CLL 702

Principles of Thermodynamics
Lecture-1

Prof Sudip K Pattanayek

Department of Chemical Engineering
Indian Institute of Technology Delhi

1
Useful information

Assignment problems from Books:

• [Atkins] Atkins - Physical Chemistry 11th Edition
• [SVA]Smith J. M., Van Ness H. C., Abbott M. M., Introduction to
Chemical Engineering Thermodynamics, McGraw Hill, 8 th Ed.
2018[Chapter 1-5 &10-14 of ]

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 What problem you can address after thermodynamic section of the
course?
• How many parameters do we need to define a system?
• If a gas expands rapidly through a narrow section what is going to happen?
• How much useful work be possible in a given process?
• X1 ml Y1M NaOH solution is mixed with X2 ml Y2M HCl solution at 298.15 𝐾 in an isolated
chamber. What will be the rise in temperature?
• If we mix A and B , will there be phase separation?
• What will be the equilibrium vapour composition of mixture of liquids?
• If increase the pressure what is going to happen to vapour pressure/melting point/boiling
point?
• A solution of certain concentration is in contact with another solution of same components
via a membrane. What is going to happen ?
• What will the effect of a salt in the above case?
• What is the equilibrium conversion of compounds in a reaction? What will be the effect of
change in pressure, temperature etc on the equilibrium conversion?

3
Facts of Thermodynamics
• Study of energy, energy transformations and its relation to matter
• Born out of a more practical interest: generating motion from heat
• Steam Engine : conversion of heat to mechanical motion
• Thermodynamics evolved into a theory describing transformation of states of
matter, motion generated by heat being a consequence of particular
transformation
• Chemical Engineering→ a wide variety of problems
• Heat and work requirements for physical and chemical processes
• Determination of equilibrium conditions for the transfer of species between
phases
• Determination of equilibrium conditions for chemical reactions

4
Facts of Thermodynamics
• Gives the idea of the possibility of the process BUT Not the Rates of Chemical or
physical process
• Rate depends on (i)driving force (ii) resistance
• No clue to the mechanism of either physical or chemical process
• Laws of Thermodynamics are based on experience, experiments
• Deals with the properties of the matter in bulk (Classical & Statistical)
• Properties which can be measured on samples of material in the laboratory

• Not concerned with Molecular theory

• Statistical averaging of the behavior of large numbers of molecules leads to
thermodynamic laws

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Classical & Statistical Thermodynamics
28cm

Classical Thermodynamics (Macroscopic system)

• Molecular information is not required
• Concerned only with continua
• Averaged information (properties) are measured and
appropriate laws are made
• Required for engineering/practical purposes
108

Statistical Thermodynamics (Microscopic)

• Matter may be described at a molecular level using the
techniques of statistical mechanics and kinetic theory
• Molecular properties are averaged over a large number
of molecules to get the bulk properties of molecules

N P (Pa) T(K) V(m3) mass(kg) Molecule/unit volume Size of a Molecules dimension (m)
6.023E+23 103000 298 0.0224 2.90E-02 2.69E+25 3.00E-10 0.281891949
1E-24 2.69E+01
6
10nm
System and Surrounding

System : Any thing of our

interest
• Surrounding: Everything
remaining outside the system
• Boundary: may be real or System
(Es)
imaginary, rigid or flexible Boundary

E=(Es)+(Ee) Surrounding/Exterior
(Ee)
• Total energy of
System +Exterior =constant
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Interaction Between System and Surrounding

System
Isolated System : No exchange of energy and matter (Es)

Surrounding/Exterior
(Ee)
• Closed System: No exchange of matter
• Exchange of energy is allowed
• Open System : Exchange of energy and matter
System
System (Es) E
(Es)
Surrounding/Exterior
Surrounding/Exterior (Ee)
(Ee)

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 State of a System: Properties
State : It is the condition of the system defined by certain set of properties

• Extensive Property: Depends on • Intensive Property: Independent

the mass of the system on the mass of the system
• Mass, M (kg) • density,  (kg/m3)
• Total Volume, V (m3) • Temperature, T, (K)
• Total Energy, E ( J, Joule) • Pressure, P=F/A ( N/m2)
• Total Heat, Q (J)

• Specific Value : Extensive property per unit mass or mole of the system ;
independent on mass
• Specific Volume, v (m3/kg),
• Molar volume: v m3/mol
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Properties

• Fundamental
• Time , t (s)
• Length, L (m)
• Mass, m (kg)
• Force, F (kg m/s2 (Newton, N)).
• Temperature, T, (K)
• Secondary
• Volume, V (m3)
• Pressure, P=F/A ( N/m2)
• Energy, E ( J, Joule)
• Work, W (Nm ( J))
• Heat, Q (J)

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 Equilibrium

• The thermodynamic state of a system in which properties have

definite value and invariant as long as external conditions are
unchanged is called an equilibrium state.
• Thermal equilibrium: Temperature unchanged
• Mechanical equilibrium: No unbalanced force
• Chemical equilibrium: Chemical composition is unaltered

Mechanical Equilibrium

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 THE ZEROTH LAW OF THERMODYNAMICS

If System B is in thermal equilibrium with system A and system C

Then System A is in thermal equilibrium with system C

B C
Consequence:
Equilibrium Systems have a well defined spatially uniform
temperatures
A For such systems, the energy is functions of state as
expressed
U= 𝑈(𝑇, 𝑉, 𝑁𝑘) or S= 𝑆(𝑇, 𝑉, 𝑁𝑘)

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 Work F
dl
F is the component of force acting along the line m
dl is the displacement along the line t>0
t=0
Work done, dW=F.dl +ve if directions of dl and F is same

-dVt=A.dl => dl =-dVt/A

in
Fout=P.A
b a
dW=-PA(dVt/A)=-PdVt

𝑉2
A Fout
W=-‫ 𝑉׬‬PdVt
1

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 F
Energy dl
m
t=0
t=dt

External forms of energy : Energy due to Macroscopic Change in

position, configuration, or motion
•Kinetic Energy = 1/2mV 2
• Potential Energy : If a body is in a force field ( e.g. gravitational force
field, electric field etc)
If the mass, m is in gravitational filed at a height z, the PE=mgz

Law of conservation of mechanical energy: potential and kinetic

energies are fully inter-convertible
EKE+EPE=Constant
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 Heat, Q (J)

• Heat is that form of energy that is

exchanged between system and its
surrounding owing to a temperature
differential between the two.
• Heat always flows from a higher to a lower
temperature regions in space.
• There is no flow of heat energy between
two points in absence of temperature
gradient/difference.

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 Concept of a ``Process'‘ and “Path”
• Process : Any change that a system undergoes from
one equilibrium state to another.
• Path: The succession of states through which the
system passes during the process.

