.. _, ,;=~_~_<", ~~ =-_~~ ~,"-="_."__" ~_,_,,,,,,,,,,_=_, J ~ __ ""_' ,...,__ =_ :=_ ~ ,.. . ~ ::- '- ~~....

_- "-'~ "
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f .

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I
. \.

UNIVERSITY
/

~.·.,i'·"

OF
VEND,A

DEPARTMENT 0 F PHYSICS

. "

.; :.. ,

-
THERMAL AND STATI~;TICAL PHYSICS '

LECTURE t\IOTES ; -

. -- .. ------ ..:.-.--~ :_.._--:,. __ - .- :..-~ ,"""'--. "'""" ~ _"_ .;;,::'-".=--"~""" ~--'- -.-;_" --"._.- " .. _ - - _ .. -.
 (
i'

THER1\1AL AND STATIST]CAL PHYSICS

1. FUNDA1Y1ENTAL CC NCEPTS

Thermodynamics and Statistical mechanics are two of he most important tools of physics
Thermodynamics is the exact mathematical science that (.escribes the relationships of heat and
mechanical energy. The~odynamics constitutes a very: ubtle study in physics, chemistry and
engineering and has innumerable applications. It is ba ted upon three general laws; namely
-'
(i) the first law or the law of conservation of energy whi ~hrepresents the connection between
heat and mechanical work; (ii) the second law which ceals with the entropy changes in the
system and manner in which energy changes takes plac ::, and (iii) the third law which deals
Ij
with the absolute value of entropy.

* THERMODYNAMIC SYSTEMS:

A thermodynamic system is that part of the urn verse which IS being subjected to
thermo iynamic scrutiny; everything else in the univers e constitutes the surroundings. A
[Link] system can not exchange matter with the surro mdings but an open system can. A
closed system can exchange only energy (not matter) wl ile an open system can exchange both
matter and energy with the surroundings. If a system c. 1,1 not exchange-matter or energy With

its surroundings, it is called an isolated systems. N there is no barrier to gravitation, a'

perfectly isolated system is impossible, but the influen: e of gravity is often negligible. The
boundary of the closed system must be impenetrable by matter while the boundary of an I,/
isolated system must not be crossed by matter, heat, n diation or other forms of energy and
.;-" -
must not be displaced against a force. These definiti: 1'1S require that according to the non
relativistic view of the universe, mass and energy ar e not interconvertible, they must be

conserved separately in any exchange.

The properties of the system are classified as intensive Jr extensive according to whether the
given property is independent of or dependent on rna: 51 of the substance, A homogeneous
 system is one whose intensive properties like density snd pressure are continuous functions of

position. If the intensive properties properties of a system are discontinuous, the system is
said to be inhomogeneous or heterogeneous. A heter ogeneous system may be considerd to be
composed of a number of homogeneous ones sep: rated from one another. by surfaces of

discontinuity, each separate portion being caned a phi rse.

The state of a system is determined by ascribing v: lues to a sufficient number of variables -

,
called thermodynamic co-ordinates or its state var ables. (e.g.) pressure, volume, density,

temperature, etc, _ ~

The specific value of an extensive property is definer as the ratio of the value of the property
to the mass of the system, or as its value per unii mass: Since any extensive priperty is 0
( proportional to the mass, the corresponding specific, alue is independent of the mass and is an
intensive property. The ratio of the value of an. exte isive property to the number of moles of

a system is called the molal specific value of that pro ierty.

* THERMAL EQUILIBRIUM

The concept of temperature, like /:Jiatof force, origir ated in man's sense of perceptions. -The
first step toward attaining an 0.: .ctive measure 0~the temperature; sens-e is to set up a
criterion of equality of temperature. When two bod es are brought into contact, whether the
bodies are of the same material or not , an end state is eventually reached in which there are
no further observable changes in the measurable pre perties of the bodies. This state is then

defined as one of thermal equilibrium.

Observations led us to infer that all ordinary 'objects have a physical property that determines
whether or not they will be in thermal equilibrium v·hen placed in contact with other objects.
This property is called temperature. If two bodies I re in thenna1 equilibrium when placed in
contact, then by definition their temperatures are e pial. Conversely, if the temperatures of
two bodies are equal, they will be in the_rmal equilibriur 1 when placed in contact. A state of
thermal equilibrium can be described as one in which he temperature of the system is the

same at all points.

The zeroth law:

When two bodies each .separately in thermal equilib, tum with a third, they are also in
ther;nal equilibrium with each other.

The above statement is known as the zeroth law of the rmodynamics. This statement forms -:
(
\

the basis of concept of temperature. All the three syste ris can be said to possess a property
that ensures their being in thermal equilibrium with I ach other. This property is called
temperature. Thus temperature of a system may be de ined as the property that determines
whether or not the system is in thermal equilibrium with he neighbouring systems.

Thermodynamic Equilibrium:

When there is no unbalanced force between the system and its surroundings and none exists
between different parts of the system itself, the system s said to be in a state of mechanical .
equilibrium. If the temperature in all parts of the systerr is uniform and is the same as that of
the surroundings, the system is said to be in thermal equ librium. .If the chemical composition
of the system is the same throughout, the system is S< id to be in chemical equilibrium. A
system which is in thermal, mechanical and chem 'cal equilibrium is said to be ill
thermodynamic equilibrium. The state of a system iJ thermodynamic equilibrium can be
represented by specifying its pressure, volume ar d temperature. The subject of

thermodynamics deals chiefly with systems which are in 1aermodynamic equilibrium.

 *' PROCESSES

When any of the properties of a system change, the sate of the system changes and the system
is said to undergo a process. If the process is CarTI( cI out in such a way that at every instant

the system departs only infinitesimally from the -quilibrium state, the process is caUed
quasistatic (almost static). Thus a quasi-static proc ess closely approximates a succession of
equilibrium states. If there are finite departu ~es from equilibrium, the process is
nonquasistatic. - ~

,
All actual processes are nonquasistatic because they take place with finite difference of P, T
I

etc. between the parts of a system. Nevertheless t' le concept of a quasistatic process is a

useful and important one in thermodynamics.

Many processes are characterised by the' fact tha' some property of the system remains
constant during the process. A process in which volume of a system is constant is called
isovolumic or isochoric. If the pressure is constant, .he process is called isobaric. A process
at constant temperature is called isothermal. A pro .ess carried out by a system enclosed by
an adiabatic boundary is an adiabatic process. Such l process can ,also be described
.
as one in
which there is no flow of heat across the boundary. A process can also be made adiabatic by
adjusting the temperature of the surroundings as the irocess proceeds so thatthis temperature

is always equal to that of the system.

A reversible process can be defined as one whose dir ection can be reversed by an infinitesimal
change in some property of the system. Thus if the temperature of a system within a
diathermal boundary is always slightly lower than the t of its surroundings, there will be a flow
of heat from the surroundings into the system; whi reas if the temperature of the system is
sl,ightly greater than that of the surroundings, then will be a flow of heat in the opposite
direction. Such a process is therefore reversible as v. ::11as quasistatic.

4
If there is a finite temperature difference between the s) stem and surroundings, the direction
--):-

of the heat flow cannot be reversed by an infinitesimal change in temperature of the system
and the process is irreversible as well aJ nonquasistatic. Suppose, however, that the boundary
of the system is nearly, but not completely adiabatic, so that the heat flow is very small even
with a finite difference in temperature. The system is tl: en very nearly in thermal equilibrium
at all times and the process is quasistatic although it is no: reversible.

The slow compression orexpansion of a gas in a cylinde .provided with a piston is quasistatic
if there is a force [Link] friction between piston and ( ylinder when the piston is 1.'1 motion,
the process is not reversible. All reversible processr s are necessarily quasistatic, but a
quasistatic process is not necessarily reversible. The te rn reversible and irreversible have a

deeper significance in thermodynamics.

(Recal! your knowledge about different temperatt re scales. Example: Centigrade,

Fahrenheit, Kelvin etc.)

I ~
 2. EQUATION JF STATE

From the experimental considerations it can lie observed that only certain rmrurnum
number of the properties of a pure substance car be given arbitrary values. The values of

the remaining properties are then determined by the nature of the substances. In
thermodynamics there exists a certain relation between the properties P, V, T and m,

which can be expressed in general as

f(P,V,T,m) =0 [1]
This relation is known as the equation of stat ~ of the substance. If any three of the

properties are fixed the fourth can be determined .

The equation of state can be "Writtenin a fom which depends only on the nature of a
substance and not as how much of the substanc ~is present, if all extensive properties are
replaced by their corresponding specific values :per unit mass or per mole). Thus if the
properties V and m are combined in the single intensive property v = VIm, the equation

becomes
1(P,v,T) = 0 [2]
The equation of state varies from one substance to another. In general, it is an extremely
complicated relation and is often expressed as a converging power series. A general idea
. . . .
of the nature of the function is often better cor veyed by presenting the data in graphical

form.

" IDEAL GAS

From the experimental data collected at a given emperature T, the value of the ratio Pv/T
was calculated for each individual measuremer 1. These values are plotted as ordinates
against the pressure P as abscissa. It is found I xperimentally that these ratios all lie on a
smooth curve, whatever the temperature, but t iat the ratios .at different temperatures lie

on different curves. The plot for three differen . temperatures for carbon dioxide is given

in the next page:

. "
 -:L-,, Ideal gas

2 4 6 8 J( lOT
Pressure (N I \ -')

The salient feature of these curves is (1) that they ill converge to exactly the same point
on the vertical axis, whatever the temperature, and 1(2)that the curves for all other gases
converge to exactly the same point. This common limit of the ratio Pv/T, as P approaches
/.7"
i
I
(
zero, is called the universal gas constant and is denr ted by R

The value ofR is 8.3143Xl()3 Jkilornole' KI

It follows that at sufficiently low pressures we can , 'rite, for all gases,

Pv/T = R, or Pv = RT.
It is convenient to postulate an ideal gas for which, by definition, the ratio Pv/T is exactly
equal to R at all pressures and temperatures. Tl e equation of state of an ideal gas is

therefore
Pv = RT, or since v = Vln, PV = nRT. [3]

" REALGAS
(
Many equations have been proposed which descril E: the P-v- T relation of real gases more
accurately than does the equation of state of an ide, gas.
Van der Waals obtained the following equation:
(P+~(v- b) =R.r [4]
The quantities a and b are constants for any gas bU1differ for different gases.
(Note: a/v1 - arises from the existence of interm: lecular forces and b is proportional to ,
the volume occupied by the molecules)
On expansion, van der Waals equation takes the fo m

( p +:3=-~ J L'\) ,.. b ) = R1

'2-
Cf~} .-t-lt) ('V ~b )
= Rlv
 pv5 + 0. \) - f\j'l b - a._b
3 ~.
PV - (Pb+ R"9 V -+ a..'\) - a.b = ( [5]

It is therefore a cubic in v and for given values 0 f' P and T has three roots, of which only
one need to be real, (WHY?! I). At low tempe] atures real roots exist. As temperature
.increases, the real roots approach one another md at critical temperature they become
equal,

Another useful form of the equation of state of a real gas is

Pv = A
B C
+;; +U"l.+.. ,... .... [6]

where ~ B, C etc. are functions of temperature a nd are called the virial coefficients.
For an ideal gas it is evident that A = RT and all «ther virial coefficients are ZERO.

The van der Waals equation cambe put in the viri d form as follows:
(p + % 1-) C 'J..-~) ::: QT c1 R CP +v3~) :::l'\.JF2T -.tf~
r-: 1)

p'\.) + 5l. - P l> -~ ~ -: (.2 T

'"V '1)'1.-

.. .
Hence

or Pv = R'T.-\- [10]
and for a van der Waals gas
A = RT; B = (RTb - a: and C = RTb2

3
 P-v- T SURFACES

The equation of state of a PvT system defines a surface in a rectangular co-ordinate

system in which P,v and T are plotted along the thre e axes. The PvT surface for an ideal
gas is shown in the figure below. A quasistatic pr xess is represented by a line on the
surface. The full lines represent processes at con tant temperature (isothermal) . The
dotted lines represent isochoric processes, and the de s:hedlines, isobaric processes.

Figures below are the projections of the lines in the' igure above onto P-v and P-T planes.
(

....
.-.-
......
-.-·-1 --- ...-- ---;-- ........••...

: __
W
II:
. ---- --------. ---~.::
..... ::
/
-----.~.-.
w
0::
.... .: ....

\lOLUIoiE -

(b)
(a)

Projections of the ideal gas P-v-T surface or lata) the P-I! plane, and (b) the P~T plan~.. :

4
 The diagrams below shows (J4) P-v-T surface for a VE.1 der Waals gas (8) P-v-T surface
for a substance that contracts on freezing and (C) }'·-v-T surface for a substance that
expands on freezing.

A 'B c
. Real substances can exist in the gas phase only at Sl fficiently high temperatures and low
pressures. At low temperatures and high pressures tr msitions occur to the liquid phase to
the solid phase. The P-v- T surface for a pure substance includes these phases ;is well as
the gas phase.

lit PARTIAL DERIVATIVES

. .

The equation of state of a PVT system is a relation between the values -of pressure,
volume and temperature for any equilibrium state of 1 he system. If the equation of state is
solved for V, thus expressing V as a function of the two independent variables P and T,
. .F~. the value ofV corresponds to the vertical height oft1 e surface above the r-r
plane, at any
given pair of values of P and T. Instead of specifyin ~ the height of the surface above the
P_T plane, at any point, the surface can be described by giving its slope at any point. we
can specify the slope, at any point, of the lines of intersection of the surface with the
planes of constant pressure and constant temperature .

5
 The figure D is a graph of the Vollllme V as a funcuon of T for the isobaric curve along
which the pressure P equals P, .

The slope of this curve at any point means. the slop e of the tangent to the curve at that
point and this is given by the derivative of V with re ;pect to T at that point. The tangent
has been constructed at the point 1 at which the emperature is T, and pressure is PL
However the volume V is a function ofP as well as of T. Since P is a constant along the
curve, the derivative is called partial derivative if V with respect to T at constant
pressure and is written:
== of the tangent =
Suppose the volume of the system were to increase'
~) p
vith temperature, not along the actual
curve but along the tangent at point I. The increase in volume when the temperature was
increased by I:::..
T would then be represented by the length of the intercept of the tangent
on the veri cal line through point 2 or it would be giv en by
(
,
f)p t:Tp
the product of the slope of the tangent line , ~) f' a nd the base "''1> 0

T P approaches
Vp' but the two ap iroaches equality as I:::..
The intercept is not equal to I:::..
zero. Then
. A~~%-JITp~Np .
Ifwe let dV and dT to represent the~iting values of I:::..V
~d I:::..TpQ.,s
I:::..T~ 0 we can
write f r P
_[nJ

" EXPANSIVITY AND COMPRESSmILTIl"

Instead of giving the value of the slope itself at any point, it is convenient to give the value
of the slope, (~~, divided by the volume V a' the point. The quotient is called the
( coefficient of volume expansion of the material or i s expansivlty p, defined as .
p=~~ p -Ul-J
Thus for an ideal gas
o •• 0" P~ ~ ~ ~ + ~
and the expansivity deoands only upon the tempe .ature and IS
[
13 J .
equal to the reciprocel of
the temperature. The unit of expansivity is K:'

the isothermal compreSsibiltj, 1(, of a material is d fined in a similar way as its expansivity,
namely as the slope of an isothermal curve at any I oint, divided by the volume.

