LECTURE

CY11001

1 Spring 2022-23

• Course introduction
• Introduction: Basic Concepts,
Introduction Definitions
• Partial Differentia tions

Department of Chemistry
Indian Institute of Technology
Kharagpur

L1 – Page 1 Department of Chemistry

Preamble >

Dr. Nilmoni Sarkar

Room NO: 103, JCG-PCR Chemistry Building
Ph: 83332
Email: nilmoni@chem.iitkgp.ac.in

Ground Rules for the Class

• Switch of mobile phones
• Attendance is must – will be checked occasionally/surprisingly
• Do not talk/smile among yourselves during class
• Vast syllabus and fast paced, must take classes seriously
• You can always approach me after the class in my office

L1 – PagePreamble2 > Department of Chemistry

Preamble >

CLASS SCHEDULE:
Lecture Schedule: Monday Tuesday
12PM-12:55PM 10 AM-11:55 AM
Dr. Nilmoni Sarkar
Phone no: 83332
e-mail: nilmoni@chem.iitkgp.ac.in
Room No: 103 (JCG-PCR Chemistry Building Block 1)
The 1st year (theory and lab) classes for the spring semester will start on March 7, 2023.

1st year Theory Class Distribution Spring 2023

Section 1 - 6 (Mon-Tue) Section 7 - 10 (Wed-Thur-Fri)
Duration #hr Duration #hr
Physical Mar 7 to Apr 3 12 Mar 9 to Mar 31 11
Inorganic Apr 17 to May 9 11 Apr 13 to May 12 13
Organic May 15 to Jun 6 12 May 17 to Jun 9 12
Midsem April 5 to 12, 2023
Endsem Jun 12 to 16, 2023

TUTORIALs: As per routine

Distribution of Marks:
Mid Sem (Only Physical): 30%
End Sem (Inorganic & Organic): 50%
 TA: 20% [Physical (6%), Inorganic (7%), Organic (7%)]

Books
Atkin’s Physical Chemistry by Atkins & de Paula
Physical Chemistry by Levine
Physical Chemistry by Silbey, Alberty & Bawendy
L1 – Page 3 Department of Chemistry
Preamble >

Course outline
Thermodynamics
• Essential concepts and definitions
• Revision: heat, work & energy; Real gas
• First Law of Thermodynamics
• The Second Law of Thermodynamics
• Entropy
• Gibbs Free Energy
• The Chemical Potential
• Phase and Reaction Equilibria
• Electrochemistry
Chemical Kinetics

L1 – Page 4 Department of Chemistry

Preamble > Units

Units

L1 – PageIntroduction5 > Units Department of Chemistry

Preamble > Units

Units

L1 – Page 6 Department of Chemistry

I. Introduction

Thermodynamics

• The study of the transformations of energy (work, heat, energy

and their effect on the state of the system) . Concerned with
equilibrium positions of systems
• Provides a framework of relating the macroscopic properties of a
system to one another.
• Not concerned with the dynamics of systems but rather their
equilibrium positions

L1 – Page 7 Department of Chemistry

I. Introduction > Basic Concepts

THE BASIC CONCEPTS:

† System – Open, Closed, Isolated

† Surroundings

† Boundary / Wall

• Rigid and Nonrigid (movable)

• Permeable and Impermeable (no matter is allowed to pass through it)

• Adiabatic and Nonadiabatic (diathermic boundary - permits the passage of
energy as heat )

A system surrounded by a rigid, impermeable, adiabatic wall

– Isolated system

L1 – Page 8 Department of Chemistry

I. Introduction > Basic Concepts > Equilibrium

Thermodynamic Equilibrium
For Isolated system:
• Macroscopic properties do not change with time

For Nonisolated system:

a) Macroscopic properties do not change with time
b) Removal of the system from contact with its surroundings causes
no change in the properties of the system

• A system in thermodynamic equilibrium is an equilibrium system

• State only defined by the present values of the state variables, not
by the history

L1 – Page 9 Department of Chemistry

I. Introduction > Basic Concepts > Equilibrium

Mechanical equilibrium

the 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

L1 – Page 10 Department of Chemistry

I. Introduction > Basic Concepts > Equilibrium

Thermal equilibrium

between system and the surroundings, is

a condition in which no change in the
properties of the system or surroundings
when they are separated by a thermally
conducting wall.

