Thermodynamics Somanath Gosh

Physical Chemistry
Somnath Ghosh
Indian Institute of Petroleum and Energy (IIPE), Visakhapatnam
somnath.chm@iipe.ac.in
August 23, 2019
Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 1 / 93

Contents
15 Adiabatic changes in state for

1 System-State-Process
ideal gas
2 The properties of gases
16 Application of 1st law: Heat of
3 The zeroth law
reaction
4 (Ideal) Gas laws
17 Motivation for 2nd law
5 The Vander Waals Equation
6 Work-Heat-Energy
18 Heat engine: Carnot cycle
7 State and Path Variables
19 Concept of Entropy
8 Thermodynamic first law 20 The Clausius Inequality
9 Work expression 21 Spontaneity and Equilibrium
10 Concept of reversibility 22 The Helmholtz and Gibbs energy
11 Changes in U; Cp and CV 23 Fundamental equations of states
12 Joule’s Experiment 24 Application of Equations of state
13 Joule-Thomson Experiment 25 Gibbs-Helmholtz equation
14 The sign of µJT and change in T 26 Entropy and Probability

System of Evaluation
Marks Distribution
Assignment and Class tests: 20M
Mid-Sem-Exam: 30M
End-Sem-Exam: 50M
Learning Philosophy: Stop-Think-Examine-Proceed (STEP)
Table: Code of Conduct/Deal between You and Me
Me You
Clearance of doubt if asked No cross talking, cell phone etc.
Lecture notes will be provided Participate in discussion
Implementation of logical suggestions No bargaining for mark
I will be friendly Maintain the learning environment

Mode of communication
Class Leader
Will act as liaison between the instructor and rest of the class
Should be responsible to pass on the information to rest of the class
Should be responsible to pass on the information to the instructor
Student
For additional information regarding the lessons:
E-mail (first preference) followed by phone call. In the e-mail always
provide your contact number.
Contact Details
E-mail:somnath.chem@iipe.ac.in
Cell phone No-8099013001

System-State-Process
set up
The object that is under study at a
given moment:System.
The variables which the defines the
state of the system: State
variables
State of the system is represented
mathematically by an equation of
state of state variables.
Figure: Fluid system contained in a The portion of the universe that is
cylinder with variable volume. Work can
out side of the system:
be done on the system by displacing the
piston, heat can be transferred to the
Surroundings
system from the bath in which it is The boundary is one which
immersed, and matter can be added to separates the surroundings from the
the system through the valve if it is open system.

System-State-Process
Transference of matter (mass) and

energy possible through the boundary
between the system and surroundings
→ Open System
Matter can not be but energy can be
transferred through the boundary
→ Closed System
Neither matter nor energy can be
transferred through the boundary
→ Isolated System

System-Sate-Process
The method of operation that can

change the state of the system →
Process
The route of change in state is
described by the initial state, the
sequences of intermediate states
arranged in the order traversed by
system and the final state → Path.
Isothermal Process: T = Constant
during each stages of the process
Isobaric Process: p = Constant during
each stages of the process
Isochoric Process: V = Constant
during each stages of the process

The properties of gases
Gas:
State of matter that fills in container it occupies → Volume (V ).
Collection of molecules (or toms) in continuous random motion →
Pressure (p)
Average speed of species that increases as temperature is raised →
Temperature (T )
Molecules (or atoms) widely separated and move in paths that are
largely unaffected by intermolecular forces.
The state of gases
The physical state of a substance, its physical condition, is defined by its
state variables. The state variables for a gas, p, V , T and amount of
substance(no. of moles) n are interrelated by an equation of state:
p = f (T , V , n) (1)

Any three of the four variables (p, V , T , n) are specified to describe

the state of the system.
The fourth one can be calculated from the equation of state.
Equation of state (Ideal Gas):
nRT RT
p= = (2)
V V̄
R=8.314 J.mol−1 .K−1 , 0.082 ltr.atm.mol−1 .K−1 , 1.987
Cal.mol−1 .K−1

Pressure(p):
Force (f ) per unit area to which
the force is applied.
[MLT −2 ]
p= f
A = [L2 ]
= [ML−1 T −2 ]
Origin of force exerted by Gas:
incessant battering of the
molecules on the walls of the
container.
Units: 1 Pa = 1 N m−2 = 1 kg
m−1 .s −2 , 1 atm=101.325 kPa,
1 bar =105 Pa =100 kPa, 1 bar
≈ 1 atm, 1psi=0.069 bar, 1
atm=760 torr
− mgh
Pressure drop: ph = p0 e RT

Temperature(T):
Indicates the direction of flow of
energy (heat) through a
thermally conducting, rigid wall.
If energy (heat) flows from A to
B when they are in contact,
then we say that A has higher
temperature.
Indicates whether two objects
would be in thermal
equilibrium if they were in
contact through a diathermic
boundary

The zeroth law
Zeroth law:
Thermal equilibrium established
if no change of state occurs if
two objects are in contact
through a diathermic boundary
If A is in thermal equilibrium
with B, and B is in thermal
equilibrium with C, then C is
also in thermal equilibrium with
A - Zeroth law
Zeroth law → temperature and
Temperature → thermometer
T (K ) = θ(o C ) + 273.15

(Ideal) Gas laws
Boyle’s and Charle’s law are strictly true for only in a certain limit of
pressure especially when p → 0
Boyle’s law: pV =Constant, at

constant n, T
Charle’s law: V =Constant. T ,
at constant n, p
Avogadro’s Principal: Equal
volumes of different gases at
the same T and p contain the
same number of molecules.

Extensive and Intensive properties
Extensive Property:
Depends upon amount of substances
present.
Summing the values (property) in every
part gives the Ext. Prop. of the system.
Examples: Volume, Mass, Energy, No.
of moles etc.
Intensive Property:
Independent on substance or substances
present.
Measured at any point, and each has a
uniform value throughout the system at
equilibrium.
Examples: Pressure, Temperature,
density, molar properties etc.
Mixture of gases
Consider, a mixture of gases described by the mole numbers n1 , n2 , n3 , ...

in a container of volume V at temperature T
Total no. of moles nt = n1 + n2 + n3 + ...

ni
Mole fraction xi = nt
sum of all mole fraction
Pn Pn ni 1 Pn nt
1 xi = 1 nt = nt 1 ni = nt =1
Equation of State pV = nt RT
For each component pi V = ni RT
Pn Pn
Hence, 1 pi V = RT 1 ni = nt RT = pV
Pn
Therefore, p = p1 + p2 + p3 + .... = 1 pi
ni RT
pi ni
p = V
nt RT = nt = xi ⇒ pi = xi .p
V

The partial pressure
The result of the 2nd expt. is

exactly the same as in 1st expt.
The H2 behaves exactly as if
the N2 were not present.
In 1st expt.:
nH2 RT
pi = V = 1 atm,
nH2 RT
pf = 2V = 12 atm
In 2nd expt.:
nH2 RT
pi = V = 1 atm,
nH2 RT
pH2 ,f = 2V = 12 atm
nN2 RT
pN2 ,f = 2V = 12 atm
pt,final = pH2 +pN2 = 12 + 12 =1
atm

Real Gases
Real gases do not obey the Ideal gas law exactly in all p and T range,
particularly at high p and low T (gas is at the point of condensation
to liquid)
The deviation from ideality is expressed by the compressibility factor
z = V̄re /V̄id = p V̄re /p V̄id = pRT
V̄re
To display the deviation, Z vs p for different gases are plotted.
For H2 gas, Z > 1 at all pressures.

