CHEMISTRY(CY11003)

Professor: Prof. Amita (Pathak) Mahanty

Office: Room # 305 (PCR-JCB Building, Chemistry Dept.)
e-mail: ami@chem.iitkgp.ac.in
phone: 83312 (office)

Ground Rules for the Class

• Mobile Phones in switched off mode
• Attendance is a must and will be checked regularly
• You are advised to take class notes
:Class Schedule (SECTIONS 11 & 12):
Sections Day Time
Monday 12:00 – 12:55 PM Full Semester
S-11 +S-12
Tuesday 10:00 – 11:55 AM Full Semester
Tutorial Wed (S-11): 11:00 – 11:55 AM; Wed (S-12) : 10:00 – 10:55 AM
 TEACHERS OF SECTIONS 11 & 12 CHEMISTRY (CY11003)

ME

Prof. Amita (Pathak) Mahanty

(Physical Chemistry)

Dr. Sanjib Kumar Patra Dr. Suman Kalyan Samanta

(Inorganic Chemistry) (Organic Chemistry)

1st year COORDINATORS - CHEMISTRY : Prof. Amita (Pathak) Mahanty (PC),

Dr. Pradip Kumar Chakrobarty (IC), Dr. Partha Pratim Jana (IC); Dr. Suman
Kalyan Samanta (OC)
 LECTURE SCHEDULE FOR SECTIONS 11 & 12
CHEMISTRY THEORY (CY11003)
Topics From To Total
Physical Chem:
07.08.2023 (Mon) 04.09.2023 (Mon) 11
Prof. APM
Inorganic Chem: 05. 09.2023 (Tues) 16.10.2023 (Mon)
11
Prof. S. K. Patra
Organic Chem: 17.10.2023 (Tues) 14.11.2023 (Tues) 11
Prof.S. K. Samanta

IMPORTANT DATES:
PHY. CHEM. CLASS TEST (Tentative: Taken during class hours)
MID SEMESTER EXAM 18.09.2023 (Mon) to 26.09.2023 (Tues)
AUTUMN BREAK 21.10.2023 (Sat) to 28.10.2023 (Sat)
END SEMESTER EXAM 16.11.2023 (Thurs) to 24.11.2023 (Fri)
 TUTORIAL SCHEDULE FOR CHEMISTRY
(CY11003) AUTUMN 2023-24

Sections 11 and 12
Section Day Time Room No. Roll No.

F-131 Sent through Email

S-11-(A+B) Wed 11.00 – 11.55 AM

F-132 Sent through Email

S-11-(C+D) Wed 11.00 – 11.55 AM

S-12-(A+B) Wed 10.00 – 11.55 AM F-131 Sent through Email

S-12-(C+D) Wed 10.00 – 11.55 AM F-132 Sent through Email

 CHEMISTRY(CY11003)

Distribution of Marks:
Mid Semester Exam (Only Physical): 30%
End Semester Exam (Inorganic & Organic): 50%

Teachers Assessment (TA): 20%

TA Break up: [Physical (6%), Inorganic (7%), Organic (7%)]

TA marks to be based on ATTENDANCE / CLASS TEST

Text Book:
Atkin’s Physical Chemistry 8th Ed
Reference Books:
Physical Chemistry by Silbey, Alberty & Bawendy; Wiley.
Physical Chemistry by I. N. Levine; McGrew.
Physical Chemistry by Gilbert W. Castellan; Narosa
 CHEMISTRY (CY11003) (L-T-P : 3-1-0; Credit : 4)

Thermodynamics of Chemical Processes:

• Review of Essential Concepts and Definitions
• Revision: Heat, Work & Enthalpy; First Law of
Thermodynamics
• The Second Law of Thermodynamics
• Concept of Entropy
• Gibbs Free Energy, Helmoltz Free Energy
• Equilibrium conditions for Closed Systems, Mixing
• Maxwell Relations
• The Chemical Potential
• Concept of Open Systems
• Phase Rule and Reaction Equilibria
 Lecture -1

Thermodynamics of Chemical Processes:

Review of Essential
Concepts and Definitions
 Chemical Thermodynamic

Primary Goal of Chemical Thermodynamics

• Determination of the equilibrium state that eventually results

when the system undergoes a change in state
• Quantitative study of energy transformations associated with
physical or chemical processes
• Thermodynamics provides a framework of relating the
macroscopic properties of a system to one another based on
few fundamental laws

• How and to what extent we can harvest energy from different

sources
 Chemical Thermodynamic

Chemical Thermodynamic: ↔ Classical, Statistical and Irreversible

Classical Thermodynamics is the study of macroscopic properties of
system/matter at equilibrium (which does not change with time) using the
laws governing transformation of energy from one form to another.
It is concerned only with macroscopic quantities and ignores the
microscopic variables that characterize individual molecules.