L1 – Page 11 Department of Chemistry

I. Introduction > Basic Concepts > Equilibrium

Material equilibrium
Concentrations of the chemical species in the various parts of the
system are constant with time

a) No net chemical reactions are occurring in the system

b) There is no net transfer of matter from one part (phase) of the ) f h

system to another or between the system and its surroundings

For thermodynamic equilibrium, all three kinds of

equilibrium must be present

L1 – Page 12 Department of Chemistry

I. Introduction > Basic Concepts

Phase: a homogeneous part of a system is called a phase

Intensive properties
Extensive properties
Homogenoeous system
Heterogeneous system

L1 – Page 13 Department of Chemistry

I. Introduction > Basic Concepts

How do we define a system? State of a System

Macroscopic state of a system can be specified by the values of a small
number of macroscopic Properties/Parameters/Physical
characteristics or attributes of a system - Thermodynamic variables

Thermodynamic variables which are experimentally measurable

• Composition – mass of each chemical species that is present in
each phases,
• pressure (p or P), volume (V), Temperature (T), density, etc. etc
• field strength, if magnetic/electrical field act on the system
• gravitational field

Microscopic state of a system needs description about each

molecules – a very complicated picture

L1 – Page 14 Department of Chemistry

I. Introduction > Basic Concepts

Thermodynamic state

If the value of every thermodynamic property in system A is same as

in system B – same thermodynamic state

The state of a thermodynamic system is defined by specifying the

values of its thermodynamic properties – not necessary to specify
all the properties to define the sate

Thermodynamic state of a system of a single-phase of fixed amounts

of non reacting substances can be described by two additional 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).

L1 – Page 15 Department of Chemistry

I. Introduction > Basic Concepts

A very important thermodynamic 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 the zeroth law of thermodynamics:

A well-defined quantity called temperature exists such that two th t t

systems will be in thermal equilibrium if and only if both have
the same temperature.

L1 – Page 16 Department of Chemistry

I. Introduction > Basic Concepts

Essential concepts / Definitions

Processes: When one or more of the parameters of a system changes, the state of the state of
the system also changes and system is undergoing a process

Isothermal (T),
Isobaric (p),
Isochoric (V)
Exothermic,
Endothermic
Cyclic

L1 – Page 17 Department of Chemistry

I. Introduction > Basic Concepts
Essential concepts / Definitions
Reversible process:
• Ideal
• 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 wrt forward
direction
direction

Irreversible Process:
• Real / Spontaneous
• Occurs suddenly or spontaneously without the restriction of occurring in
successive stages of infinitetesimal quantities.
• Not remain in the virtual equilibrium during the transition.
• The work (w) in the forward and backward processes would be unequal.

L1 – Page 18 Department of Chemistry

I. Introduction > Basic Concepts

The Equation of State of Ideal Gases

An equation of state - a equation that relates macroscopic variables (e.g., P, V,
n bl ( PV
and T) for a given substance in thermodynamic equilibrium.
† perfect/ideal gas equation, pV = nRT.
† perfect/ideal gas, a gas that obeys pV = nRT exactly under
all conditions.
† real gas, an actual gas.

† gas constant, R (with R = NAk, where NA is

Avogadro’s constant and k is Boltzmann’s constant).

The van der Waals model of real gases

2
nRT n
p= −a
V − nb V

L1 – Page 19 Department of Chemistry

I. Introduction > Basic Concepts

† partial pressure: of an ideal gas, the pressure a gas would

exert if it occupied the container alone; in general,
pi = xi p.
† Dalton’s law: The pressure exerted by a mixture of gases is
the sum of the partial pressures of the gases.

p= ∑ pi .
i

† vapour pressure, the pressure of a vapour in equilibrium

with its condensed phase.

L1 – Page 20 Department of Chemistry

 Partial differentiation:
Consider a function of two variables  f(x,y)
A partial derivative of one of the variables: the rate of change of the
function w.r.t. that variable with all other variables kept fixed.

Example: For z=f(x,y),

∂z f ( x + Δx, y) − f ( x, y) ∂z f ( x, y + Δy) − f ( x, y)
= Lim Δx→ 0 = Lim Δy → 0
∂x ∂y
y Δx x Δy
∂z ∂z
3
dz = dx + dy 3 2
2 3
∂x y
∂y
x For example: z = axy, dz = 3ax ydx + ax dy

Properties of partial derivatives:

∂2z =? ∂2z =? ∂2z = ∂2z

∂x∂y ∂y∂x ∂x∂y ∂y∂x

L1 – Page 21 Department of Chemistry

 Properties of partial derivatives:
For example: z = ax3y,
The cyclic rule
If z = f(x,y), then dy 1
=
dy dz dx
dz x ax 3
. . =?
dz dx dy z dz
x y = 3ax 2 y
dy dz dx
dx y
. . = −1
dz x dx y dy z z
dx
=− 2 2
dy z 3ax y
V=f(P,T); P=f(V,T); T=f(P,V)
∂ 2T 1 ∂ 2T
PV =RT
∂P∂V = R = ∂V∂P
dT P dT V dP dT dV
= = = −1
dV P R dP V R dT V dV P dP T

L1 – Page 22 Department of Chemistry