For N2 gas, Z < 1 in the lower part of
the pressure range, but Z > 1 at very
high pressure.
for other easily quantifiable gases (e.g.
CO2 , CH4 , NH3 ) Z dips sharply below
the ideal line in the low-pressure region.

Modification of Ideal Gas Equation; The Vander
Waals Equation
Volume term correction: Even at 0K, gas molecules occupy some

volume
RT RT
V̄ = b + ⇒p= (3)
p V̄ − b
Pressure correction term: Attractive forces between the gas
molecules tend to pull them together diminishing the outward thrust.
RT a
p= − 2 (4)
V̄ − b v̄
From eq. 4, we get
a
(p + 2 )(v̄ − b) = RT (5)
v̄
an2
⇒ (p + 2 )(v − nb) = nRT (6)
v
Significance of vander-Waals constant: ’a’ and ’b’
’a’ measures the vander-Waals forces of cohesion between the gas

molecules.
Greater the value of ’a’, the greater is the strength of cohesion, easier
to liquefy.
Dimension of a, [a]=[M.L.5 T.−2 ], unit= atm.dm6 .mol−2
∂U an2

∂V T = V2
’b’ measures the excluded volume by the gas molecules
Dimension of b, [b]=[L3 ], unit=dm3 .mol−1
∂H

∂p T = nb
Gas a(Pa.m6 .mol−2 ) b(m3 .mol−1 )

H2 0.0247 26.6
CO2 0.366 42.9

Implication of Vander-Waals-Equation
a
Vander-Waals-Equation: (p + V̄ 2
)(V̄ − b) = RT (6)
When pressure is very low, (p → 0 :) As p is very low, V̄ will be
high enough to approximate: V̄a2 ≈ 0 and (V̄ − b) ≈ V̄ and hence the
eq. 6 become
p V̄ ≈ RT (7)
When pressure is neither very low nor very high: As the p is
intermediate, V̄ is high to approximate (V̄ − b) ≈ V̄ but not high
enough to approximate V̄a2 ≈ 0 and hence the eq. 6 become
a a a

p + 2 V̄ ≈ RT ⇒ p V̄ = RT − ⇒Z =1− (8)
V̄ V̄ RT V̄
As p ↑ within the intermediate pressure range, V̄ ↓, V̄a ↑ and

therefore, Z become smaller and smaller. This explain the initial dip
in the Z vs. p plot of most of the real gases at constant temperature.
Discussion of Vander-Waals-Equation
When the pressure is too high: As the p is very high, V̄ will be

quite small. Now, p + V̄a2 ≈ p but not (V̄ − b) ≈ V̄ and hence the
eq. 6 become
pb
p(V̄ − b) ≈ RT ⇒ p V̄ = RT + pb ⇒ Z = 1 + (9)
RT
As p ↑, pb ↑ and therefore, Z become more and more greater than
unity. This explain the final rise in the Z vs. p plot at moderate
constant temperature.
When the temperature is too high: At a given pressure, as T is
very high, so also the V̄ and V̄a2 ≈ 0 and (V̄ − b) ≈ V̄ . Hence the eq.
6, become
p V̄ ≈ RT (10)

Conclusion
C-1
Vander Waals Equation is a very good model to explain the real gas
behaviours
C-2
Vander waals Equation could predict the ideal behaviour of real gases at
very T and low p.

Work-Heat-Energy
Work(w):
Motion against opposing force is
equivalent to raising/lowering weight
somewhere in the surroundings.
Appears only at the boundary of a
system.
Appears only a change in the state.
Manifested by an effect in the
surroundings
The quantity of work: Wsurr = mgh,
where m is the mass lifted against the
gravitational acceleration g up to a
height of h.
Work is an algebraic quantity, it can be
both positive or negative
Work-Heat-Energy
Heat(Q):
A quantity that flows across the boundary
of a system during a change in its state in
virtue of a difference in temperature
between the system and its surroundings
and flows from a point of higher to a point
of lower temperature.
Manifested by an effect in the
surroundings.
Heat flows out is proportional to the mass
of water in the surroundings that is
increased by one degree in temperature.
Heat is an algebraic quantity, it can be
both positive or negative

Work-Heat-Energy
Energy:
The energy of a system is its capacity to do work.
When work is done on an otherwise isolated system, the capacity of
the system to do work is increased; in other words, the energy of the
system is increased
When the system does work (piston moves out) the energy of the
system is reduced and can do work less than before.
The energy of a system may be changed by means other than work
itself.
When the energy of a system changes as a result of a temperature
difference between the system and surroundings we say that energy
has been transferred as heat.

Molecular interpretation: Work-Heat
Heat Work
Transfer of energy in disorder Work is the transfer of energy in
manner through chaotic organized manner through
molecular motion ordered motion of the molecules.
The distinction between heat and work is made in the surroundings.

Internal Energy(U)
Internal Energy (U):

In thermodynamics, the total energy (KE and PE of
molecules/atoms) of a system is called its Internal Energy (U)
The change in U when a system changes from an initial state-1 with
internal energy U1 to final state-2 of internal energy U2 :
∆U = U2 − U1
The internal energy is a state function in the sense that its value
depends only on the current state of the system and is independent
of how that the state has been arrived i.e. on the path of arrival.
Almost impossible to estimate or determine the U of a system as it
depends on the position, chemical structure etc. of the
molecules/atoms of the system.
Work and heat are equivalent ways of changing system’s internal
energy, U .

Work-Heat-Internal energy
Let us, consider one banking system.

