deal with 2-dimensional phase
space.
 The generalization to N particles is straightforward, it is multidimensional
phase spaces.
 Consider a system with f degrees of freedom. Hence
The system is classically described by
q1, q2 ..... qf be the generalized coordinates of a system with f degrees of freedom
and
p1,p2,p3, …pf. f generalized momenta
 (N particles, 3-dimensions  f = 3N!).
 A microscopic state of the system is defined by specifying the values of (q 1, q2 .....
qf, p1 p2..... pf) which are regarded as a point in the 2f-dimensional phase space of
the system
7
 Each q & each p label an axis (analogous to the 2-d phase space
for 1 particle in 1 dimension).
 Again, we subdivide this phase space into small cells of 2f-
dimensional volume:

q1q2q3…qfp1p2p3…p1f ≡ (ho)f

 The classical State of the system ≡ the cell in this 2f-dimensional

phase space the system occupies.
 That State of the system requires specifying each cell in this
phase space for each particle in the system occupies.
 The quantum mechanical and classical descriptions are thus very
similar,
 a cell in phase space in the classical discussion being
analogous to a quantum state in the quantum-mechanical
discussion.
8
 Statistical Ensemble
 As we know, Statistical Mechanics deals with the behavior of systems of a large
number of particles.
 Statistical Mechanics handles many particles by calculating the most probable
behavior of the system as a whole, rather than by being concerned with the behavior
of individual particles.
 A Statistical Ensemble is a large number (≡ N) of identically prepared systems.
 In general, the systems of this ensemble will be in different states & thus will
have different macroscopic properties.
 We ask for the probability that a given macroscopic parameter of interest will
have a certain value.
 Example: Consider the spin problem again. But, now, let the system have N = 3
particles, fixed in position, each with spin = ½.
 Each spin is either up (↑, m = ½) or down (↓, m = -½).
 Each particle has a vector magnetic moment μ. The projection of μ along a z-axis
is either: μz = μ, for spin up
μz = -μ, for spin down

9
 Now, put this system into an external magnetic field H. Classical
Electromagnetic(EM) tells us that a particle with magnetic moment μ in an external
field H has energy: This tells us that each particle has 2 possible energies:
for spin up and
 So, for 3 particles, the State of the system is specified by specifyingm = ½ and we
have , (2)3 = 8 POSSIBLE STATES
The Possible States of a 3 Spin System

Given that we know no other information about this system, all we can say about it is that it
has equal probability of being found in any one of these 8 states.
However, if (as is often the case in real problems) we have a partial knowledge of the system
(say, from experiment), Then, we know that the system can be only in any one of the states
which are compatible with our knowledge (That is, it can only be in one of it’s accessible
states). 10
 The States Accessible to the System ≡ are those states which are compatible with all of
the knowledge we have about the system
 For instance, For our 3 spin system, suppose that we measure the total system energy &
we find that E ≡ - μH

 This additional information limits the states which are accessible to the system. From the
table, there are clearly only 3 states which are compatible with this knowledge.
 The system must be in one of the 3 states:
(+,+,-) (+,-,+) (-,+,+)

11
 The Basic (or Fundamental) Postulate of Statistical Mechanics
 Definition: An isolated system is a system which has no interaction of any kind
with the outside world.
 This is clearly, an ideal situation! Such a system has
 No Exchange of Energy with the outside world. The laws of mechanics tell us
that the total energy E is conserved. E ≡ Constant
 So For an isolated system, the total energy E is constant & the system is
characterized by this energy. So,
 All states accessible to it must have this energy E.
 For many particle systems, there are usually a very large number of states with the
same energy.
 What is the probability of finding the system in any one of these accessible states?
 Before answering this, let’s define the term “Equilibrium”.
 A System in Equilibrium is one for which the Macroscopic Parameters
characterizing it are independent of time.
 Now, consider an isolated system in equilibrium:
 In the absence of any experimental data on some specific system properties, all we
can really say about this system is that it must be in one of it’s accessible states
(with that energy).
 So, it seems reasonable to assume that the system is equally likely to be found in any
one of its accessible states 12
 So, it seems reasonable to assume that the system is equally likely to be found in any one of
its accessible states
 In equilibrium statistical mechanics, we do make this assumption & elevate it to the level of
a postulate.
 The fundamental(basic) postulate of statistical mechanics (equilibrium)
 An isolated system in equilibrium is equally likely to be found in any one of its accessible
states.
 This is sometimes called the Postulate of Equal a priori Probabilities.
 This is the basic postulate (really the only postulate) of equilibrium statistical mechanics.