THE BASIC CONCEPTS:

 System: Part of the Universe, the properties of which is of interest.
Surroundings: the region outside the system where we make our
measurements.
Boundary, a hypothetical/real barrier between system and
surroundings.
System + Surroundings → Universe
 Chemical Thermodynamic
System and its Interaction with the Surroundings

Equilibrium
System Wall
State
Open Diathermal Rigid Permeable Equilibrium
T, V, μ
Closed Diathermal Rigid Impermeable T, V, N

Diathermal Flexible Impermeable T, p, N

Isolated Adiabatic Rigid Impermeable U, V, N
 Thermodynamic Equilibrium
Equilibrium thermodynamics deals with systems in Equilibrium

Isolated system is in Equilibrium when its :

a) Macroscopic properties do not change with time

Non Isolated system is in Equilibrium when its:

a) Macroscopic properties do not change with time
b)Removal of the system from contact with its surroundings can
causes no change in the properties of the system
• A system in thermodynamic equilibrium is an Equilibrium System
• Thermodynamic State only defined by the present values of
the state variables, not by the history.

What are conditions of Thermodynamic Equilibrium?

 Thermodynamic Equilibrium
Thermal Equilibrium Mechanical Equilibrium Material Equilibrium

Porous wall for matter flow

Equal chemical potential

For Thermodynamic Equilibrium, all three

kinds of equilibrium must be present
 Thermodynamic Equilibrium
Thermal Equilibrium between system and the surroundings, is a
condition in which there is no change in the properties of the system or
surroundings when they are separated by a thermally conducting wall or, a
condition in which no change of state occurs when two objects A to B are in
contact through a diathermic boundary

Mechanical Equilibrium
•There is no change in the properties of the system or surroundings
when they are separated by a movable wall / boundary
•A condition of equality of pressure on either side of a movable wall.
•No unbalanced forces act on or within the system – system does not
undergo acceleration or no turbulence inside the system

Material Equilibrium
A condition of equality in concentrations of the chemical species in the
various parts of the system are with time. There is no net transfer of
matter from one part (phase) of the system to another or between the
system and its surroundings
 An Important Macroscopic Parameter: Temperature
Temperature is a property associated with random motion of many
particles. Introduction of the concept of temperature in thermodynamics is
based on the 0’th law of thermodynamics:

B acts as Thermometer.
A, B, C all are at the same “temperature”.

A well-defined quantity called Temperature exists such that two

systems will be in thermal equilibrium if and only if both have the
same temperature.
 How to define a Thermodynamic State of System
What properties does thermodynamics use to characterize a system in equilibrium?

Macroscopic State of a System can be completely defined by a set of

small number of macroscopic properties/parameters/physical
characteristics or attributes of the system - Thermodynamic Variables

Thermodynamic variables which are experimentally measurable

• Composition – mass of each chemical species that is present in
each phases,
• Pressure (P), Volume (V), Temperature (T), Density (ρ) etc.
• Field strength, if magnetic/electrical field act on the system
(N.B.: only the average values are considered, all fluctuation and
perturbations are ignored).

On the other hand, Microscopic State of a System needs description of

each molecule – a very complicated picture
 Thermodynamic Variables
Intensive Properties
 Does not depend upon size (the quantity/amount of matter present) of
the system [e.g. Pressure, Temp, Viscosity, Density etc.]
Total Property = property of part of the system
Extensive Properties
 Depends upon size of the system [e.g. n, V, surface area etc ]
Extensive properties depend on the amount of substance in the system.]
Total Property = Σ property (in each part of the system)
Other variables:
Compositions, Surface area, Electrical/magnetic strength
Gravitational field can/are generally ignored
Homogeneous system, a system having its intensive macroscopic
properties uniform throughout → a single phase solution / pure
substance.
 Heterogeneous system, a system with more than one phase.
 Thermodynamic State Variables / Properties
The change in a STATE VARIABLE depends only on the INITIAL and FINAL
state of the thermodynamic property, and is INDEPENDENT of the PATH
taken during execution of the process

HOW MANY STATE VARIABLES WILL BE REQUIRED TO DESCRIBE A

MACROSCOPIC STATE??

• ONLY 3 of these 4 variables (T, P, V and the amount of species) are needed to be
specified to describe a System. Of these, ONLY 3 variables need to be specified;
while the 4th variables can be calculated from the Equation of State

• A Thermodynamic State of a specified amount of PURE SUBSTANCE (i.e., no

of species = 1) in fluid state can be described by specifying ONLY 2 of these 3
variables (T, P, V) , when the amount of the substance is fixed - (i.e., T and P; P
and V or, T and V). All other thermodynamic variables are fixed and the system is
in Equilibrium.

Therefore, more variable have to be specified to describe the Thermodynamic

State of a homogeneous mixture of different species
 Thermodynamic State
• If the value of every thermodynamic property in system A is same as
in system B – then they are in the same Thermodynamic State

• The state of a thermodynamic system is defined by specifying the values

of its thermodynamic properties – However, it is not necessary to specify
all the properties to define the state of a system.