• Quasi-static or Quasi-equilibrium process: A process

proceeds in such a manner that the system remains Quasi-static
infinitesimally close to an equilibrium state at all the
times.
P
• Complete description of a process: Specify initial and Non Quasi-static
final states, the path it follows and the interaction
with the surroundings.
V

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 Cyclic Process and “Path”
• If, at the end of the process, the properties
have returned to their original values, the
system has undergone a cyclic process or
a cycle. P
• Note that even if a system has returned to
its original state and completed a cycle, the
state of the surroundings may have V
changed.

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 Sign Convention
Cengel Approach
• Heat Transfer: heat transfer to a system is positive
and heat transfer from a system is negative.
• Work Transfer: work done by a system is positive
and work done on a system is negative.

Culham Approach
• Anything directed into the
system is positive, anything
directed out of the system is
negative.

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 Equations of State (EOS) for substance of a System
• Experiments: Only a certain minimum number of properties of a pure
substance can be given arbitrary values to define a state a pure
• EOS : f(m,V,P,T)=0 if m, V, P and T are needed to completely describe the system substance/
• IF more properties are required, those properties must be incorporated in this eqn. homogeneous
• Any three of the properties are fixed, the fourth is determined mixture consists
of a single phase
• The EOS varies from one Substance to another
• => f(v,P,T)=0 independent on the mass of the system
• If Two variables are fixed other will be determined
Single-Phase Regions: v=v(T,P) 𝑑𝑣 =
𝜕𝑣
dT+
𝜕𝑣
dp
1 𝜕𝑣 𝜕𝑇 𝑃 𝜕𝑃 𝑇
Volume expansivity 𝛽=
𝑣 𝜕𝑇 𝑃 𝑑𝑣/𝑣 = βdT − 𝜅dp

1 𝜕𝑣
Isothermal Compressibility 𝜅=−
𝑣 𝜕𝑃 𝑇

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A few Basic Definitions & standard conditions
NTP (Normal temperature and pressure): 293.15K and 1 atm 1.01325×105Pa
SATP: standard ambient temperature and pressure (298.15K and 1 bar (105Pa)
STP: standard temperature and pressure: Imperial and USA system units (273.15K and 1 atm
(1.01325×105Pa) :molar volume of perfect gas 22.4 14 litre; IUPAC: 273.15K and 1 bar
(105Pa)
Thermodynamic Processes are categorized based on how the properties behave:
❑isobaric (P = constant)
❑isothermal (T = constant)
❑isochoric or isometric (V = constant)
❑adiabatic (no heat transfer, Q=0)
• isentropic (s = constant)
• isenthalpic (h = constant)

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 Phase & Phase Rule
• Phase is a region of a system, throughout which all physical
properties (density, index of refraction, magnetization or chemical
composition)of the material are uniform.

• Degree of Freedom (DOF), F : “For a multiphase () system at

equilibrium, the number of independent variables that must be
arbitrarily fixed to establish its intensive state is called the number
of degrees of freedom of the system.”
• Phase Rule
F=c-+2-r c=no of components
r= no of independent chemical reactions at
equilibrium within the system

Ex: Liquid water in equilibrium with a mixture of water vapor and nitrogen. F=2-2+2-0=2
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 PVT BEHAVIOR OF PURE SUBSTANCES
Single component Pure material
Fluid
Liquid Critical point

Solid Gas
P
Vapour
Triple point

Adapted from SVA

22
 Equations of State for Ideal Gas (perfect gas) &Kinetic model
PV=nRT; Pv=RT R=Universal Gas Constant =8.314 J.mole-1K-1
Kinetic Model of Gases
• The gas consists of molecular mass m random motion
• The size of the molecules is negligible (diameter is much smaller than the
average distance travelled between collisions 𝑢𝑥 ∆𝑡
• Collision is elastic (total translational kinetic energy is conserved)
ux
RMS velocity u
2
𝑢 = 𝑢𝑥2 + 𝑢𝑦2 + 𝑢𝑧2 A
𝑢𝑥2 =𝑢2 /3 𝑐 2 = 𝑢2 = 𝑢𝑥2 + 𝑢𝑦2 + 𝑢𝑧2
n,V,T

No of molecules in the volume nt = 𝑢𝑥 ∆𝑡 A 𝑛𝑁𝐴 /𝑉

Total rate of change of momentum along x per unit A
No of molecules striking the wall=1/2* nt
P = m𝑢 2 𝑛𝑁 /𝑉
Momentum change per molecule = 2𝑚𝑢𝑥 𝑥 𝐴
𝑛𝑁𝐴 𝑚𝑐 2
Total Momentum change along x = 𝑚𝑢𝑥 𝑢𝑥 ∆𝑡 A 𝑛𝑁𝐴 /𝑉 PV = 2 3𝑘𝑇 3𝑅𝑇
2
= m𝑢𝑥 ∆𝑡A 𝑛𝑁𝐴 /𝑉 3 𝑐 = = 23
𝑁𝐴 𝑚𝑐 2 𝑚 𝑚𝑁𝐴
Pv = =const
3
=RT (if ideal)=𝑁𝐴 kT
Determination of Absolute zero and R values

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Real Gas: Compressibility factor

Compressibility factor, Z=v/vi Z < 1 indicates that attractive forces dominate

repulsive forces under these conditions
=Pv/RT

Pv=RT Z for several gases at 0 °C.

Z

calculated from PVT data for25 methane

From Atkins: page 20
 VIRIAL EQUATIONS OF STATE
• Isotherms for gases and vapors, lying to the right of the saturated-
vapor curve, are relatively simple curves for which v decreases as
P increases.
• No difference between ideal and real gas behavior at low
pressure and high volume.
• product Pv for a given T varies much more slowly than either of
its members At critical point

• Pv is more easily represented analytically as a function of P.

Expressing Pv for an isotherm by a power series in P

𝑑𝑍
= 𝐵 𝑝 + 2𝐶 ′ 𝑃
Pv B C
= 1+ + 2 𝑑𝑃
RT v v
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 2nd and 3rd VIRIAL Coefficients
• Expansion till third term is known
• However C/v2<<B/v

• B describes the contribution of the pair-wise potential to the pressure

of the gas.

How B and B’ are related?

What is v-vi?

𝑑𝑍
=𝐵
1
𝑑( )
𝑣

Virial coefficients B and C for Nitrogen. 27

B=0 : Ideal gas behaviour
Real Gas: Boyle temperature For a perfect gas, the slope
is zero, but real gases may
have either positive or
negative slopes, and the
slope may vary with
temperature.
At the Boyle temperature,
the slope is zero at p = 0 and
the gas behaves perfectly
over a wider range of
conditions than at other
temperatures.

Boyle temperature: Z→1 and dZ/dp=0

28
 Critical Constants
. The single phase that fills the entire volume when T > Tc may
be much denser than considered typical for gases, called
supercritical fluid

What does it signify?