Example 1
 Back to the previous example of 3 spins, an isolated system in equilibrium.
Suppose that the total energy is measured & found to be:

 We’ve seen that the only 3 possible system states consistent with this energy are:
(+,+,-) (+,-,+) (-,+,+)
 So the fundamental postulate tells us that, when the system is in equilibrium, it is
equally likely (with probability = ⅓) to be in any one of these 3 states.
 Note: This probability is about the system, it is NOT about individual spins.
 Under these conditions, it is obviously NOT equally likely that an individual spin
is up &down. In fact, it is twice as likely for a given spin to be up as down.
13
 Probability Calculations
 To calculate the probability of finding a system in a given state: Use the
Fundamental Postulate of Statistical Mechanics:
 An isolated system in equilibrium is equally likely to be found in any one of it’s
accessible states and its energy is constant E
 There will always be an uncertainty in our knowledge of the system energy ≡ δE.
 Suppose that we know that the energy of the system is in the range E to E + δE.
 Define:
 Ω(E) ≡ The total number of accessible states in this range[E to E + δE. ].
 y ≡ A macroscopic system parameter (pressure, magnetic moment, etc.).
 Ω(E;yk) ≡ a subset of Ω(E) for which y ≡ yk (a particular value of y)
Let P(y = yk) ≡the probability that a parameter y of the system assumes the value ofy k.
The Fundamental Postulate of Statistical Mechanics:

What is the mean (expected or measured) value of y?

From probability theory, this is simply:

Clearly, to calculate this, we need to know both Ω(E) & Ω(E;y k).

14
 Example: 3 particles of spin ½ in an external magnetic field again. Suppose that we
know from measurement that the total energy is
E = - μH.
 As we’ve seen, there are only 3 accessible states for E = - μH.
– These are: (+,+,-) (+,-,+) (-,+,+).
• Question: What is the probability of finding spin #1 in the up position? In this
case,
Ω(E)  Ω(E = -μH) ≡ 3 and
Ω(E;yk)  Ω(E = -μH; spin 1 is up) ≡ 2
• So, the probability that spin #1 is up is:
P(spin 1 up) ≡ (⅔)
• Also, the probability that spin #1 is down is:
P(spin 1 “down”) ≡ (⅓)
• So, the Mean (average) magnetic moment of spin # 1is
(sum goes overm = up &down)

• = (⅔)(μ) + (⅓)(-μ) = (⅓)μ 15

 Behavior of the Density of States
 We’ve just seen that the probability that a system parameter, yhas a valuey k is:

 Ω(E) ≡ number of accessible states with energy between E & E + δE.

 To do probability calculations, we need to know dependence of Ω (E) on the E
 Let us take a macroscopic System, which contains many degree of freedom (f ), fis
a very large numberf ~ 1024.
 For macroscopic systems, very small δE physically may contains many possible
states Ω(E) in the range between E to E + δE.
Ω(E) depends up on the magnitude δE, such that
Ω(E) δE
The proportional constant be define as

ω(E) ≡ Density of states, which measure the number of states per unit energy
To get how Ω(E) (or ω(E)), dependence on the E
How many accessible states are there for a macroscopic
(f ~ 1024) system at energy E?
 We want an order of magnitude estimate of the behavior of Ω(E) as a function of E
Let Φ(E) ≡ total # of quantum states for all energies E to E + δE.
16
 Consider 1 typical degree of freedom. ε ≡ energy associated with that degree of freedom.
 Let φ(ε) ≡ total of quantum states for this degree of freedom when it has an energy ε or less
 In general, φ(ε) increases with increasing ε. So, we can write:
φ(ε)  εα ( α ~ 1) φ(ε)  ε
 Let us now return to the whole system having an energy E and described by f quantum
numbers {sl, s2, . . . , sf }.
 Then the energy ε per degree of freedom is the order of an average energy for a system of f
degrees of freedom: ε  (E/f)
 The total # of states associated with f degrees of freedom
≡ the product of the # associated with each one:
Φ(E)  [φ(ε)]f
 The total # of accessible states for all energies E to E + δE is roughly:

Φ(E) ∝[φ(ε)]f∝[E/f]f∝Ef ≡ Aef A = constant

 Then Ω(E) ≡number of accessible states with energy between E&E + δE

Ω(E) ≡ Φ(E + δE) - Φ(E); δE<<< E

 Now, expand Φin a Taylor’s series & keep only the lowest order term:
(f >> 1) Ω(E) = Ef δE (f ~ )
Ω(E) is a rapidly increasing function of E. Hence the no of accessible states Ω(E) is an
extremely increasing function of energy E of the system
17
 Example: The Ideal, Monatomic Gas
 To make this clearer, consider a classical ideal, monatomic gas, with N identical
molecules confined to a volume V.
 Calculate Ω(E) for ideal, monatomic gas. Before we calculate the No. accessible
states,
 The total energy of the system is

 U – the potential energy due to interaction &E int –interamolecular energy

 If the molecules are not monoatomic, It depends on the relative separations
between the molecules, i.e., on their center-of-mass positions r i.
 Hence for ideal gas, the conditions are
 Large ri , or small N/V( rarefied gas)
 Ideal gas consists of non-interacting particles,
 and Eint –interamolecularenergy, Eint =0
 The only energy for ideal, monoatomic gas are the translation(kinetic) energy.
Hence the total energy of the gas simply becomes

To find Ω(E) for the classical case. We assume that the number of states Ω(E) inthe
range E & E + δE Which is equal to the no number of cells in phase space in the range
δE 18
 Example: Classical ideal gas (cont’d)
• General procedures of deriving
omega:
• 1) write system energy as a
function of p and q;
• 2) integrate in phase space over E
to E+dE to get the number of
states (proportional to the phase
space volume
E +δE E+ δE
between E and
E+dE)
Ω( E)= ∫ … ∫ d
3
r 1 d
3
r 2 , … , d
3
r N .d
3
p 1 , … , d
3
p N d Q1 , … , d QM . d p 1 , … , d p M ¿
E E ¿
The whole integration is the element of volume in phase space. Since the position
integrals for each ri can be done immediately: ∫d3ri ≡ V
There are N such kind of integrals
∫d3r1d3r2…d3rN ≡ VN
Then the number of states is simply

Or simply the number of states is simply

19
• ≡ volume of the “spherical shell” betweenE&E + δEThis
is shown schematically for 2 dimensions in the figure:
• Sine the only energy is kinetic, in this simple case, the
total energy E of the gas is the sum of the kinetic energies
of the N molecules, each of mass m:

 Briefly consider case of 1 particle only. In that case, is:

 The expression represents a sphere in momentum space of

radius. For 1 particle

The volume of the sphere in f dimension is directly

proportional to

So, the 3N dimensional sphere volumeis  [R(E)]f  [R(E)](3N/2)

•  Ω(E)  VN(E)(3N/2)
• Ω(E) = BVN(E)(3N/2) ,
B = constant
• Ω(E) = the number of accessible states for an ideal gas
• in the energy interval E to E + δE 20
 Equilibrium Conditions & Constraints
Reversible & Irreversible Processes
• Consider an isolated macroscopic system A in internal equilibrium with specified energy E.
The number of accessible states is Ωi(E).
• Suppose that A contains at least one Internal Constraint
• Constraint  A system property that limits the number of accessible states Ωi(E).
• The constraints can be described by yl, y2, . . . , which the number of states accessible to the
system depends on the values of these parameters; i.e.,

Yn may denote volume, energy, …, etc of some system or subsystem

• Example: A gas in a container. The container is divided by a partition into 2 equal
volumes V.
• The gas is in equilibrium & is confined by the partition to the left side. See Figure. Now,
Remove the Partition.

• The new situation is clearly NOT an equilibrium one. All accessible states in the right side
are NOT filled. Wait some time. As a result of collisions between molecules.
• They eventually will distribute themselves uniformly over the entire volume 2V. This is
the final equilibrium situation.
21
• Compare the initial number of accessible states Ωi(E) before removing the partition to the

final number of accessible states Ωf(E) after removing it. Clearly, Ωf(E) > Ωi(E).

