Thermodynamics

Lecture : 142 Thermodynamics and statistical Mechanics 09/01/2022

→
Thermodynamics :
Misnomer

* we deal with
systems that
change from one state to another
* These states are
equilibrium stats

observations :

-
There are
very few principles that the
subject uses
-
Practical subject
Mathematical moderate
challenges are
-

"
"
-

couple with microscopic Nieve .

P-m-req.es :

Multivariable calculus
-

Theory of probability / statist's + combinatorics ( Pne)

-

least till
Uh thermo at
before VLE
-

" "
→ Whole thermo is
taught in Postulancy approach
↳ General principles
reference / insights about
No world
→
microscopic
.

4.

in Total energy of an isolated

system is constant ( First Land

isolated spontaneous
in In
systems ,
entropy of process can
only increase
with time ( second 2am )

The
entropy of all perfect and
pure monoatomic crystalline substances at
absolute zero is Zero ( Third Lane )

Equilibrium conditions

not with
in Properties do
change time
"
state
1in
History independent
-
( system depends only on the current coud
of the doesn't
depend hour it was
brought to that state )
iii ) Properties of identical
large number
of copies are .

Note on in :

G L

Tin
n

stout
✗
Yi ✗
i

> Heat
Exchanger C pink Absorption
Tough <
column

G
¥2
^

42 ✗
→
Egm is a time -

independent state because of the absence

of deceiving forces .

These invariant
systems are in
steady state because
they operate in king -

manner even
though the deceiving forces always exists :
They are not

in
Equilibrium
"
i

water
/ Glass of
at
is equilibrium

-
portion velocity
, ,
orientation are
changing
with time .

→ When we
say
that
system is at eqm : late are
referring that its measurable
and macroscopic properties (
they
.
do not
change with time )

All
macroscopic properties the microscopic properties
* are
ouvrage sum
of
.

→ Time -

window
of measurement
of macroscopic properties is
far for more than

microscopic properties
when we take time
average , every fluctuations that occurred within Pico / micro
seconds turns out to be constant value
.
a on a
macroscopic
scale .
 Lecture :3 Combinatorics 09/01/2022

' '
'

k pick R'
' '

Number to balls bins No to

→
of peace in
of
=

ways ways
.

objects
' '

from n

¥ : k balls are
of different colours ( distinguishable -
so order matters )
→ 1T€
3÷
6
!
=
= 3 =
=
6

Totals In k -111
of ways mln 1) In -4 ( Formula for permutation)
. : -
- - - -
-
=

( n -
k
)!

( red ,
asquen ) 4
Cased : 3 balls to be
1 a- blue
, placed in bins

→
1¥
Here the order matters :

bins
n
g
=
no -

k no
of objects
: .

Toted
µ4÷
i. me .

of map
= =
24
,

The question of order matter What happens ?

indistinguishably : doesn't .

No k halls bins
of mags to peace indistinguishable in n
.

order doesn't matter

Here the
concept into
of ouercounting picture
→
comes .

k= identical balls
3 no
of
- .

n =
3 me .

if bins .

Total
}÷µ
: no
of mags ÷
1
lmay )
. =
=
.

, .

↳ over
counting factors
balls to be
2¥ 3 blue
placed in 4 bins

4
µ4÷,,✗
Total no
of ways :

÷
=
.

@?¥µ ( )
to that
Foundations out to be similar of
=

combination
The distinguish ability still holds What
happens ?
question of replacement : in .

k
No .

of ways to peace indistinguishable balls in n bins

,
with replacement
= me .

of ways
to peace k
indistinguishable balls in n bins
,
when
one bin can have multiple balls .

EE :
3. balls fall blue ) ,
2 bins
; multiple balls or zero balls in one bin
allowed :
( STARS and BARS
type combination null helps)
O
o between two bins there will be one
separator
0

{
-

0001
-

0
> Same
problem is translated to a

0 0
- -

70010 problem of arranging 3 balls and

0
Q -0 > 0100 one
separator - i -

e .

Same as no .

g mags
0
1000 peace 4 objects ( separator )
0
> to 3 balls -11 in 2
-
-0 bins .

§÷, 4
mags
=

ones
counting
1
factor overcoming factor >

of
of
3 balls 1
separator .

Genest
"
:
n bins Ln 1)-

separators
k balls

Total no .

of objects to be placed =
k -1 In -1 )

i. Total No .

of ways
=
@ + n -

1) !
k ! In -11 !

EE Pick 2 whole numbers to

get a sum
of 3
 Week 2 : Lee 1

#
Entropy
For isolated it state
→ an
septum when reaches an
equilibrium do we

get a definite nature

of entropy
Isolated system i. e
Ecenugyl ,
lllvohum) ,
Nlmass ) fixed .