An isotherm slightly below Tc behaves as already described: at a certain

pressure, a liquid condenses from the gas and is distinguishable from it by
the presence of a visible surface. 29
 Equation of State for Real Gas: van der Waals EOS
Reduction in pressure is due to the reduction of Reduction of free space
(1) collision frequency at the wall
(2) magnitude of force of each collision

30
 Calculated P as a function of v for various values of T for a and b

“dome” representing states of saturated liquid and saturated

vapor

vaporization does not occur, and liquid persists

alone to pressures well below its vapor
pressure
At critical point
v
Adapted from SVA

31
Critical constants and van der Waals coefficients

32
 Corresponding States
Experimental compressibility-factor data show that values of Z for different fluids
exhibit similar behavior when correlated as a function of reduced temperature Tr and
reduced pressure Pr.

Independent of parameters

33
Find out pressure of 1 mol methane gas at 0˚C when contained in 250ml. Assume gas follows behavior
(i) ideal gas
(ii) van der Waals gas [a 2.2725 litre2 atm/mole2 b=0.043litre/mole]
Ans: 89.54 atm, 71.78 atm, 74.14 atm
(iii) Virial equation [B=-53.4 cm3/mole, C=2620cm6/mole2

If pressure is given, how would you determine volume?

34
Interrelation between van der Waals and Virial equations

35
36
Interrelation of van der Waals eqn and interaction parameter

37
Relations between Partial Derivatives 1 𝜕𝑣
v=v(T,P) 𝑃 = 𝑃(𝑇, 𝑣) 𝜅=−
𝑉 𝜕𝑃 𝑇
𝜕𝑃 𝜕𝑃 dv
𝜕𝑣 𝜕𝑣 𝑑𝑃 = dT+ 1 𝜕𝑣
𝑑𝑣 = dT+ dP 𝜕𝑇 𝑣 𝜕𝑣 𝑇
𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝛽=
𝑉 𝜕𝑇 𝑃
𝜕𝑣 𝜕𝑣 𝜕𝑃 𝜕𝑃
𝑑𝑣 = dT+ dT+ dv
𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑣
𝑃 𝑇 𝑣 𝑇 𝑑𝑣/𝑣 = βdT − 𝜅dp

𝜕𝑣 𝜕𝑃 𝜕𝑣 𝜕𝑣 𝜕𝑃
1− 𝑑𝑣= + dT
𝜕𝑃 𝑇 𝜕𝑣 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑣

38
Relations between Partial Derivatives Isothermal Compressibility
1 𝜕𝑣
𝜅=−
𝑉 𝜕𝑃
𝜕𝑣
+
𝜕𝑣 𝜕𝑃
=0
Volume expansivity
𝑇
𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑣 1 𝜕𝑣
𝛽=
𝑉 𝜕𝑇 𝑃
𝜕𝑃 𝜕𝑣 𝜕𝑣 𝛽
=− / =
𝜕𝑇 𝑣 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜅 𝜕𝑣 𝜕𝑣
𝑑𝑣 = dT+ dP
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝑝2 𝑇2 𝛽
‫𝑝׬‬1 𝑑𝑃 = ‫𝑇׬‬1 𝜅
𝑑T
𝛽
𝑑𝑣/𝑣 = βdT − 𝜅dp
p2-p1= (T1-T2)
𝜅

dT≠0; 𝑑𝑣 =0
dT = 0; 𝑑𝑣 ≠0 𝜕𝑣 𝜕𝑃 𝜕𝑣 𝜕𝑣 𝜕𝑃
𝜕𝑣 𝜕𝑃 𝜕𝑣 𝜕𝑣 𝜕𝑃
1− 𝑑𝑣= + dT
𝜕𝑃 𝑇 𝜕𝑣 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑣
1− 𝑑𝑣= + dT
𝜕𝑃 𝑇 𝜕𝑣 𝑇 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑣
𝜕𝑣 𝜕𝑣 𝜕𝑃
𝜕𝑣 𝜕𝑃 𝜕𝑣 𝜕𝑃 + =0 𝜕𝑣 𝜕𝑃 𝜕𝑇
1− =0; =1/ 𝜕𝑇 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑣
𝜕𝑃 𝑇 𝜕𝑣 𝑇 𝜕𝑃 𝑇 𝜕𝑣 𝑇
=-1
𝜕𝑃 𝑇 𝜕𝑇 𝑣 𝜕𝑣 𝑃
𝜕𝑇 𝜕𝑣 𝜕𝑃
1/ + =0
𝜕𝑣 𝑃 𝜕𝑃 𝑇 𝜕𝑇 𝑣
39
 Exact Differentials
𝜕𝑣 𝜕𝑣 𝜕𝑣 𝜕𝑣
𝑑𝑣123 = dT+ dP 𝑑𝑣143 = dP+ dT
𝜕𝑇 𝑃1 𝜕𝑃 𝑇2 𝜕𝑃 𝑇1 𝜕𝑇 𝑃3

v 2 𝜕𝑣 𝜕𝑣 𝜕𝑣 𝜕𝑣
dP + dT = dT+ dP
𝜕𝑃 𝑇1 𝜕𝑇 𝑃3 𝜕𝑇 𝑃1 𝜕𝑃 𝑇2
3
1 𝜕𝑣 𝜕𝑣 𝜕𝑣 𝜕𝑣
− dT = − dP
4 𝜕𝑇 𝑃3
𝜕𝑇 𝑃1
𝜕𝑃 𝑇2
𝜕𝑃
𝑇1

𝜕 𝜕𝑣 𝜕 𝜕𝑣
=
𝜕𝑃 𝜕𝑇 𝑃 𝑇 𝜕𝑇 𝜕𝑃 𝑇 𝑃

T2
P1 T T • Independent of the order of differentiation=>independent of path
P P T1 • A Thermodynamic property of a system is exact, example V, T, P
P 3
• Work or Energy interchange is not exact; not a Thermodynamic
property but rather process quantities

40
 CLL 702
Principles of Thermodynamics

Internal Energy,
First Law of Thermodynamics
and Enthalpy
Prof Sudip K Pattanayek
Department of Chemical Engineering
Indian Institute of Technology Delhi

41
 JOULE’S EXPERIMENTS
Procedure:
Known amounts of (i)water (ii)oil, or (iii)mercury
in an insulated container and agitated the fluid
with a rotating stirrer.
The amounts of work done on the fluid by the
stirrer and the resulting temperature changes of
the fluid were accurately and precisely
measured
h W=hMg
Observations
For each fluid a fixed amount of work per unit
M mass was required for each degree of temperature
rise caused by the stirring
System
The original temperature of the fluid was
restored by the transfer of heat through simple
Surroundings contact with a cooler object
Inference
1. Existence of a quantitative relationship between work and heat
Question: Where does this energy reside after its 2. Work and heat are interconvertible
addition to, and before its transfer from, the fluid? 3. They are different form of energy 42
Molecular picture of Energy