• In fact, the macroscopic state of a system can be compeletely defined by

a small set of macroscopic variables – these are called the
Thermodynamic Properties / Parameters / Variables of a system.
For instance: The thermodynamic state of a single-phase system of fixed
amounts of non reacting substances can be described by any two of the
three state functions (P, V and T)

Equation of State, an equation that interrelates pressure, volume,

temperature, and amount of substance: P = f (T, V,n).
 The Equation of State of Ideal Gases
• Equation of State - an equation that relates macroscopic variables (e.g.,
P, V, and T) of a given substance in Thermodynamic Equilibrium.
• In equilibrium (≡ No macroscopic motion), just a few macroscopic
parameters are required to describe the state of a system.
• Geometrical representation of the equation of state: f (P,V,T) = 0
The Ideal Gas Equation of State: PV = nRT
P – pressure [Newtons/m2]
V – volume [m3]
n – number of moles of gas
T – the temperature in Kelvins [K]
R – a universal constant = 8.314 J mol-1K-1
 The Equation of State of Ideal Gases

All the possible states of an ideal gas can be represented by a pVT surface

http://hyperphysics.phy-astr.gsu.edu/hbase/Kinetic/idegas.html
 The Gas Laws and Definitions (Recap)
 Boyle’s law: At constant temperature, the pressure of a sample of gas is
inversely proportional to its volume, p ∝ 1/ V at constant temperature.

 Charles’ law: At constant pressure, the volume of a gas is proportional

to the absolute temperature V ∝ T at constant pressure.

 Avogadro’s principle: Equal volumes of gases at the same pressure and

temperature contain the same numbers of molecules

 Partial pressure , of a gas is the pressure the gas would exert if it

occupied the container alone; in general, pi = xi P
 Vapour pressure, the pressure of a vapour in equilibrium with its
condensed phase

 Mole fraction, the amount of i species, expressed as a fraction of moles of

the moles of ith species (ni) to the total amount of moles, n, in the sample,
xi = ni/n
 Appendix
 Perfect / Ideal gas equation, pV = nRT
Perfect/ideal gas, a gas that pV = nRT exactly under
obeys all conditions.
Real gas, an actual gas. e.g.,
Standard ambient temperature and pressure (SATP),
298.15 K (25 °C) and 1 bar (or, 0.986 atm or 100 kPa).
Standard temperature and pressure (STP)
273.15 K (0 °C) and 1 bar (100 kPa, 0.986 atm.)
Normal temperature and pressure (NTP)
273.15 K (0 °C) and 1 atm (101.325 kPa, 760 Torr)
gas constant, R (with R = NAk, where NA is Avogadro’s
constant and k is Boltzmann’s constant).

1 atm =(101.325 kN/m2, 101.325 kPa, 14.7 psi, 29.92 in Hg, 760 torr).
Appendix
 Lecture -2

Thermodynamics of Chemical Processes:

Review of Essential
Concepts and Definitions
Thermodynamic Process: Operation for Change in State
Change of State: Transformation
e.g., 3 H2 (g, 5 bar, 100 °C) → 3 H2 (g, 1 bar, 50 °C)
(initial state) (final state)
Path: Sequence of Intermediate states, arranged in order, through which a
system passes to attain the final state

Process: Operation through which a system undergoes a change in state.

Process describes the path.
Path
Path can be:
 Reversible (always in Equilibrium)
 Irreversible (describes direction of time)
 Cyclic(initial and final state have the same value)
Processes can be:
• Adiabatic (No heat transfer between system and surrounding)
• Isobaric (Constant pressure process)
• Isothermal (Constant temp process)
• Constant Volume process • Endothermic & Exothermic process (q<0 & q>0)
 Thermodynamic Process: Operation for Change in State
Processes : When one or more of the parameters of a system changes,
the state of the system also changes and the system is said to have
undergone a process.

Each process can be either carried out either

REVERSIBLY or IRREVERSIBLY
 Thermodynamic Processes in a Closed System
From an initial equilibrium state to a final equilibrium state

Various types of Processes:

• Isothermal (constant T),

• Isobaric (constant p),

• Isochoric (constant V)

• Adiabatic (no heat transfer)

• Isenthalpic (constant enthalpy, H)

• Exothermic & Endothermic

• Cyclic
Each of these process can be
either carried out Reversibly
or Irreversibly
Thermodynamic Processes can be :
Reversible process: Ideal process
• Change must occur in successive stages of infinitesimal quantities
• Infinite duration
• Virtual thermodynamic equilibrium, at each of the small stages.
• Changes of the thermodynamic quantities in the different stages will be
the same as in the forward direction but opposite in sign w.r.t. forward
direction. The system and surroundings can be put back in their original
states by exactly reversing the process.
Irreversible Process: Real / Spontaneous
• Occurs suddenly or spontaneously without the restriction of occurring in
successive stages of infinitetesimal quantities. Irreversible processes
cannot be undone by exactly reversing the change to the system.
• Do not remain in the virtual equilibrium during the transition.
• The work (w) in the forward and backward processes would be unequal.
Cyclic process: • Is one in which the initial and final states are the same.
In such process:
• There is no change in the STATE VARIABLES (e.g., ∫dU = Uf-Ui = 0)
• In contrast, path functions generally have non-zero values for cyclic
processes, dependent on the path (e.g., ∫δw ≠ (wf – wi) ≠ 0]. PATH
VARIABLE
 Thermodynamic Processes: Irreversible Process
Spontaneous Process (Irreversible Process)
• Spontaneous processes are those that can proceed
without any outside intervention.
• The gas in vessel B will spontaneously effuse into
vessel A, but once the gas is in both vessels, it can
not spontaneously go back to B