• In this simple example, after the gas comes to a new equilibrium, Ωf(E) > Ωi(E)
• More generally, consider an isolated system A, in internal equilibrium at energy E, subject to
one or more constraints. The number of accessible states is Ωi(E).
• Remove one or more constraints. Except in very special cases, the new situation is NOT an
equilibrium one. Wait some time until a new equilibrium is reached as a result of interactions
between particles in A.
• Compare the initial number of accessible states Ωi(E) before removing the constraints to the
final number of accessible states Ωf(E) after removing them.
• Generally, it will be true that Ωf(E) > Ωi(E).

• In some very special cases, it will be true that Ωf(E) = Ωi(E).

• After the system A comes to a new equilibrium, it will be true in general that Ωf(E)  Ωi(E)
• If the equals sign holds, Ωf(E) = Ωi(E) & the removal of the constraint is called a
Reversible Process.
• If the greater than sign holds, Ωf(E) > Ωi(E) & the removal of the constraint is called an
Irreversible Process. 22
• A Reversible Process is an idealization! All Real Interaction Processes are Irreversible!
 Interaction Between Macroscopic Systems
• We’re focusing on isolated Macroscopic Systems. So far,
we’ve been interested in the statistical treatment of the
dependence of the number of accessible states Ω(E) on
the system energy E. We’ve found that

Ω(E)  Ef δE (f ~ 1024)

(f = number of degrees of freedom of the system).

• Now, we want to focus on how to characterize the

macroscopic properties of the system & to do this
especially when it is not isolated, but is allowed to interact
with another macroscopic system  The Outside World23.
 Energy Distribution Between Systems in Equilibrium
• Immediately after the constraints are removed, the systems in the ensemble occupy
then only a fraction pi of 𝛀f .
• Suppose that a constraint is removed or one of the parameters (call it simply y),
which originally had the value y = yi, is now allowed to vary.
• Since all the states accessible to the system are a priori equally likely, the
equilibrium probability distribution P(y) of finding the system in the range between
y and y + 𝛅y is proportional to the number of states accessible to the system when
the parameter lies in this range; i.e.
• The situation tends to change in time until the uniform equilibrium distribution of
systems over accessible states is attained, i.e., until the various values of y occur
with respective probabilities.
• Let that constraint variable be energy E, and let systems A & A'. are weakly coupled
so they can exchange energy.
• Find the most probable energy E.
 Consider the thermal interaction between two macroscopic systems A and A'. The
respective energies of these systems by E and E'.

24
 Let Ω(E) the number of states of A in the range between E and E + 𝜹 E, and Ω’(E')
the number of states of A' in the range between E' and E' + 𝜹 E'.
• Let the two macroscopic systems are interact thermally but the combined system
A(0) = A + A' is isolated and its total energy E(0) is therefore constant.

A E A' E'
• Assume that the interaction between the systems is weak so that their energies are
simply additive. Consistent with Energy Conservation:

• Then the corresponding energy of A' is known to be

• The number of accessible states of A'

• The number of states accessible to the entire system A (0) can thus be regarded as a
functionof a single parameter, the energy E of system A
• 𝛀(O)(E) the number of states accessible to A(O) when A has an energy between E
and E + 𝜹E.
• By a priori postulate asserts that in equilibrium A(O) must be equally likely to be
found in any one of its states. 25
 energy between E and E + 𝜹E is simply proportional to the number of states 𝛀(O)(E)
• The probability P(E) of finding this combined system in a configuration where A has an

accessible to the total system A(0) under these circumstances. This can be written

• where C is a constant of proportionality independent of E.

• Thus using normalization condition

its 𝛀'(E1)= 𝛀1(E(0) - E) possible states.