K = ~~(t6.,- --U4J

\I

b
 The negative sign is included because the volum :,alawys decrease with increasing pressure
at constant temperatue so that (~) is inherent ly negative. The compressibility itself is a
therefore a positive quantity. The urIt of x is m N-'.

-RT
heY'c.e ( aP )
en) ,. ...:- CV-b) 2

- RTc.
(ve..- I.;, ) "2-

Qv.1C( 21(Tc

Qi_b)3

.,". "

-t- .fQ_~ ~. 0
( ,
Vc.3( vc..1, )
\ _'

G< ~v '"

40- =0 oR-
~c 0\ (v e. .:-~ )

oR. - 2..
'LJc.-1;>
-_ !!.'V c.. I

lVc -.'

RIc. ...(-
').~
:::.
D
. . _ f2Tc
--
_ 2Q.
...,
U
(} r:) 3 (_2J:,) 2. 21b_.)
C3bL~)2

t2-
 eTC
_ '20. 1<- \ C
:::
_-
-:;: 21 6
4b rL 2.7S") £i

lie :;~J ~ [22 J

AI:: C'I' l h'c ,J ( 0'1 cl h c.:.v Ctb) b2. C (,'r'f) eS

QTc. [2.}.J
Pc ;
Q.....
- c~v,- } -7
It.,t. - ~ ) 2.-

~c:JJS h hLrw,_9 'ckL vc..lL....e.~ t-. \)(_ ~.'vy-.. ct "T c [Link]~. \-

R C_l!3_ ')
Pc -:;

(3b- b)
Q.'1JZ.l;,
- q

Cq,b) 2..-

, g-Q o. ce_
4a.. -Q ./C'
-= 962-
L1~L
I

21'b2 ~
271S C1..~)

-:; - [4_-
Q6L..
<L
3
fJ. ::-
_:3:_ (4~~)
q(,i. :>.
'::'
~(~
qL:,2
)

Pc z
I
Pc- -;:-
---
a..
21b '2
I
-=t~ !.c0 "
"'" '1J~ ::::
~1b2.

'51
3a;
-~[24J
It -::: . 2-7R..b

A/sa r(~ o..~ I

0.21
,f
". lb 0
'V~
.3
b I
~s-o.)
0rfI. ct.
b

3 '[Link] z,

OMd._ ~
;
-
2j<b
~Q
-- -g-Cf
27 Rl~1c ) --
9'q

fjR_Vc,

o'R [Q "2 -}RVc J7l~b bJ \G

 * RECIPROC~l AND RECIPROCITY THEOREMS:

Suppose we have three variables connected by Cl general relation of the form

F(x,y,z) = 0 which is assumed to be solvabl~ for any of the three as a dependent
variable. If we choose x such that x = xC) ,z) from the fundamental theorem of
the calculus for the differentiation of a flnction of two variables, dx is given
as

dx = (~x]dy (~~LdZ
y z .
+ (27)

With z regarded as a function of x and y

dz =
(:~]/X (az) d +
By
x
Y (28)

Substi tuting the values of dz in (2.7) we get

.. ,
\
~
~ dx = (ax]
By [~~L
dz y[[~~
L dx [~;Ld
+ +
Y]

dx = [:~U~~Ldx [[:~L (~~U:;L1IY

+
+ .

The last results must be true, whatever vari ab les are chosen as independent. If
we choose, say, x and y, then it must be t -ue, whatever independent values are
assigned to dx and dy. If in particular dy=( and dx~O then the second term drops
out and
1
(~~y -(29)'

.' ". ~
...-; The above equation is the reciprocal theorem. This theorem enables us,to replace
any partial derivatives by the reciprocal of .he inverted derivative, provided the
same variables is held constant in each case.
Similarly with dx=O and dy=D I the coef f Lc lent dy must vanish and therefore
(WHY! ! ! ) .

so
[ ~~]
z
+ [~~J[~~-= Y., JI(
o

or
[ ~~]
[~ :'1 [~~]
x -. z y
with the application of reciprocal theorem to the term in the right

(30)

This is called the reciprocity theorem. it Cell always be written by starting with
(J!n'j of Ue f::t.n es [Link]..'vrd...11e.~ Jy ~ (\.Q0 r
'OCP-l J 0'vY> c{_ ~'Y'<'1 tA (~ 9 tL.. ~ 'cd,~
a:
.J Uj c.J___ ~ I c.{.0 GlL.v..-se. C!>-"(\-\1' d Lk. "".;~ ~ . 0

~,.
Ilf'
 t I

~ EXACT DIFFERENTIALS
The so-called mixed second partial der i va [Link] e of Y w.i th respect to F and T is
written as

[~p[~~lpJT or
a'l-y
aFaT '7 (~I)

It can also be written as (explaint}

[~T[~~Hp or
a'i..y
BTBF
--:) ( ;1-)

("J-y alv
We therefore have an important result that
BFin =
aTap -7 (3~)
That is , the value of the mixed second part a I derivative is independent of the
( order of differentiation. Note that the abox e resul t is true only if
r:
the vOlwit(
difference dV between the states is the same for all processes between the states.
A differential for which this is true is callE:l an exact differential.

A test as to whether or not a differential is exact can be determined as follows:

The exact differential dV can be written

av] dP ' .---)

(34)
[ ap T .
The partial derivatives are the coefficients af the differentials dT and dP; and.
the partial derivative with respect to P of t Ie coef'f i cIent. of dT is equal to the
partial derivative with respect to T of the co ef f'Lcient of dP. In general, if for
any three variables x,y,z, we have the relatiol of the form

dZ = M(x,y)dx + N(x,y)dy,

the differential dz is exact if

aM aN
ay = ax

___ -0 _ _--

ID
 3. FmST LA VV AATD.: S01\1£ CONSE0UENCES

:I: WORK. sr, = P, dA

Consider a volume V and the boundary

which is represented by full line.
Let it be acted upon by a uniform
external pressure P. Suppose the
system expands against this pressure
to the shape shown by dotted out line.

The external force acting on an element of the bot ndary surface of area dA is dF =
e
P dA. When it moves out ward through a distance I ls, the force and displacement are in
e
opposite direction and the work of the force is ( ]2 ds = P dAds. when all surface
e e
elements are included, the work d' W, in the p ocess is found by integrating the
product P dAds over the entire surface
e

d: W = pJ dAds [1]

The integral equals the volume between the two b iundaries or the increase dV in the
volume of the system. Therefore
a-w = P dV
e
dV is positive when the system expands against th ~ external 'pressure' and the work is
done by the system. ,', '
dV is negative when the system is compressed and 1 r,Le~wor~is done an th'e system.
The work of the external forces exerted on the bour dary of a system is often spoken of
as the external work. The external work in a volurr e change is .given by d W = P dV. I
e
If a process is reversible the system is essential] y' in mechanical equilibrium at all
times and the external pressure Pe equals the press Ire exerted against the boundary by
the system. Hence in reversible process we can 'rep [ace P with P and write
e
d'W == PdV
In finite reversible process in which the volume ch mges from V to V the total work
a b
IS

1
 W =.
V
f Vb
PdV [31
a

PdV work:
The work in any isochoric process is evidently zei () since ))'1... such a process V 1S

constant. In a isobaric process the pressure is constant and

Vb
W = P dV P(V -\ ) [4]
V f
8
=
b II

If P is not constant it must be expressed as a functi in of V through the "equation of

state". If the system is an ideal gas P = nRT/V. F Jr the case of isothermal process,
T is constant.

W = nRTv(bdV/V = nRT In[~l [5]

8
I
1
r":
i
If Vb> V. th eprocess is an expansion In [~l is posi ive and the work is positive. If i.

Vb < V. the process is a compression and In [~l is ne, .ative and the work is negative.

Work depends on path: p

Suppose that a PVT system is taken from an b .

initial equilibrium state a to a final

equilibriumstate b by two different
Q
reversible processes, represented by
the two paths I and II. Although the work
(
. along either path is given by the integral
. . .
PdV, the pressure P is different function of V along 1: e two paths and hence the work
is different also. The work in process I corresponc s to the total area under path I
and the work. in process II corresponds to the area t nder path II. Hence in contrast
to the volume change Vb-Va between the states a and b, which the same for all paths
between the states,. the work depends on path and not simply the end points. The , I
quantity d'Vi is an~xact differential and the work W is not a property of the system.
o .
Work is a path function and not a poirit function lil :I~V and the work in a process

2
 cannot be set equal to the difference between the alues of some property of 3 system
in the end states of a process.'

If the system is taken from state a to state b ~~ing path I and then r= turned from
state b to state a along path II, the system peronns a cyclic procesc. -r~e oositive
work along path I is greater than the negative wo k along path II. The net work in
the cyclic process is then positive or work is: done by the system and the net work is
represented by the area bounded by the closed pat). If the cycle is traversed in the
opposite sense, that is from a to b along path II ;,nd back from b to a along path I,
the net work is negative and work is ·done 011 the system. In either case the
magnitude of the net work W is
W = §d/W = §P(V [6]
This is in contrast to the integral of an exact differential around a closed path
,
{,
which is always equal to zero.

* INTERNAL ENERGY

The total work in any adiabatic process is the sum of the works d' W in each stage of
ad
the process
b

'0/ad
Id/W
a
ad

Although in general the differential d' W is inexact and the. work has different values,
...- --
for different path, the differential d' Wad is exact in the sense that the work is the
same along all adiabatic paths between a given pai: s of states having the same kinetic
( and potential energy. It is therefore possible t)l define a property of a system
I
represented by U, .such that the ,difference .betwe ~n its value in states a and b is
equal to the total work done by the system along ; 11y adiabatic path from a to b, we
call this property the infernal energy of the system.

The values of the internal energy depends only on tl e state of the system and hence dU
is an exact differential. . It is conventional to de fine dU as the negative adiabatic
work d' Wad done by the system or as equal to the adiabatic work done on the system.
(dU == -d'W ad
).

3
 For two states that differ by a finite amount
Ub b

JU dU = Ub - UB = - fd/W ad
= -w ae OR U - U
a b
W
ad
a

That is, the total work W ad done by the system in a y adiab vtic process between vo
states a and b having the same kinetic energy is [Link] to the decrease CUa -U)b in the
internal energy of the system. Thus a gas expanding against a piston, in an adiabatic
process, can do work even though there is no change in its kinetic energy or potential
[Link]; the work is done at the expense of the interna. energy.

* HEAT FLOW
When the system is not thermally insulated from its surroundings but makes co~tact ~I\~J.,'-I

through non adiabatic boundary with one or more ot ier systems ~ temperatu~ ~
( different
,.;
from that of the systems under consideratior. Under t~ese circumstances '~e
say that there is a flow of heat Q between the system and the surroundings. '(
"

The total work W in a non adiabatic process between a given pair of equilibrium states
differs from one such process to another and differs also from the work W ad in any
adiabatic process between the same pair of states. W ~ define the heat flow Q into the
system in any process as the difference between the wo ~k W and the adiabatic work Wad'

Q W - Wad; but Ua - Ub = Wad; Ther .fore Ub - Ua = Q - W

0

That is, the increase in the internal energy of a systr rn 'in any process in which there
is no change in the kinetic energy and potential en( rgy of the system, equal to th~,
net heat flow into the system minus the total work W done by the. system. Q is
positive when heat flow into the system and W is pc sitive when work is done on the
. .~ 'r' . r/ l
I
j ,I / I : ./. : ~~

sys t em. Ij, _ )(1 -, - r _ ~', '//'," (-1.. : :7 c~/ (

I '/ -

First law of thermodynamics: .

If the heat flow and work are both very small, the change in internal energy is very
small also then,
du = d'Q-d'W
the above equation, (lin the differential form) is commonly referred to as the
analytical formulation of the first law of thermodynamii '.'I.
Heat, like work is a path function and not a point fun: tion.

4
 * HEAT CAPACITY
Heat capacity C of a system is defined .as the ratic of the heat energy absorbed by the
system from the surroundings to the increase in terr perature of the system, that is
. C = ~ ( to)

Heat capacities can be measured at constant volume and at constant pressu.:e. The heat
capacity at constant volume, CV' of a system s defined as the ratio of the heat
energy absorbed by the system from [he surroundin is to the increase in temperature of
the system, while the system remains at constant vo »me, that is,

CV -- « I

In this process there is no work energy because t le volume is constant and the only
energy involved is the heat energy, i.e.. dW = Pd ' = 0; therefore application of first
law of thermodynamics to this process yields

( CV -
-
The beat capacity at constant pressure, CP' of a ! ystem is defined as the ratio of the
heat energy absorbed by the system from the surroundings to the increase in
temperature of the system, while the system remains ;;.{constant pressure, that is,

Cp [~)p= (13)

The concept of heat cal- icity applies to a given sys em. The specific heat capacity or
the heat capacity per unit mass or per mole is tl e characteristic of the material of
which the system is composed and is represented by cp or c.,

.,:... .' ....

* ENTHALPY

<- Consider a portion of an isothermal process in ei her the solid-liquid, liquid-vapour

or solid-vapour region and let the process proceed n such a direction that a mass m
is converted from solid. to liquid, liquid to vapour or solid to vapour. The system
then absorbs heat, and the heat of transformation e is defined as the ratio of the
heat absorbed to the mass m undergoing the change (If phase.
Changes of phase are always associated with changes :in volume, so that work is always
done on or by a system in a phase change (except' ritical point), If the changes takes
place at constant temperature, the pressure is cor stant also and the specific work

<:.
done by the system i~, therefore
w =_ P(v2 - VI)

where v and v are the final and initial specific vo' urnes. 1hen from the first law,
2 I
the changes in internal energy is

u - u
2 I
= e- P(v
2
- V)
I
since du dQ - dW lIlt-)

This equation can be written as

e =(uz - ul) + (Pv2 - I VI)
= u -u
2 1
+ Pv
2
-P'
1
= (u2 + Pv 1) - (u 1 T ) 'V I) C!S )
The sum (u + Pv) occurs quite frequently in therrnodj namics. Since u, P and v are all
properties of a system, its sum is a property also ar d is called the specific enthalpy
and is denoted by h. i.e..
h = ,(u + Pv) {unit: J/kg or .Ikmole} (_tb) i!

Now t = h2 - hI' that is, the heat of transformation in any change of phase IS equal
to the difference between the enthalpies of the system j 1 two phases.

* ENERGY EQUATION:

Consider a device through which there is a fulid flow . If there 'are no restrictions on
the nature of the device, we assume that a steady :tate exists, that is). the state of'
the fluid does not change with time. The fulid en ers at' an elevation - Zl' with a
velocity Viand at a pressure PI and leaves at an elex ation Zz, with a velocity V 1 and
at a pressure P2. During the time in which a mass m passes through the device, there
.is a heat flow Q into the fulid, and mechanical work W., (called ,SHAFT WORK) is done
by the fluid. Then the energy equation for steady flow is given by

(h 2 + 2'1 V 22 + gZ2') - (h 1 + 2'1 V 2 1 + gz I') = q - Wsh

(11)

Also the equation which expresses the internal energy of a substance as a function of -
the variable defining the state of the substance .s called its energy equation.
Energy equation can not be derived from the equation of state but must be determined
independently.