Energy of the molecules comprising the

substance In Microscopic scale
Molecular scale:
Because of their ceaseless molecular motion,
all molecules possess
(A)kinetic energy of (i)translation motion,
(ii)rotation (iii)internal vibration [last two are
NOT present in monoatomic molecule]
B. Potential energy associated with https://chem.libretexts.org/
intermolecular forces:
Molecules attract or repel one Submolecular scale: energy is associated
another, and potential energy is stored
through these interactions. with the interactions of electrons and nuclei
of atoms, which includes the energy of
chemical bonds that hold atoms together as
molecules. 43
 Internal form of Energy, U
• In a fundamental sense, the ultimate repositories of energy in matter are the atoms
and molecules that comprise it.
• The addition of heat to a substance increases molecular motion, and thus causes an increase in
the internal energy of the substance.
• Absolute values are unknown.
• It cannot be directly measured; there are no internal-energy meters;
• Only changes in internal energy are required in thermodynamic analysis
• In the context of classical thermodynamics, the details of how internal energy is
stored are immaterial.
• Ut is the total internal energy of the system; Ut =n*U=>extensive property
• U is internal energy per unit mole/mass =>intensive property

44
 THE FIRST LAW OF THERMODYNAMICS
Conservation of energy

“Although energy assumes many forms, the total quantity of energy is

constant, and when energy disappears in one form it appears
simultaneously in other forms”
System
Symbolic representation: (U+E +E )
KE PE

E (system)+E (Surroundings) =0=E (Universe) +Q , +W

surr surr

System Surrounding/Exterior
(U+EKE+EPE) (Ee)

+Qsurr, +Wsurr

Surrounding/Exterior
(Ee) 45
Mathematical Form of 1st Law of Thermodynamics
ENERGY BALANCE FOR CLOSED SYSTEMS
• All energy exchange between a closed system and its surroundings is in
the form of heat or work
• the total energy change of the surroundings equals the net energy
transferred to or from it as heat and work.
• Δ(Total Energy of Universe)=0 System
• E (system)+E (surroundings)=0 (U+EKE+EPE)

• E (system) =Total energy input to system in all forms

+Qsurr, +Wsurr
= Q+W
• If the energy transfer across the system boundary takes place only the Surrounding/Exterior
form of work and heat (Ee)
• (U + EKE + EPE)system= Q+W
U + EKE +  EPE=Q+W Heat Q and work W always refer to the system
Qsurr = −Q and Wsurr = −W

46
Mathematical Form of 1st Law of Thermodynamics
ENERGY BALANCE FOR CLOSED SYSTEMS
U + EKE +  EPE=Q+W
The above equation may also be written in a differential form
dU + dEKE + dEPE=Q+W

• If there is no change in potential and kinetic energies (Macroscopic) for the

system or it is negligible – as is usually true for most thermodynamic
systems of practical interest
dU =Q+W
• relates state variable (U) with two path variables (Q, W)

47
Heat and Work vs Potential, Kinetic, and Internal energy

• Heat and work

• represent energy in transit across the boundary dividing the system from its
surroundings
• represent energy flows to or from a system.
• These are NOT possessed by a thermodynamic System
• Potential, kinetic, and internal energy,
• represent quantities of energy associated with a system
• reside with and are stored with matter;

48
Internal Energy at Constant Volume process 𝑉1
𝑉1
𝑊 = −න PdVt = −𝑛𝑅𝑇𝑙𝑛
𝑉2
T1,v1 𝑉2

T=0, U=0
dU =Q+W P
dU=dQrev + dWrev=dQrev – Pext dV T1,v2
w=0
dUv=dQv T2,v2
For a measurable change Uv=qv
v
Measurement of internal energy of the System going from one state to
another

Measure the energy supplied to (obtained from) the SYSTEM at

CONSTANT VOLUME process (qv). The Uv=qv

49
 Heat Capacity at Constant Volume

𝜕𝑈
𝐶𝑉 =
𝜕𝑇 𝑣

𝐶𝑉 per mole of Mono-atomic Gas =3/2R

𝐶𝑉 per mole of diatomic Gas / Linear molecules at room temperature =5/2R
𝐶𝑉 per mole of nonLinear molecules like methane at room temperature =3R
∆𝑇𝐶𝑉 = ∆𝑈𝑉 =𝑞𝑉

50
 Internal Energy of Gases
Monoatomic
Only Translational Kinetic energy
1 2 𝑘𝑇
𝑚𝑐 = ഥ =3×
𝐾
Average KE of each molecule 2 2
(Each direction x, y, and z contributes)
Internal energy=K1+K2+K3+K4+K5+..
Internal energy/per mole = 3𝑁𝑎𝑣 × 𝑘𝑇=3𝑅𝑇
2 2

• At low temperatures, a diatomic gas acts like a monatomic gas

Di-atomic (Hydrogen, H2) • At Room temperature Rotational kinetic energy
• At a very high temperature Vibrational energy will be important

Translational 3(Each direction x, y, and z contributes)

Rotational 2
Vibrational 2

Internal energy =Translational + Rotational + Vibrational

5𝑅𝑇 7𝑅𝑇
Internal energy/per mole at room Temperature and extremely high temperature 𝑎𝑛𝑑 51
2 2
 𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑣
Joule’s Experiment U= 𝑈(𝑇, 𝑣) 𝜕𝑇 𝑣
𝜕𝑣 𝑇

𝑑𝑈 𝜕𝑣
=𝐶
𝑑𝑇 𝑃 𝑣
+𝜋𝑇 𝜕𝑇 𝑃

𝜕𝑈
= : Internal Pressure
𝜋𝑇 𝜕𝑣 𝑇
𝜋 𝑇 <0
22 vacuum Repulsion dominant
atm

U ideal
𝜋 𝑇 >0
Attractions dominant
Cyclic rule
Observation: No Change in temperature If dU=0,
𝜕𝑈 𝜕𝑈 𝜕𝑣
V
Explanation: W=0, U=0; + =0
Issues: heat capacity of the apparatus is too large 𝜕𝑇 𝑣 𝜕𝑣 𝑇
𝜕𝑇 𝑢
And because for the gas that 𝜕𝑈 𝜕𝑣
=−
𝜕𝑈

underwent the expansion into an open 𝜕𝑣 𝑇 𝜕𝑇 𝑢

𝜕𝑈 𝜕𝑣 𝜕𝑇
𝜕𝑇 𝑣
52
space, 𝜋𝑇 must also be zero! 𝜕𝑣 𝜕𝑇 𝜕𝑈
=-1
Internal Energy at varying Volume process at constant
pressure: Concept of Enthalpy
dU =Q+W
dU=dQrev + dWrev=dQrev – Pext dV

dQrev=dU+ Pext dV=d(U+PV) at constant pressure

=dH => H=U+PV

Measure the energy supplied to (obtained from) the SYSTEM at

CONSTANT pressure Process (Qrev). p= Qrev =qp
53
 𝜕𝑈 𝜕𝑈
Heat Capacity at Constant Pressure 𝑑𝑈 = 𝑑𝑇 + 𝑑𝑣
𝜕𝑇 𝑣
𝜕𝑣 𝑇