For and entropy defined

E. V. and M the system reaches
egm be
→ :
can
every
.

→ It is a mathematical function i. e 5--5 ( EH, N ) for a

single component
system .

This at ?
fir exists
only eg

For a multi -

component system
: 5 =
5. ( E X
, ,
Ni , Ni , - . .

Properties regarding Entropy

.

(E) ÷
→ -
-

→µ

→
1¥ ) =¥
→
#-) ¥ µ is chemical potential
=

,= ,
,

→
Property of extensively
:
slit XV, IN )
,
= X SIEN,N ) ; tis -11 No
.

ftp./yaE0:.ds- (Y-E)yndE+(s-)e.ndV+fE)em{dNds- 1-
→
Property of concavity
:

DE DN
Igd F-
+
" -

Fundamental "

Eq
DE =
Tds -
Pdt + µdN

Exaiupe :
Ideal
gas , P=Nk☐T/y
Volume dependence of entropy Pz NkyB_
: =

ds= DX "
¥ Nk÷d
=

5 =
Nkrslnll +
f- IE,N )
✗
 Week 2 : Lee 2

Entropy :
from statistical mechanics
viewpoint
For isolated system Boltrman 's
define entropy by Equation
: we
an .

5 =
hrs lnr(E,V,N )

hers =
Boltzmann constant R

Nauagadro
ICE .HN ) states
density of .

r
gives a number
of microscopic molecular level
configuration that the system can

can have
for a
fixed value
of macroscopic property E V
,
and N .

→ Micro - state is the snapshot of the

system at
eqm.at regimen instant
instant in time .

To state, have to orientation and

define a micro we
define position velocity
-

each atoms
of continuing
.

short count
of these micro states
for fixed
→ In : r is the each
of a
-

E, V and N .

Toy Problem ( Ex 2. 2)

2-Dlatl

Each these boxes be filled

→
of can
by only one

time
molecule at a
single .

→ These are total V lattice sites and 2 molecules

that can be absorbed on these lattice sites .

→ If two molecules are at adjacent sites then we will have an

energy of
interaction E
If
not then interaction Zero
of
is
.

as
-

energy
.

Calculate r !!

N lattice sites both fixed E is Variable

2 v
theywhich only
=
: since are
, ,

due to different micro -

states can be

obtained .

E
-

have two →
→ Here the
system can
only energy states
↳
( Assumption
of boundary
# sites 0
→ is negligible
For distinguishable molecules
distinguishable Molecules
: :

I. ( E- = -
E) =
4 -
V r ( E E)=
411/2 !
-
= =
24

inductee # Firstmolecule
n(E=o) =
\É_ -

41 r(E=o ) =
VIV 1)- -
411
2
Total
Interacting
To get entropy use : 5. =
kosher
 Week 2 : Lee 3

Calculating density of states in a Real system

→ E
,
V
,
N fixed .
Calculate r

I
×
↳ No .

of molecules
/ atoms
Boundaries are
fixed

→ Total
energy is fixed .

O O O

→ N molecules in a
fixed volume V -
o o o

o 0

→
List all possible micro -

states
→ For micro state calculate E
every
-

( that
,
→
If the calculated E matches with the contraint E is fixed) ,
we count
it else we
ignore the micro -
state .

→ At the end , the count gives r .

Classical Thermodynamics

/
Statistical Mechanics

Bulk properties and connections Molecular bulk

their
origin of the
properties
→ .
→ .

and it deals with microstates .

> Boltzmann Equation (

"

Vocabulary of
"

Thermodynamics :
Page 15

# Combinatorial Approaches

need
→ n
objects ; k objects to be selected

in Replacement is not allowed ,

Onder matter :
mpg =

µn÷µ .

Iii) No Replacement ;
order doesn't matter i 7k =

µ?÷qµ
nh
Iii) With replacement :
order matters :

Civ ) with
replacement : order doesn't matter : In -1k -1 ) !
kl.tn D ! -

Stirling 's approximation mm ! nlnn !

Yep
: = -
n or n ±

en É am Binomialtuoeam ✗+
rÑ=%y?÷ayNk
:
=

m=o MT
 Week 2 : hee 4

# Interactions in the
Microscopic world

→ state of a
system ( at
any point in time ) is given
by a wave
function
4th ,
,
-92 . -
- -

→ [ Yttlñ ,ñ 74th ,ñ D joint that particle position

probability
, ,
- - -

,
-
- -

is 1 is at at

particle 2 is d- position at and so on .