6
 I ArJD V ] N DErCNRJtN I

Le) LA be C{ ~ Lh ~ 0.( ---[Link] d 1) , T[r_Q_ c.0_ ~'YC U-

W \./~ H2A,,,__Q ~ J :f J l{_ be ~ ~ ~ vv ·.(>iw.-' L' ~T'\' ~ S /-z:,.. kJ W-'

L,-J h: ( ~ l C,ry'"I c( f\j UCvYL) e b') d '7 eN' J: dv I_,~

du,_ = C~ ) dT "]111
-+( ~:;1v)T'\ O{'\) C 18)

(<.·su(hG ....,'c_) . (1~o\:-he ....'Y1"'"'~ )

hn-' G-t- t~f- LCJ..;-J ~CY 0.. 'I',~.ed,'f:,ll ru-s.J

J''1; ~ c;{~ + pc{ ...' (fl)

U.S';';} @ ~cf. ® ltJ L 9.e L-'

o!~ 0 l~ )v J-t + [Cf';)""' f' Jd v. (2DJ

s""" ~ S'pe.c-..'c.J! Cc".s.e. o,.f w r(_~s~ C<---C G.rn5nVl"l- v~e. dv :-1l

o,..,_J d.. '1.1 ::;:: ClJ d -r

c; colT v ~ ~ ~)'" d'i,v) all (", C~ L (2.1)

'~';' ~ gC_QiT\Q-I''7'1'ccl ($1'cj.;.~·~LL d~ :~v ~ t:l.e_ 6~~Fe of Cl"r"V'

u- 0 c LO"I: c f.";'e_ . CJYI ex. W- T- 'V ~"'r.N\ t<v<:. C Q.,-r. c1._ b ~~ "\A_' .."."", Y\ f-z:_Q
<iY\£!.'\.6v,,I\.t'"tY\b'l. ~ oJ C-J de..~,""",,,,~e.s ~ ("({"o)?e. c--J- a.'-)'_j pu,,~ t ,

c;'l LAC\ h,~ (_20) ~~. W'Y; \~ C'\ .s

0.
If
1;.....
_ C d'f
V
-r
.
rC LV.)
L OV 'f
rtPJ J\I, ,
:c "tV £i).- \)YO (r.2.1s:- 0.);' (.cy;~~ r, ~ ~.S L',JLL I J.. (1;: CF d T

C\)d-r -+- [(~)

-..::JV T
~P] dV "

(23)

IT~ (.t~'-~· ~ A,_~t~ t:::r:o_ h.-v0 'lMO'rl' h'h·.I.2-:!

C_ p C¥li d.. C oJ . , S'~ u... C\. \I a..:. (.(_.I..A 0-,-.'1 )-" I .{') (v..'_9 hr J.~o[ h"c.l..L.
C0.-('\ be: C ,J~; Cl r ~C( ~ -k: \\..l(~ h ("~, (rt f ~t'.. k:.. ,. WQ_ f:,', c.t. C.v l~

CP ~) t\r;:"" n.~-,.J.
~ a r~~~
kc~
0-{- CM s ro.-r. t ~ :'X..JI.-cJ.~
J
JT :: 0 C 0, 0 ~ -rnJ. )

fct_ v-p- \rJ ;.., (21-) "

d~ 'T
-;: [~)1 <- P)'lv 1" {~~ )!Vf _,_ fJ"T
7
 r~Y Xv__ppL-J t;, !A ~~ V--o 0. YQ\rV-~:~lz_ 0Jo~'lY'-c--ll ~LU)

_.f~J:, ka ~ at tuL Vv-u--<LccA~I-- b'-( ~ /dcjS~ ~ llJ_

\' .
~ CN e». Je. ~ \l S [t(l tv.. nJ ~ eN:') 'j .

~ c.. C"\Q..,~~~6La._ C\ct/o..kh'-c. frr"oc.a..u d(£,:. 0 (.Q. 0r;}-fTl)P7

/1h"~J Cn.J?,:(~) ~ _[(~ )T +fJ (Ll)

"* I A NJ> r IN1>E fEN D E-NT

lhe ~~p _::1 %. e>-f a. ? I '/LQ... ~b~ ~t:L COX" b.Q._
~[Link]{ OS 0. ~t_L/Y"Ic.. h~ .01- CV'0_\1 two oF t~Q_ V[lJ1A'o.-.b(.Q.s ~ \)1

~ct -r . ThQ_ ev-~)' oLft-u ~ l.Q._ ~~""' ewo ty\ 3

.Q.-".j "'-k..rt ...:..

S/D.~S' ~~
J.{ =- C~)
?T f
d -t(! ~_!_) T
)P T
dP
( /0 J.'",..La k ~ )p L2,~ "" U'>L :'-<- ~; Yo "" f..,. ci?,. ---(
"

~ ~ tA + fv
~ CHv-i ~)S r-C'. \-.e_.$ d..o.-t-. cl'~ b'1' dv d. . ct \Cl 0vY\

at ~ ;: cL.A.. + P d '\) + '\J d f d e. d A - v d.f:- cd 4 -t fel. '\)

~: J(~~ d VI. -+ f 'd. rJ _. , cd:v -: d -t; - 'U d. p ~ QS).
pre,.ir( ~ ~. J_ ~ -~
12):. -2~h~ @ ~ ~
J (~:::(26) ?1 r
J. 'T +' o~ ~ , c\ P . -
~~f ~
'\J dP
.
J (eu ~ (26) cA re' + [,(~~.) •.,.~vJ J: f . (~-b)
~'( f ,~-
0- F 'I J
'"T rY'I cv rrr 0 (Q_ SS 0:..1-- CcfY\ f ~ I:::. ~)y .e. J S" VV'.e..) J_ .f :: b [)vv-,. c{_
(. d. ~ ~ c:n cJ. 'T ~ (I.__~~ (~) .~ Cp . LQ.. tJj_ If tJpe o!~
\ T, L'd-1 - f p , ~.
k;,e_ 0Yl rt.,-T-f ~~ ,~ (J:_,_ .~eclY,1.. ~ t:'
r-
(S"bcvu.'c
CotCYV.- 'k-; M Con {' f-c-<vF- s s ,-,._lLt2_ •
I~ ~ [Link]-¬ ... (d ~ ) .
l c9T F. {(J..-r) ffi r(..e~
- k /LQd,(~
.-J (/.n' h-, Cp

cL I'f, - C,d. 7 .,_ [(.1;U" - It] cI f - 07--:J . I

-:t", "" fro uiS ok [Link]~ f vir: ."",.e I ,1 l'i' (" d.,
o~ C'c) d r ;: c..f .a'T -r [C~:) - V 7 c1. F
'dP . 1 :J

Cp -C\I ~ - rC ~ t.. V] 7'(

. Ll CJf /,'7
dt 'I -

~ ~ c;_ ~ f'flJ a_jJ t.S {--d_v:"_j /A CM:JL M {fr..!~(- ~'PVl -¬ __ '\)

l). ~ b.e "'n· [Link]. Ot J

lA...
Cf - C :: - 'r: A ~ - v'")~~~.~
,L~~p~~ Q_£ I
g . 27
I
 ---- 0---

-~

r~ C-( f~JCCJ ~ CC( ~ j

~ ~J ~ OJ"'! ~ "':' y<?Y1 "0 ;;J-/\ (J"J'O '11 CUf1N~

(56) _L C~ + t~~r(~l" d(~ j

~

( +i zJ -
CV( ~-.)
__. _ .L e_ .
CV(- ~
'y) e-j
, :: ~(~)

\~'0 -
('fCC ~}_dOri'C ~~)] + J r [0-( ffi"(«JJ "~tJ
fz9r""'-O (1'05~y'OY)'3,d- d-Ja-'-Q iNit(TfV'--Id<j _,l..;'P O--1'OvV~·VOO vv<J] ~M

(-c") ~ \" t ~n+ d'f "( :~=J .l-\-,x:

Ot) - '; r-r.1-( ~ }~- .L 'F n-( ~~0 n'P r, ~

p".L\YJ4~

~ -;r~~ 1~ ~-p
d (' r-e._ '\
\,;-e) ~
f\J( J
n4[
el ~,,-"'~~yV'-/)

€2t) A'f d( ;~;l

+ d 'p ~( ~~ l ~'f r,

r (\.
'f tJ"IN\O J 'P t. '1 ~jO C\J ~ d \"p~ v:' <; ~ -a..J S
6 ~~~'1 G,"tO u, 0 rn =j r-">'7~ ~-uq Q'JvV;! 1-'0 tJ--:vr h W--a \Nd" o'iJ_
J-N3GNad:=JerNI n, (i~ J ~

r~GJ [/I ~..J- ( ~~ ~ ]] - ~ (ii) dJ

o ~ ~ p S( ~ p -<7 J,\.{4-O.~D UAO 'J
d -e ]
1- j
G r
YJ [r n_ -
.J.,
1_)
\ ::te .
1.
-:. 16) P
J 'TI_
 .., JOULE- THOl\fSON EXPERIMENT

Free expansion:
It is possible that the configuration of a system car change without the performance
of work. Fc:rr [Link]"'T'Tlple:
[. vessel is divided into two parts 'IY a diaphragm. The space
above the diaphragm is evacuated and that below the diaphragm contains a gas. If the
diaphragm is punctured, the gas expands into the ev rcuated region and fills the entire
vessel. The end state would be the same if the di tphragrn was a very light piston,
originally fastened in place and then released. The process is known as free
expansion. Since the space above the diaphragm is evacuated, the external pressure P,
on the diaphragm is zero. The work done in a free expansion if therefore zero even
.y.
though the volume of the gas increases.

I,
("
'x. The partial derivatives [~~lT and [~lT (which descr bes the way in which the internal

energy of a substance vanes with volume and in which the enthalpy vanes with
pressure at constant temperature), can be calculated rom the equation of state of the
substance.

The earliest attempts to determine the dependence

of internal energy of a gas on its volume were
made by Gay-Lussac and later by Joule. Vessel A
contains the sample gas which is connected to an
evacuated vessel B by a tube in which there is a.
stop cock, initially closed. The vessels are
immersed in a tank of water of known mass, whose
Principle of the Gay-Lussac- Jo~le experiment.
( temperature can be measured by a thermometer. Heat
losses from the tank to the surroundings will be assurnd negligible.
The entire system is first allowed to come to thermal equilibrium and the thermometer
reading is noted. The stop-cock is then opened and 1 he gas performs free expansion..
In a new equilibrium state pressure is the same in botl vessels.
The temperature change if any was too small to bl ~ detected. All experiments of
similar nature showed the temperature change is not lai ge .
. Hence an additional property of an ideal gas is postu .ated that its temperature change

10
· I
in free e.r iansion IS zero. That IS both Q and W are zero. Therefore the internal
energy is constant.

F<Jr an ideal gas [~~l~.

l.t
O· The partial derivati Ie [~~L JS called .oule coefficient

and is represented by". i.e m = [~~t.

Although Ti is zero for an ideal gas, Ti of a real gas is NOT zero.

JOULE-THOMSON (JOULE-KELVIN) EXPERIMENT

T,

1",__ P, _ .• _1",

Principle of the Joule-Thcrrs,co-, I '""--\:;>Q.,,..,,: .........Qv"-'ir_

A continuous stream of a gas at a pressure PI and temperature TI is forced through a

porous plug in a tube from which it emerges at a lover pressure P2 and temperature T2.
The device is thermally insulated and after it has a xrated fora time long enough for
a steady to become established. (At steady stale, nr heat flow from the gas to change
the temperature of the walls). From the energy eq iation of steady, 'we have h; = h2
(initial and final enthalpies are equal). At stea dy state the gas.' enters with a·
velocity ul and at a pressure PI; it leaves with a velocity ~ and at a pressure P2...
During the time a mass m passes through the devi: e, there is a heat flow Q into the
fluid and a mechanical work, called shaft work, W sh is done by the fluid. ..
A series of measurements are made by keeping initial pressure PI and temperature TI,
the same but varying the pumping tate ul so that tle pressure P2 on the down stream
side of the plug is made to take on a series of values P2, P3 etc.. Let the
temperature be T2, T3 etc. Since hI =h2=h3 etc. the enthalpy is the same at all these
points and a smooth curve drawn through the pain S IS a curve of constant enthalpy.
(refer the figure).

II
 By perforrnng other senes of experiments, again ke eping the initial pressure and
temperature the same .n each series but varying them from one series to another, a
family of curves corresponding to different values of h C in be obtained.

T T
1.- ~ .
: -_ - -~~,:>~.'

<,...... -~ •
~~
Coolin;
.---r-----
\ b

I
Q Heatinr;

~~;~
.,~~
-In~rsion cut ~:

'------- --------p
(I) (b)

'1
( , (a) Points of equal enthalpy. (b) Isenthalpic curve and the inversion curve, I

If the initial temperature is not too great, the curves pi ss through a maximum called
the inversion point, The IDCUS of the inversion point is the inversion curve. (see
the graph above).

When Joule-Thomson experiment IS to. be used in the liquifiaction of gases, it is

evident that the initial temperature and pressure and f Ie final pressure must be so.
chosen that the temperature decrease during the process The slope of an isenthalpic

curve at any point is the partial derivative (~)h' II is calle<l the 'Joule-Thomson

. [aT]'
.(
coefficient and is represented by

At lDW pressures
J.L.

and high temperatures,

That IS J.L = BP h'

where the pn iperties of real gas.. approach. \'

I
those of an ideal gas, the isenthalpic curves become nearly horizontal and their slope
approaches zero. we can postulate that an ideal gas show; no temperature c~ange when

forced through porous plug. Hence for such a gas ~ = ( and (~)h' = 0."
- - - -- - - -
--------------- - - - - -_-

(2..
 ·~--.,

4. SECOND LA \V

* CARNOT CYCLE

Carnot first introduced into the theory of them .odynamics a simple cyclic process now
known as Carnot cycle. Carnot cycle can be CaJ ried out with a system of any nature.
A Carnot cycle for an ideal gas is represen eel in the graph by the shaded area.
Starting at state a, the system at temperature T2 is _brought in contact with a heat
reservoir at this temperature and performs a .eversible isothermal process that takes
it to state b. In this process there is
a heat flow Q2 into the system and work W2 p

is done by the system. At state b, the

system is therrnall y insulated and performs o
(
\
a reversible adiabatic process to state c.
Here temperature decreases to a lower value
T1• The system is next brought in contact
with a heat. reservoir at temperature T I and .
performs a reversible isothermal process to T,
T,
state d. There is a heat flow Q1 out of the
system and work Wi is done on the system.
The Carnot cycle.
r: State d ITIUst be chosen so that a final
. adiabatic process will return the system to its in. tial state a.·
"';>
The significant features of any Carnot cycle are: (i) the entire heat flow into the
system takes place at single higher temperatue T2; (ii) the entire heat flow out of
the system takes place at single lower terr perature Tj; (iii) The system, often
I \ referred to as the working substance, is cam ed through a cyclic process; and (iv)
all the processes are reversible. In general, . any cyclic process bounded by two :
reversible isothermals and two reversible adiabatc constitutes a Carnot cycle.
It can be shown that ~ = '-f. .
8~
~j j

For an ideal gas, the ratio depends only' 01 T2 and Tj.