𝜕𝐻 𝑑𝑈
=𝐶 +𝜋𝑇
𝜕𝑣
𝐶𝑝 = H=U+PV=U+nRT 𝑑𝑇 𝑃 𝑣 𝜕𝑇 𝑃
𝜕𝑇 𝑝 𝜕𝐻 𝜕𝑈
𝐶𝑝 = = +nR
𝜕𝑇 𝑝 𝜕𝑇 𝑝
𝑑𝑈 𝜕𝑣
𝐶𝑝 =𝐶𝑣 + nR =𝐶
𝑑𝑇 𝑃 𝑣
+𝜋 𝑇
𝜕𝑇 𝑃
∆𝑇𝐶𝑃 = ∆𝐻𝑃 =𝑞𝑃
= 𝐶𝑉 + 0 (For Ideal Gas)

𝐶𝑃 per mole of Mono-atomic Gas =3/2R+R

𝐶𝑃 per mole of diatomic Gas / Linear molecules at room temperature =5/2R+R

𝐶𝑃 per mole of nonLinear molecules like methane at room temperature =3R+R

54
Effect of temperature on heat Capacity
𝐶𝑝
= 𝐴 + 𝐵𝑇 + C𝑇 2 + 𝐷𝑇 −2
𝑅
• Either C or D usually zero
• Effect of pressure might be there
• For liquid and solid effect of pressure is small
𝜕𝐻
𝐶𝑝 = 𝑑𝐻 = 𝐶𝑝 𝑑𝑇
𝜕𝑇 𝑝
𝑇1
∆𝐻 = න 𝐶𝑝 𝑑𝑇
𝑇2

See values Tables C2 and C3 of appendix C of SVA

55
 Adiabatic Change in Ideal Gas
dU =dQ+dW ∆𝑈𝑉 = ∆𝑇𝐶𝑉
T1,v1 ∆𝑈 = q+ wad ;
T
q=0
T2,v2
v

56
Adiabatic Change in Ideal Gas

57
 Reversible vs Irreversible Processes
m2
m2 m1

Irreversible :
P2,V2,T2 uses a different
P2,V2,T2 P1,V1,T1 path to return to
the starting
Reversible work position, thus
(1)uses the same changing the
m1
process, in reverse, to surrounding
return to the starting environment
position
(2)the entire system (2)heat is given off into the
(including the Surroundings
surrounding ) can be
returned to the starting P1,V3,T3
state.

58
 Work Done in Isothermal Reversible Processes
Weight-less Frictionless piston Reversible compression (work on the system +ve)
Pext=Pin + dP

Pin
dP is insignificant such that Pext=Pin
Pin V2 Ideal gas
Pin
V1 Final
Reversible work by the system (expansion)
Initial

Pext=Pin- dP

Pin V2

59
 Work Done in Isothermal Irreversible Processes
Weight-less Frictionless piston Irreversible work on the system (compression)
Pext=Pin + P

Pin

Pin V2
Pin
V1 Final Irreversible work by the system (expansion)

Initial

Pext=Pin- P

Pin

60
H=U+PV=U+nRT
H= U+(PV)= U+nRT
Hm= Um+(PVm)= Um+RT

61
62
63
 Joule Thomson Effect
Thermocouple

• Important in understanding Liquefaction of gases

• Isenthalpic Process [Proof : Self study ]
Insulated Barrier

Gas at low pressure

• Gas Cools during this expansion

Porous Barrier
𝐻 = 𝐻(𝑇, 𝑃)

𝜕𝐻 𝜕𝑇 𝜕𝑃
= −1
𝜕𝑇 𝑃
𝜕𝑃 𝐻
𝜕𝐻 𝑇 J T Coefficient
Gas at high pressure 𝜕𝑇
𝜕𝑃 𝜇𝐽𝑇 =
𝐶𝑃 𝜇𝐽𝑇 = −1 𝜕𝑃 𝐻
𝜕𝐻 𝑇

𝜕𝐻
−𝐶𝑃 𝜇𝐽𝑇 = 𝜕𝑃 𝑇
=𝜇 𝑇 Isothermal J T Coefficient

64
Joule Thomson coefficient and Inversion Temperature

JT>0
Z<1 JT<0
𝜕𝑇
𝜇𝐽𝑇 =
𝜕𝑃
Z>1 𝐻

For three real gases 65

 CLL 702
Principles of Thermodynamics

Thermochemistry

Prof Sudip K Pattanayek

Department of Chemical Engineering
Indian Institute of Technology Delhi

66
 Standard Enthalpy Change

• Changes in Enthalpy are normally reported for processes taking place

under a set of Standard conditions.
• A standard state is defined as the state of a substance at specified
pressure, composition, and physical condition as, e.g., gas, liquid, or
solid.
• Standard-state pressure is 1 bar (105 Pa)
• All conditions for a standard state are fixed except temperature,
which is always the temperature of the system. Standard-state
properties are therefore functions of temperature only.

67
 Standard Enthalpy Changes in a Physical Changes
Standard Enthalpy Change𝚫𝑯𝟎 : Enthalpy change per mole for a process in which the initial
and final substances are in their standard states.

Standard Enthalpy of Vaporization ∆𝒗𝒂𝒑 𝑯𝟎 : Enthalpy change per mole when a pure liquid
at 1 bar vaporizes to a gas at 1bar
=Latent heat
Process: Vaporization 𝐻2 𝑂 𝑙 → 𝐻2 𝑂 𝑔 ∆𝒗𝒂𝒑𝑯𝟎 373 𝐾 =+40.66 kJ/mol

Latent heat accompanying a phase change is a function of temperature only, and is related to
other system properties by an exact thermodynamic equation “Clapeyron equation”

𝒅𝑷𝒔𝒂𝒕
∆𝒗𝒂𝒑 𝑯 = 𝑻𝚫𝑽
𝒅𝑻
68
Standard Enthalpy Changes in a Physical Changes

Ref : Atkins

69
 Thermochemistry: Heat effects of chemical processes
• Chemical reactions are accompanied by the combination of
(i)transfer of heat, and (ii)temperature changes during reaction.
• Two ways of reporting the change in Enthalpy that accompanies a
Chemical reaction aA + bB → cC + dD 𝚫𝑯𝟎 / 𝚫𝑟 𝑯𝟎
• Change in standard enthalpy 𝚫𝑯𝟎: Change in enthalpy for the
process given by

Pure, separate Pure, separate

reactants [A, B] in Reaction products [C, D] in
their standard aA + bB → cC + dD their standard
states states