Equations in Quantum Mechanics (OM )

→
Schrodinger Equation :

Particle potential energy field Ulñ )

travelling
:
in a

_h÷mÑYlñ,t ) -1 Ulñ ) lñit ) it

2Y§ñf# I
hay mossy
=
is
=
m
;

particle

;÷+÷g+±
=

222

→ we use
separation of mortally to solve this
egm
.

Ylñ, ) lflñltlt)
t
substituting this in
Schrodinger Eep we
get
=

ÑYlñ)
t÷mTH ) + Ulñ ) Yleiltlt ) i
tTYlñ7ñy
-
=

dividing throughout by Ylñ ) Ttt )

-

# Ylñ ) Ulñ )
t÷mµ÷, 21T€
-
+ = i I 1-
TH ) 2T
" 1 i ,

fan of a-
fin oft
+ Ulñlulñ ) E Ylñ)
I÷mÑWñ) in
- = -

"
Time -

independent form of Schrodinger Eg

It 415 ) =
EYlñ ) ( An
Eigenvalue Problem )
it H =

_h÷mÑ+ vlñ )
-

→
Discrete set of solutions .
.ie .

particles only exists at discrete

energy
level .

E →
Eigenvalues
Y fin
→
Eigen

Example :

1. A
particle in a lion :
 U = 0
in the bow
U =
N outside the box
L bore
length
=

)
h÷omy(nI+ ring ME )
/ energy t
Elecigen values levels = + nu ,
my
& nz iii.
- -

= -

2)
Single e-
orbiting a
single proton :

Uta) = -
et
UTE .
lñl

E = - much t N = 1,2, -
- .

( Eigenvalues) 8%212 m2
ma =
mpme_ : Mp
=
mass
of proton
mptme of e-
=
me mass

orbitals
→
Eigen fois are atomic

Week 3 : Lecture 1

Classical Methods :

→
Energy levels are discrete in
quantum mechanics and other
energy levels are inaccessible

where in classical mechanics all and accessible

energy are .

classical ?
why methods
→
can we use

Moderate to
High temp ? live with )
-
are
dealing
The
energy gop at such
high elevated
temperatures becomes much smaller .

continuous
that the
energy
level
spectrum gets .

continuous
Energy spectrum comes in classical Picture .

Localization of electron clouds

-

→
Particles have
definite position and momentum and time evolution is
given
Newton's haves
by
.
# classical Description of molecular interactions

-
Fundamental particle is atom ( Non -
breakable)
-
Each atom has
position te
,
and momentum f- .

Interactions btw these atoms are

given by the classical potential Energy function .

"
that is
only a
function of ñ ( set
of position of N particles )
U ( ñi ,
tea ,
-
. .

Ten ) = Ulñ " )

Gradient of U gives the forces on each atom .

( fi ) ( also called force field )
Ii Fillet ) 2- V19 )
"
"
= -
= -

2mi

f- 201M )
=

,
-
201am ) ,
-
2UlñN )
Mi Jyi Thi

mi Tai =
Ii
21-2
outer " )
Alternatively ;;÷=
2
: -

Ñi

Total E the classical Hamiltonian

Energy is
given by
- .

kinetic
) Ulan) k(p_µ)→ Energy
Htp
" "
,ñ =
+

)
÷¥÷m
"
=
Ulñ +

( Proof Book )
dd|±=0
-
in

Hour is Ulñ " ) formed ?

total
"

Break interactions into

"

the modes
up
-

Ulñ " ) is divided into two

types :

bonded interactions
ulñN ) → Modes -
→
- Non -
bonded interactions

Bonded interactions :

Bond
1
stretching
.

"

U= ald do ) t bond
D=
length
-

d-I Bond
1- do
Egm length
-
.
-

interaction
2
body
 Bond
2.
Angle stretching
:

U =
lilo -00T A 0 is bond angle
go bond
Oo is
eqm.

angle
3
body interaction
3 .

Bond Torsions :

"

Central
U =
I Cnloslw )
Bond
t is torsional
w
angle
he body interaction

central bond
→

Non -
Bonded Interactions :

1. Electrostatics :

Coulurnb 's Lane :

U =
Gigi ( fair -
Wise )
hTEoMij
2. Van der Waals :

9ij°
"

Attractive Term London ( interaction )

U
pair
"

dispersion faces
: ✗ -
Wise

short
range repulsion
:
Uxeiijm ( m > 6)

Combination these two Lennard Jones Interaction Potential :( LT)

of gives :

"
• = ↳
U÷T -

l÷T]
Summey
Week 3: Lecture 2

Limiting case :

T-dealhasi.CIMolecules one
point masses

1in These molecules do not interact with each other .