The thermal efficiency lj of a heat engine is del ined as the ratio of the work output W
to the heat input Q2:

~;W t h at IS
.
lj = it follows hat 1) (1)

22
A refrigerator is rated by its coefficient of p irformance, c, IS defined as the ratio
of QI to W. So we can write
QI. QI TI
C = -w; that IS C = Q2 - Ql ' it follows hat c = T2 _ T I (2)

In the above equations the relation between th.. temperatures T2 and Tl and the heat
flows Q2 and Ql in a Carnot cycle, were express ed in terms of absolute values I Q21 and
I Q11. However, since Q2 flows into the system md Q1 is a heat flow out of the system,
the heat flows have opposite signs; and hence fc r Carnot cycle we should write
~ = - ~ or.-% + -% = 0 (3)

Consider any arbitrary reversible cyclic

process (as that represented by a close curve).
The net result of such a process can be
'1I
approximated as closely as desired by
performing a large number of small Carnot
cycles. If one of the small cycles is .
carried out between temperatures T2 and T,
and LlQ2and LlQ1 are the corresponding heat
flows, then for that cycle
LI~l + 6~2 = 0; when all such terms are ar .ded for all cycles then we have
1 2
L LI~[ = 0; Here the subscript '.' denotes the I eversible process.
1
The sum can then be replaced by an integral ar::1 we can write for the original process
§ d~Q[ = 0 . -. .

Since the integral of any exact differential sue h as dv or du around a closed path is
zero, we can see that although d Q, is not ar exact differential, Qf is
't'
I the ratio d I an
exact differential. .' v

It is therefore possible to define a property S of a system whose value depends only

on the state of the system and whose differenti: J. ds is given by
d I -~

ds = 1'::~
Then for a cyclic prc cess, §dS = 0
Another property of an exact differential :s" that its integral between any two
equilibrium states is the same for all points I etween the states. Hence for any path
between states a and b is

2
 --- ~ - ~- _--c--------------------

. /
,I

b
JdS = Sb-S• (4)
a
This property S is called the entropy of thr system. (unit:IIK). The specific entropy
s is the entropy per mole or per unit mass.
The entropy of an isolated system is fully c anserved in every reversible process, that
is, for every reversible process the sum of ill changes in entropy taking place in an
isolated system is zero. If the process is I ot a reversible one, then the sum of all
changes ill entropy taking place in an is: lated system IS greater than zero. In
general we can say that in every process, taking place m an isolated system, the
entropy of the system either increases or remains constant. (This statement is

generally re fered as the principle of increase of. entropy)

In any reversible adiabatic process d' Qr=O & ds=O; (constant entropy or isentropic)
b b
d Q
In any reversible isothermal process S,-S a =
,r = +Id
l

J l Qr= ~ (5)
a a
* TEMPERA TIJRE-ENTROPY DIAGRAM ~
Since entropy is a property of a system, is value in any equilibrium state of the
system can be expressed in terms of the Y3.1
iables specifying the state of the system.
We can specify the state in terms .of the e .tropy S and one other variable. If the
temperature T is selected as the other variab le, every s~te of the system corresponds
to a point in a T-S diagram and every rev: rsible process corresponds to a curve in
this diagram. A carnot cycle (fig: 1) has an es iecially simple form in such a diagram.
Fig:1 (T-S diagram of a Carnot cycle) :'ig:2 (T-S diagram at P,Y,T etc. constant)

( ,
!'iCnlropic
T

T, - - -Qf=.:........."",-"..!;

I;~
/

T, dl Ie
I , I
I I
·~--~S-,----~S-'----S
isoLhermic

----------------------~s
3
 The area under such curve representing any reversible process in a T -S diagram is
b b
JTdS = J d' Qr = Qr so the area under such cu rye represents the heat flow in the same
a a
way that the area under a curve in a P- V diagra n represents work. The area enclosed by
the graph of a reversible cyclic process cor .esponds to the net heat flow into a
system in the process.
d'Q
If two equilibrium states are infinitesimally near then d' Q = TdS (OR) CIT

at constant volume [d~~]v

~ v ~ T[~L (7)

at constant pressure [d~~ p ~ 'p ~ T 1 [~l P (8)

If the temperature 'variation of Cv is known, :he entropy change during an isochroic

. process may be calculated from the equation
f (

Sf - S = J ? dT (iso .horic) (9)

i
Similarly for isobaric process
f

J t- dT (isob sric)
C .
Sf - S = (10)

Slope of TS diagram for isochoric process will re [*L =

cy
r (11)

Slope of TS diagram for isobaric process will b : [*1 p .= cp

T .. (12)

ENTROPY OF AN IDEAL GAS

From the first law, we know that

d'Q = du + pdv also c, ~ [~L (13)

. In a special case of anideal gas, v is a f merion of TonI y. Therefore partial

derivatives with respect to T is the same as the total derivative,' Consequently
du
c, = CIT (14)
Therefore d' Q = c..d'.' + pdv (15)

4
 Also from the equation of state Pv -= nRT. On [Link] we get Pdv + vdP = nRdT
Therefore
Pdv = nRdT - v:IP (16)
Substituting (16) in (15) we get
d' Q = cvdT + nRdT - vdP or d' Q = (c, + nR)dT - vdP (17)
Dividing through out by dT we get
d'Q dP
CIT = (cy + 'lR) - "ar
At constant pressure [d~~l' = cp andvg = 0

Therefore Cp = cy + nR (18)
Using (18) in (17), we get
d'Q = CpdT - v .P (19)
If the system absorbs an infinitisimal arno rnt of heat d' QR during a reversible
process, the entropy change of the system is ei lual to ds = d' QR/f.
Now consider equation (19). Divide again by ~'. We get
uo = cp l~j
-r rd(' v
- (T)dP
or ds = cp
raTI - nR-pdP
l~ (20) V,;ince Pv = nRT and y/T = nk/P}

Let us now consider the entropy I:!.s of the g IS between an arbitrary chosen reference
state with coordinates Tr, P, and any other state with. coordinates T,_ P. Integrating
between these two states, we get
T .. :. .

M = f cp~ - n ~Jn~
. r
(21)
Tr

f
Suppose that we ascribe to the reference stan an entropy s, and choose any arbitrary
( numerical value for this quantity. Then an er tropy s may be associated with the other
state where. s-sr = cs. To. make our discussior simpler let cp be constant. Then
T P
s-sr = cplnT.: - nR .lOp (22)
r r

Which may be written as

s-sr = cplnT - cplnTr nRlnP + nklnl',
s = cplnT 67 nRlnP + {s, - [Link]'T, + nRlnPr}
Let So = {Sr- Cph T, + nRlnPJ
Is cplnT~ nRlnI ~~ . (23)

5
 Coming back to equation (20) ds = cp ~J-
l"T ' - n ;l~ and again if cp is constant

s =' ~plnT ~ nRlnP + so; where So is the xmstant of integration. SInce this is
precisel y the equation obtained previousley, .'Ve see that, in taking the definite
integral of ds, we do not obtain an absolute entr lpy. Thus for an ideal gas
Is = JCplnT + nRlnP .~~ (24)

To calculate the entropy of an ideal gas as a f inction of T and v, we use the other
expression for d ' Q (equation of an ideal gas d Q = c.d'T + pdv. Now dividing by T
tJ.,
)5" d' Q dT P ~
---y- = Cy-r -t Tdv
dT
ds = cV1 + nRydv {si
SInce Pv .= . nRT and PIT = nRlv}
Proceeding in the same way as before
II
[s ~ Jc_ .<!;f + nRlnv ~ (25)

If c, is constant s = [Link]'T + nRlnv + So

STATEMENTS OF SECOND LAW OF THER \10DYNAMICS

Clausius Statement:
No process is possible whose sole result is a h uu flow out of one system at a given
temperature and a heat flow of the same magru 'ude into a se~[Link] at a higher
temperature.

Kelvin-Planck statement:
No process is possible whose sole result is a I eat flow Q out of a resevoir at a i

single temperature, and the performance of work W equal in magnitude to Q.

(For detailed discussion refer "Thermodynamics by Sears and Salinger")

6
 5. COMIHNE.D FrRST [Link] SECOND LAW

The first and second law can be combined to obtain several important thermodynamical
--_
-relations.
The differential form of first law of therrnodyi lamics can be written as
d'Q = dU + C'W (1)

The second law states that for a reversible pre cess between two equilibrium states
d' Q, = TdS (2)

Also, the work in a reversible process, for a J'VT system, is

d' W = PdV (3)

It follows that

TdS = dU + d' W i.e. Td: = dU + PdV (4)

Equation (4) is one formulation of the com rined first and second laws for a PVT
system.

Although equations (2) and (3) are true for a reversible process, it is important to
notice that equation (4) is not restricted to a process at all, since it simply
•
expresses a relation between the properties of a system and - the. .~ifferences between
the values of these properties, in two neighborring equilibrium states.
A large number of thermodynamic relations Cal. be derived by selecting T and v, T and P
or P and v as independent variables. Siner. the state of a pure substance can be
( defined by any two of its properties, the partial derivative of anyone property with
respect to any other, with anyone of tr ose remaining constant, has a physical
meaning. Every partial derivative can be expressed in terms of {3, K, cp and Cv along
with the properties P, v and T themselve s, . so that no physical properties. of a
substance other than those already discussed need [Q be measured. A derivative 1S

said to be ir standard form when it is express ed in terms of the -luantities above.

Using the general method by which the der vatives are evaluated, let us try to work
out a few relations that will be needed later .

1
 " ~ ~vj S' oGj 0S"\'O ~J -11-

d -
/I (-~J
JE: l
_1(
t:
.~
_t-~ J
a..-r '50,'1':t ~ ~ S ,-,\"J ~ M

. (b) [ei ~j_(~Tjj c~ ~ [~( ~~:)_ "~~ ] ~ - l~~~ ~

~90 oM

L C8 -r:Y~lSOA ~ ,I M f7vvna Y' ?j~I d" vX) f\ cC:j t fa ~'S'O(( "1-t~ n ,V,l) =,'-\V'{)~
-1~t f~--o.L-lvVO~1-VP J pVVO C}_J s ~y~o- ~ 0J'N0f1

~:~e~
__l-~:;
I (. ~

0" C~C+)~J= [Ie n) "ee-j i: .

. ,). )~, ' ~Lr'O,L1~ ~ VOfAD ~ +0
, 'fvVJ('1/V(Jcjop ~'v1 Q\('O () o/[Link]./I,nfcr; Q P,'-1v'Oc.} ~ya__..w rWJ~ ''P('rY:'.MJ '!:lJ ')
n )O'--V\O.L o..J -fJ'd cJ S' (}..c.' ~ ,l M Y) --p w.o 5 f0 ~/\.'-1"0/\ :va 'r }Ova Joy' '6 '1J.-
• (~ ) Vl'-'(:~)J _L

I
z: _L( ~J
(L) ~(~~)4 ~-
/':~
( f[./ ',-
-OO-YY~)d 0'1 -1 rYl u.u ('J j' P 'W{)

(c(sj ':"'" f-i~:"1.+fa-OJ .[Link] :V/QjO'NO~op~ OVD fI'P )JVvO.1'p OJ~S

(9) 1\ r -1( ~~ )-t- Ep--~E·;~j c. ) f

i
I.
?_(1 .N MaS I "0 VV'OJ ()' M

<' cpj
-r [J + _L ( ~~ ) Jy 4- ~ r ~( ~ ) 4-" s~

1\ 'P~ _L -yo ~Y'J~J -0 ~1J Y) (~l.[()"P!SUJ)J

: (\p J + 'rl pJ- !j. ~ 5 "p jV\..9 N

, L-V/() -1 yJ; Y "\('OJ '\Y) ,Lj \JO q
r-;-l..V'(_' fO S'f'ouz., cr'i-=J -jo ~v"'c 'f'-""C~Cll:J':'-' -aVe) i-J(f':'''OiJ 0-':11 ~1'1'J'-1.l o~
r 5 '0 Y 1.1
0 v.r() LJ_. VJd ~ f
'-fb -:) to 5 Uf_ U3 -r~N) f'-"O lj --0 "Yfbcr lA/'O 0-I ,'hM ')Yl -\ tJ'j
 The.. C\Q_~~C\~'\Cx_ of VnlV\-'Y\~ -CY\:v,''3':J ~ \rolvVJY>Q__ Ov\ C(f),Sr-UJ,-,t
lvm,fV'uA\lJ-;LQ_ c~ U(2r<~e_ k C c,y__G..Jo-.r-_Q_d. 4'YlJ-yT) ~ _Q_CUAe<_ h .:
01 f ~Y-.e_ CrY .f "1J'rr"\ 01 J ):_ I I Vvv-- d - P,
~~Q (h\
-aT )\J
1- c, €_C.J.A-c\__h{/V\c5) (~~Q VJ'Y'lIVvc (LS

01 LA ~ eve) T -+- [ ~~ T C-¥ )0_~ F] d V ( If')

lrJ Q_ e _s
[ c~)»>,
-~ Q_Q_ 'Y'- ~

Cf' -Cv ~
T
--t eJ (~) ~T P

f~ 0) ().rA_c{ (?) CJV'0J

Cv
~) -~
';7'1 V 'I

~o{
(Jv )~ ~~)
V
( I
 Try) t-K_V'YYI ~ at -ernti,£_'J_'plj ,J; l .: u -r fv ~ Cc--,-,., /:)(.,,:, o c{.
-+\S,f- Ov-n (i\. he.c c:Y1, ct )20.'''',0'-f ~ b? C 'Jr( ~ H-f;-.--... C\, n, j

cLs z: ~~~f d,t - Vo{l)) ({ 7)

.-{:_ ~ 0c v
+ /":) 'd h : cri G{ f- f d G' +- v d f
(6i_;__tc ds i,'. t'{d.4. +- Pdv./ ::- 1- (d~~fdl/ _vj, P-f fc{v)
( , T ~
OwtJ ~r,"-U- as':
,
_L (d-t - l/d(:J)
T
1

d}_ ~ -: ~) ct 7 .f- { () ~ )' cI p ( /s ) I

'cJ'"f" f l'JP T !

dr, +R#)pdT+(;?)/f_vJf]
:::J_ (25) ~1 .{ JV.2E.)
T ?---r P , ,7 \._ r -r
,--vJ '0
elf

.; . it

1"i.B" r;'.e_ ('fk) ,

Q
;1T P
z: j_
T
c?E-)
d-r p
C\NI c:t ( 2_ 0 )

~ -!r [[' ;~ )'f - '- ]

I,"

(~)-r ~I) ~,

Also
[{p C-~ )rJ T z: [~

,
ant l ?;~ F ~

c?~
J_ __
T 'oP)i ~ [~;~i'- (;; )p]_.: ~[(~)~ vl

(2.2 )

~t CCM[ A lso be 37
 (hQ dQPc'Y\c(Q'~'\C_;_ c(; .(-:,,~-c~t;{p/ (J'1 )-"k)SU.'\.J(:_, C\J (msi'c\Ylt, t;:""'r:z\(
~'< c tl"t'1e f1;~.Q_ GQ (~lc.~'- [Link] 1:7GWI CWJ ...-el. hc:,~ l(t; S ki-(:_
r
DvY\ LlC'_

U O"y-> d. -( ,

5:,~~ (){;) . . ~'T P

r:'p : Q'Vc'~'00 (18) C"", b? Cv" f!{" ~ S i.: G.~
c) i ~c~Crt - r T( ;<)p .. J d f' V ( 2) )

LA S h-..3 ,.Q_'1P- CL Yi V,l C tiS) OvY\ d. vY~ (2 0) 0,,,<-t(;

~ pOV"\ h'cJ.. elc \-'~ h' 'v Q <;

\iCI. OJ;

/ ? s' ~
-
Cp {2v.-)
~,~
)p "