• At the same time A' must then have an energy E' = E (O) - E so that it can be in any one of

• Since every possible state of A can be combined with every possible state of A' to give a
different state of the total system A(0),
• It follows that the number of distinct states accessible to A (0) when A has energy E is simply
given by the product
Stated another way:
• Each configuration is equally probable, but The number of states having a particular energy
E is unknown.
• We find this number by finding the energy where the left side of the above equation has a
maximum
• The Corresponding, probability () of system A having an energy near E is simply given by

• A and A’ have many degree of freedom and

 If E increases Ω increases extremely rapidly While (E (0)-E) decrease extremely rapidly
26
• To find where lies in E scale
• If the number of states exhibits the behavior discussed in () so that Ω ∝ Ef and Ω’ ∝f’
, then gives
• To locate the position of the maximum of P(E), or equivalently, of the maximum of
its logarithm, we need to find the value E= , where

 But we know that

• where E' = E (O) - E. Hence () becomes
,
• The relation () is the equation which determines the value where P(E) is maximum.
• where E and E’ denote the corresponding energies of A and A' at the maximum, and
where we have introduced the definition
 The parameter 𝛃 has the dimensions of a reciprocal energy. It is convenient to
introduce a dimensionless parameter T defined by writing

27
 Since then
 Define entropy of a system
 The parameter T is then by () defined as
 Condition of maximum probability P(E) of a system is then by (), expressible as the
condition that the total entropy

• Entropy & Temperature are both related to the number of accessible states Ω(E).
• The Fundamental Postulate leads to:

1. An Equilibrium Condition. Two systems are in thermal equilibrium when their

temperatures are equal. (Obvious, but can be proved!)

2. A maximum entropy for the coupled systems when they are at equilibrium. As
we’ll see, this is related to the The 2nd Law of Thermodynamics and

3. The 3rd Law of Thermodynamics

28
 Equilibrium between interacting systems
• Consider two systems A and A' which can interact both by exchanging heat and
by doing work on each other.
• Consider a quasi-static process in which the system A, by virtue of its interaction
with system A', is brought from an equilibrium state described by E and x 𝜶 (𝜶 =
1, . , n) to an infinitesimally different equilibrium state described by E + dE and x
+ dx ,
• What is the resultant change in the number of states accessible to A?
• Since = (E; x1, . . . , xα), one can write for the resultant change in the purely
mathematical result
Or simply )
• The last term in the parentheses is just the macroscopic work dW done by A in
this infinitesimal process.
• Equ() is a fundamental relation valid for any quasi-static infinitesimal process. In
general, it can also be written in the form
• Equivalently
• Note that in the special case when the system is thermally insulated (i.e., when the
process is "adiabatic") the absorbed heat dQ = 0 and this asserts that
• If the external parameters of a thermally isolated system are changed quasi- 29
 The System & It’s Surroundings
Abstract Sketch An Example

Three Kinds of Systems

1. Open Systems:
Systems that exchange both matter & energy with their surroundings.
2. Closed Systems:
Systems that exchange energy with their surroundings, but do not exchange matter.
3. Isolated Systems:
Systems that do not exchange either matter or energy with their surroundings. 30
 Thermal, Mechanical and general Interactions
• There are two Kinds of Interactions between systems. These are:
1. Thermal Interactions
 The external parameters x1,x2,x3,…xn remain fixed.
The quantum energy levels Er(x1,x2,…xn) are unchanged.
However, the POPULATIONS of these levels change, so the occupation
probability of these levels also changes.
2. Mechanical Interactions
The external parameters x1,x2,x3,…xn DO change
Þ The quantum energy levels Er(x1,x2,…xn) are shifted.
• In the most general case of interaction between two systems their external
parameters do not remain fixed and the systems are not thermally insulated.
• As a result of such interaction is general interaction under this situation the
mean energy of a system is changed by some amount, but not all of this
change is due to the change of its external parameters.
31
 Thermal Interaction
 In one case all the external parameters remain fixed
so that the possible energy levels of the system do
'not change; in the other case the external parameters
are changed and some of the energy levels are
thereby shifted
 The first kind of interaction is that where the external
parameters of the system remain unchanged. purely
thermal interaction.