(Mechanical)work-Heat equivalency and
(Internal)Energy
Joule’s Experiment:
A falling mass turned a stirring paddle to
raise the temperature by doing work on
water.
The raise in temperature was measured and
the amount of work done was compared
with that of heat required to produce the
same change in temperature.
Ratio of work required to the heat required
was always the same; 4.18 J of work to 1
w
calorie of heat. Q = J(⇒ w = JQ)
There was no detectable difference in the
final state of system whether carried out
work done on or heat supply to the system.
State and Path Variables
Any thermodynamic state is characterized by its macroscopic (observables)
properties (such as p, V , T , U etc.) Change in state associated with the
change in macroscopic properties.
State Function: Property of a system that only depends on the initial

and final state of the system and is independent of the path followed in
getting from one to another.
Path function: Does depend on the path followed in getting from initial
to the final state.
Exact and Inexact differential
Exact Differential Inexact Differential

An exact differential integrates An inexact differential integrates
to a finite differences: to a total quantity:
Z 2 Z 2
dU = U2 − U1 = ∆U δQ = Q
1 1
is independent of the path of which depends on the path of

integration. integration.
The cyclic integral of an exact The cyclic integral of an inexact
differential is zero for any cycle: differential is usually not zero:
I I
dU = 0 δQ 6= 0
The function is state function The function is path function

Note on symbolism ∆Q and ∆w
Symbolism ∆Q and ∆w is meaningless.

If ∆w meant anything, it would mean w2 − w1 ; but the system in
either the initial or in final state does not have any work w1 or w2 ,
nor does it have any Q1 or Q2 .
Work and heat appear during a change in state; they are not the
properties of the state, but properties of the path.
Properties of the state of as system, such as T, p, V, U, have
differential that are exact.
Q: How would you check whether a function would be state or path
function?
R: Check whether it has differential exact ot inexact. If exact then state
otherwise path function.

Exact differential and Euler reciprocal relation
If z = f (x , y ) to be state function of two independent variables, x and y ,

then total differential become:
∂Z ∂Z

dz = dx + dy (11)
∂x y ∂y x
In order to have z as state function or dz to be exact differential, mixed

second derivatives has to be equal:
∂ ∂Z ∂ ∂Z

= (12)
∂y ∂x y x ∂x ∂y x y
Euler’s reciprocal relation:

∂2z ∂2z
= (13)
∂y ∂x ∂x ∂y

State function and cyclic rule
Let, f (x , y , z) = 0 where x , y and z are functions of each other.
∂x ∂x

dx = dy + dz (14)
∂y z ∂z y
∂y ∂y

dy = dy + dx (15)
∂z x ∂x z
Substituting dy in eq. 14, we get
∂x ∂y ∂y ∂x

dx = dz + dx + dz (16)
∂y z ∂z x ∂x z ∂z y
∂x ∂y ∂x

⇒ dx = + dz + dx (17)
∂y z ∂z x ∂z y
Comparing both sideof eq. 17, we conclude that the coefficient of dz
∂x ∂y ∂z
must be zero ⇒ ∂y z ∂z x ∂x y
= −1
Geometrical representation: Total differentiation
∂U ∂U

Let U = f (T , V ) then dU = ∂T V dT + ∂V T dV
U0 ∂U

=U+ dV +
U0 ∂U
U0 ∂U ∂V T

=U+ ∂V T dV =U+ ∂T V dT ∂U
∂T V dT

Thermodynamic first law and Internal energy (U)
First law of thermodynamics:
Energy can neither be created nor be destroyed, it can be transformed
from one form to another.
The internal energy (U) of an isolated system is constant.
It is impossible to construct perpetual machine
System took Q amount of heat and did

some work, w and thereby appeared at
state-2 from state-1.
Applying 1st law:
∆U = U2 − U1 = Q + (−)w = Q − w
(18)
dU = δQ + (−)δw ⇒ δQ = dU + δw
(19)
Work:Expansion and compression
Work done(by the system):

A quantity of a gas contained in a cylinder, fitted with frictionless
piston and immersed in a thermostat to maintain the T of the system
constant.The space above the piston is evacuated to ensure no air
pressure is pushing down the piston
Upon alteration of volume against an opposing pressure a system
produces a work effect in the surroundings.
If pint > pext = pop = Mg

A then the gas
expand against pop such that its volume
changes from V1 to V2
(+)wsurr = Mgh = (−)wsys
(−)wsys = Mgh = pop (Ah) = pop ∆V

Two stages of Expansion
Stage-1: Expansion V1 → V 0 ; then

stage-2: Expansion V 0 → V2
In such a two-stage expansion, we apply
different pop to each stage then
w = w1 + w2
0 00
w = pop (V − V1 ) + pop (V2 − V 0 ) (20)
0
The work produced in the two

stage-expansion is represented by the
shaded area.
Comparison of two figures (single and
two-stages) shows that for a same
change in state the two stage expansion
produces more work than that of single
stage expansion.
Multi-stage-Expansion and concept of Reversibility
Same change of states carried in a multiple stages against different

pop at different stages.
P
In such multiple-stage-expansion, (−)w = wi , the amount of work
done is greater.
If we want to have maximum work (maximum area under the curve)
then infinitesimally small steps with pint = pop at each stage is
required.
X Z V2
(−)w = lim pop (∆V ) = pop dV (21)
∆V →0 V1
pop = pint , How to achieve?
Proceeds via a series of steps that are so small (infinitely small) that
the system never displaced from equilibrium during the process.
Represents a limit that we can not reach in real life, we can get pretty
close.
Such process is termed as Reversible process
Z V2 Z V2 Z V2
nRT V2

(−)wiso = pop dV = pdV = dV = −nRT ln
V1 V1 V1 V V1
Why do we call it ”Reversible”?
Returning our system where we started retracing path back

maintaining the equilibrium
Since we were in equilibrium all the way for expansion, we will exactly
retrace our steps in compression
Z V1 Z V1 Z V1
nRT V1

(+)wiso = pop dV = pdV = dV = −nRT ln
V2 V2 V2 V V2
Reversible process and its characteristics
Definition
A process which is carried out infinitesimally slowly such that the system
and surroundings can be restored to the initial state from the final state
without producing any changes in the thermodynamics properties of the
universe is called a reversible process.
Characteristics or importance
The system remains at equilibrium with surroundings throughout the
process.
The maximum amount of work done on the surroundings.
The minimum amount of work required from the surrounding.
Defines good way to calculate the change in thermodynamic state
variables
For path variables, it provides a well defined limiting case that serves
as a useful point of reference.
Work(done)Expression
Work done(-w)
Process Ideal Gas Vander-Waals Gas
Isothermal-
Reversible
V2 V2 − nb

1 1

nRT ln 2
nRT ln +an −
V1 V1 − nb V2 V1
Adiabatic- δQ = dU + δw ⇒ (−)w = ∆U [For adiabatic pro-

Rev./ 0 = dU + δw ⇒ cess, work done by the system is
Irrev. (−)w = ∆U nothing but the change in internal
energy of the system]