Ulñ " ) = 0
for any ñ,ñ ,
-
- - -9°

What is the PUT

relationship of an Ideal Gas ? ( E V
, ,
N fixed )
Since Ulñnl -0 total that hour ( isolated )
we can
of system
-

energy
-

a
,

E
just comes
from the kinetic
energy
i. e- =
K

For
fixed E V, N
, for an ideal
gas ,
we need to
compute r( EN NI ,

#
of ways to choose V positions and momentum of N ideal gas
molecules
in volume such that the total is E.
a ,
energy
UlñN )
since (
always ) the in which the
position chosen will
→ = 0
,
ways are

E.
no
influence on

The
ways of
momentum
distributing
-
only when
ULIN)=0
is

Independent of the

mags to
picking up
positions

RCE.tl N ) Shmonenta (E, N)

deposition ( Hiv )
→ =
✗
,

remount a ( E, N) =
# to momenta to N molecules
ways assign
.

( X, N ) # to peace N
particles volume V.
reposition in
=

ways

We
focus on reposition (viN ) :

→ To be able to count ,
we need to be able to Discretion the
space
We divide the total volume V into lattice cakes
→

v
of small ,
each
of volume

that
→ Also assume
only one molecule
of
ideal small
gas can
occupy each cube .

No ( N) than
→ .

of particles is far smaller

the no -

of small cubes while

placing
a man molecule in a cake ,
we can
neglect
already occupied cakes -
 For each molecule the
of to place molecule
Ig
→ is
ways
no
any
.

i. to peace N particles spontoon

ie

N
reposition ( vim ⑦ ( if particles distinguishable )
=

→ For
indistinguishable particles
wit )
reposition ¥
=

Hey ,

rCENiM shmomta (E N) ✗
reposition CMN )
=
,

rmomtaCE.mx#.CgY
Boltzmann 's
Sqn :

kBlnn( ENIN )
5 =

f Stirling
's
Approximation N
!=µeY
=
krslnfrmomta LEIN) ) + krsln (¥) +
krstnfrjfd
5 =
krslnfrmomta CEINI ) + Nkrs
(F) + Nkrsln
( vz)
RINAU
¥ #-) N÷B
Nav
m÷
✗
= = = n =

x
,gµ

¥ mpg
Ideal Gas
= .

Week -3 : Lecture 3

E Internal the Potential

→
Energy of system ; U → classical Energy fñ .

:( system size )
#
Range of Microscopic Intonations
Scaling with

Fallacy
:

bonded interactions
Ad non are
pair wise
- -
-

interactions N2 increase the

#
of scales as
if we
system size
by 2 times
-
.

Hone can E -
N ( and not N2) ?

Features
of Microscopic interactions :

in Atoms have a
repulsive force .

These short
Iii ) interactions are -

ranged
let's think
of a
liquid . :

Each atom interacts with other atoms

only within
→

'

distance
'
which lie a s

interaction ( 5=2.5 to 30 )
of
→
8 is the
range
to
→ contribution
of each atom the E doesn't depend upon N

→ 8
depends only on the nature
of
interaction
,
it doesn't depend on 11

Scaled the
system
N → 4N

No
of spheres of interaction
→ .

to No atoms ( )
is
equal of
- w

has
→ #
spheres of interaction
increased 4 tiny . and
NOT 42 times

→ E should
go up 4 tins ! !

N
'
E -
NOT E -
N
.

Existence
of spheres of interactions give rise to extensiveness
of the

properties
.

→ Due to short-range nature of interactions

the
, energetics of surfaces
and boundaries negeegible compared to the total
typically are
.
.

atoms ices )
#
interacting across the interphone a

EAB ✗ 25h2

Ead E Ers ✗ i } as
per previous arguments
boundary
EA÷÷B+EyAB_y
E = Interactions at is
negligible
to
as
compared energy of
interactions the balk
in
of the
liquid
.
 Weekly : Lecture 1 Microstate and Macrostate

To chartering need N IF
→
completely system 6N
pieces of information
-
a we
, ,

1
Microscopic degrees
{ from
}
> 3N
Names
from " comes

of freedom
.

positions ,
ñ momenta
, p-N

" "

A micro state configuration the

→ is one
of system when all microscopic
degrees of freedom are
specified .

For isolated system Eiland N constant

rigorously
→ an are
.

* We can use Eid ,N as

descriptors of the
system
.

There other not constant

→ exists
properties in thermodynamics that are
rigorously
with but
and
vary time the variations are
barely noticeable .

These tanned
* variations are as
fluctuations
scales
and
they are
extremely
small
compared to
macroscopic
.