Standard Reaction Enthalpy 𝚫𝑟 𝑯𝟎

70
 Standard Reaction Enthalpy
Pure, separate Pure, separate
reactants [A, B] in Reaction products [C, D] in
their standard aA + bB → cC + dD their standard
states states

𝚫𝑟 𝑯𝟎 = 𝑐𝑯0𝑚 𝐶 +d𝑯0𝑚 𝐷 - a𝑯0𝑚 𝐴 − 𝒃𝑯0𝑚 𝐵

𝑯0𝑚 𝑖 𝑖𝑠 𝑡ℎ𝑒 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑚𝑜𝑙𝑎𝑟 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑎𝑡 𝑡ℎ𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑜𝑓 𝑖𝑛𝑡𝑒𝑟𝑒𝑠𝑡

𝚫𝑟 𝑯𝟎 = ෍ 𝜈𝑯0𝑚 − ෍ 𝜈𝑯0𝑚
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

71
𝚫𝑟 𝑯𝟎 From standard enthalpies of the intermediate reactions
Since enthalpy is a state function, the heat of reaction depends only
on the final and initial states, not on the path that the reaction takes

R→B 𝚫𝑟 𝑯𝟎
B→C R P
C→P 𝚫1 𝑯𝟎
𝚫3 𝑯𝟎
R→P
Hess’s law: If an overall reaction takes place in several steps, its 𝚫2 𝑯𝟎
standard reaction enthalpy is the sum of the standard B C
enthalpies of the intermediate reactions, at the same
temperature.
CO2(g) → C(s) + O2(g) 393.5 kJ
C(s) + 1 /2 O2 (g) → CO(g) −110.5 kJ
H2 (g) + 1/2 O2 (g) → H2O(l) −285.8 kJ
H2O(l) → H2O(g) 44.0 kJ

CO2(g) + H2(g) → CO(g) + H2O(g) 41.2 kJ 72

 STANDARD HEAT OF FORMATION
A formation reaction is defined as a reaction that forms a single
compound from its constituent elements.
C + 1/2 O2 + 2H2 → CH3OH

Standard enthalpy of formation 𝚫𝑓 𝑯0 : The standard reaction

enthalpy for the formation of the compound of interest from their
elements in their reference state
Reference state of element: element in its most stable state at the
specified temperature and 1 bar.
In general temperature is 298.15K

73
𝚫𝑟 𝑯𝟎 From STANDARD HEAT OF FORMATION

P
𝟎
𝚫𝑟 𝑯 = ෍ 0
𝜈𝚫𝑓 𝑯 − ෍ 0
𝜈𝚫𝑓 𝑯 𝚫𝑟 𝑯𝟎
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
R
𝚫𝑓 𝑯𝟎(𝑹) 𝚫𝑓 𝑯𝟎(𝑷)

Elements
CH4(g)+2O2(g)=CO2(g)+2H2O(l)

From data tabulated in Appendix Table C4 of SVA at 298.15K 𝚫𝑓 𝑯𝟎

-74.5 0 -393.5 -285.8 kJ /mole

𝚫𝑟 𝑯𝟎 298.15= -890.6 kJ/mole of methane

74
Calculating a standard heat of reaction at temperature T from the value
at reference temperature T0.

T 𝚫𝑟 𝑯𝟎T
Products
𝚫𝑟 𝑯𝟎 T

H 𝚫𝑟 𝑯𝟎 T0
Reactants

T0 T
𝚫𝑟 𝑯𝟎T0

𝑻
Kirchhoff’s law 𝚫𝑟 𝑪0𝑝 = ෍ 𝝂𝑪0𝑝𝑚 − ෍ 𝝂𝑪0𝑝𝑚
𝚫𝑟 𝑯0298 = 𝚫𝑟 𝑯0𝑇 + න 𝚫𝑟 𝑪0𝑝 𝒅𝑻
𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
298

75
Calculating a standard heat of reaction at temperature T from the value
at reference temperature T0.

T 𝚫𝑟 𝑯𝟎T
Products
𝚫𝑟 𝑯𝟎 T

H 𝚫𝑟 𝑯𝟎T0
Reactants

T0 T
𝚫𝑟 𝑯𝟎T0

𝑻
Kirchhoff’s law 0 𝚫𝑟 𝑪0𝑝 = ෍ 𝝂𝑪0𝑝𝑚 − ෍ 𝝂𝑪0𝑝𝑚
𝚫𝑟 𝑯 (𝑻) = 𝚫𝑟 𝑯0298 + න 𝚫𝑟 𝑪0𝑝 𝒅𝑻
𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔 𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
298

There is no phase transition in this temperature range. You need to take appropriate correction
in case of phase transition
76
Sign of H

• Negative value means Exothermic reaction:

𝚫𝑟 𝑯𝟎 = −𝒙
• Positive means endothermic : Heat is supplied to system

𝚫𝑟 𝑯𝟎 = +𝒙

77
78
 Enthalpy of solution, or heat of solution (or enthalpy of
dissolution or enthalpy of solvation) 𝟎
𝚫𝑠𝑜𝑙 𝑯
•The enthalpy change associated with the nH2O+ NaCl Na+(aq)+Cl
dissolution of a substance in a solvent at constant -(aq)
𝚫 𝑯𝟎 𝚫1 𝑯𝟎
pressure, resulting in infinite dilution. 2
𝚫3 𝑯𝟎
• breaking of bonds between solute molecules(+ve)
• breaking of intermolecular attractions between Broken
solvent molecules (+ve) hydrogen Na+ Cl-
•formation of new solute-solvent attractive bonds (-ve). bond in
water
•Energy change during ions in gas phase hydrated
with solvent 𝚫 𝑯𝟎
ℎ𝑦𝑑

Na+(aq)+Cl
NaCl Na+ Cl- -(aq)
79
Q3. From the following given data, find out the heat reaction between 1M NaOH and 1M HCl solution (along with
explanation)
H2O(l)➔H+(aq)+OH-(aq) ∆𝒓𝑯𝟎 298.15 𝐾 =55.8KJ/mol
Next, find out the change in temperature, when 50ml 1M NaOH solution is mixed with 50 ml 1M HCl solution at
298.15 𝐾 in an isolated chamber. (Densities of all solutions are equal to 1gm/ml, Cp of mixture is 4182 J.K-1 kg-1)
Minor exam 2020:

80
Q3. From the following given data, find out the heat reaction between 1M NaOH and 1M HCl solution (along with
explanation)
H2O(l)➔H+(aq)+OH-(aq) ∆𝒓𝑯𝟎 298.15 𝐾 =55.8KJ/mol
Next, find out the change in temperature, when 50ml 1M NaOH solution is mixed with 50 ml 1M HCl solution at
298.15 𝐾 in an isolated chamber. (Densities of all solutions are equal to 1gm/ml, Cp of mixture is 4182 J.K-1 kg-1)
Minor exam 2020:
The reaction can be written as:
Na+ (aq) + OH- (aq) + H+ (aq) + Cl- (aq) H2O + Na+ (aq) + Cl- (aq)
Given
(1) ∆rH (298) = 55.8 KJ/mol
H2O → H+ (aq) + OH- (aq)
(1) Na+(aq) and Cl- (aq) are both sides of the reaction
We can write ∆rH (298) of NaOH +HCl = -∆rH (298.15) = -55.8 KJ/mol
Negative sign means heat will evolve
m cp ∆T = 55.8 × 103 J/mole × 1/20
0.1 × 4182 × ∆T = (55.8 × 103 ) /20
∆T = 6.67 0 C or K 81
 Constant Pressure Calorimeter
Constant pressure
Adiabatic
Product (T2) +
Calorimeter (T1)+Reactant (T1) Calorimeter (T2)

III. Isothermal
reaction at constant II. Cooling/Heating
pressure 𝚫 𝑯?
𝑟
Product (T1) + Calorimeter (T1)
Reaction
Chambe
r

Step-I: Adiabatic, q=0=H

𝑻𝟏
Step-II: 𝒒𝒑 = 𝚫𝑯𝑰𝑰 = න 𝚫𝑪𝑝 𝑠𝑦𝑠𝑡𝑒𝑚 𝒅𝑻
As enthalpy is thermodynamic property 𝑇𝟐
Step-III:
𝑻𝟐 𝚫𝑟 𝑯
𝚫𝑟 𝑯 = න 𝚫𝑪𝑝 𝑠𝑦𝑠𝑡𝑒𝑚 𝒅𝑻
𝑇𝟏 82
Constant volume Calorimeter
Constant Volume
Adiabatic
I Product (T2) +
Calorimeter (T1)+Reactant (T1) Calorimeter (T2)

III. Isothermal
reaction at constant II. Cooling/Heating
Volume 𝚫 U
𝑟
Product (T1) + Calorimeter (T1)
Reaction
Chambe
r
Step-I: Adiabatic, q=0=U
𝑻𝟐

Step-II: 𝒒𝒗 = 𝚫𝑼𝑰𝑰 = න 𝚫𝑪𝑣 𝑠𝑦𝑠𝑡𝑒𝑚 𝒅𝑻

𝑇1
𝑻𝟐
Step-III: 𝚫𝑟 𝑼 = −𝒒𝒗𝑰𝑰 = − න 𝚫𝑪𝑣 𝑠𝑦𝑠𝑡𝑒𝑚 𝒅𝑻 𝚫𝑟 𝑯= 𝚫𝑟 𝑼+ 𝚫 𝑷𝑽 = 𝚫𝑟 𝑼+ 𝚫 𝒏𝑹𝑻
𝑇1 =𝚫𝑟 𝑼+ 𝚫𝒏 RT
83
Find out following for Ideal Gas, Reversible process
𝑑𝑞𝑟𝑒𝑣 dU =Q+W
∆𝑈, ∆𝐻, ∆𝑞, ∆𝑊𝑎𝑛𝑑 ‫׬‬ 𝑇
at each step

A: T1,v1
I
IV
P q=0 B:T1,v2
II
D:T2,v4
III C:T2,v3

v
Step II
dU =Q+W➔ dU =W
𝛾−1 𝛾−1
∆𝑈 = 𝑊 = 𝐶𝑉 (𝑇2 − 𝑇1 ) 𝑇1 𝑣2 = 𝑇2 𝑣3
∆𝐻 = 𝐶𝑝 (𝑇2 − 𝑇1) 𝑇1 𝑣
𝒅𝒒𝒓𝒆𝒗 𝑇2
= (𝑣3)𝛾−1
∆𝑆 = න =𝟎 2
𝑻 84
Find out following for Ideal Gas, Reversible process
𝑑𝑞𝑟𝑒𝑣
∆𝑈, ∆𝐻, ∆𝑞, ∆𝑊𝑎𝑛𝑑 ∆𝑆 = ‫׬‬ 𝑇
at each step
dU =Q+W➔ dU =W
Step-III: dU =0=Q+W➔
A: T1,v1
I dU =Q+W=0 ➔  Q=−W
IV
P q=0 B:T1,v2 𝑉4
QIII= −𝑊 =− − ‫𝑉׬‬3 PdVt = 𝑛𝑅𝑇2𝑙𝑛
𝑉4
𝑉3
II
D:T2,v4 𝑉
III C:T2,v3 SIII= 𝑛𝑅𝑙𝑛 𝑉4
3

Step-IV:
v ∆𝑈 = 𝑊 = 𝐶𝑉 𝑇1 − 𝑇2 ∆S𝑖𝑣 =0 as dq=0
𝛾−1 𝛾−1
𝑇2 𝑣4 = 𝑇1 𝑣1
𝑇1 𝑣4 𝛾−1
𝑇
= (𝑣
) 𝑉4 𝑉1
2 1 =
𝑉3 𝑉2
‫ 𝑰𝑺∆ = 𝒗𝒆𝒓𝑺𝒅 ׯ‬+ ∆𝑺𝑰𝑰𝑰 =0 𝑇1 𝑣 𝑣 𝑣 𝑉1
𝑇2
= (𝑣3)𝛾−1 ; 𝑣4= 𝑣3 SIII =nR ln
𝑉2
2 1 2
Carnot Cycle 85
Entropy: Mathematical significance
dU =Q+W
Qrev=dU −W 𝐶𝑣 𝑑𝑇 = 𝑑 න 𝐶𝑣 𝑑𝑇 + 𝑘
=CvdT+PdV
=CvdT+nRTdV/V 𝑑𝑉 𝑑𝑉
𝑛𝑅𝑇 ≠ 𝑑 න 𝑛𝑅𝑇 +𝑘
𝛿𝑞𝑟𝑒𝑣 𝑑𝑇 𝑑𝑉 𝑉 𝑉
𝑇
= 𝑑 ‫𝑣𝑐 ׬‬ 𝑇
+ 𝑘 + 𝑑 ‫𝑅׬‬ 𝑉
+𝑘 =dS
inexact

Qrev is inexact
dS is exact differential independent of path

86
 A: T1,v1
I
Carnot Cycle P IV
B:T1,v2
S=0
𝑉2 𝑉2 𝑉2
‫ ׯ‬Q𝒓𝒆𝒗 = 𝑛𝑅𝑇1 𝑙𝑛 𝑉 − 𝑛𝑅𝑇2 𝑙𝑛 𝑉 =𝑛𝑅𝑙𝑛 𝑉 (𝑇1 -𝑇2 ) II
1 1 1 D:T2,v4
III C:T2,v3
𝑉2
‫ ׯ‬w𝒓𝒆𝒗 = − 𝑛𝑅𝑙𝑛 𝑉 (𝑇1 -𝑇2 )=net work output, W
1

net work output Q1 −Q2 Q2

v
Efficiency 𝛈 = = =1 - Reversible Heat engine
ℎ𝑒𝑎𝑡 𝑖𝑛𝑝𝑢𝑡 Q1 Q1
𝑉2 𝑉2
= 𝑛𝑅𝑙𝑛 (𝑇1 -𝑇2 )/𝑛𝑅𝑇1 𝑙𝑛
𝑉 𝑉
Q1,T1
1 1
(𝑇1 −𝑇2 ) 𝑇2
= =1−
𝑇1 𝑇1
-W
Q2 𝑇2 Q 2 Q1
= ; =
Q1 𝑇1 𝑇2 𝑇1
-Q2 T2 87
Carnot Cycle