Changes in U in relation to changes in properties of
the system
∂U ∂U

U = f (T , V ) ⇒ dU = dT + dV (22)
∂T V ∂V T
∂U ∂U

δQ − pop dV = dT + dV (23)
∂T V ∂V T

Changes under isochoric condition (V=Constant)
From eq. (24) and (25), we get
∂U ∂U

dU = dT , δQV = dT ⇒ δQV = dU (24)
∂T V ∂T V
Heat Transaction (Q/ δQ)

Process Physical Significance
Isochoric,
V=Const., Heat withdrawn from surroundings, Qv is solely
dV = 0 utilized to raise the T and hence increase in U of the
system
No expansion work has carried as dV = 0

δQV ∂U
The ratio: dT = ∂T = CV ⇒ dU = CV dT
V
R T2
Integrating form: ∆U = T1 CV dT

Heat Capacity (at constant V, CV )
Heat Capacity
The quantity of heat required to raise the temperature of one unit of
a substance is called its specific heat (C).
The quantity of heat required under constant pressure and volume
condition for a substance may vary and hence, heat capacity is of two
types: Cp , CV
Geometrical interpretation of CV
CV is the slope of the tangent

of the curve: U vs T when
V =constant

Changes under isobaric condition (p=Constant)
First law: dU = δQ − δw = δQp − pdV
Heat Transaction (Q/ δQ)
Process Physical Significance
Some part of Qp withdrawn from

surroundings is utilized as work of
expansion
R2 R2 R V2
dU = 1 δQ + V1 pdV ⇒
1
(U2 − U1 ) = Qp − p(V2 − V1 ) ⇒
(U2 + pV2 ) − (U1 + pV1 ) = Qp
U, p, V are state function and hence
Volume changes (U + pV ) become state function and
from V1 to V2 defined as enthalpy H = U + pV
Piston moves until Therefore, (H2 − H1 ) = ∆H = Qp or
pop = p dH = δQp

Heat capacity (at constant p, Cp )
Since H is state function:

∂H ∂H

H = f (T , p) ⇒ dH = dT + dp (25)
∂T p ∂p T
For a transformation at constant pressure, dp = 0:
∂H ∂H

dH = dT ⇒ δQp = dT (26)
∂T p ∂T p
Therefore,
δQp ∂H

= = Cp (27)
dT ∂T p
Integrating form:
Z T2
∆H = Cp dT (28)
T1

Cp is always greater than CV (specially for the gaseous
system)
δQ
We know that: Cp = dTp , CV = δQdT
V
The above expression made us to conclude that:

The heat withdrawn from the surroundings is completely used to
increase the Temperature (T) and hence internal energy (U) of
the system under constant volume as there would not be any work
(due to expansion)
When a gas is heated at constant pressure, there will be increase in
its volume and do some external work. Therefore, some extra heat
(in addition to increase the internal energy) must be supplied.
So, heat required to raise temperature by one unit at constant
pressure is high than that at constant volume and hence, Cp > CV
For liquid or solid system, Cp − CV is very small as change in volume
due to heat is small. For solid and liquid Cp ≈ CV

Mathematical relation between Cp and CV
From eq. (25), we get
∂U ∂U

δQ = dT + dV + pop dV (29)
∂T V ∂V T
For a change at constant pressure with pop = p, this equation becomes
∂U ∂U

δQp = dT + dV + pdV (30)
∂T V ∂V T
Dividing both side by dT , we get
δQp ∂U ∂U ∂V

= + p+ (31)
dT ∂T V ∂V T ∂T p
δQp ∂U

Since, dT = Cp and CV = ∂T V , the above equation become
∂U ∂V ∂U ∂V

Cp = CV + p + ⇒ Cp − CV = p +
∂V T ∂T p ∂V T ∂T p
(32)
Extra on Cp and Cv
The excess of Cp over CV is made up of a sum of two terms. The

first term, p ∂V
∂T p is the work produced, pdV , per unit increase in
temperature under isobaric condition.
∂U ∂V

The second term, ∂V T ∂T p is the energy required to pull the
molecules farther apart against the attractive intermolecular forces.
Cp
γ= CV is always greater than one as Cp > CV
∂U ∂V

Cp − CV = p +
∂V T ∂T p

∂U

Measurement of ∂V T : Joule’s Experiment
The stopcock is opened, the gas

expands, fill both the container
uniformly. After allowing time for the
system to come to thermal equilibrium
with bath water, temperature of the
water measured.
Joule observed no temperature
difference before and after.
Work done δw = 0 due to free
expansion, δQ = 0 as no change in
temperature.
∂U

By first law: dU = δQ − δw ⇒ dU = 0 Since dV 6= 0, ∂V T =0
and also dT = 0
∂U

From eq. (24) du = ∂V T dV =0

Conclusions from Joule’s Experiment
∂U

∂V T = 0 suggests U is independent of volume. Therefore
U = f (T ) only (Joule’s law).
It is contradictory to our previous logical assumption U = f (T , V )
and is due to the large differences of heat capacities of vat water and
the gas used.
Actually U = f (T ) only for ideal gas as there is no force of attraction
between the gas molecules.
Later experiment, Joule-Thomson experiment, have shown that
Joule’s law is not precisely correct for real gases.

∂H

Measurement of ∂p T : Joule-Thomson Experiment
We know that H = f (T , p) and U = f (T , V ) are state function and hence
∂H ∂H ∂H

dH = dT + dp ⇒ dH = Cp dT + dp (33)
∂T p ∂p T ∂p T
∂U ∂U ∂U

dU = dT + dV ⇒ dU = CV dT + dV (34)
∂T V ∂V T ∂V T
H = U + pV ⇒ dH = dU + pdV + Vdp (35)
Substituting dH and dU from eq. (35) and (36) in eq. (37), we get
∂H ∂U

Cp dT + dp = CV dT + + p dV + Vdp (36)
∂p T ∂V T
Restricting this formidable equation to dT = 0, and dividing by dp, we
can simplify to
∂H ∂U ∂V

= p+ +V (37)
∂p T ∂V T ∂p T

Joule-Thomson Experiment cont...
For liquid and solid the first term of the eq. (39) is very small than
the second term, therefore, ∂H

∂p T = V (solid and liquid)
For ideal gas H̄ = Ū + RT and hence molar enthalpy is function of
∂ H̄

temperature only; ∂p T = 0
∂ H̄

∂p T is very small for real gases, but can be measured. The Joule’s
experiment, in which the gas expanded freely, failed show a
measurable difference in temperature between initial and final state.
Later, Joule and Thomson performed a different experiment known as
Joule-Thomson Experiment.
J-T effect: If a stream of a gas at high pressure is allowed to pass
expand by passing through a porous plug into vacuum or a region of
low pressure, under adiabatic conditions, it gets cooled appreciably.