Pressure
Eg
:

A macuostate is characterizes
7 a set
of bulk descriptors that the

equilibrium state
of a
system .

macuostate the all

→ While in one
, system can evolve
through
micuostate
compatible
one macuostate collection of microstates
→ is a
many compatible .

"
"

Ensembles
→ are collections
of microstates that are
compatible
with the macuostate that is given
.

# Lattice Models # Two State Model

Weekly : Lecture 2 Probability of microstates

For
microstates
a
system at
eqm ,
the
system continuously
with
evolves
through
tote
all
compatible
that are
compatible the macros that is
specified .

On Ensemble all the microstates and also

specifying
an we
specify
microstates
we
specify
the probability all these to occur
of
.

Miuuestate
Probability :

It that the will pass

is the
probability system through a
given micnostate
for a fined macaostate .

* At
Eq ? ,
these microstates
probabilities do not
change with time
for a specified macuostate .

Principle of equal a
priori probabilities
> Postulates that, at
eq
?
, for an isolated system ( E.HN is fixed ) ,
all microstates
rnacnostate
that are
compatible with the
given are
equally likely
.

Probabilities ( sum should

*
of all
compatible microstates are
equal
be 1)

Probability of microstates with different value

of E
* is zero
any
a .

microstates
→
Recifie for calculating probabilities .

Equally probable
Prohibit
☒

¥¥y }
of all these micnostate is

÷
÷
eqm
"
"
that this
principle called
→
Systems are at . and
obey are ergodic .

principle Non
Glasses are never at
egm :
they don't this
obey and i e
ergodic
-
-

?
They are
evolving very sohuly they are
yet to achieve
leg
Weekly : Lecture 3 Microstate probability (contd.)

Macrostote All these microstates

probability
to
to occur is
exactly same

each other i. e
113

Pm that
:
Probability the system is in micuostate
-

me

↳ Index that all

run
through
microstates
( Edl,N ) known then
possible
is
,
:

\
I
Pm =

it Em =
E
e. ( ENN )

0
if Emt E

{
Pm Em
§y¥,÷ 5Em,E
-
= it =
1 it -
- E

, kuomkn
delta
•
if Em -1-0

→ r( ENN ) I 5En,E
µ through all nuicuostate that
compatible with
)
=
runs is
n
V and N

# Ensembles and Time

itneuages
i. atpuopeuty
→ We can construct the evolution ✗ It ) in time .

observation internal ( t ) define

long enough
00
→ For a e →
,
we can

average of the property

-

[
< ✗ Time bin ✗ It)dt
it < > indicates
E- average
=

e-so
 → ⇐ → a) means that our observation tin is much more than that time scale

from changing from one microdot to another .

→ we can also calculate

"
the
average based on the microdot puobobilities :
"
Ensemble Average
< × >ens =
I Pmxm
m

For at ?
→ a
system eq ,

< ✗ > = < ✗ >

ens time

week 5 : Lecture 1

and their
→ For each macnostate
"
,
then
"
are list
of
microstates
tpeeobolities -

together
called
they Ensembles -

are

isolated cope
→ For an
system in a
fined macros all
compatible microstates
have equal probability


Thermal equilibrium upon energy exchange

→ Example from UG thermo. A B

hotter colder

Case I

each

Isolated from

other

exchange
Even when the

is V. Mi and

occurring

the Ne are always fixed

Case II

free exchange of energy

takes place

Case I: Isolated, independent

# microstates available for system 1 : r

CE Ni Ni

# microstates available for system 2:

rz Ez Vz N2

→ consider this isolated combined "Supersystem".

( No Energy exchange

)
The # microstates for the supersystem is

a simple combination :
NZ

IT D Ei Vi Nr Rz Ez V2

Entropy of the supersystem :

Sz Ez V2 Nz

KB Ln IT S Ei Vi Ni t

ST

→ some justification for the Boltzmann eqn.

 Thermal equilibrium upon energy exchange

E 1

CA

(combined Super system )

can be fine) or

S E2 C- ne )

CA

CASE 2 : Systems are allowed to freely exchange energy.

— Consider AE energy transferred from 1 to 2.

— Constraint : E t

constant
( Isolated system )

Ez ET

t AE ET Ei

Ef E AE E Ez
— # of microstates of the combined system:

r't r CE Y N
Nz Et E h Nz

is only a function of E

IT

we need to consider all possible

microstates : by considering all possible E

— For a particular value of E

I I

NTI r l Ei Vi Nr Rz Et Ei V2 Nz

— Total number of microstates for the supersystem :

1 age er Ei Vi Ni R2 ET Ei V2 NL

- For a particular F

I
7

121 ET Ei V2 Nz

RTI Ri Ei Y Ni x

- Total # microstates for the supersystem :

r CEI Vi Ni R2 Et Ei Va Nz

rt age
}
Macro

E is a

P Ei XD Ei Vi Ns Rz Et E Time state

Ex. 4.3 : 1 and 2 are 2-state models.