• Consider two macroscopic systems A & A',

interacting with each other & in thermal equilibrium. The total system Ao = A + A',
• Consider the case where there are Thermal
is isolated & at equilibrium.
Interactions Only, & no mechanical interactions. So
Fig
 The energy of system Ao is
• Focus on system A with mean internal energy
conserved, so
Ē(x1,x2,x3,…xn)
Ēo = Ē + Ē' = constant
• No mechanical interaction means that all external
parameters x1,x2,x3,…xn remain fixed (so that no
work is done!)
•  xi = constant, i = 1,…n 32
 Definition
• Heat ≡ The mean energy transferred from one system to
another as a result of a purely thermal interaction.
• More precisely, due to it’s interaction with A', the mean
energy of A is changed by Ē
Ē ≡ Q ≡ the heat absorbed (or emitted) by A
(Q can be positive or negative)
Similarly, for , A', the mean energy is
Ē' ≡ Q' ≡ the heat absorbed (or emitted) by A'
Ēo = Ē + Ē' = const
 Ēo = 0 = Ē + Ē'
Or Q + Q' = 0; Q = - Q'
Þ Heat absorbed (given off) by A = - heat given off (absorbed) by A'.
Þ This is Conservation of Total Energy for the combined system!

33
 Mechanical Interaction

 When two systems are thermally insulated, they are still capable of
interacting with each other through changes in their respective external
parameters.
 This represents the second kind of simple macroscopic interaction, purely
mechanical interaction. The systems are then said to exchange energy by
doing "macroscopic work" on each other.

• Consider again two macroscopic systems A & A', interacting with each
other & in thermal equilibrium.
• Consider the case where there are Mechanical Interactions only, & no
Thermal Interactions.
• For this to occur, they need to be thermally isolated (insulated) from each
other.
• This is achieved by surrounding the systems with an “Adiabatic
Envelope”.
• “Adiabatic Envelope” ≡ An ideal partition which separates the 2 systems
A & A', in which external parameters are fixed & each of which is in
internal equilibrium, such that each subsystem remains in its Macrostate
indefinitely.
34
• Physically, this Adiabatic Envelope is such that no energy (heat)
transfer can occur between the two systems A & A'. Clearly, an
idealization!!! But many materials behave approximately as is shown
in the Figure:

A A'

• When two systems, A, A', are thermally insulated from each other,
they are STILL capable of interacting. How?
• Through Changes in their External Parameters ≡ Mechanical
Interaction

• In this case, the two systems do MECHANICAL WORK on each

other & This Work Can Be Measured. 35
 A Physics Example!!
• A gas is enclosed in a vertical cylinder w
closed by a piston of weight W.
• The piston is thermally insulated
from the gas. Initially, the piston is
clamped in position at height si. It is s gas
released & the height changes to some
final height sf (higher or lower than si).
System A  gas + cylinder
System A'  piston + weight
• The interaction between them involves
changes in the system’s external
parameters (i.e. gas volume, piston height s).
• Consider system A. Due to mechanical interaction with system A', it’s
external parameters change:  So does it’s mean energy.
• Denote this change as xĒ.
• The macroscopic work done ON the system is defined as
W  xĒ. 36
 Example
w gravity
Continued

A  gas + cylinder,

A'  piston + weight

s gas
• Interaction involves changes in the
system external parameters (gas
volume & piston height s).

• A is in mechanical interaction with A',

so it’s external parameters change: 
It’s mean energy change is xĒ. The • The macroscopic work done
macroscopic work done ON the system BY the system is defined to
is: be the negative of this:
W  xĒ W = -W  - xĒ 37
 General Interaction
• In the most general case of interaction between two systems their external parameters do not remain
fixed and the systems are not thermally insulated.
• As a result of such interaction is general interaction under this situation the mean energy of a system is
changed by some amount, but not all of this change is due to the change of its external parameters.
• There is work done as well as heat transfer
• Consider two interacting macroscopic systems A, A', in thermal equilibrium. Thermal
Interaction  One with no mechanical work.
 The energy exchange between A, A' is HEAT EXCHANGE:
• Conservation of energy for the combined system gives:
Ēo = 0 = Ē + Ē'
Ē ≡ Q = heat absorbed (emitted) by A
Ē' ≡ Q' = heat absorbed (emitted) by A'
So, Q + Q' = 0 or Q = - Q'
• Mechanical Interaction  One in which A, A', are thermally insulated from each
other.  No heat exchange is possible.
• They interact by doing MECHANICAL WORK on each other through changes in their
external parameters. Work done ON A: W  xĒ.
• The work done BY A: W = -W  - xĒ.
• Conservation of energy for the combined system gives
38
o
• The most general case is one with Thermal & Mechanical
Interactions at the same time.
• The external parameters are NOT fixed. A, A' are NOT thermally
insulated from each other.
• As a result of this General Interaction, the mean energy of A is changed
BOTH by a change in external parameters AND by a transfer of thermal
energy. This mean energy change may be written:
Ē = W + Q oroo
Ē = - W + Q so