A steady flow of gas passes through an insulated pipe from left to right
through the porous plug at A.Passage through porous plug ensure drops in
pressure from left to right side.
The measured decrease in

temperature ∆T and in
pressure ∆p are combined in
the ratio: ∆T

∆p H .
R0 R V2
wnet = V1 p1 dV + 0 p1 dV =
The J-T coefficient (µJT ) is −p1 V1 + p2 V2 = (p2 V2 − p1 V1 )
defined as the limiting value
Since the pipe is insulated, Q = 0 and from
of this ration as ∆p → 0:
first law:
µJT = ∂T

∂p H U2 − U1 = 0 − w = −(p2 V2 − p1 V1 ) ⇒
(U2 + p2 V2 ) = (U1 + p1 V1 ) ⇒ H2 = H1
Isenthalpic process
From eq. (35),
∂H

dH = Cp dT + dp (38)
∂p T
Under isenthalpic condition, dH = 0 and hence
∂H

0 = Cp dT + dp (39)
∂p T
Dividing by dp at constant H condition, we get
∂T ∂H ∂H

0 = Cp + ⇒ = −Cp µJT (40)
∂p H ∂p T ∂p T
Finally,
∂T 1 ∂H

= µJT =− (41)
∂p H Cp ∂p T

The sign of µJT and change in T
µJT = ( ∂T
∂p )H , Here dp is negative
Points Ideal Gas Real Gas
µJT 0 +(Ve) -(Ve)
Effect No change Cooling Warming

∂(U+pV )
µJT = − C1p ∂p
T

Expression ∂(pV )
∂U
= − C1p ( ∂V )T ( ∂V
∂p )T + ∂p T

= − C1p ( ∂V
∂U
)T ( ∂V
∂p )T + RT ( ∂Z
∂p )T
Interpretation Both terms: 0 Both terms: -(Ve) Competition

µJT and Inversion temperature (Ti ) for V-W Gas
Since a and b are very small, the term Vab2 in the V-W-E can be neglected
and pV = RT provided the pressure is not too high and hence
RT a
V = − +b (42)
p RT
Differentiating w.r.t T at constant p, we get
∂V R a

= + (43)
∂T p p RT 2
Rearranging eq. (44), we get
R v −b a
= + (44)
p T RT 2
R
Substituting the value of p from eq. (44) in eq. (45), we get
∂V 2a

T −V = −b (45)
∂T p RT
Using the well known thermodynamic relation
∂V ∂H

V =T + (46)
∂T p ∂P T
Equation (47) can be written as
∂H 2a

− = −b (47)
∂p T RT
Therefore,
1 2a

µJT = −b (48)
Cp RT
It is evident from the above expression that J-T coefficient is positive as
2a 2a 2a
long as RT > b. It becomes zero if RT = b and negative when RT < b.
Clearly for a particular gas the sign and magnitude of µJT depends on the
temperature at which the gas is allowed to expand. At inversion
2a
temperature, µJT = 0 and hence for V-W-G the Ti = Rb

Adiabatic changes in state for ideal gas
From the first law: dU = δQ − δw = 0 − pdV = −pdV

Since no heat flows from or into the system, the w (= −pdV ) by the
system appeared by the expense of U
A decrease in energy in a system is evidenced almost entirely by a
decrease in temperature of the system.

∂U
For ideal gas, ∂V = 0, hence du = Cv dT , Therefore
T
dV
CV dT = −pop dV = pdV = −nRT (49)
V
Z T2 Z V2
dT dV
CV =− nR (50)
T1 T V1 V
¯ T2 V2
CV ln = −R ln (51)
T1 V1
¯ T2 ¯ ¯ V2
CV ln = (Cv − Cp ) ln (52)
T1 V1
T2 V2
ln = (1 − γ) ln (53)
T1 V1
γ−1
T2 V1

ln = ln (54)
T1 V2
γ−1
T2 V1

= (55)
T1 V2
T1 V1γ−1 = T2 V2γ−1 (56)
γ−1
p1 V1 T1 V2

p1 V1 = RT1 &p2 V2 = RT2 ⇒ = = (57)
p2 V2 T2 V1
p1 V1γ = p2 V2γ (58)
γ 1−γ
T1 p2

= (59)
T2 p1
Comparison of Isothermal and Adiabatic Expansion
(pi , Vi ) → (piso , Vf ) (pi , Vi ) → (pf , Viso )

(pi , Vi ) → (pidia , Vf ) (pi , Vi ) → (pf , Vidia )
pi Vi = piso Vf
Isothermal pi Vi = pf Viso
( VVfi ) = ( ppisoi )
pi Viγ = padia Vfγ pi Viγ = pf Vadiaγ
Adiabatic pi
( Vvfi )γ = padia pi
pf = ( Vadia γ
Vi )
Viso Vadia γ
Vi = ( vi )
Expansion: Vf > Vi and γ > 1,
Reason Since, γ > 1, VVadia < Viso
hence ( VVfi )γ > VVfi ,padia < piso i Vi
Viso > Vadia
Application of 1st law: Heat of reaction
After a chemical reaction takes place, the T of the system generally

changes than from the before. To restore the system to its initial T ,
heat must flow either to or from the surroundings.
The heat of the reaction is the heat either withdrawn from or given
to the surroundings in the transformation of reactants to products at
the same T &p. Therefore, ∆H = Qp
The ∆Hr in a reaction at a particular T &p can be viewed as
∆Hr = ∆Hfinal − ∆Hinitial
For Fe2 O3 (s) + 3H2 (g) → 2Fe(s) + 3H2 O, the
Hfinal = 2H̄Fe (s) + 3H̄H2 O (l) and Hinitial = 2H̄Fe2 O3 (s) + 3H2 (g), so
∆Hr = [2H̄Fe (s) + 3H̄H2 O(l) ] − [2H̄Fe2 O3 (s) + 3H̄H2 (g)].
Above equation can be simplified if we consider the heat of formation
H2 (g) + 12 O2 (g) = H2 O(l),
∆Hf (H2 O, l) = H̄H2 O (l) − H̄H2 (g) − 12 H̄O2 (g)
2Fe(s) + 32 O2 (g) = Fe2 O3 (s),
∆Hf (Fe2 O3 , s) = 2H̄Fe (s) − 32 H̄O2 (g)
Hence, ∆Hr = 3∆Hf (H2 O, l) − ∆Hf (Fe2 O3 , s)
The change in enthalpy is independent of the enthalpies of the
elements in their stable states of aggregation.
∆Hr = [3(−285.830) − 1(−824.2)] kJmol−1 = −33.3kJmol−1 ⇒
Exothermic