12 Ez Sb

N 6 E I b Nz

R E

In Eet

NICE N'IN R2 Et Ei Va Nz

PCE

RT

- Location of maximum
SHE

Effy Ni rhet EF V2 NZ

def
Er v vyN nF

trdEt EF1dfeTlEFY

o r CEE
fE.tt

or I

s4CEi
IddffIz c 1 true DE

In 4 EF ankle'z "

Boltzmann

2E DEZ

5- kBlnr

OS CEE DECEIT

DE DEL

T _Tz

f It

T is the condition for thermal equilibrium

_Tz

IT
is maximum when 1-1--1-2 i. e lieunnal Eqm

↳ Here the system remains

for maximum

time
.


Thermal equilibrium

T T2

The system is most likely to be in EF Ez

—can we see other macrostates?

—> For typical macroscopic systems, the maximum

has an extraordinarily sharp peak. the system will

spend nearly all its time at EF EE

IT 1 EF Y N rz Ez Vz Nz
Maximum-term method.

St S LEF v N t Sz CEI Va Nz


General forms for equilibrium

I 2
- Real systems exchange energy,

volume, mass (particles)

- consider energy + volume exchange ( 1)

case

- #microstates for the supersystem for a particular Ei Vi

rt I CE Y Ni 22 ET Ei Vt Vi Nz

- we maximize Then :

RT

same condition as before:

rt o

T Tz

Ev Er Ei Vi Ndr2fEt E's in
iz NEO

and

offs DVL

EE

It II

thus P P2

rt is maximum

and T Tz comet the number of

At this ,

micuostate is maximized for

the given macros tate


- For energy and mass exchange,

exchange )

T T2 ( Energy

uz ( Moss Exchange )

ft If u

is maximized when

It
T Familiar

Tz

conditions

Ii m
of equilibrium.

- Note: these are derived for maximizing

IT 5412

under conditions that something is exchanged

between 1 and 2, but conserved in total.

- Equivalent to maximizing S t Sz
St
→ compare to the second law:

In an isolated system, all spontaneous processes

can only increase the total entropy of the system.
 Microstates

I o o o o o

o o
a

0 o

o a o

Z o

o
o
or o
so o
u o

o
o

a d

o e o

a o

r o

o o
o o

o o o

o o

n o

a o o

o
o

o
o
o

o o o

o o

— For real systems, the macrostate with the max. # microstates

would have an immensely large # microstates compared to a
macrostate that is slightly away.

— Systems do not have any inherent bias.

They will spend equal amount of time in every possible

microstate.

— We talk in terms of macrostates and some macrostates have

many more microstates than any other It "appears" that the
system "selects" this macrostate on its own.

— The second law just says that we observe the macrostate

with the most number of microstates .
— The second Law is just an effect of the principle of

equal a priori probabilities.

— Second law also "suggests" a "direction" of

exchanges as the two coupled systems approach

equilibrium from an arbitrary initial slate.

of eqm
"

causes
increase in
in the dirt

30 [
Travelling

number
of
microstates Increase in Entropy

1ST

AS ASI 30

tf AE t
Pf Av
YI an fzAEztPf V2

ft Anz 30

— If only energy exchanges are considered:

0 AN O

AV

AE A Ez
O

AE t A Ez

AE 30
Thus,
ft 2
Tz Z T 2 is hotter energy
AE is positive
If enters 1

1 is hotter energy
If AE is negative T Z Tz
leaves 1
 Peasants exchange from one

part qtr system to

y
Second law and internal constraints other
part
i

v N
S NCE

ICE V N internal constraint

l

- An alternate version of the second law:

S E V N1internal constraint s S CE N

the internal

spontaneous process afterisolated

removing
constraint
system will
- what are internal constraints ?

of an

• Physically imposed
only
increase

Entropy

• Natural ( Internal kinetics )

—> Internal constraint" is anything that prevents the system

from having access to all microstates
E V N G

S EV N G kg Lnr

G can have values G Ge

S E v N
GI E S CE v N G

G value of G that maximizes S

Alternate view of the second law :

At equilibrium, S is maximized at constant E, V, N

conditions where the maximum is found with respect to

any internal perturbations of the system, or unconstrained

internal degrees of freedom.