-? r -(~: \ (2;- )
(
ffi )T -~
'01 " f
.... --.

oR. J
VlJ:::-
j_lJf,)
-
drrI, J CJ.i
eII._)::-'
T '~"- P r T

',," " -.

d J:: (' d S '\

\ '0\ ) P
c( T -f
.
(,11
"2> e
)'-r".c\ p,,' ,

,- 5 - I
 II

C 01 ) is: .l
'C9P v~ T) [ (v'\_?9) j4-V -v J

£?vJ:£"'~~~5 (3'l) CY11 ct (" 3 o )

pj £'
~
~ _L
T- --
c; (J_!P )v'~p-~ <---::r-"~
j
Cf C2I)
oJ f
dv

oR ! T cI s : C P ~) p d -:--~r_-+-_C_y C-:-+_~_)_v_cl_f---, C3 3 )
 PROPERTIES OF IDEAL AND VAN DER W AA ~S GASES:
.___
'2 .
From Tds equations we have t..._
z. .,.J ./
...
_.-

ds =? dT - [~11 dP and dh = cpdT -+ (34)

Let So and h, represent the entropy and enthalpy in .zn arbitrary state Po,
T P
Then s = J yr dT - f [U] pdP + So (35)
To Po ._,

and h = I cpdT + JP [
T
V -T [ff, 1 ,
p dP + h, .(36)
To 0

p. a2v ]
Also w~ c~ _9)J.~~ a relation cPo = cp + T
J 19T2 P dP. _._.__(3.7)
Po .
The integrals in equations (35), (36) and (37) are readily evaluated for an ideal \gas.
We have v = RT/P, (ay/aTh = RIP and (a2y/aT2)p := O. If cp is the function of T only
T
s = J¥ dT - Rln ~ + So (38)
To
T
h = J cpdT + h, (39) . --
-..... '. ~.
To
The expressions for the properties of a van der _\ /aals gas are simpler if T and V
rather than T and P, are selected as variables. Agai 1 from Tds equations we have

( ds = ? +[g]/v dT (40)

also
[~lT ~T[:~;La =
(41)

since P is - a linear [Link] of T. (Hint: F['( m Tds equations; equating mixed partial

second derivatives of s with respect to v and 1) That is, c, is a function of T only

and does not vary with v at constant temperature.
.~
~/\ ..'
f -
-
(I
•. I,'
......-'
d --7 , \ r-
I.;
~ \...--_.
I
;
7 -r " .' ~~;

II
 From the equation of state
(ap]
-T
_ R
-:-:--r::- (for van dcr Waals gas)
la
8
V V-U

. Then if So is the entropy in a reference state Po, vo,T I we have

T \._.
c -: v-b
s =
J ~.:r_ -:-Rln vo-b + s( (42)
To
If c, is considered to be constant >
T' v-b
s = [Link] T - Rln ~
o vo-U
+ So (43)

The internal energy can be obtained from. the equatic n C \\ \,~

du ~ cvdT + [T [ff] ,- +v
or du = .cvdT + ~
y2
dv (44)

If Uo is the energy in the reference state

T
u ;;jcvdT-- a[~- ~,] + u, (45)
o

If cv is constant

Let us consider the equation of state of a van der Waals gas again:
(P + a)(y_b) = RT (46)
v

(OR) (P + ~)
y2
=
'
RT
(v=5)
(OR) P = ~
RT
(v-o)
---
v
a
' so that [g.L ~ (v\) (47)

Also from (46) Pv + -ya - ab

Pb - -
y2
= RT (O~ T = k[p~- Pb + av' - aby-21
Now [aT]
ev P
= IJp _ ~'.~ 2ab] = 1 'RT _ s.. ~+ 2ab,] -
RF_;_ y2 y3 R: ~v b y2 y2·. y~. :I
, .

aT] _ 1 f;RT
[ay P RlY b
2a + 2ab] = 1 [~.3<-T-2ay(y-b)+2ab(y-b)
y2 v3 l{ y3 (v-b)
1
8

4-\
 Therefore [aT] - = ~[RTV3-2a {V-b)2] (48)
av p v3(v-J)

Using reciprocal theorem [av] _ Rv3(v-b)

______ aT p - RTv3 - 2a(v-b)2
Again from equation (13) we can write

c - c
p v
= 1
R [RV3(V-b)
T [v-b RTv3 _ 2a(v-b)2
] (49)

This can also- be written as (50)

The second term in the denominator is a small co rection term. So (v-b) 0= v.

(
Hence- we -get - -Cp - C
v
""- R [1 + R2T2
2ap] (assuming Pv=RT - and -v=RTfP) - (51)

The relation between T and v in a reversible a: .iabatic process is obtained by setting

(-;::+
s as constant. Again if c, is constant, then from (:+3) we get ('"'_"'- ;: "\

[Link] + Rln(v-b) constant OR T(v-b )RJcv = constant (52)

JOULE-THOMSON COEFFICIENTS: ..:.:.....

The following equations can be obtained - c n the basis of the first law of
thermod ynarnics:
(

l_
" ~[~~L C~[!~lT = - and r l*lh - . C~[~lT
=
(53)

Also from the combined first and second law

.[~~)T T[gL -
= P and [~]T " -T[tr]p+ V (54)

For a van der Waals gas

RT ~3b - 2av(v-b)2
(55)
R ['v3 - 2a(v-b)2

9
 Hence III a Joule expansion of a van der Waals gas

(c1fj a
TJ =la~ u
= ---
C v v2
(56)

and in a finite change in volume

-_-
~,[~2- ~ll (57)

Also Joule-Thomson expansion of a van der Waals gas

J.1 = [*.]h 1 b-
cp
[RTV3
RTv3 -
2av 'V-b)2]
2aC =-b) 2
(58)

The inversion curve is the locus of points at whic r [~)h ~ 0 and the temperature at

I
I

such a point IS the inversion temperature T,. Her oe setting [:~) h ~ 0 we obtain the

-equati<:ln-of--the-inversion curve of a van der Waals gas

(i_e.) T, = 2 a (v-b )2 (59)

Rv2b

When Joule- Thomson effect is to be used in the li uefaction of gas, the gas must first
cooled below its maximum inversion temperature, which occurs when the pressure is
small and the specific volume is large. Again if (\ --b) "" v then
2a . .,
T1(max) = Illi (60)
... ::.. "

***********

,
I,

10
 6. THERMODYNAMIC POTENTIALS

HELMHOLTZ FUNCTION AND GIBBS F1JN( TION

From the first law thermodynamics we know that

W = (U 1- U~ + I:~ (1)
(U1 - U~ is the decrease in internal energies.
From the principle of increase of entropy, the s m of increase in entropy the system
(S2-S1)' and that of reservoir l\SR is equal to or p-eater than zero:
(S2-SI) + l\SR :: 0
(A special case in which the only heat flov is from a single reservoir at the
temperature T and the initial and final states are", .t the same temperature).
The entropy change of the reservoir SR = - Q/T

( Therefore (S2-S1) - i ?: 0 OR (S2-S)?: i OR T(S2-S1)?: Q

Hence from the first law WT :::s (U --U2) - T(ScS~ (2)

Let us define a property of the system called its Helmholtz function, "F", by the
equation
F == U - TS (3)
Then for two equilibrium states at the same tempe rature T,(F1-F2)
Also from (2) WT:::s ~FI-F~ (4)
';.:"

That is the decrease in the Helmholtz function if a system sets up an upper limit to
the work in any process between two equilibrium states at the same temperatures during
which there IS a heat flow into the syste n from a single reservoir at this
( temperature.
If the process IS reversible, the total entre ',Y of the system plus reservoir IS

constant, Q = T(S2-S1) and

WT = (U(-U~ - T(Sl-S~ = (FI-F~ (5)
This equality sign then holds in equation (4) ane the work is maximum. If the process
is irreversible, the. work is less than this maxir (urn. Because its decrease equals the
maximum energy that can be freed in a proc: ss and made available for work, the
quantity F is sometimes called the free energy of a system.

1
 In general the work in a differential process will b: given by PdV plus a sum of terms
like work dome by magnetic field etc. For simpli city, let us assume one such term,
say, YdX.

The total work in any finite process is then the sum of the PdV work and the YdX work.
Let us now represent the former by W' and later by A. The work in any process is then
W' + A and equation(4) becomes
W~ + AT s (FI-F~ (6)
Ina process of constant volume PdV work is zero hat is W~=O and in such a process
AT,v :S (FI-F~ (7)
The decrease in the Helmholtz function therefore ets an upper limit to the non-PdV
work in a process at constant temperature and vo LIme. If the process is reversible,
this work equals the decrease in the Helmholtz fune .ion. If both T and X are constant
'j
then A = 0 and O:s (FI-F~ OR F2:s Fj (8) I

That is in a process at constant volume for whir h A = 0 and T is constant, the

Helmholtz function can only decrease or in the li nit, remain constant. Conversely,
such a process is possible only if F2 :S Fl'

Consider next a process at a constant external pre ssure P. The work W' in such a
. !.. process is P(V2-Vj) and from (6)
AT,p:S (FI-F2) + P(VI-V~ OR AT,p:S (UI-U~ - T(Sl-S~ + P(V1-V2)

Let us define a function "Gil called the Gibbsfunctu In, by the equation
G == F + PV = H - TS = U·· TS + PV '.'(9)
Then for two states at the same temperature T and I ressure P
G1 - G2 = (UI-U~ - T(Sj-S~ + P(Vj-V~ and AT,p:S (GI-G~ (10)

The decrease in the Gibbs function therefore sets a 1 upper limit to the non PdV work
in any process between two equilibrium states at the same temperature and pressure. If
the process is reversible, this work is equal to tl e decrease in the Gibbs function.
Because its decrease in such a process equals the rna' .irnum energy that can be freed and
made available for the non PdV work, Gibbs fun: tion has also been called the free
energy of the system.

2
 If the variable X is constant in a process or if t) e only work is PdV work then A = 0
and G2 =-= Gj. That is, in such a process the Cibbs function either remain constant or
decreases. Such a process is possible only if G2 -s Gj.

THERMODYNAMIC POTENTIALS

The difference between the values of the H elmholtz and Gibbs function in two
neighbouring states of a closed PVT system are from equation 3 and 9)
dF = dU - TdS - S H (11)
dG = dU - 'IdS - SdT + PjV + VdP (12)
Also dU = TdS - P jV (13)

We can eliminate dU from (11) and (12) using I 3). That is

dF = TdS - PdV - TdS - SdT
dF = r SdT - Pd' (14)
dG = - SdT + V(]P (15)
Also dH = TdS + VI P

The coefficients of the differentials on the right hand

side of the dF and dG
equations can be identified with the partial d( rivatives of the variables on left hand
side. If F is a function of T and V

dF = [aFJ
. aT V.
dT + [~]TdV .
Comparing with (14) we get - [~i]v = s That is [~]~ ~ -s (16)

Similarly if G is a function of T and P

( (17)
.dG = [aG]
aTp dT + laG]
apT dP OR

Similarly we can show that

[~]V T; [~]s -P; [~]T -P;

= = =
l aG]
ilP T = V;
= V;

From the defmitiorffF we know that U = F 'IS. Using (16) we can write
r-

U F - T[gJJ
= (18)
3
From the definition G we know that H = G + TS Using (17) we can write

(19)

Equations (18) and (19) are known, as "Gibbs-Helmnoltr" equations.

MAXWELL RELATIONS

A set of equations called the Maxwell relations c: n be derived from the fact that the
differentials of the thermodynamic potentials are exact. We noticed earlier that in
the equation dz = M(x,y)dx + N(x,y)dy, dz is e) act when

[~~L [~~L = (20)

Also we know that

, dU = TdS - PdV (21) \_

dF = -SdT - PdV (22)

dG = -SdT + VdP (23)
dH = TdS + VdP (24)

Applying the condition in (20) to (21), (22), (23) G nd (24) we get

[~ls. = -[~lv {25)

[~~lT = [~~lv (26) ....-'. :'

[~lT = -[~lp (27)

[~ls =. -[~lp (28)

Equations (25), (26), (27) and (28) are called MOX'Ijell relations.

THE CLAUSIUS-CLAPEYRON EQUATION

Suppose a liquid and its vapour are in equilibriur 1 at a pressure P and a temperature
T, so that under these conditions g" = g"'. \It a temperature T+dT, the vapour

4
 pressure IS P+dP and the specific _Gibbs func ions are respectively g; +.dg'
I I and
g: i r +dg' r I. But since the liquid and vapour are in equilibrium at the new temperature
and pressure dg ' = dg: I (29)

The differences between the values of the spec] IC Helmholtz and Gibbs functions in
two neighbouring equilibrium states of a closed P'/T system are
df = du - Tds - sdT
dg = du - Tds - sdT -+ Pdv + vdP
Since du = Tds - Pdv we have d 2' = -sdT +. vdl".
,-" ,
(30)

The changes in temperature and pressure are the i arne for both phases and hence
-s: 'dT +. Vi I dP = -s" I dT + v'" dP
OR (s'" -s") = (V'" -v")dP (31).

But s' , I - s' , (that is heat of vapourisation ~3 d vided by 1)

e 23 dT = (v' r
Hence , - r' ')dP (32)
"1

That is dP] e~~ (33)

[aT 23 = . lTv" :~

which is the Clausius-Clapeyron equation lOT liqui i-vapour equilibrium ..

THIRD LAW OF THERMODYNAMICS

(
Nernst heat theorem: In the neighbourhood of a,.soluie zero, all reactions in a liquid
or solid in internal equilibrium take place with no change in entropy.

The third law of thermodynamics can be stated as follows:

The entropy of every solid or liquid substance in internal equilibrium. at absolute
zero is itself zero, that is, u m S = (I. T~O

5
It implies that it is impossible to reduce the te nperature of a system to absolute
zero in any finite number of operations.

The most efficient method for reaching absolute ze .o is to isolate the system from its
surroundings and reduce its temperature below that of the surroundings in an adiabatic
process in which the work is done by the system .olely at the expense of its internal
energy.

Consider a reversible adiabatic process which take; a system in a state 1 to state 2

by a path which changes a property X and the temp erature T of the system.

If the substance is heated reversibly at constant volt me or pressure from T=O to T=T,
its entropy at a temperature T is
T T

S(v,T) = I cv~ and S(p ,T) = Ic 'T

dT (34)
o o
It follows from (34) that
Ta

Sl(Xa,Ts) = I~
o
dT and

In a reversible adiabatic process,

and therefore'
Ts

I
c (a
,[,
.
dT
.r '
Tb

~dT-'
T '
(3$)
o o
If the process continues until T, = 0, since each of the integral converges
Ta

I~ dT ~ (
o
However, c, is greater than zero for T, not equa to zero and equation (35) can not
a
be true. Therefore the absolute zero of temperature can not be attained.

************

6
s, ii:~

:7. STATISTICAL MECHANICS

Newtonian mechanics (classical mechaclics) describes the behaviour

of mat ter In bulk (macroscopic Sj stems) successfully. On a
molecular or microscopic scale, cLassical mechanics does not
apply and must be replaced by quan t urn mechanics. When a system
contains a large number of particles, the ordinary l~ws could not
. be used e i ther due to mathematical complications or these laws
were unable to· give proper intelpretation for the observed
pheno!1leno.I1._.,Hence _i_t., is -impos s i b l e :0 apply the ordinary laws of
mechanics to' a physical systems cor.t a i n i nq a Lorge number of
particles. More over the problem 0 E an' atom w i. th two electrons
presents such a great mathematical c)mplications that it was very
difficult/impossible to solve by use of ordinary laws of
mechanics. A new. approach has t :1 be 'followed to solve the
problems of microscopic bodies cor s i s t i nq of about 1023 atoms
WlC~ their e~eccro~s. S~2~ prob: ems have been successfully
solved by the methods of statistical mechanics.