Sequences of Reactions: Hesse’s law

Heat of reaction at Constant Volume
If any of the reactants or products of the calorimetric reaction are

gaseous, usually the reaction is carried in a sealed bomb; the isochoric
condition rather than isobaric. Hence QV = ∆U
The corresponding change: R(T , V , p) → P(T , V , p 0 ). Therefore,
n RT
∆H = ∆U + (p 0 − p)V = ∆U + ( pV − nRVRT )V = ∆U + ∆nRT

Introduction to the 2nd law of thermodynamics
All real changes have a direction which we consider
natural/spontaneous. The transformation in the opposite sense
would be unnatural/non spontaneous.
Examples: (i) Water flows from high altitude to low but never in the
opposite direction without any external aid. (ii) The thought of dry
leaves rising, attaching themselves to the tree, and later shrinking
into buds is grotesque. (iii) A metal rod initially at uniform
temperature never develops a hot and a cold end spontaneously.
The first law fails to explain this preference of one direction over the
opposite one.
It would be helpful if a system possessed one or more properties that
always change in one direction when the system undergoes a natural
change, and change in opposite direction if we imagine the system
undergo an unnatural change.
There is a need of SOMETHING other than first law which may
explain all the facts cited above.
Heat Engine
Heat engines convert heat to work. There are several types of heat
engines, but they are characterized by the following:
(i) They all receive heat from a high temperature source (oil
furnace,nuclear reactor,etc.):Reservoir
(ii) They convert part of this heat to work
(iii)They reject the remaining waste heat to a low temperature sink.
(iv) They operate in a cycle.
Output |wnet |
Thermal efficiency(η)= input = Qin
Ordinary spark-ignition auto mobile
engines have a thermal efficiency of
about 20%, diesel engines about 30%,
and power plants in the order of 40%.

The Carnot cycle
Carnot cycle (1824,Sadi Carnot), deals the principles governing the
transformation of thermal energy (Q) into mechanical energy (w)consists
of four reversible steps.
Step I: p1 , V1 , T1 → p2 , V2 , T1 Step II: p2 , V2 , T1 → p3 , V3 , T2

Step III: p3 , V3 , T2 → p4 , V4 , T2 Step IV: p4 , V4 , T2 → p1 , V1 , T1
Carnot cycle: Efficiency
1st law Ideal gas Work done

I ∆U1 = Q1 − w1 0 = Q1 − RT1 ln V2
V1 (−)w 1 = −RT 1 ln V2
V1
R T2
II ∆U2 = −w2 T1 CV dT = −w2 (−)w2 = −CV (T2 − T1 )
III ∆U3 = −Q2 + w3 0 = −Q2 − RT2 ln V 4
V3 (+)w 3 = −RT 2 ln V4
V3
R T1
IV ∆U4 = w4 T2 CV dT = w4 (+)w4 = −CV (T1 − T2 )
V2 V4
wcy = (−)w1 + (−)w2 + (+)w3 + (+)w4 = −RT1 ln V 1
− RT 2 ln V3
Q1 = RT1 ln V 2
V1 and Q 2 = −RT 2 ln V4
V3
V2 V4 V2 V3
wcy −RT1 ln
V1
−RT2 ln V3
T1 ln V1
−T 2 ln V4 Q1 +Q2
Efficiency: η = Q1 = V = V = Q1
−RT1 ln V2 T1 ln V2
1 1
Since step II and IV is reversible adiabatic transformation, hence,
T1 V2γ−1 = T2 V3γ−1 and T1 V1γ−1 = T2 V4γ−1 ⇒ V 2
V1 = V3
V4
η = T1T−T
1
2
= 1 − T2
T1 = 1 − Tc
Th
Q2 T2 Qc Tc
Hence, η = 1 + Q 1
= 1 − T1 ⇒ η = 1 + Qh = 1 − Th
The second law: Clasius and Kelvin statement
Therefore, efficiency always will be less than one i.e. heat taken from
the surroundings can not be converted completely into work in a
cyclic process (Lord Kelvin).
Kelvin statement: It is impossible to construct a heat engine that,
operating in a cycle, produces no effect other than the absorption of
energy from a reservoir and perform the equal amount of work.
Clausius Statement: It is impossible for a refrigerator in a cycle to
produce only the effect of extracting heat from a cold object and
reject the same amount of heat to a hot object OR Heat Energy does
not flow spontaneously from a cold object to a hot object.

Reversed Carnot Cycle: Refrigeration
Reversing the Carnot cycle does reverse the directions of heat and work. A
refrigerator or heat pump that operates on the reversed Carnot cycle is
called a Carnot refrigerator or a Carnot heat pump.
Step I: Adiabatic expansion (p1 , V1 , T1 → p2 , V2 , T2 ),
Step-II: Isothermal expansion (p2 , V2 , T2 → p3 , V3 , T2 ),
Step-III: Adiabatic compression: (p3 , V3 , T2 → p4 , V4 , T1 )
step IV: Isothermal compression: (p4 , V4 , T1 → p1 , V1 , T1 )
Coefficient of performance(COP)=
Output Cooling
input = workdone
V3
Q2 Q2 nRT2 ln V2
COP= win = −(Q1 +Q2 ) = V1 V3
−nRT1 ln V4
−nRT2 ln V2
V3
T2 ln V2 T2
= V4 V3 = T1 −T2
T1 ln V1
−T2 ln V2

Concept of Entropy(S)
H
First law lead to the definition of energy: dU = 0
Does second law defines some new property whose changes sum to
zero in cycle or defines a new state function of the system?
Considering the reversible carnot cycle (Operating between T1
andT2 ):
Q2 T2
η =1+ Q 1
= 1 − T1
Q2 T2
⇒Q 1
= − T1
⇒Q T
1
1
+ Q2
T 2
=0
H δQrev
⇒ T =0
Since sum over the cycle of the quantity δQTrev is zero, this quantity is
the differential of some property of state; this property is called the
entropy of the system and is given by the symbol S.
δQrev
Equation of definition: T = dS

Entropy-Cont...
H δQrev
General Proof: T =0
2nd law implies all reversible engines have the same efficiency
regardless of their construction and working substances.
Any reversible cycle can be approximated as a collection of Carnot
cycles and the cyclic integral around an arbitrary path is the sum of
the integrals around each of the Carnot cycles.
This approximation becomes exact as the individual cycles are allowed

to become infinitesimal.
The entropy change around each individual cycle is zero (as depicted
above), so the sum of entropy changes for all the cycles is zero.
However, in the sum, the entropy change along any individual path is
cancelled by the entropy change along the path it shares with the
neighbouring cycle. Therefore, all the entropy changes cancel except
for those along the perimeter of the overall cycle. That is,
P Qrev P Qrev
all T = perimeter T = 0
In the limit of infinitesimal cycles, the non-cancelling edges of the
Carnot cycles match the overall cycle exactly, and the sum becomes
an integral. Above equation of dS then follows immediately.
This result implies that dS is an exact differential and therefore that
S is a state function.