 extra
→ Internal constraints shows as an
degree of freedom i. e
q
5 ( E YN
,
,
9) ,
r( EN Ni 9)
,

S E V N G E V N

R G
would

Second law At constant E V N equilibrium

o

mean that would show a value of for

when

which I and hence s is maximized

is an unconstrained degree of freedom
)
"

what is the and of Egmwi this case

What happens if S, V, N are constant? (

(F)a-
¥1

Rule :

value of
-

Inverse
S CE at eqbm observed

v N G ,

is given as

o 87 o

leg
Tg yn EVN

E S V N G at eqbm how do you get the

1%-1,10%-1
Rule →

Tripper product -1
observed value of G→ (Eg)
-

, ,

E variation Effy 8 gffgle Tffgle

DE
(E) ; -13%1=4%1 ,

O extremam

Tg
in

check derivation

834 T
text

0 (Energy minimum principle)

Second law: At equilibrium, E is minimized at constant S, V, N

conditions with respect for any unconstrained degree of

is will happen in that total number of
If 5

fixed then
,
energy exchange
such a
way
micros
tate remains
constant .

 E is internal Energy

Fundamental equations
Entropy version DS f DE t
f du
MpdN
Energy version DE
' Tds '
Pdvi th DN
1
>
Extensive variables as
differential
de

|
T S v N
OT observable from the
yn Directly
OE fundamental cop
ar Pls v N
s n

OE
Mls v N two extensive variables)
Tn >
Intensive Variables / Ratios of
E S V N
extensive scalelinearly with system size
intensive independent of system size T P M

E TS PV t UN By Euler's theorem

Proof E XS XV XN DE CS v N
Take X derivative on both sides
RHS E S V N

HS oEH ygdN
_06 dEHf Yg 064

QE XS AV XN dCAN
dCdn ox

oekfygygdnl s.todfydIgdMv
dECds dv dN
NdCXv
 X is an arbitrary number For D I we have

Els v n s defqv.NL v t dEfSn N

T Sv N S P S v N V t MIS V N N

E TS PV t UN
s
IT V NTI
Intensive forms
Most commonly we use the per molecule basis

energy per particle

e En s E v NI
DE G V N E XS XV XN

Take X IN In Els v n E E In In
e f ECS v n E EN NI 1

e e CS ie ft of 2 independent
variables
need two
While
using
intensive form only we

to specify the system

.

variables
 transform
How does the fundamental equation

E S U ECSN.VN
N
EISN.VN
N

in OEHI.gg dHI
ds

IN DE
OS
N T

1 In OEHNFY.fi dHdI

N p
In

de Tds Pdu

How to calculate µ
E TS PV tu N
F F T
Ts Ne Pv t n

µ e Te t PU

u e
us Edie
if e sie is known
 FIRST LAW

we need to analyze what happens if a system

changes from one state to another called
a process
the process is characterized by a path
series of changes that takes the system from
one state to another

E S V N T P re changes are independent

A path ( state variables )

tiny
First Law
DE SQ t SW for closed systems

interactions can occur

part of
Two in whichenergy
Work : That port of energy ways
Heat : That
called work
interaction which SW part of energy interaction interaction
energy
produces macroscopic SQ denotes the part due to heat that doesnt product
in the system at
change any change
CT P Tz PI
can be calculated macroscopic range
.

IE Ez E

Émndy
all the
) work has come IN to the system distributed among
4- sw →
molecules moment
Net

becomes Zero .
 Integrated form
AE Q t w

Mathematically Latse are inexact differentials

For these there exists no function g that
satisfies

ga f g ft Pel g Iti R
T P

Note such a function exists for energy

de E Te Pe ECT P

µ
Example
L
Nf NL
x

df dn n
0
displacement f dn
Nl

Sg I dnt
Mgsg to
N N n

g M
Id n t f C da 2 Nz Ni
U2
 Calculation of work

work is the energy interaction due to which

there is an observable change in the system
at a macroscopic level deforming boundaries
f
Change of macroscopic constraints involve forcesto
Primary attention will
be on forces external
the system
General definition of work
Sw text d
Feet

Consider a gas filled piston cylinder

assembly
F
In
Sw Fe.edu
SW teat dCnA Pextdv

text P Sw Pdv limiting case

example Pact dependence of work heat

Pile of Eon
a-888880
11
T
sand
State1 v T State 2 Vz T
Pathi sweep all the sand instantly
text O
W E O
AE Q

Path 2 sand is removed slowly grain by grain

text O
w so
Q AE w
 Special processes
Quasi Static happen infinitely slowly at each
point in time the system is in a local equilibrium
FE is valid at each point in the path
DE Tds Pdv FE → Fundamental GW
Reversible process
there should be no dissipative frictional
Additionally
forces