• Irreversible processes cannot be undone by exactly reversing the change to

the system.
• All Spontaneous processes are irreversible
• All Real processes are irreversible.
 Thermodynamic Processes: Irreversible Process
Consider a gas restrained at high
pressure by a piston that is secured
h by a pin.
When the pin is removed, the piston
is raised and forced abruptly against
the stops

• Work, (wexp), is done by the system, since the piston has been raised by h.
• To restore the system to its initial state, force has to be exerted on the piston to
compress the gas
• Since the pressure on the face of the piston is greater on the restoring
compression process than on the initial expansion process. Therefore the work
done on the gas in this restoring compression process is greater, (wcomp), than
the work done by the gas in the initial expansion process (wexp).
• Again, to restore the gas to its original internal energy, some amount of heat
must be transferred from the gas during the restoring compression process.
 Thermodynamic Processes: Irreversible Process

• Thus, the system can be restored to its initial state, but the surroundings
have changed by virtue of the fact that work was required to force the
piston down and heat was transferred to the surroundings.

• The initial process therefore is an IRREVERSIBLE one because it could

NOT BE REVERSED TO ITS ORIGINAL STATE WITHOUT LEAVING
A CHANGE IN THE SURROUNDINGS.
Thermodynamic Processes: Reversible Process

– In a reversible process the system changes in such a

way that the system and surroundings can be put
back in their original states by exactly reversing the
process.

– Changes are infinitesimally small in a reversible

process.

– Quasi thermodynamic equilibrium, at each of the

small stages
Reversible and Irreversible Processes
 Lecture - 3

Thermodynamics of Chemical Processes:

Partial Differentiation: A Primer
 STATE AND PATH FUNCTIONS

 Some state functions, e.g., U and H etc.

– Value of a state function is independent of path
– Depends only on initial and final state, e.g. ΔU = Ufinal – Uinitial
final

∆U = ∫dU ⇒ dU is
–Overall Change: an exact differential
initial

– For ΔU, work may be done, or, heat may flow or, both

 Path from initial to final state has a functional dependence

– Equations that describe how you get to final state are path functions

–Path functions are path specific

∂q = ∫ ∂q ⇒ ∂q
final
is an inexact differential
initial
 State and Path Functions

Path 2 - Non- adiabatic

w≠0;q≠0
Path 1 - Adiabaticw≠0;q=0

ΔUpath1 = ΔUpath2 = Uf -Ui

 Is Work a STATE FUNCTION?
Assume a Reversible process so that pext = p where, Ar (gas) under goes
change of state through compression, from
Ar (g, p1, V1) (initial) → Ar (g, P2, V2) (final); such that V1> V2 and p1< p2

Compression through two paths

1st Path:
Ar(g, p1, V1) → Ar(g, p1, V2) → Ar(g, p2,V2)
First V1 → V2 when p held constant at p1;
then p1 → p2 when V held constant at V2

2nd Path:
Ar(g, p1, V1) → Ar(g, p2, V1) → Ar(g, p2, V2)
First p1 → p2 when V held constant at V1;
then V1 → V2 when p held constant at p2

Note for the closed cycle, total work = w[path (1)] - [path (2)]
 Is Work a STATE FUNCTION?

NOTE:
• Work done on the system to compress it is NOT EQUAL through
the two paths. i.e., w(1) ≠ w (2)
• ∴ Net work done on the system in the complete cycle ≠ 0
i.e., [w(1) - w(2)] ≠ 0; ∫ ∂w ≠ 0 (closed cycle)
• This means w is NOT a state function ∴ we CAN NOT write
w = f(V, p)
 Energy, Work and Heat
Energy is the capacity to do work.

Energy classification into:  kinetic potential

(by motion) (by position)
Is purely arbitrary! e.g.thermal chemical, electrical

• Heat and work are NOT “types” of ENERGY, but are processes involving
TRANSFER of energy.

• They appear and disappear at the system boundary. They are path variables.
• Heat is the transfer of energy from one body to another based on temperature
difference. They are path variables.
• Heat stimulates random motion.
• Convention: if heat flows into the system, q > 0.

• Work is the transfer of energy by some mechanism other than temperature

difference.
• They appear and disappear at the system boundary. They are path variables.
• Convention: if work is done on the system, w > 0.
• Work stimulates organized motion.
• Work “degrades” into heat.