Eence stati~tical mechanics is a branch of science whicb

( behaviour of
system in terms of its microscopir: properties. As its name
.i mpr i e s , s r a t i s t i c a I rne [Link] i c s lEO not concerned with the actual
motion of individual particles of 1 he system, but investigates
some 2\[Link]-age or most p r obab l e or s t atistical properties of the
system with out going into the interior details 6f the
cha r ac t er i s t i c s of its' cor.s c i t ue nt s The larger the number of
oa r t i c Le s in the physical system r:onsidered, the, more nearly
~orrect are the statistical predictiJns. The smaller tb~ number
of particles in a meohanical systerr the methods of statistical
mechanics cease to have meaning.

PHASE· SPACE:

In c-lassical mechanics, the Dositi)n of a oo in t particle is

described in terms of ehree' Cartesi~n coordinates x,y,z and the
particle is said to have three degre!s of freedom. The state of
ene mOLion of parcicie' lS described in terms of velocity
I

l =02pO~::;~ts ~,S·,~· Some~:~2s it is mor~ convenient to use momentum

coordinates p ,p , p, (rnx,rGy,mz) .i ns t e ad of velocity coordinates.
x y z
Tr.u s t he po s i r; ion of a s i nq.i e pc r t i c Le can be specified in
terms of Cartesian coordinates x, i,Z and its corresponding
momentum component.s p x ,p y ,p.z In order to facilitate the
application of che laws of [Link] it. is convenient to invent. a
scheme which can be used to descri :Ie the state (position and
momentum) of the particle at a par :icular .instant. For this
purpose, We imagine a six dimensior 13.1 space in which the six
coo r [Link] tes x , y, Z, Px , Py , p z aJ:e ma:ked along six mutually
perpendicul~r axis in space. The cot rbi ried position and momentum
space is then called as phase space., A point in the phase space
represen t s the pos i t ion arid rnoment un of the particle at some
particular instant.

1
 DIVISION OF PHASE SPACE IN TO CELLS;

The meaning of a point in

space ca~ be unjerstood with the help
of uncertainty principle.
The _phase spa c e ill divided into six
dimensional cells whose
sides are dx, dy, dz, dp ,dp ,dp. Such
x y z
~ells ar~ called phase cells.
Further we approach close to the
limit of a point in phase space
reducing t~e size of a cell. The
volume of each cell is given by
dr dxdydzdp dp dp
x y ;
But according to uncertainty principle
dx~px ~.h.; dydpy ==h; dzd
z
Thus d'r ==h3
A point in the phase space is actually cOlsidered to be a cell
whose minimum vol ume is of the order of h3. So the particle in
the phase space can not be considered exa ::tly located at point
):,'-',Z,D
- - x ,pY ,p2 best can only be found'some\'here with in a phase
cell centered at that point. The genera: isation of the above
remark can be made for a complex system. lor example, the state
of an assembly of N systems can be des c:.Lbe d in terms of 6N
coordinates (3N for position and 3N for n"DmentL:.mcoordinates). II
Now the state of the particle can be defi:led in 6N dimensional
space known as phase space (Tl. Let the sy~tem has f degrees of
freedom (number of coordinates needed for the description of the
svstem) . The [Link] configuration » f the system. can be
d~scribed by a set of genaralised position coordinates q , q ,q ,
'. 1 2 J
·····qr and corresponding momentum n.t t as
c oo rd.i PJ,P2,P3' ..... Pr
by a total of 2f parameters. This' 2f di lensional coordinate-
momentum space so formed is called phase sface of T space. The
set of numbers (q I q, q, ..... q, p, p, p, .p) 1S
1 2 3 ·f J 2 3 f
regarded as point in phase space of 2f dimen3ions ..

s t a t s c : a. s y [Link],
-=-2-_'--':'s t.h e dy·;-·c.;-:-,i[Link]'):)2 :peci::ied Dy l()cating
",2:'"
a point in a 2N dimensional space (in g~neraL); th~ co6iain~te of
ehe poin~s being ehe values of the N coordinates and N momenta
wh i ch specify the state.. The space is ref or to as phase space
a~c the point:.is called phase poi~t.

(
ENSEMBLES; '.

If you have a collection of particles we shall refer to a single

particle as a system and to the collection cf particles as whole
as an assembly. The collection of large nurrber of assemblies is
called as a~ e~s2~ble.· The pe~be~s of the ersemble are identical
an features, (like volume, energy, total .iumbe r of particles
etc.) and are known as elements _ The e Lems nts differ in their
states, that is, they differ in coordinates and velocities.

Thus an ensemble is defined as a collecti :!n of a very large

lumber of assemblies which are essentially ildependent (that is,
in calculating the possible eigen state of a'l assembly we do not
1aVe to worry abour .any interaction betwe:on the assembly of
Lnteresc. .arid any of the o the r assemblies) of one another but

2
 which have been made macroscopically as identical as possible.
By being macroscopically iden_tical, WI! mean that each assembly is
characterised by the same value of set of macroscopical
parameters which uniquely determine the equilibrium state of the
assembly .

.MICRO CANONICAL ENSEMBLE:

The micro canonical ensemble is a co L. ection

of essentially independent assembly hiving
the .s arne erie r-qy E, -_volume -V--and -numbe:~-N of
the systems I all the system are of t hr. same
type. The individual assembly are s ej-a rat.e d
by rigid, impermeable and well insula ed
walls such that the values of E,V and N a~e
not affected by the presence of other systems.

CANONICAL ENSEMBLE:

The canonical errsernble is a collectioJ. of

essentially independent assemblies ha, ing the
( same temperature T, volume V and numbl r of
identical particle N. To assure-ours( If that
all the assemblies have the same [Link],
we could brin~ each in thermal contact with
the large heat reservoirs at temperatl re T
or we could simply bring all of the a!semblies
in thermal contact with each other.
The figure represents symbolically canonical ensemble. The
individual assemblies are separated by rigid, impermeable but
diathermic walls, .Since energy car be exchanged between. the
assemblies, they will reach a comr on temperature. Thus in
canonical ensemble system can exchangE. energy but not par:ticles.

GRAND CANONICAL ENSEMBLE:

Grand canonical -ensemble lS a ..o Tl ec t i on of essentially

independent assembly having the same cemperature T, vol urne V and'
a chemical pqtential ~.

( LIOUVILLE'S THEOREM:

Consider an ensemble consisting of 2 large number of identical

non-interacting systems. We know thaI the instantaneous state of
a system can be represented by a )oint in the phase space.
Similarly the instantaneous states of other systems constituting
the ensemble can be represented by other points in the phase
space. Thus the instantaneous state of the entire ensemble can
be represented by a number of phase points in the phase space.
The densi ty of the points, also [Link] as density of states in
phase space, is denoted by p. If the state of. an [Link]
wi th time the posi tions of phase po i i it. s in the phase space w i Ll
change with time. The motion of thes~ points in the phase space
is governed by the canpnical equation
8H 8H
ap. 1 aq.
1

3
 Here H = H(q 123
,q ,q ,'....q ,p ,p ,p ,....p)
r 123 f
is the Hamil t on i an of
t he systems. Due to the motion of phase points, the density of
scate~ in t he phase .space p c hariqes w i t h time. Liouville's
t he orem gives information about the' ratE of cllange of phase
de nsLt y in the phase space. The theorem may be stated in two
parts:
(i) The rate of change of density of pha st points (representing
the system) in the neighbourhood of a mavin] phase point in the r
space is zero. This part represenLs the prilciple of conservation
of density in the phase space).
Mathematically dpldt = 0
.i i) Any a rb i t ra'ry element of \r01urrie-
or' ext .n si on in space in the
"[-space, bounded by a moving surface and c ont a.i n i nq a number of
phase points do~s not chang~ with time deEpite the displacement
and distortions. This part represent the principle of
conservation of eXLension'in phase'space.
.
Mat,h ernat acaI
IILv d(aT) ~,(ndq,-_'lD~,)'
;_ 1 o
.:i:' ~l.. 1 1

STIRILING FORMULA (STIRILING APPROXIMATI01'):

'i
t
For a very large value of n, ,the calculati)n tif n! becomes very
croublesome. Stirilinq's formula qives a suitable analytic
approximation of In n 1 for large valu-es of n , That is, as n is
v[Link]-y
lar-ge
In n! n In n - n
STATISTICAL EQUILIBRIUM:

An' ensemble is said to be in statistica equilibrium if the

probabilities of finding the phase' poilts in the various
r eq i on s'of phase and the average values of t he properties of its
s ys t ern 3.::::-e '2: t i r.e. [Link]!!:
i:::.~epe;,;C:-=:::.t ,tically, it, can- be
eXDressed as

[~~t,p = 0 for. all values q md p. -.:'" "

~tis means t~at for an ense~ble to be in st!tistical equilibrium

~he dens:""LY p 8JS"L be :"ndependenc of "Lime a all points in phas~
seace.

POSTULATE OF EQUAL A PRIORI PROBABILITY:

Accor-ding to this postulate, the probability of finding the phase

point ~or a given system in any region of phase space is
identical with that for any other region 0: equal extension or
\'C 1. ume .

PROBABILITY:

The probabili~y of an event may be de~ined as the ratio of the

:::.umber
c~ cases l~ which the event occur to the tOLal number of
cases. That is
The probability of an eyent
numb~r of cases In which the evelt occur
T6tal number of cases

4
 '\
Thus, if an event can happen in JI a ways and f ai 1 to happen in
I

"b" ways, then the probability- of [Link] n i nq of the event = a/aTb

and the probability of failing of th2 event = b/a+b.

MICROSTATES AND MACROSTATES

Let us consider an ensemble consisting of a large number of

independent system or a gas consi s r i nq of' a large number of
rroLe cu Le s , in the phase space - Each system or molecule may be
represented by a point known as p) ase point or representatt. ve ..
point ~n. the phase space. Let- ,pflase -space'''bf:' divided .Ln 't-o cells
numbered '1,2; 3 ..... i etc. adj oi n i n« one another and having a
vol ume e qu a 1 too q ,0 q ,0 q, .... (q ,0 P ,0 P ,<5 p, " .. 0p. .A
123 r 123 t
phase point for' any system or mcI.e cu l e may be supposed to be
inside one of the cells. III order to define the microstate of
the ensemble we must. specify the j ndi vidual posi tion of phase
p ci n t s for each s ys t er, m81ec":J2.e c f the ensemble. In other
words microstate of the en s ernbLs may be defined by .the
specification of the individual position of phase poirits for each
system or melecule of che ensemb:e,

?rom the point of view of gros~ observable properties or

~acroscepic behavio~r i: ~s i~~ace~~~l which particular system or
melecules are occupyi~9 che speci :1eo cells. Therefore, a
[Link] the ~nsemble may be def_ned by the specification of
phase point, in each cell. That is by specifying the numbers only
and overlooking the identities of thl: system or molecules. Note
that there may be many differen: microstates which may
correspond to the same macrostate.

NUMBER OF MICROSTATES ACCESSIBLE TO A MACROSCOPIC SYSTEM:

Consider a macroscopic system vii th total energy E. Let the

e:"lel-gy scale 0:: cne s ys t en, .[Link] c.:.\':.:::ec. i~-:o· eq'ual and small
interval of fixed magnitude oE such t lat
t i ) 0E is very srnaLl compared to :.he [Link] energy E of the

~i) a~i[e ~a~ge compa~ed :e.c~e e~er IY of sing~e particle in the

system,
( ;':'~lj cne energy incerva: at:: . '::0;'",[, :..:-"s r.a ny possible quantum
states of the system and
(iv) this is quite large compared to
the separation In energy between a d j acent energy states of the
system.
Let D (E) bet. hen LCmr e r 0 f s tat e s v .i the nerg .i e sly .ingin the
interval between E and E+oE. H2re D(E) must be simply
p r op 0 r ; i C nc. ::_ too:C:, :L f p (:2) bet he dell S :_t y s ~0: t e s (numbe r 0 f
states per unit energy range at the g:ven energy (E), then
D(E) p(E)oE
It should be remembered that p (E)' is independent of the size of
oS. :;:f ',,;e k riow [he c:;:-;"':.3.:1[ity
q. ;:S) .he t or aI number of states
I

havin? energies less than E, then It is possible to obtain D(E).

The number D (E) of states having en· .r q i e s lying between E and
E-i-oE 1S glven by
D(E) q:'(2.;.oE) - '*(E.:,

\.
5
NUMBER OF STATES OF A, SINGLE PARTICLE IN ONE DIMENSIONAL BOX;

We know that the energy values of a single particle enclosed ln

one dimensional box of length L 1S· giyen by

E n2 ,. here n 1,2,3 and n is d quantum number.

From this expression n (2mE)1/2 (2L/h) . and the successive

quantum state correspond to the values of n jiffering by unity"
Now the total number ~(E) of quantum states having energies less
than E, or quantum number less than n i~ simJly (n-1) It may be
regarded equal' to n as n is very large. Thu3
~ (E) n (2L/h), (2mE)1/2 ,

d~
£I (E) dE ot ~t [(2mE) 1/2 (2L/h) J
"'2 • .-~
Tria t is 12iE_; (Lin; i 2:,-t,' ~-' "5£
This expression gives the nurnber of states ac ce s s iol e to a free
oarticle confined in a t2X of length L.

I,
THERMODYNAMIC PROBABILITY

The fundamental postulate of statistical t l ermodynamics is that

all pass ibl e mi c r o s t a t e s 0: an .is oI a ted' .rs s ernbLy are equally
possible. The number of eqilally probab: e microstates that
corresoond to a [Link] ::~ac::.-os:::aLek as call ed the thermodynamic
pr oba b i I i t y (\~k) of "Ch::: [Link] r c s t a r.e . tO2_'" rn:,s t macros t aes of an
assembly of a large number of particles the thermodynamical J

probability -is a· very large number. ThE total number 12 of

possible microstate of an assembly or the thermodynamic J

orobabi 1i tv o'f the assembl v , eaual to the sum over all

~acrostates of the thermOdyn~m"i~a~ ~~obabili:y of ea'ch macr os t a t e
k k. -.._
The pri~ciple 0: qU3~t~= =e=ha~ics leads tc eXDressiori~ for the
possible d if f e r e nt; ways in which the pa r t i.c Le s may be distributed
amo~g the energy states of a single 3ssemb.y at one instant of
time. ·That is, the rni cr os t ar e at each instant for a single
2ssemblv or of each of the large number of replicas of an
assembly at one instant. The observab _e properties of a
macroscopic system depend on the time a\erage value of its
r.i c t c s c op i c p r cpe r t i e s . ;:';--;e pr i nc i p Le (foal of statistical
thermodynpmics 1S to derive an exr::_ress1on fer the average number
of N. in each of the permitted energy level:: j of the assembly.
J
The expression to be derived is called th ~ average occupation
number of the level j.