T-S representation of Carnot cycle
|w | Q1 +Q2
η= Q1 = Q1
T1 (S2 −S1 )−T2 (S2 −S1 ) T1 ∆S−T2 ∆S
|w | Q1 +Q2 T2 = T1 (S2 −S1 ) = T1 ∆S
η= Q1 = Q1 =1− T1 T1 −T2
= T1
= 1− T T1
2

The Clausius Inequality
We now show that the definition of entropy is consistent with the

Second Law.
We know: |δwrev | − |δwirr | ≥ 0
If we consider the following diagram:
From state 1 to 2, the change in internal energy

(dUrev = dUirr ) and entropy (dSrev = dSirr = dS) will
be same.
Irreversible Path: dUirr = δQirr − |δwirr |
Reversible Path: dUrev = δQrev − |δwrev |
⇒ δQirr − |δwirr | = δQrev − |δwrev |
⇒ δQrev − δQirr = |δwrev | − |δwirr |
⇒ δQrev − δQirr ≥ 0
⇒ δQrev ≥ δQirr
⇒ dS ≥ δQTirr

Clausius Inequality Cont..
Non-isolated System
produce effects in the system
and in the immediate
surroundings.
Isolated System dSsys + dSsurr ≥ 0
δQirr = 0 ⇒ dS ≥ 0 The system and its immediate
In an isolated system the surrounding constitute a
entropy cannot decrease when a composite isolated system in
spontaneous change occurs. which the entropy increases as
natural changes occurs within it.
Thus the entropy of the universe
increases continually as natural
changes occurring within it.

Entropy changes accompanying specific processes
Considering First law:

p
dU = δQ − pdV ⇒ dS = CV dT
T + T dV ⇒ dS = CV dT
T + nR dV
V
Considering the definition of enthalpy:
dp
dH = δQ + Vdp ⇒ dS = Cp dT T − V
T dp ⇒ dS = C dT
p T − nR p
Entropy Ideal Gas: pV = nRT

Process
Change T=constant p=constant V=constant
Expansion ∆S = nR ln V2
V1 C p ln T2
T1 C V ln T2
T1
∆Htrans
Phase Change ∆S =
R T2 Ttrans
dT R T2
Heating ∆S = T1 C p T T1 CV dT
T

Spontaneity and Equilibrium
The basic difference between reversible and irreversible process lies in

presence or absence of equilibrium between system and surroundings
for reversible and irreversible transformation respectively.
Therefore, for reversible process or rather to say under equilibrium
condition: dS − δQTirr = 0
Condition for irreversible or spontaneous process need to be
established at different situation of state changes.
δQirr
Clausius Inequality:dS − T >0
Heating at Constant V Heating at Constant p

⇒ δ(Qirr )V = dU; consequently ⇒ δ(Qirr )p = dH; consequently
dS − dU
T >0 dS − dH
T >0
⇒ TdS > dU ⇒ TdS > dH
⇒ dSU,V > 0|dUS,V < 0 ⇒ dSH,p > 0|dHS,p < 0

The Helmholtz and Gibbs energies
The conditions for spontaneity: dU − TdS < 0 and dH − TdS < 0

They can be expressed elegantly by introducing two more
thermodynamic quantities: Helmholtz Energy (A) and Gibbs Energy
(G) as:
A = U − TS and G = H − TS
When the state of the system changes at constant temperature, the
two properties changes as follows:
(a) dA = dU − TdS and (b) dG = dH − TdS
Introducing the spontaneity condition here, we get:
(a) dAT ,V < 0 and (b) dGT ,p < 0
Both A and G are state function

Significance of A and G
Significance of A Significance of G
dS ≥ δQTirr ⇒ TdS ≥ dU + δw dS ≥ δQTirr ⇒ TdS ≥ dU + δw
⇒ −dU − δw + TdS ≥ 0 ⇒ −dU − δw + TdS ≥ 0
Under isothermal change: ⇒ −dU − pdV − δwadd + TdS ≥ 0
⇒ −dU − δw + d(TS) ≥ 0 ⇒ −[dU + pdV − TdS] ≥ δwadd
⇒ −d(U − TS) ≥ δw At T & P constant
⇒ −dA ≥ δw ⇒ −∆A ≥ w ⇒ −d[U + pV − TS] ≥ δwadd
This work includes all sorts of ⇒ −d[H − TS] ≥ δwadd
work including work of ⇒ −dG ≥ δwadd ⇒ −∆G ≥ wadd
expansion: δw = pdV + δwadd It reveals that the decrease in Gibbs
The work produced in an energy associated with a change in
isothermal change: −∆A ≥ w state at constant T and p is equal
The equality sign applies to the to the maximum work(wadd,rev ).
reversible transformation, so the wadd is the non-expansion work
maximum work obtainable in an which is obtainable during
isothermal change:−∆A = wmax transformation
Table: Condition of spontaneity and Equilibrium
Condition For spontaneity For Equilibrium

Isolated system dS > 0 dS = 0
Non-isolated system dSsys + dSsurr > 0 dSsys + dSsurr = 0
Heating at
dAT ,V < 0 dAT ,V = 0
T , V constant
Heating at
dGT ,p < 0 dGT ,p = 0
T , p constant

Combining the 1st and 2nd law: Fundamental Equations
In addition to the mechanical properties p and V , a system has three

fundamental properties T , U, and S, defined by the laws of
thermodynamics, and three composite properties H, A, and G, which
are important.
We now want to develop the important differential equations that
relate these properties to one another.
For the present, we restrict the discussion to systems that produce
only expansion work so that δwadd = 0
From 1st and 2nd law: dU = TdS − pdV

Using the definition of composite functions,
H = U + pV , A = U − TS and G = U + pV − TS
⇒ dH = dU + pdV + Vdp, dA = dU − TdS − SdT and
dG = dU + pdV + Vdp − TdS − SdT

Fundamental Equations
In each of these three equations, dU is replaced by its value from the
above equation and we get four fundamental equations of states:
dU = TdS − pdV and dH = TdS + Vdp
dA = −SdT − pdV and dG = −SdT + Vdp
All the expressions on the RHS is an exact differential expression and
hence cross-derivatives are equal. From this we immediately obtain the
four Maxwell relations :
∂T
= ∂V