 Qualitative observations by Count Rumford (Ben Thompson)

 Quantitative measurements by James Joule
 WORK
•Work: Expansion work, work of expansion (or compression)
Non-Expansive / additional work: any other work
w=F×l
applied force distance
• pex = external pressure
𝑭𝑭 = 𝒑𝒑𝒆𝒆𝒆𝒆𝒆𝒆 𝑨𝑨 • A = piston area
• dz = displacement
• dV = Adz = volume
change for the gas
𝒘𝒘 = − 𝒑𝒑𝒆𝒆𝒆𝒆𝒆𝒆 𝑨𝑨 × 𝒅𝒅𝒅𝒅 = −𝒑𝒑𝒆𝒆𝒆𝒆𝒆𝒆 𝒅𝒅𝒅𝒅

Work is required to move an object a distance dz against

an opposing force F

Total work done,  Reversible process

• Work done on the system  0<w i.e., Compression

• Work done by the system  w<0 i.e., Expansion
 WORK
• Expansive work, work of expansion (or compression)
F = mg
pex= F/ A = mg/A
piston held down by pins

F= pex.A m

mg dz

Area = A

pi , Vi pf , Vf

w = − F × dz = mg × dz
w = − pex × A × dz
w = − pex × dV = - pex (Vf - Vi )

• Work done on the system  0<w i.e., Compression

• Work done by the system  w<0 i.e., Expansion
 V2 > V1

0 ≤ Pext ≤ P2

V2 < V1

0 ≤ Pext ≤ P2
Thus, MORE WORK has been PRODUCED in MULTI stage EXPANSION than in the
single stage expansion

V2 < V1

Thus, LESS WORK is DESTROYED in MULTI stage COMPRESSION than in the single
stage compression
 vf

Therefore, the Maximum and Minimum quantity of Work = w = - ∫ pexdV

in a REVERSIBLE PROCESS vi
 CONDITION FOR MAXIMUM WORK
• For WORK to be MAXIMUM,
pext should possess the LARGEST possible value at each stage of
the expansion process.
• This means, if the gas is to EXPAND, then pext must be LESS
than pressure of the gas inside the cylinder, which let us say is p
• Therefore, the condition for obtaining the maximum work
should be, pext = p – dp
vf vf vf

wmax = - ∫ pext dV = - ∫ (p - dp) dV = - ∫ (pdV - dpdV)

vi vi vi

Neglecting infinitesimals of order higher than 1, we will get:

V2

wmax = − ∫ pdV
Vi
(p1, V1) (p4, V4)

(p2, V2) (p3, V3)

 REVERSIBLE AND IRREVERSIBLE WORK

Irreversible Reversible
Expansion Expansion

Irreversible Reversible
Compression
Compression

For a Reversible Process:

• Work of Expansion = Work on Compression (for the same path)
For an Irreversible Process:
• Work of Expansion (is less than) ≠ Work on Compression (for the same path)
 REVERSIBLE AND IRREVERSIBLE WORK

• Work done on expansion by the system on surroundings (sign negative)

operating between specified initial and final states and passing through and
specified path is maximum work available from a system when the changes
take place reversibly

• Work is a path dependent parameter, path function (so as Heat)

 Solved Example

|wrev (compression)| = |wrev(expansion)|

 WORK: Irreversible
Initial volume and final volume SAME

Initial condition Case I Case II Case III

Work done in each case? All are Irreversible form of Work
Case I : Stops removed – system allowed to reach equilibrium.
pex = p f ; w = − p f ∆V
Case II : System expansion restricted as
pex < pi ; w = − pex∆V
Case III: Expansion against vacuum pex = 0; w = 0
 WORK: P-V diagrams

P- V diagrams:
Conecting an initial state and a final state by three paths

Isothermal
V2
Constant pressure Won gas = − ∫ PdV = P(V1 − V2 )
V1

V
Won gas = − ∫ PdV = 0
2
Constant Volume
V1

n RT V
Won gas = − ∫
V2
Constant Temperature dV = −n RT ln 2
V1 V V1
 WORK EXPRESSIONS

Reversible Isothermal Expansion: wmax = −∫ (pex − dp)dV = −∫ (pdV −dpdV)

wmax = −∫ pdV = wrev
𝑽𝑽𝒇𝒇

𝒅𝒅𝒅𝒅 𝑽𝑽𝒇𝒇
when, p = p(V) and p = nRT/V for ideal gas 𝒘𝒘𝒓𝒓𝒓𝒓𝒓𝒓 = −𝒏𝒏𝒏𝒏𝒏𝒏 � = −𝒏𝒏𝒏𝒏𝒏𝒏
𝑽𝑽 𝑽𝑽𝒊𝒊
𝑽𝑽𝒊𝒊

𝒑𝒑𝒇𝒇
𝒘𝒘𝒓𝒓𝒓𝒓𝒓𝒓 = 𝒏𝒏𝒏𝒏𝒏𝒏
𝒑𝒑𝒊𝒊

• At higher T, work done is more for

same expansion of volume.
• Maximum work is obtained when
expansion is reversible
Irreversible Isothermal Expansion:
Vf

wirrev = −pex ∫ dV ≡ −pex (Vf −Vi ) = −pex ΔV

Vi
 WORK: SUMMARY
Reversible Isothermal Expansion wmax = −∫ (pex − dp)dV = −∫ (pdV −dpdV)
: wmax = −∫ pdV = wrev
when, p = p(V) and p = nRT/V for ideal gas

Irreversible Isothermal Expansion:

Vf

wirrev = −pex ∫ dV ≡ −pex (Vf −Vi ) = −pex ΔV

Vi

Free Expansion:
pext = 0 → w = 0

Expansion against constant final pressure:

w = − p f (V f −V i )