Q = Ē + W
• The equation is a statement of The First Law of Thermodynamics
• The physics of this law is simply Conservation of Total
Energy
– Total Energy ≡ Heat + Mechanical Energy
–
• Notice that, for two interacting systems at equilibrium, The 1st Law
of Thermodynamics says that total energy is conserved,
39
 Thermal equilibrium, Temperature and Heat
• Heat is the flow of energy from a high temperature to a low temperature. When
these temperatures balance out, heat stops flowing, then the system (or set of
systems) is said to be in thermal equilibrium.
• Thermal equilibrium also implies that there's no matter flowing into or out of the
system.
• The zeroth law of thermodynamics uses thermal equilibrium to define how two
different systems can be said to be at the same temperature.
• For example, when molten rock comes up from a volcano, it will give off heat to
the atmosphere until the rock and the atmosphere are at the same temperature. Even
though the two systems (rock and air) are very different, thermal equilibrium allows
a definition of temperature for both.
• All systems tend towards thermal equilibrium over time and some systems will take
a lot longer than others.
• Knowing that interacting systems will tend towards the same temperature allows for
important applications in all areas of science. For example, the specific heat
capacity of a substance can be determined by placing it in water and measuring the
temperature after a period of time.

40
 Figure . The zeroth law of thermodynamics.

heat transfer
movement of energy from one place or material to another as a result of a difference in
temperature
temperature
quantity measured by a thermometer, which reflects the mechanical energy of molecules in a
system
thermal equilibrium
condition in which heat no longer flows between two objects that are in contact; the two objects
have the same temperature
zeroth law of thermodynamics
law that states that if two objects are in thermal equilibrium, and a third object is in thermal
equilibrium with one of those objects, it is also in thermal equilibrium with the other object

41
 Properties of Ideal Gases
 Various assumptions are made in the ideal gas model. They are as follows:
I. Ideal gases are a very simple system of noninteracting particles. The only energy
involved is the kinetic energy of the gas particles. There is no potential energy.
II. Gas molecules are considered as indistinguishably very small and hard spheres.
III. All motions are frictionless and the collisions are elastic, that is there is no energy
loss in motion or collisions.
IV. All laws of Newton are applicable.
V. The size of the molecules is much smaller than the average distance between
them.
VI. There is a constant movement of molecules in random directions with distributed
speeds.
VII. Molecules don't attract or repel each other apart from point-like collisions with
the walls.
VIII. No long-range forces exist between molecules of the gas and surroundings.
• One way is microscopic and uses phase space; the other way is macroscopic and
just uses the equation of state pV = RT.

42
 The Pressure of an Ideal Gas: Calculation
• For the calculation let us consider an ideal gas filled in a container cubical in shape. One
corner of the container is taken as the origin and the edges as x, y, and z axes. Let A 1 and
A2 be the parallel faces of the cuboid which are perpendicular to the x-axis.the change in
momentum of the molecule is: = (-m) – (m) = -2(m)
• Suppose, a molecule is moving with velocity 'v' in the container and the components of
velocity along three axes are Vx, Vy and Vz. As we assume collisions to be elastic when
this molecule collides with face A1 x component of velocity reverses while the y and z
component remains unchanged.
• After the collision, the molecule travels towards the face A2 with the x component of
the velocity equal to – Vx. Now, the distance traveled by a molecule from
• Now, the distance traveled by a molecule from A1 to A2 = L . Therefor, Time=
• After a collision with A2 it again travels to A1. Hence, the time between two collisions
= . So the number of collisions of molecule per unit time, n =
• From (1) and (2), Momentum imparted to the molecule by the wall per unit time
=n=
• Therefore, the total force on wall due to all the molecule is
F= = = = …(symmetry)
Therefore, F =
43
Pressure is force per unit area so that P= = =
Where, M = total mass and = density of the gas
Now is written as and is called the mean square speed. P=
Let’s go over the microscopic proof. Let ri denote the position of the ith particle and let pi be it’s
momentum. The number of states (E) lying between the energies E and E +dE is proportional to
the volume of phase space contained between the surface in phase space with energy E and the
surface with energy E + dE:
Ω(E) ∝… …