P Peat
SWreu Pdv
a rev
DE SQreu Pdu airst law for
process

SQreu Tds
Compare
SQrev
DS
T

8
For an ideal reversible process ds

For a real process 8 IS

as SET
 consider process whose
a initial and find States

are known
2 different isothermal paths

her timer
SQirrev isothermal
SQrev

Sandexam
For an ideal gas AE O

E ECT N for an ideal gas

Q w
w Ssw
Edu NKBT Ln
 Baths
If the body is infinitely large lathy reservoir
T is constant
heat transfer is differential and reversible
any
is called
Teath Idseach ISQian Often surrounding
bath
Oath
.

Aseaq
teach

Types of processes
adiabatic no heat transfer
reversible
If adiabatic and
Tds
Comes from reversibility
SQ
→

ds o adiabatic and isentropic

dswo.ru DS t dssarr 3 O { By second-team

when dswored 0 process is reversible

Reversible means quasi static

dswored 0
Real process
O
ds SEE reversible dswored

dswored o i Real process

SQ o adiabatic
adiabatic
DS o isentropic and reversible
 Extremamotworkf
First law AE Qt W

differential change
let's consider a
DE DS because system
is

DS t dssarr Negative
d swore loosing heat

added to
y
Heat is
←

surrounding ,
so
SQsarr SQ
↳ extra -( ve) makes 8Qswn time) n Surround
it should telnet I
system
Assume that the surrounding
is an ideal heat bath i Tsurr
DS SQsure SI
um TSarr
Tsar
dswored DS
Sarr

DS
DE SW
Tsurr
IS world 7
dESw_ o
ds
Tsurr
the
work done by DE
system < Sw C Tsurrds
to the surrounding
Sw is bounded by a maximum
f
Sw DE Tsarrds minimum
work done
by the
to
surrounding
the system
 Heat Engines
It's a machine that absorbs heat from a source

damps heat to a sink and performs some

macroscopic work

They operate in cycles

Let's assume that each cycle consists of
I Transfer of energy from the hot source at Tt
I Transfer of energy to a cold sink at Tc

TH
QH
HE W

r Qc

Tc

I First step
ds world DS t dssar
ASEarr
bath is loosing
Integrate ASfored ASI t >
heat so fuel sign
I
ASword ASI Qt
TH
work WI AEI Qa
heat
DE =
Q+W but here system is
gaining

w = DE -

OH
I ASwotted as t Assifrr heat
I Q -1W but system is loosing
ASworld E DE ;
=

as t
Tc DE = -
Qetw

work WI AEI 1 Qc w =
DE + Qc

Over one complete cycle

ASword A Satoru t A Satoru

aft as
Eff FE
W WIT WII
AEI t AE't Qf t Qc

§ any
and E
AS ASI AS O
cyclic nature state for
AE AEI f AEI

0
ASworld t
off
W Qu 1 Qc
 It is C- uh
because
Energy is
going away
µ from the system
→ This makes IN fuel as
y
Efficiency M watt cannot be t.ve )

y tQtat i QfYt
0
Apply 2nd law Asword 9 t 30
0
It
I I 1 TEH

n Ei Et H

Bounded by a maximum

Maxima is only a fit of only Tc TH

 Mass and
both
> energy
can
exchange

Open steady flow systems

Conservation of mass
)
at
considering system
is
steady
Easimi Eiusnii ( state No accumulation

in the fig
in tmz ing

Conservation of energy
stream
i internal energy per unit mass of each

Net rate into the system

infinite Eiji 5
 Herework is done by the surrounding
to the system while pushing the fluid
i PV work element inside the system

Swiniet Pdv

wince P d
Jin
C:) . p

outlet
Pini

h KE PE

mid ring z
streams
combine the total energy transfer due to flowing

infinite it Pii t EE t 8Zi qq.j.msleftPijtuftgzj

Define enthalpy I Et PF

ni hit t 8 Zi ftp.g.jmjhi tufztgzj

Es
of energy biansfer
Mechanisms independent of flow streams

Ci 1 Shaft work Ivs

Cii Heat exchange Oi
 By combining all the firms

offsets ni it Ift 821 ingests hit uIzt8Zj

vis t Q

second law
Sword 3 0

i Entropy carried by the streams

Easini i EiremiI
Ii Heat exchange with surroundings
Each heat exchange term
contributes tsar } Doubt In
sign

sword Eiasinisi Eustis EE wr

DS Sark

surrounding is loosing
{ heat so _
is a