Expansion, i.e., Vf > Vi , w < 0 (Work Done by the System on Surrounding)

Compression, i.e., Vf < Vi , w > 0 (Work Done on the System by Surrounding)
SUMMARY OF WORK EXPRESSIONS
 Work is Path Dependent: Assignment
Ideal gas, closed system, reversible process
Calculate wf and wb

wrev depends on the path used to go from 1 to 2, and wrev can

have any positive or negative value for a given change of state
 WORK: Assignment
25 L of gas is enclosed in a cylinder/piston apparatus at 2 atm of pressure and 300 K.
A 100 kg of mass is placed on the piston causing the gas to compress to 20 L at
constant pressure. This is done by allowing heat to flow out of the gas.
• What is the work done on the gas?
• What is the change in internal energy of the gas?
• How much heat flowed out of the gas?

• Po = 202,600Pa, Vo= 0.025 m3,

• To = 300 K, Pf = 202,600Pa,
• Vf=0.020 m3, Tf= ?

• n = PV/RT W = -PΔV Δ U = 3/2 nR ΔT

W = - PΔV = -202,600 Pa (0.020 – 0.025)m3

= 1013 J energy added to the gas
Δ U =3/2 nR ΔT=1.5(2.03)(8.31)(-60)= -1518 J

Q = -505 J
 WORK: Assignment
A gas confined in a cylinder with a movable piston
Work done on the system, Won , is the energy transferred as work to the system. When
this energy is added to the system its value will be positive.

The work done on the gas in an expansion is

V
Won gas = − ∫ PdV
2

V1

Won gas = −Wby gas

P- V diagrams Constant pressure

V2
Won gas = − ∫ PdV = P(V1 − V2 )
V1

If 5 L of an ideal gas at a pressure of 2 atm is

cooled so that it contracts at constant pressure
until its volume is 3 L what is the work done on
the gas? [405.2 J]
 WORK: Assignment

A diatomic ideal gas undergoes a cycle starting at point A (2 atm, 1L). Process
from A to B is an expansion at constant pressure until the volume is 2.5 L,
after which, it is cooled at constant volume until its pressure is 1 atm. It is
then compressed at constant pressure until the volume is again 1L, after which
it is heated at constant volume until it is back to its original state. Find (a) the
work, heat and change of internal energy in each process (b) the total work
done on the gas and the total heat added to it during the cycle.
 WORK: Assignment

A system consisting of 0.32 mol of a monoatomic ideal gas occupies a volume of

2.2 L, at a pressure of 2.4 atm. The system is carried through a cycle consisting:

1. The gas is heated at constant pressure until its volume is 4.4L.

2. The gas is cooled at constant volume until the pressure decreases to 1.2 atm
3. The gas undergoes an isothermal compression back to its initial point.

(a) What is the temperature at points A, B and C

(b) Find W, Q and ΔU for each process and for the entire cycle
The Laws of Thermodynamics
First Law of Thermodynamics
First Law of Thermodynamics
First Law of Thermodynamics
 The First Law of Thermodynamics: Work, Heat & Energy

T1 → T2

T1 → T2 h

Joule Heat Equivalent Experiment

 1st Law of Thermodynamics

Consider an example system of a piston and F

cylinder with an enclosed dilute gas characterized
by p, V, T & n.

What happens to the gas if the piston is moved

inwards? Compression

• If the container is insulated the temperature will

rise, the atoms move faster and the pressure rises.

• Is there more internal energy in the gas? Yes

F
External agent did work in pushing the piston
inward. ∆x
A
𝒘𝒘 = − 𝑭𝑭 × 𝒅𝒅 = − 𝒑𝒑𝑨𝑨 × −𝜟𝜟𝜟𝜟
𝒘𝒘 = 𝒑𝒑𝜟𝜟𝜟𝜟
• Work done on the gas equals the change in the
internal energy of the gas:
𝒘𝒘 = 𝜟𝜟𝜟𝜟
 1st Law of Thermodynamics

• Change the situation:

• Keep the piston fixed at its original location
• Place the cylinder on a hot plate.

What happens to gas?

• Heat flows into the gas.
• Atoms move faster, internal energy increases.
• 𝑸𝑸 = heat (in Joules) flows in
𝜟𝜟𝜟𝜟 = change in internal energy in Joules. Q
𝑸𝑸 = 𝜟𝜟𝜟𝜟
 1st Law of Thermodynamics

What if we added heat and pushed the F

piston in at the same time?