Ω(E) ∝ 𝜒(E) where 𝜒(E) ∝ … is independent of V since the

Since there is no interaction between the particles (U = 0), the integrals over position are trivial:
• So = V
particles’ momenta does not depend on their position, so that the integral does not depend
on the volume.
• The total energy of the ideal gas is simply the kinetic energy of the particles:
2mE =
where the sum over is the sum over the x, y, and z components of the momenta. The sum
contains 3N = f terms. For E= constant, eq. (6) describes a sphere in the f−dimensional space of
momentum components. The radius of the sphere is
R(E) =

44
(This is just like a spherical surface in 3D which is described by the equation x2+y2+z2 =
constant = R2.) The volume of the sphere in f−dimensional space is proportional to
=
The number of states (E) lying in the spherical shell between energies E and E + E is then given by
Ω ∝ ∝ ∝ combining this with our factor
of we obtain
Ω(E) = β

where β is some constant independent of E and V . It’s easy to calculate the inverse temperature
β.
=+N +
β = = solving for E yields
E= =T

Notice that the energy is just a function of the temperature, and not of the volume as
advertised. If Na is Avogadro’s number, then N = Na υ where υ is the number of moles. Then

E= T= T
Where R = is the gas constant

45
 Specific Heat of an Ideal Gas
• We can now go on and calculate the specific heat at constant volume. It’s
important to specify what macroscopic parameters are being kept constant. As
we mentioned earlier, the specific heat we measure at constant volume is
different from the specific heat we measure at constant pressure. In either case
we start with dQ = dE + pdV At constant volume, dV = 0 and dQ = dE , So
the molar specific heat at constant volume is = =
• Using our result E = 3 RT/2 we see that = R

In general, for any system, not just an ideal gas, the energy is a function of both
temperature and volume: E = E(T, V ), So dE = dT +
For an ideal gas where the energy is just a function of T, this reduces to
dE = dT dE = dT for an ideal gas.
Now let us obtain an expression for the specific heat at constant pressure. We start with

dQ = dE + pdV = dT + pdV
At constant pressure the equation of state tells us pdV = RdT
Substituting this into yields the heat absorbed at constant pressure
dQ = dT + RdT By definition = this becomes = + R
Note that > in agreement with earlier statements. The ratio of the specific heats is then given
by = = 1+ which states that = 3R/2 for a monatomic ideal gas,
we have = R+R = R and by = ==
46
 Adiabatic expansion or compression for an ideal gas
• For an ideal gas, we can make certain statements concerning p, V and T when the
gas expands under certain conditions.
• If the gas expands quasi-statically under isothermal conditions (constant
temperature), the equation of state tells us that
pV = constant
• Suppose, however, that the gas is thermally isolated so that no heat is absorbed
during the expansion, i.e., dQ = 0. This is called an adiabatic expansion. Adiabatic
conditions correspond to thermal isolation. When the gas expands, it will do work
and lose internal energy. As a result, its temperature will decrease.
• How will the pressure be related to the volume of the gas under adiabatic conditions in a
quasi-static process? We start with dQ = dE + pdV
Adiabatic means dQ = 0. We also have dE = dT for an ideal gas. So
0 = dT + pdV
• Now let’s eliminate T in favor of p and V . From the equation of state
d(pV ) = RdT or dp V + V dp = RdT Use this to substitute for dT.
0 = (pdV + Vdp)+ pdV =( + 1)pdV + Vdp
( +R)pdV+ Vdp = 0 47
Since = + R, we can write pdV + V dp = 0 Dividing both sides by yields
+ = 0 where =

 For most gases it is a pretty good approximation to assume that is independent of

temperature over a limited temperature range. Then we can integrate to obtain
γln V + ln p = constant or p = constant

Since γ > 1 ( > ), p will vary more rapidly with increasing V than in the isothermal
case where pV = constant.
We can use the equation of state to eliminate p in favor of V and T. Using p = υRT/V,
we get T = constant
Note that the two equations
p = constant and T = constant
are true for adiabatic quasi-static processes.

48