From H: ∂p S ∂S p
∂S
∂p
From A: ∂V T = ∂T V
∂S ∂V

From G: ∂p T = − ∂T p
∂T
∂p
From U: ∂V S = − ∂S V

Application of thermodynamic Equations of state
∂U

we said that is (+)Ve for
∂V T we said that ∂H

is (+)Ve for
∂p T
real gas and related to the real gas and related to molecular
intermolecular forces of volume.
attraction.
From 1s t and 2n d law:
From 1s t and 2n d law: dH = TdS + Vdp
dU = TdS − pdV ⇒ ∂H

= T ∂S
∂U
∂S ∂p T ∂p T + V
⇒ ∂V = T −p ∂H
∂V

∂U
T ∂V
∂p
T ⇒ ∂p T = −T ∂T p + V
⇒ ∂V T = T ∂T V − p ∂S
∂V

∂S
∂p [As: ∂p T =− ∂T p ]
[As: ∂V T = ∂T V ]
Using V-W-Equation:
Using V-W-Equation: nRTV 2
V = pV 2 +an2 + nb
RT an2
p = V −nb − V 2 ∂V
nRV 2
∂p R ⇒ ∂T p = pV 2 +an2
⇒ ∂T V = V −nb
∂H nRTV 2

⇒ ∂V T = VRT
∂U
⇒ = − pV 2 +an2 +V
−nb − p
∂p T
∂H

⇒ ∂U

= an2 ⇒ ∂p T = nb
∂V T V2

Temperature dependence of G: Gibbs-Helmholtz
equation
By the definition of G, we can write:

∂G

dG = −SdT + Vdp ⇒ ∂T p
= −S

∂ G 1 ∂G G
we also can write: ∂T ( T ) = T ∂T − T2
p p
G

∂( T )
∂T = −[ TS + G
T2
] = − TS+G
T 2 = − H
T2
p

∂( ∆G )
⇒ T
∂T = − ∆H
T2
p

Entropy and Probability:Statistical view
Entropy is a measure of the disorder of the system.

A state of high order equivalent to low probability to occur and high
probable state will be of low order.
In a spontaneous process, the universe moves from a state of low
probability to a state of higher probability i.e. from a state of
relatively high order to a state of low order.
We will illustrate the concepts by considering the isothermal
expansion of gas (ideal gas for simplicity) from volume Vi to Vf .
Microstate: A description of a system that specifies the properties
(position and/or momentum, etc.) of each individual particle.
Macrostate: A more generalized description of the system; it can be
in terms of macroscopic quantities, such as P and V , or it can be in
terms of the number of particles whose properties fall within a given
range.
In general, each macrostate contains a large number of microstates.
Continuation of Entropy and Probability
An example: Imagine a gas consisting of just 2 molecules. We want to

consider whether the molecules are in the left or right half of the container.
No. of macrostates: 3 (both on left, both on right, one on each side.)

No. of microstates: 4 (LL, RR, LR, RL).
How about 3 molecules? Now we have:

LLL, (LLR, LRL, RLL = 2L, 1R), (LRR, RLR, RRL = 2R, 1L), RRR
Macrostate: 4, Microstate=8
How about 4 molecules? Now we have:

LLLL, (3L, 1R ⇒ 4), (2L, 2R ⇒ 6), (1L, 3R ⇒ 4) RRRR
Macrostate: 5, Microstate=16

This table is generated using the formula for number of possibilities

N!
for picking x items from N total: WN,x = x !(N−x )!
W6,2 = No. of ways 6 molecules can be distributed in the container
such that left compartment will accommodate 2 and the other will 4:
6!
W6,2 = 2!4! = 15
Fundamental Assumption of Statistical approach: All microstates are
equally probable.
Thus the probability that the 6 molecules will be distributed such that
left compartment contains 2 and other contains 4 is
W6,2
Ω6,2 = P W = 15
64
i,j
Similarly, Ω6,3 = 20
64 ; therefore higher the no. of microstates higher
will be the probability i.e. ΩN,x ∝ WN,x
Therefore, probability of finding N molecules in volume Vi and Vf are
ΩN,i ∝ WN,i and ΩN,f ∝ WN,f respectably.
Ω WN,f N
Hence, ΩN,f
N,i
= WN,i , It is intuitive that, W N,i/f ∝ (Vi/f )
WN,f Vf N
Therefore, WN,i = Vi
For isothermal expansion: ∆S = nR ln VVfi

n WN,f n WN,f
∆S = Sf − Si = N R ln WN,i ⇒ Sf − Si = nNA R ln WN,i
WN,f
Sf − Si = kB ln WN,i = kB (ln WN,f − ln WN,i )
Therefore, S = kB ln W
The End

Thermodynamics Somanath Gosh

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Thermodynamics Somanath Gosh

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Physical Chemistry

Indian Institute of Petroleum and Energy (IIPE), Visakhapatnam

August 23, 2019

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 1 / 93

15 Adiabatic changes in state for

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 2 / 93

Table: Code of Conduct/Deal between You and Me

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 3 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 4 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 5 / 93

Transference of matter (mass) and

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 6 / 93

The method of operation that can

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 7 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 8 / 93

Any three of the four variables (p, V , T , n) are specified to describe

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 9 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 10 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 11 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 12 / 93

Boyle’s law: pV =Constant, at

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 13 / 93

Consider, a mixture of gases described by the mole numbers n1 , n2 , n3 , ...

Total no. of moles nt = n1 + n2 + n3 + ...

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 15 / 93

The result of the 2nd expt. is

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 16 / 93

To display the deviation, Z vs p for different gases are plotted.

For H2 gas, Z > 1 at all pressures.

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 17 / 93

Volume term correction: Even at 0K, gas molecules occupy some

’a’ measures the vander-Waals forces of cohesion between the gas

Gas a(Pa.m6 .mol−2 ) b(m3 .mol−1 )

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 19 / 93

As p ↑ within the intermediate pressure range, V̄ ↓, V̄a ↑ and

When the pressure is too high: As the p is very high, V̄ will be

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 21 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 22 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 24 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 25 / 93

The distinction between heat and work is made in the surroundings.

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 26 / 93

Internal Energy (U):

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 27 / 93

Let us, consider one banking system.

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 28 / 93

State Function: Property of a system that only depends on the initial

Exact Differential Inexact Differential

is independent of the path of which depends on the path of

The function is state function The function is path function

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 31 / 93

Symbolism ∆Q and ∆w is meaningless.

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 32 / 93

If z = f (x , y ) to be state function of two independent variables, x and y ,

In order to have z as state function or dz to be exact differential, mixed

Euler’s reciprocal relation:

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 33 / 93

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 35 / 93

System took Q amount of heat and did

Work done(by the system):

If pint > pext = pop = Mg

Somnath Ghosh (IIPE) Thermodynamics August 23, 2019 37 / 93

Stage-1: Expansion V1 → V 0 ; then

The work produced in the two