• Work is done on the gas,

• Heat is added to the gas and
• Internal Energy of the gas increases:
𝜟𝜟𝜟𝜟 = 𝒘𝒘 + 𝑸𝑸
Q

 ΔU INCREASES with INCREASE in TEMP of the system, when:

1. work is done on the system by the surrounding or,
2. heat flows into the system from the surrounding or,
3. both, heat and work flows from the surr. into the system
 1st Law of Thermodynamics: Sign convention

• Work done on the system bysurr + ve i.e., Compression

• Work done by the system on surr - ve i.e., Expansion

Alternate Statement: If a system is subjected to a CYCLIC

transformation the work produced in the surroundings is EQUAL to
the heat withdrawn from the surroundings.
Q = - w (change in U is zero as it’s a State function)

If w is +ve (compression, work done on the system) then q will be –ve (heat will be
released by the system) andvice versa
 Heat Transactions and Heat Capacity:
In general change in the internal energy
of a closed system is given by dU = dq + dwexp +dwadd

• For dV = 0; dwexp = 0 , and if dwadd = 0, then

dU = dq (constant volume, no additional work) = dqV
For a measurable change ∆U = qV
Measurement of ΔU
- Heat Capacity, C, the ratio of the heat supplied to
the temperature rise it causes. C = dq/dT; C = q / ∆T
- Heat Capacity at Constant Volume,
𝒅𝒅𝒒𝒒𝑽𝑽 𝒅𝒅𝒅𝒅
𝑪𝑪𝑽𝑽 = =
𝒅𝒅𝒅𝒅 𝒅𝒅𝒅𝒅 𝑽𝑽

-Molar Heat Capacity, the heat capacity divided by

the amount of substance, Cm = C /n (unit: JK-1 mol-1)
- Specific Heat Capacity, the heat capacity divided by
the mass, Cs = C /m (unit: JK-1 gm-1)
Adiabatic bomb calorimeter
Heat Capacity at Constant Volume and Internal Energy
 Heat Capacity for Constant Volume Processes (Cv)

• Heat is added to a substance of mass m in a fixed volume enclosure, which causes a

change in internal energy, U. Thus, 𝑸𝑸 = 𝑼𝑼 − 𝑼𝑼 = 𝜟𝜟𝜟𝜟 = 𝒎𝒎𝑪𝑪 𝜟𝜟𝜟𝜟
𝟐𝟐 𝟏𝟏 𝑽𝑽

Heat Capacity for Constant Pressure Processes (Cp)

• Cp > CV

• Heat is added to a substance of mass m held at a fixed pressure, which

causes a change in internal energy, U, and some PV work.
 Heat Capacity at Constant Pressure and Enthalpy:
In general change in the internal energy dU = dq + dwexp + dwadd
of a closed system is given by:
For dV ≠ 0 ; dwexp ≠ 0 ; Even if dwadd = 0, dU ≠ dq
By Definition: 𝑯𝑯 = 𝑼𝑼 + 𝒑𝒑𝒑𝒑
∴ 𝒅𝒅𝒅𝒅 = 𝒅𝒅𝒅𝒅 + 𝒑𝒑𝒑𝒑𝒑𝒑 + 𝑽𝑽𝑽𝑽𝑽𝑽 = 𝒅𝒅𝒅𝒅– 𝒘𝒘 (𝒂𝒂𝒂𝒂 𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄 𝒑𝒑) = 𝒅𝒅𝒒𝒒𝒑𝒑
At constant pressure with no additional work: 𝝏𝝏𝝏𝝏 = 𝝏𝝏𝒒𝒒𝒑𝒑
► Heat Capacity at constant pressure:

► Enthalpy change and Temperature change: 𝒅𝒅𝒅𝒅 = 𝒏𝒏𝑪𝑪𝒑𝒑,𝒎𝒎 𝒅𝒅𝒅𝒅; 𝜟𝜟𝜟𝜟 = 𝒏𝒏𝑪𝑪𝒑𝒑,𝒎𝒎 𝜟𝜟𝜟𝜟
(if Cp is independent of T)

Heat Capacity at Constant Pressure:

Empirical expression:

Measurement of ΔH done by:

• Isobaric Calorimeter ; •Differential Scanning Calorimeter; •Adiabatic Flame Calorimeter
 Heat Transactions and Heat Capacity:
• The internal energy of a substance
increases when its temperature is raised.
The increase depends on the conditions
under which the heating takes place and for
the present suppose that the sample is a gas
in a container of fixed volume.
• The slope of the tangent to the curve at any
temperature is called the Heat Capacity at
Constant Volume at that temperature.
• Note that the heat capacity is greater at B
than at A
• The slope of the tangent to a curve of the
enthalpy of a system subjected to a constant
pressure plotted against temperature is the
Heat Capacity at Constant Pressure .
• The slope may change with temperature, in
which case the heat capacity varies with
temperature. Thus, the heat capacities at Aand
B are different.
• For gases, at a given temperature the slope of
enthalpy versus temperature is steeper than
that of internal energy versus temperature,
and Cp,m is larger than CV,m
 Heat Transactions
• Variation of heat capacity at constant 𝒄𝒄
pressure over a wide range of temperature 𝑪𝑪𝒑𝒑,𝒎𝒎 = 𝒂𝒂 + 𝒃𝒃𝒃𝒃 + 𝟐𝟐
𝑻𝑻
is given as (Empirical expression)

• Perfectly general expression of

ΔH that is valid for any
transformation at constant p
PROVIDED NO PHASE
CHANGE or NO CHEMICAL
REACTION occurs