Let; N",,_be the oc cupa t i or, nurnber of the Le ve I j In macrostate k.

j ........

group average value of the occupation nLmber level j, N~, 1S

J
found by multiplying N'k by the n0mber of replicas in macrostate
J c

k, summing over all macrosta~es and dividin9 by the total number

 ",

of replicas,N,of a given assembly. The total number of replicas

of given assembly that are in macrco;tate k equals the product of
the number of replicas liN that ar.: in some microstate and the
number of microstates Wk included III the ·macrostate. Therefore

N~ ~ t NikWkllN
But N = L WkllN
k
and since liN is the same for all r ac r os t a t e s , we can cancel it
from the numerator and denominator.
The group average lS

N~ . (a)
J \"L W,K
k
Similarly we can calculate the tir e av e r aqe of the occupation
-L
number of level j, N, . The total time of the assembly is found
J
i~ ~~=rosca~e k is t~E~ :~e prod~ct of the time interval lit and
;:~-:e :-.·_::::::2rv,l., ::: ::-:2 :.'1=::'-:5::3.:e i.e: 'he rnac r c s t a t e k . the sum of
r:

these products over all macrostates ~qual to the total time t is

L
,
= Lk vJk! t

The time average value 0:: the occuf~tion number of level j, N"
t
J
is found by mUltiplying the occupatLon number N'k of level j in
, J
macrostate k by the Lime WKllt ria t the assembly spends in
macrostate k , summing [Link] s e product s over all macrostates I
and
d~vid~ng by Lhe total cime t, The tlem average is therefore
, L N~~W~~t
t ~,1\ J' k W k,ll
r,
C ==, ~
14:~ ,IIt ','
c • -

k K. '

Sir:c::= 6.t lS t he sarr.e f or a2.l ::"icros :ates, we c an cancel it from

the numerator and denominator, gi v i n.;
L K ..
J .~c .-
\4
, , .. (b)
/ Lk W._
J"~

Comparison of (a) .e rid (b) shows that all microstates if

are
e qu a 11~' p r oba o l e the time I average of OCCUDa tion an
number lS
equal to the group average and we cal, represent it hy N"
J

BOSE - EINSTEIN STATISTICS (B-E)

The :hermcdynamical prcbabi1icy, ~k of a macrostaLe of an

assembly depends on the pa r t ac u La i statistics obeyed by the
assc~t·=-y' .

In B-2 statistics the part~cles are considered indistinguishable

and there is no restriction on t h., uumber of particles that can

7
 occupy any energy state. The energy states, however, are
distinguishable.

Let the particles be a,b,c,.. Thouqh the particles are

indistinguishable we assign the letters to them for the purpose
of explanation.
[(l)abJ [(2)c] [(3)J [(4)defJ (x)
If the number and letters are arranged in a.l possible sequences,
each sequence will represent a possible dis .ribution of particles
among states provided the sequence begins [Link] a number.

There are g. ways in which the sequences Cin begin 9ne fo~ ,each
. , -. J
of the g. states and in each~i['eq~e~~:-"<
~'~'~";(~.--1·)} numbers and
J , I J
letters can be arranged in any order.

The number of different sequences in wh i ch N distinguishable

objects can be arrarige~ is N! (There are N choices for the first
cerffiin a sequence. For eac~ of these there are (N-I) choices for
the' second, (N - 2) choices for the third anit so on down the last
term, for which only one choice remain.

~~e ~o~a~ ~umber of poss~b:e seq0ences is ~~~r2fore 'i

I
N(N-1) (N:"2) (N-3) (N-4)... .. :1) N!

The number of different possible sequenc~s of the

(g.+N.-1)
J J
numbers and letters is therefore (g:+N.-1)! and the total number
J J
of possible sequences of g..:~umbers and N. letters lS
J J
g. [(g. + N. - 1)!J .. 1)
J J J

Although each of these ~equences represents a, possible

distribution of particles among the energy levels many of them
represe~t the same distri~~~~o~.

Example:
[ (3 ) J -. ;'
~fl\2b: ~'~)defJ :(2)c]
[ (1) abJ [(2)cJ [(3)J [(~)defJ
o,,'=.::,- the bracke t ed grou~s appear in a differ sn t sequence.

Tr.e re are a.
~J - rou ~o s
q in the sequence, one fer each state, so the
n~mber of different sequences of groups , and we must divide
is g.!
~ """"., =: ~ - .-......... ( ... \
'- '-:J. ............ .._..:......._ _.. " - I bv
J
o.!
-' J s"r:',e
distribution more
than once.

,Also, s~~ce the particles are act~ally ~ndistinguishable a

~differ~nt sequence of letters such as
[ (1) ali) [ (2) eJ [(3) ] [( 4) bd f ] ... (y)

.a Ls c r e pr e s e r t s t he sa,,;;::
d i st r i bu t aon as (::) because any given
states contains the same of particles The N. letters can
J
22 arr2:-lg2G in Se::;~eT:C2 :.:-_ ~.~,! d.i f f eren t ry s . So
\.-,' equation (1)
must also be divided by N.1.
-;
.J
Hence the nurnb e:r of different
distribution for the jth level is

·r
 For each of the possible distributicns in any level, we may have
anyone of the possible distribution in each of the other levels_
.So the total number of possi~le distributlons or - the
thermodynamical probability BE 0: a macrostate W
in the B-E
staListics is the product over all l:\'els of the values of w. for
J
each. level ..
.o.r
..
(g.+N.-1)!
WBE Wk n w.
J
n J J
(g.-l)'!N!
j j . J

Where the symbol n means that one i3 to form the product of all
l
the Lerms following ie, for al~ valu!s of subscript j_

FERMI - DIRAC STATISTICS (F-D)

This statistics applies to indistin~uishable particles that obey

Pauli's exclusion principle, (No two particles have same
permitted energy states) _

Evidently, the number of particles 0:i In [Link] cannot exceed

the number of states g. in that leve._
J
To calculate the thermodynamical prcbability of a macrostate, we
again temporarily assign numbers to energy states of [Link] and
Le t t ers to t he par t. i c Le s , and We r epre sent; a possible arrangement
z : ~::e p3.::'-~:·=:"-=s i r; :;, 2_'2~.:"-=:' ::-": ~ r;; .):-=8. ·seq\i'ence of numbers· and
letters. A possible arrangement migllt be the followlng:
~(l ; c. J : ~ 2 ;,b: [( 3 j J [( -4 ) c] [( 5 ) ~J . . . .

The.: , -; \
.. ..:.... I
( ') \
• ,_. I
(,1 '.
;-:. :
.. ,
w i t.r: quota of one
par':i c 1e \.,1 hi 1e (3) , are empty.

For a given sequence of numbers, we first select some arbitrary

sequeI?-ce of let ters. There are g. possible .locations for the
l .
first let ter, following anyone of :he g. numbers. This leaves
J
cnLy : (g. - 1) possible location for the second letter, (g. -' 2)
J J
for erie rni ro down co (g.
l g N. + 1) locations
IN -1) or
j 'j J J
for the last 1et ter . Since for anyc»re Le tter we may have anyone
of the possible locations of each of the others, the total number
cf wa y s zn \-/h: ch a g l \'E-::: seque nc e 0: l\'. let te rs can be assigned
J
for the g. scates lS
J
o.
~J
!

9
Because the [Link] are .irid-i st Lnqu i s hal xLe , a state occupied
regardless of the particular lecter that follows the number
representing the state, and since there are N.! different
J
s eque nc es in which the N. letters can be 'Jritten,'we divide the
I J
above expression bv N~. Therefore
..)

w.
J (g. -N.) !N.!
J J J

F~~ally, .since for every arranqement In anyone level we may have

anyone of the possible arrangement in 1 he other levels ,. the
tr:-2rmodynamic probability W-=_ of a macrostllte in the Fermi-Dirac
statistics is

~'JFD. VI.K nJ .u.J nJ.~~N.)!N.!

I,

J J J

MAXWELL - BOLTZMANN STATISTICS (M-B)

The main feature of the MB statistics is t [Link]; the particles of an

assembly are considered distinguishable bu: as in BE statistics
there. is no restriction on the number 0: particles that can
o~cupy the same energy state.

a mi crostate specified bv
the occupation numbers NI, N2 .... N. '. rr e degenerac-ies -o f the
J
12:vels

Ao a in COnSlQer a nv j, including g. states and some

. J
.c f ;~.; I_:; ar ; :.c =- ~ s . ~article may be placed
J
anyone of che g..: s t a t es . But since th~re is no restriction
J
the numDer of particles per state, the second particle can
also be placed ,~
....L.. ...... any one of g. states, naking a total of 2
g.
.,........ . J J
~~5siD~e ~cca~~C~5 f c.r .t.h e f i r s t, ~vJC p sr t I.cL2:s. [Link] there are
N. particles In that level, the total number of possible
J
distribution in this level is

N'
u. g. . J
J J

10
 Example:

I i
I lab: I Ib a !b !;
I ! I la ! I i
I
II 1 ·1 ab! ib la I ia b
1111 !, lab!,
I
I ) la ,!b
I
a

Here N, = g. = 3 (I, 11,11:) and w. = 9

J J . J

Since for anicli~iiibu~ion of particles in one level we may have

anyone of the possible distributions in each of the other
levels, the total distributions including all levels, with a
spec ified set of' part icl es in each Lr .v eI is
N.
n w-, n (~~J J
j J

Bc.:t n w. is not [Link] ~~ the othe~ statistics since an

-' J
:"[Link] e;_- cnanqe of. [,0.1--: ic j_ c.s
.Dc:' ·.·,t·e-2:-:.
..
.
L. n"( also gl"ve rise
to different macrostate.

Imagine that th~ N letters represent:ng the particles are written

in all possible sequences we hav~ shown ~hat there are N!
seque nc es . Let. the first N, letter:: in each sequence represent
.L

the particles in levell, the next N" lecters those in level 2

..:.

and so on. Out of N! possible sequo nc es there will be a number

in which the same letters appear in the first Nl places, but in
different order. Whatso~~er the o~der in which the. letters
aooe ar . the same Darticle as a ss i cie d to levell, so we must
dl~ide N! by the number of different sequences in which the same
lett-ey o;.pea:: .:..:-! t r.e =:'~'s~ ~'~1 r:::"o.::es ·;·;:-.':"c;-~:,:; :;:\1.1. : .. In tDe same
wt':"ch N ;a~ticles can be
.Li s t r i but ed among the levels, with ~l particles in levell, .N2
parc':"c:esin level 2 and sc o~, lS

( ,,-I
,1.\ •

._~2 )
n N. l
j ::.'

The total number of differen: distributions or the

ther~~dynamical probability W
MS of a macrostate in the MB
st~tistics is therefore the product cf equation (1) and (2). That
1S

, ..
(?-,)"'j
j

II
!

".,-~'- .''''~''- .~.~----

.....,~.

'l1~g' THE STATtsTICAb IIHEl1ftfiFTATlON OF ENTHOPi'

In the three preceding sections, I... vernge occupation numbers, of I,he energ! n dl(O)
'. levels of a system were calculated fO,r ~aniclet~ obeying I~C Dose~Elnsleln, Fermi- dO
....t:nra~')d Maxwell-Boltzmann siausucs. 11,,I'o:as stated In Section 11-4 that the k dO
dl(O)
Ihcrm~[Link] variables of a 'Ylle'ln were related 10 the average' occupali~n DO'
numbers of ils energy levels, In thissection we derive the connection ~nd be~ln
and hence )(0) ~ kD In fl;
by 8~king what properly of a statistical model of a syste m can be a ss oc ia tc d 'Illh
its entropy. ,,'
S = kD In 0,
For two equilibrium llalcs of an april ['[Link] In which the temperature, (I 1-:'~)
pressure, and chemical pOlen!!!!} arc the same, bUI in which the en:r~y, volume, Th~s the only function of 0 which latisr,[Link] c£ndition thJt enlropies arc tuldit! r !
and number of particles are differr nt, the principles o,f Ih,ermodynamlC> lead 10 ~he whde IhcrnlOdy~.!!mic p:obabilitiesl arc m,ullip!irariut is Ihe logarilhm.
result that the entropy diffe.r.(!Jlce between t hc stares IS given by This equa,tlOn..provldes th'T co~nectlng link bctween stalislical and classical
thcrmodYI,lafIllf.!, ~h,~ rumef1~f' value of the proporlionalily conltant kn mUI{
".'~..~S ~,!l!!_+ I'!l V - I' oN, (11-22) be chosen so Ihal Ihel{I~5SiFal np~ slalislical values of Ihe enlropy will agrce. We
Frol]1 Ihe' sla~ poinl ~f';\,i;w, changes in Ihe energy of an assembly, in ils IhWhow~Sc~~on:LI~I~ Ih~rku i~rns out 10 be none olher III"n Ihe Doillmann
volume, and in Ihe number of panicles resull ill changes in Ihe lolal numbcr of -colTItant k ~ R~NA' : __ ' '; 'nl ;\' . _~
possible micrusl~les:~hich Ihe syslcm can exisl. For example, If Ihe energ~ U From n sta tlStlcnl,-po,nl 0 ,~Iew IIle cnlropy of a SYSlo'lll consilling or a very
of Ihe syslem in Fig, :LI-4 is increased from 6( 10 7<, Ihe num,ber of pOSSIble large~q,~ber, of panicles ,is ~. pOrli~:llal 10 .~he nalural logarilhm of Ihc lotul
microslales increas" from (5)210 2)40 Hnd Ihe average occupallOn numbers of numberqf [Link]"abIA· 0 Ihe SYllem, If We could prcpare all assemuly
each ievel change, (Sec Problem II-Y,) so that energelicallY,only one mi,roslale is available 10 ii, [) ~ I, In 0 ~ 0, Bnu
However, enlropy is nn exlensive properly and Ihe lotal, entr?py S of two the enlropy would Ge zero,. This ~:;,.qem is perfeclly ordered since Ihe Sin Ie 01' eJch
indep~ndent sySlems is the sum oflhe enlropies S, and S, oflhe ,ndlv,dual syslems: particle cnn be uniquely specilled, If more energy S[.ales become availauic 10 Ille
syslem, 0 becomes giealer Ihan I nnd the enlropy is larger Ihan zero. In Ihis case '
. S=~+~. f il is not possible 10 specify uniquely Ihe SUite or each panicle since th~ stale of;
On the other hond, if 0,and Il, arc Ihe Ihermodynamic probabilities of the systems, particle may be differenl when Ihe syslem is in differenl microSlalcs, Thu, Ille
and since i"or every microslale or either system the other may be in anyone of ils 'system becomes more disordered ns more. [Link](.I.4II"''' hrrf"lm,. UVAil!.1hl,.. f,... ;,
possible micros,lales, the number 0 or possible [Link] the two syslems is The enlropy of the syslcm may be Ihoughl of as a mCJsurc of the disorder of the
;."lhe·l2~o~~Cr of 0, nnd 0,: f sYSlem,'