Reversible Heat engine

Can we make Q2=0?; Perpetual Motion Machine of the Second Kind Q1,T1
(PMM2)
Kelvin states that “No process is possible in which the sole result is
the absorption of heat from a reservoir and its complete conversion
into work”; First law does
Can we make Q1, -Q2=negative? -W

-Q2 T2 88
 Reversible Heat Pump
Refrigeration Cycle
Ideal Gas, Reversible process
T1
A: T1,v1
II net heat gain
𝐂𝐎𝐏 =
P III B:T1,v2 𝑊𝑜𝑟𝑘 𝐼𝑛𝑝𝑢𝑡 W
S=0
I
D:T2,v4
IV 𝑇1
C:T2,v3 =
𝑇1 −𝑇2
T2
v
Clausius statement: Heat cannot transfer from a low-temperature body to
the high-temperature body until unless there is an external force on the
system.
89
90
 Effect on S of System and Surroundings during Isothermal Expansion
Reversible and Irreversible process
𝑉
QISystem= 𝑛𝑅𝑇1 𝑙𝑛 𝑉2 = −QISur ∆𝑺𝑰,𝑺𝒚𝒔 + ∆𝑺𝑰𝑺𝒖𝒓 =0
Ideal Gas, Reversible process 1

A: T1,v1 Irreversible (say expansion against zero pressure)

I w=0, hence Q=0 as dU=0
P B:T1,v2 𝛿𝑄𝑠𝑢𝑟 𝛿𝑄𝑠𝑦𝑠
SI,Sur= =- =0;
𝑇1 𝑇1
v 𝑉2
SI,Sys=nR ln As S is a state function
𝑉1
𝑉2
(−Wrev) > (−Wirr ) STot=SSys +SSur= nR ln >0
𝑉1
For the System
dUrev = dUirr=0 • SSys independent on the path
• Change in total entropy depends on the process
Qrev+Wrev= Qirr+Wirr=0
➔ Qrev > Qirr • SSur depends on the path, as depending on path final
state of the surroundings will be different

91
Gas expansion into vacuum chamber

Spontaneous
process

V1, P1 V2,0 V1+V2

𝑉1 +𝑉2
STot=SSys +SSur= nR ln >0
𝑉1

92
Mixing of two gases, 1& 2 at constant temperature and pressure within
an isolated system
Spontaneous
process
V1,P1,T V2,P1,T
n1 n2

𝑉1 +𝑉2
S1= 𝑛1 R ln
𝑉1 +𝑉2
=-𝑛1 R
𝑉1
ln𝑉 +𝑉 S2= 𝑛2 R ln 𝑉2
𝑉1 1 2

𝑉 𝑉
Stotal= S1+S2 = −𝑛1 R ln𝑉 +𝑉
1 2
+ −𝑛2 R ln 𝑉 +𝑉
1 2 1 2

Stotal= −𝑛1 R ln𝑛

𝑛1
+ −𝑛2 R ln 𝑛
𝑛2 For ideal gas, V∞ n at constant T and P
1 +𝑛2 1 +𝑛2

Stotal/𝐧𝐑 = −𝑦1 ln𝑦1 −𝑦2 ln𝑦2 , 𝑛 = 𝑛1 + 𝑛2 , 𝑦𝑖 = 𝑛𝑖 /𝑛

Stotal
>𝟎
𝐧𝐑 93
 Molecular interpretation of Entropy T1< T2
• A molecule can possesses only certain energies
• One particular molecule may be in one low energy state at one instant,
and in an excited state a moment later.
• Molecules in a system have different energy levels (micro sates) if T>0,
• No of molecules having energy Ei is given by Boltzmann Distribution

𝑁𝑒 −𝐸𝑖 /𝑘𝑇
𝑁𝑖 =
σ𝑖 𝑒 −𝐸𝑖/𝑘𝑇

 is the ways in which the molecules of a system can be arranged keeping the total energy constant

S= 𝑘𝑙𝑛Ω
• A perfectly ordered system at a very low temperature has entropy zero.
• The greater the molecular motion of a system, the greater the number of possible
microstates and the higher the entropy.

94
Entropy changes accompanying phase transition

• If two phases are at equilibrium, qp=trsH

𝚫𝑡𝑟𝑠 𝑯
𝚫𝑡𝑟𝑠 𝑺 =
𝑻𝑡𝑟𝑠

95
 Summary of 2nd Law Of Thermodynamics and interpretation
along with 1st Law
It talks about the possibility of the direction of process
𝛿𝑄𝑟𝑒𝑣
S= =0 For reversible process
𝑇
S >0 For spontaneous process
dUv=dQv dU =Qrev+Wrev
dQrev,p=dH => H=U+PV
dU =dS-PdV
𝜕𝑈 𝜕𝑆
𝜕𝑈 =𝑇 −𝑃 𝜕𝐻
𝐶𝑣 = 𝜕𝑉 𝑇
𝜕𝑉 𝑇
𝐶𝑝 =
𝜕𝑇 𝑣 𝜕𝑇 𝑝
=> dU=𝐶𝑣 𝑑𝑇
𝜕𝑆 1 𝜕𝑈
= +𝑃
𝜕𝑆 𝜕𝑉 𝑇 𝜕𝑉
=> 𝐶𝑣 /𝑇 = 𝑇 𝑇
𝜕𝑇 𝑣
96
Variation of S with temperature
𝑇𝑓𝑢𝑠 𝑇𝑣𝑎𝑝 𝑇2
𝐶𝑃 ∆𝑓𝑢𝑠 𝐻 𝐶𝑃 ∆𝑣𝑎𝑝𝐻 𝐶𝑃
𝑆 𝑇 −𝑆 0 =න 𝑑𝑇 + +න 𝑑𝑇 + + න 𝑑𝑇
0 𝑇 𝑇𝑓𝑢𝑠 𝑇𝑓𝑢𝑠 𝑇 𝑇𝑣𝑎𝑝 𝑇𝑣𝑎𝑝 𝑇

S is positive, Ss<Sl<Sg

S S
L
G
S is discontinuous at transition point
𝑇𝑚 𝑇𝑏

97
How to solve a numerical problem
• Draw a sketch of the problem
• Identify system
• Write given data
• Convert them in appropriate unit
• Write the process

98