• In case of a Transformation
𝑸𝑸𝑽𝑽𝑽𝑽𝑽𝑽 = 𝑸𝑸𝒑𝒑 = 𝜟𝜟𝑯𝑯𝑽𝑽𝑽𝑽𝑽𝑽
where PHASE CHANGE occurs:
Example: Vaporization of liquid 𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺, 𝑸𝑸𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇𝒇 = 𝑸𝑸𝒑𝒑 = 𝜟𝜟𝑯𝑯𝒇𝒇𝒇𝒇𝒇𝒇
at constant T and p
Example: Calculate ΔH for heating 1 gm of ice at 0 °C to vapor at 100 °C under
1 atm pressure.
 Heat Transactions

• Therefore, for a constant pressure process, the

HEAT withdrawn from the surrounding (> 0) is
equal to the INCREASE in ENTHALPY of the
System

− Thus, the relation between ∆U and 𝑯𝑯 = 𝑼𝑼 + 𝒑𝒑𝒑𝒑 = 𝑼𝑼 + 𝒏𝒏𝒏𝒏𝒏𝒏

∆H for an Ideal/perfect gas 𝜟𝜟𝜟𝜟 = 𝜟𝜟𝜟𝜟 + 𝜟𝜟𝒏𝒏𝒈𝒈 𝑹𝑹𝑹𝑹

∆H is the ENTHALPY change occurring during reaction of gas molecules

under constant T and p
 Joule’s Experiment
Joule’s Experimental Set Up Flask A: Gas at high pressure of 22 atm
Flask B: Vacuum
Both flasks connected by a valve and placed
in a water bath for which the temperature is
monitored The whole setup is kept in an
A B B
insulated container
(22 atm) vacuum
OBSERVATIONS:
• No Temp difference of the water before
and after opening the stopcock; ∆T = 0
• free expansion into vacuum, ∂w = 0
• Insulate container: ∂q = 0

Thus, dUT = 0 within the accuracy of the expt. Thus, under the conditions mentioned
U is INDEPENDENT of V and U = U(T) Joule’sLaw
Joule’s Experiment
Appendix

U = f (V ,T )
 Adiabatic Processes
No heat flows into or out of the system

P-V
Diagrams
Adiabatic Expansion
Reversible Adiabatic Expansionof Ideal Gas
Reversible Adiabatic Expansion and Compression

TV γ −1 = constant
PV γ = constant
VT c = constant
T γ P1−γ = constant
CV
where, c =
R
 Reversible Adiabatic Process for Ideal Gas
Rev.Adiabatic
1 mole gas (V1, T1) 1 mole gas (V2, T2)
Adiabatic Process:
From 1st law:
From Ideal gas:

Work (Reversible) =

From 1st Law:

⇒ where,

⇒ Define:
use:

⇒ ⇒ ⇒ ⇒
 Reversible Adiabatic Process for Ideal Gas
Adiabatic Conditions for an Ideal Gas

TV γ −1 = constant
PV γ = constant
CV
VT c = constant where, c =
R
T γ P1−γ = constant
Adiabatic Irreversible Expansion of an ideal gas against a CONSTANT
EXTERNAL PRESSURE
 Numerical Problems on some Thermodynamic Cycles

For the Reversible Ideal Gas processes: Find ΔU,ΔH, q, w,dq/T

Path :

; ;
 Numerical Problems on some Thermodynamic Cycles

Path :

Path :

; ;
 Numerical Problems on some Thermodynamic Cycles

Path : ;

; ;

Path :

; ;

;
 Numerical Problems on some Thermodynamic Cycles

Now, compare path [A] verses path [D] + [E]

Path : Path :

We will discuss this term later while dealing with 2nd Law of Thermodynamics
 Numerical Problems on some Thermodynamic Cycles

Calculate the final temperature of a sample of carbon dioxide of mass 16.0 g that is
expanded reversibly and adiabatically from 500 cm3. at 298.15 K to 2.00 dm3.

A sample of nitrogen of mass 3.12 gat 23.0°C is allowed to expand reversibly and
adiabatically from 400 cm3 to 2.00 dm3 . What is the work done by the gas?
 Numerical Problems on some Thermodynamic Cycles

Calculate the final pressure of a sample of water vapour that expands reversibly and
adiabatically from 87.3 Torr and 500 cm3 to a final volume of 3.0 dm3 . Take γ = 1.3
 THE JOULE-THOMPSON EXPERIMENT

The Linde process

Joule Thomson Coefficent for a van der Waal Gas:

T (∂V ∂T ) −V
 ∂T 
μJT =   = p

 ∂P H Cp

Virial Equation
[Using inert gas law
Approximation]
Appendix
 Thermodynamic Response Functions Appendix

Property PD Value for Perfect Gas Info:

Internal  ∂U 
πT =   πT= 0 Strength/nature of
Pressure  ∂V T interactions between
molecules

α = 1  ∂V  α =1 / T
Expansion The higher T, the less
responsive is its volume
Coefficient V  ∂T  p to a change in
temperature

1  ∂V 
Isothermal
Compressibility
κT = −  
V  ∂p T
κT =1 /p The higher the p, the
lower its compressibility

 ∂T 
Joule-Thomson
Coefficient
µ=
∂p
 µ=0 Another indication of
 H molecular interactions.