O'F 0,0" (11-2) This sialislic:" inlerprcl"lion of enlropy allows "ddilional insighl inlo Ihe
meaning of the aUlOlule zero Ol'lclI'pcrillure, According 10 the Planc:, Ilatcment
II follows thaI the enlropy cannot be simply DroDonional 10 Ihe Ihermodvp"m;e
··-· 'e .'1nC ~~: term c: the fUFlctrcliHii rciuiionship .'bc{ween Sand
r·----····J' ...
nnn
IIIClII;.tnll·lIv- n approaches zero as the temperature approaches zero, Thc(tfore systclils in inlernal
such :that the conditions above arc sal·isfieaJ, we assume Ihat S IS some unknown equilibriul11 must be perfcclly ordered al absolule lero, '
[Link] 0, say S ~ J(O), Then since S = S, + S,' and 0 = 0,0"
Docs Ihe qualllily kll In 0 have Ihe olher properlies ofenlropy? Wc givc somc
qllolilafiu(! ~n5wc:rs. I
1(0,) + 1(0,) = 1(0,0,), r-i
Now take Ihe parlial deriv~tivcs or uoth sides orlhis eq~at'iDn, fi[st with respect -...
L·lf:~~, is a revcrsible now of heat '/'Q, inil~ a systelll ;'1 a iclnpcralurc T, tlae
100, wilh 0, crhstanl, and then with respect tp n, wilh 0, COn51ani. Since J(O,) enlropy of ti,e system incre,lses bydS ~ ,/'Q'/T, Iflhe 'yslelT1 is ill conSI"nl volume
of 0, only, ils panial derivalive .wilh respeel 10 fl, IS eguol 10 ils sq''!hat the work in the process is zero, Ihe increase dU ill internal energy of Illc

If
is a funclion
tOlal derivalive ol(D,) 111(0,) , l{tem equills d'Q,. Hul for an ns"muly of noninlcracling particles, the valucs of
---= I energy Itvds Jcpcnu upon Ihe volullle; anu if Ihe volume is COflS!ilnt, Ihe~c
,~ 00, clO, V; lues uo nol ch;'");e, If Ihe elle'gy of an assell\bly illueascs, rnorc o( Ihe higher
The partial dertvalive oi" 1(0,) wilh rcSprtl io 0, is Lero, 5'lnce 0, is constunl. c).:rgy kvels Decullle ava"able 10 Ihe particles of the assemuly, wllh a corre-
sponding inere"se in the n"'nbcr of nv;,ilable microslatcs or Ihe thcrlliodynJl11ic'
On Ihe righl side, the parlial derivalive of )(0,0,), wilh ropcci 10 0" cqllnll pruL 'Jilily n, lienee bOlll S anti III n increase when Ihe energy of Ihe sy,;em is I,
the total derivative or J(O,O,) with rcspcci 10 ils argumenl. (f1,l!,), lIlulliplied increased,
by Ihe'partial deriYJlive of it,S argumenl,wid, r<specI '0 0" which ;s s;l1lply Ih, 2. The el1tropy or nn iuc:..!) S·15 increaSe) in an irrl'uCrsibll' (rcc ~xpansion (rom J
conslanl 0" Then if we r"pres~rl by J'(O,O,) Ihc Jeriv"live of )(n,n,) wilh volume V, 10 a volume V,. There is no changc in i"lL'ln~1 cnergy in Ihe procCll,
'respect to its argument, we h~ve . . _"d no wurk is dune, [Jul thc permiltctl cnergy kvels become n\Or~ clostiy spaced
because of Ihe inCt'ensc in voluille. ror a conSlant 101,,, energy, more micrOltJleS
'r: I 1 :~~:)II~
0,)'(0,0,) . bccome aVilil"blc "IS Ille sp;,cing or Ihe enerGY levels decrease" Jnd "Gain bOlll S
In the same way, II ~ alll.J In 11 incrcJse ill tht.: irn:vusiblc fret: expansion.

.'l\~'\:= 0-1'([1,0,),
), In :I
CUIIS(~1l1.
.--allhe exI'
revcrsiule r((/io/'ali( cxr"nsio'n I)f Jil itJeJI G'IS, Ihe enlropy S rem"i"s
)_:'Q~rt.: i:-. no liCit I 11 ow into Ihe !.:[Link], Jlld !h~ wCJrk ill the o;pJnsion ;., dUlle
o( Ihc inlern;" el\efJ;y, which tlecreilsel in Ihcprocess. I( the sp"ci"G-'
II rollows from these equations h of the cllcrby levels tJid not chJngc, a rcuucrion in intern,!.l t:ncfr,y woulLl [csulr in
... ,_~ 11-- _
 FV,r d eve.(up0' ~ ~ CGnCJLfJt- 0-( pC\:(h'h~ ~c_h~/ w- v.? Gnh'dw
&n O1/I'J0rfibl; erG c'~ JCV? 'QIlJ{ u_uJQj o~~3 c)D-Jrl"cc.-Q J~JALS..
{.Q}- rz; dM(_-;YL\ ~h~ 00 3C\s ihlol ew._(~J f:x2_ i;)LLCJ-.. tt-at- ;V; ?Ylo {_QCv-LM 0CUfI
t/:D jlh'J1«f-e- UJiTG 0n-Vr9j {2j {YtlJ fJ,:d(j C/-'Y)c( Je_Jf.Me_~ 9j ,Th.0.v
(JL(_~ fu dc-sf l'cJl c:;{;; r'-;hv-h~ "-
fJj fa, ~ 0:p (t<:j -K )
tJ)
Y oe
k"t',
e:x__p P-/,L1 &-f .,..
~
!J/;c-r

," - , "oQ 70 =: 0~ [Link]<:.7 -&-jj-~)/L7

[;"'__';'CQ. ?;-Nj -; rJ evnd. ,cr.e_ C~t"cv.Q r~h~!Z ~eJ 'hDr krO--r-d aN~/

L} t>
r It~ ft_ck 2:
)N) ~rJ' ~ e )ub\,
fl.1!f-'( ~.t)
J ..)
r ' e">cb
- -I
-qJjI'L 'I ("'. ~
.,,0" .f)
~0
\ -P '
z= N_s
r-»; ' fJJ
(I~"-?- 9...;~
-til
C iU Cd
,
Q (..I tl vl-{3 r,"'; b,,-hc-> ~d'1''-' :::N ~ Q.'0p
J
J(!"t
-
~r J&f ~l{_l ': A (' CmlS~~,) ,

'n-G'A N::- Pr "?= C)_,; ex.. r ~ .;j =~'T ~ Q )

(
(l--e. ~-m'~ v), ctQ ~t>+ (-.trLnY\ ~ (C-c-clle~ ~ll _Fv"-I;\l;', ~YLn~ I, oK
,~~ ~~f-¬ ;;) ().MJ ~ll be nJ.j~~}--e_o( 0'1 Z
~l. 7;: '?0_; ~pC-~S;~"f) ,
T~ 0lY-C"-.rt1h ~ '2 ~ ciA H:_,a h.\iv (fo.. J \.l:Q 900 (m ulQ.(M_ lv.J at (y(\ Vi Sj-0lY1'v ~

(}JLQ_ utGy-r(; Gv...re. ct . (Y{ f od\ r; h ~ e. J Oft '1 cJY\ ~ ,h...Q t;OJ\A\ cv-6 Cv\ Q-i'] '-1 la.N-e l5 ,
TIh- j=' Flo~ ~ch ~ dQ_yO-oJ S ~ \ "" twL f:<>""'F"'"'o, 1vv',Q__ CYY' ~ 6V' rw,_
~ 'rv'& ~) ~ dcleN,"(\ ~ (lQ .~ B i')~ Q.o~l~., -. 1- .
-u fnLLljYD,~ M ~ ~ ~~bJ_V (~ ~d'1(7~ ($oJ 0cp <C-!fz-1 :. 7. ~8
l ~ fM Iin;'" -f-v.....ch ~ ewe- ~ "' f¬ & f~ ~ ~ hXo") ill \fcvc; """ U4r'l-co ~
( c1-j~c..L rpOAY'e) at ~6l<'V) ~""j vnJef~~ ~~
CDb~ V<~ ck ~S' \\c~ /6 d-ZiJ,I ~.c~ _..R__o_Vw':3, ' df-. cL:r-e,o _Ill ()~ ()Y"tl__ ~ [Link].-Q_ 0- ~

. C/-/(}0r<'60V) .. ~ ~~5\A-\'~~h_~ ~chf_w~

_?~ __~~h:05~.~-?-~
M~·b., .'.-... . ..----.- -..-.., -.__.. .--.'.--. .. ' .
cCo__ ~s;Cc-.( ~_.C6 .--5 c0. __
fTYlO~Cv--.le_-.1 ~;_ OJP ~ e ~_to_8?_ _~ uC ~ ~- ..
\
~~~~
'
,~.~ __ (J4 iD~, ~R/cq~ .. cf\._CIA_8QJ)./TI'.D.la_~~
r
~ p.--0£~·Ccl__~_1
-eq)JJJL tv \t.-Q_. A-vv'rY\ ~ V~ ~k..~Cl:h.c.. ~ ~CJ ~ _~.~ c).oJ ~ ~:c(/_Q. ~ ~\
t1-o ~~~~.hc~_.ui ~~~L1 .r6~~JU? . ~. ~~r{.~!d.._Ctij1_~0:rtI~N, l~
'Y\v.m"b£f\_ cJ1,.. ~~'1. ho~l\ ~. n:f"~_A_~ ~Y'c _~ /M'J. . r<fo{r
l/) tJ'~ h':j ...... ----. -- ...,- .... ---.... -- . --
I '.

.'-Ij-
 - I
i
I
!

.
,
!
';

I
!

<,'. -\~.
,jV\fT'l':-\.J\! ("l-L_.) -, --tr-» IV r VlSIf(\t;)ln,tQN 0 t- Vt:-[...D£.l._'T( ~ ;

\.;Jr re, tLn ~Q_(? o.f ~[Link] _~ a-t 9C7S~' { f!LG\Xw(2 (! bH cf6 CA I[ ~'veJ
:tpJ_ c::G1rrY>b\.,-h~1 ~ % ~Lo()._'h'e--s crt - rrr>o eC0<-lQ_s ' l~ (a__w C0v0 l:;,J2_

~\rtt-l (Ai dot. CD V&Jf cb MLR~~l\ ~ ISo If-; -'YY\CV(VT\ ~yry{ bv._ho:., (~ e Lv. Q.
/~;n,F"t>-e J. ~.,." Cf.t; M~G M rnA bvJx:" \, tv-! I~.

, ,d N ~ N C Q - !k I" 0 d'2. cJ. l ot p~ d. P 2

~ Q:_ .,{ >L _ (I )

W hQ.ye_k ~ ~1;,5h}v, /--QcJ_ tro w._~ d6 ~ C0 Y k -r . '(l-Q ~ ell- C ~

1 -- - - ' " 3r; - - ,_ -,
&-Ti ?iI k T) 2- v-
"f"~h ~ (_t) ~ Ga tr':0r.e_c;Ju-j-e_J OIjeJ\.._ Q0 C_?oYcLv:1CJ'~ ~ x_ I 'ji 2 [Link]
-+00
~v fJ 5 dYt J:j d7. ;. tV· '-(2)
, - ~(k..-r -'
N V e ... cd px..cf Pi '{/?2- - (3 )
(ill rrr, k -r ) y1. '1) __ '
(
~'(_h ;'ol4_5 :firy oJ/ f)Y)()I~uw w) \U Cry JfAJ, ~3 l/[Link]

lIAe ~Q.~-c CrrTD<Tl~(':.)7(i~cd ) -0nen9:J E 'Yi1i_C{ 'hJW bQ. 9"~.Gy

~:
J
'2 ')yI
12..'2..
('J.- + Y
'2...)
-'-2. -: (~f-)

.t,~ he,v.Q. ; (y £. 2. G...AL Ch'Y'('J)\.J~fj.[6 VQ.(eX,\11 ~ 'fl,,-Q_ 'JYIO~1-0 C 0-<'(\ ~

.e_ x_ fo1L SS ed- OJ.) p~ ;0 ~ P'i ~

;' r;-YI ~ "- p Z -:. ( /1'\ -2. ;) _ (5)
(/y J pJ(;_ ()Y) J; ~'u\_J) 'i := ?71 J ~ L:- q p;z_ ,;0 1r1 & 'Z- J
Su..b) h tv. rv;._9 (4) $(_?) ,~ \.3) .. '. ' . ", ',',"
C~-r yiL e 6
ON :::- /'I -'M ~-f~ L +z L) / 'lId ~ J~ J l -Zh)
1h2. C\52-~;-~r~~ t~~~ a-t. ~ .. s)c;J\C-~.) (./ db o_ 'f1\t>Lew.(~ ~ Cy't/0f\ G'1
(
C ;:::: 'X + i...{ , + 2. "', _ \:]..) . '_'__ . _, _ ..__ ,
B,,-/r ~ ,potOJL CO~~.~ __
. d_iJ~ d i ~C 2. SJ; <B_ J G J cP.4 .S-_. 4) __
....
S\_0_f.h'~rW_0 (r) bG_ }__vi:, (r;_)_~e_.5et '.,....... __
. .' ._..__.__
cZt0;- tJ c.~l~~~
__
e~.~c71Y-:-r c_'L ~9- ~t8.J~d c. .-~Cg.j __.

'11lQ_ Qx.{o-reJ ~lo.~-.lc{-J-CJ\'yXL_ ~ __ 9levm~._cCt __~~ ~~ ...~rln SlQ~ S

betvJ~. ,C(W\c2._c._-t_J,c __~ __~ __ ~~0~ ~ !~~ .. __~~~_~ C4-_ _0rA~.d~

JLw'l9 £- D- ru ~ td5! Qh0:{ __ q rp 4 + d cr. ,
:ern ~.fu 0 6 rq_~. ~ _r:'0.W"0~. c:l:_b, __®? ,~~ __
Vv{~ .#-~.~ _~_~
c_ QHccQ c~~tC;_1~F-\:_'!'¬ ~Ob \-t-Q_ M~~ I VJ~. ,.~ t? ~ K-~re~_
~S~!;.J (q) ~ It, ~.f~- ~ :~ CWtJ ..Lf_ .. ~ ~.tf:~ __~ih ·OJ2),D. ,Rw -9-_~cR _
( '. .~ l§:- bSo
 v ;~, :' C~);~~e
- rynC/,IL-< C2" C J rs";&dS f~cp
~ c ~ -r)?(L. e ~'TtlC%l_;.
- fJ )f7 IL c 7...d ~: C4)1 )
:: 4T1tJ C7P1 r) -;y'-
')Yi
c
'\
e.-
\i"C: /
/.2-JLI C\::lc - (lo) ....
~ h~ (r ~) M.f~ r.:s (1.a_ III L,V«\ G-e. - at C)-rlo~ ~ w rr. )c;rcY bQ ~
C. Off' J c -to. c ~ ~ ~ 'r ~ o« c\[Link]. 9 ov.:J GJy-. ~ ~ ~ IV tr\.:, ~~

.- ·af cAb$~G~f-c~~k 'T, (~0, !ev-.~ ~ M~I] £J-rribtAhcf'-v ..

(CLJ,A) ~ sr:" .~M C)1\C ~ W ' ~-J~ '. C ~ ~~(/ / {Jj_ e~rIYl2rf1 h"~
UA 'fYI &P (- 'hl (_ 2./2- R-r) ~ Cio _Qxpres S cv- (I.l en tXv\ ~ v.7i ~h:1 (}«\ l.. ~ (Q_

fM rn LVy7\~ at ry,\o~Lv? JrV( ~ cL'.tU --~ ~F hv;' v- \ ro C2-. W ~&v, C ~

(AA9.e/ tra <0<-f()f\0V')\'02 ~,u,_'YY] [Link]-rrl :(2Jc..--C) ~''YI..'-~ [Link]

(1:.Q/{\ d Y\ 0 cLv~u_ ~G; fo'u p<'Y hV:, ~ +0 cl , 1:0 IN G:, p[o (-tB:Q [Link]\. vIoS r C :"

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