Chapter-6

Thermodynamics -chemistry

Introduction:

In chemistry, thermodynamics refers to the study of energy and its

transformations during chemical processes. It provides a set of fundamental
principles and laws that govern the behaviour of energy and matter in chemical
processes. Thermodynamics helps chemists understand and predict how
reactions occur, the conditions under which they occur, and the amounts of
energy involved.

Thermodynamic terms:

1. System:

A "system" refers to the specific part of the universe that is under

consideration for analysis. It is the specific portion of the universe that
we focus on to study and analyse its energy and matter.

Example: Consider a cup of hot coffee. The coffee inside the cup is the
system.

2. Surroundings:

The term "surroundings" refers to everything in the universe outside

the system under consideration. The surroundings play a crucial role in
understanding and analysing the behaviour of a system because
interactions between the system and its surroundings often involve the
transfer of energy and matter.

Example: In the case of the hot coffee, the air in the room, the cup itself,
and anything else around the coffee make up the surroundings.

SYSTEM + SURROUNDINGS = UNIVERSE

 3. Boundary:

The "boundary" refers to the imaginary or real barrier that separates

a system from its surroundings.

Example: The walls of the cup containing the coffee form the boundary.
It's the interface that separates the coffee (system) from the air and cup
(surroundings).

Thermodynamics System or types of system:

There are 3 types of systems. They are,

i) Open system
ii) Closed system
iii) Isolated system

Open system:

An open system refers to a system that can exchange both energy and
matter with its surroundings. This means that substances
can enter or leave the system, and energy can be
transferred between the system and its surroundings.

Example: Coffee in an open glass, energy (heat) and

matter (coffee) are exchanged to the
surroundings.
Closed system:

A closed system allows the transfer of energy (in the form of heat or work
or radiation) with its surroundings but does not allow the
exchange of matter. The boundary is sealed but not
insulated. In other words, the system's mass remains
constant, but energy is exchanged with the
surroundings.

Example: Coffee in a glass which is closed with a plate,

energy (heat) is exchanged with the surroundings but the
matter (coffee) are not exchanged with the surroundings.

Isolated system:

Isolated systems are the perfectly insulated system and

cannot interact with the surroundings. It does not allow the
system to transfer of heat or matter with its surroundings.
The boundary is sealed and insulated. Universe can be
considered as an isolated system.

Example: Coffee in a thermos flask, both energy (heat)

and the matter (coffee) are not exchanged with the
surroundings. The boundary is completely isolated.

States of the system:

 The properties which determine the state of the system is known as

state variables.
 The state variables are pressure (p), volume (V), temperature (T).
 If any one of the properties change, then the state of the system is
changed.

Example: If we increase the temperature of an ice cube, the state of

the ice is changed into the liquid state. This shows that the state of
the system is depends upon the state variables (p ,V,T).
State function:

State function depends only upon the initial state and final state of the
system, it doesn’t depend upon the path or the mechanism followed by the
system to achieve final state.
ΔSF = final SF – initial SF
ΔT = final T – initial T
Example: Temperature
Pressure
Volume
Internal energy
Enthalpy
Entropy
Gibbs energy
Real time example to understand state function:
Two boys Motu and Chotu are standing at the top of a building. Motu used
the lift to come down and Chotu used the steer case to come down from the
building. The potential energy among them are equal while they are at the top
and bottom of the building. This shows that it considered only the initial floor
and final floor but not the path of them.

Path function:

Path function depend upon the initial state and final state of the system as
well as the path or the mechanism followed by the system to achieve final
state.

Example: Heat
Work
Heat capacity
Real time example to understand state function:
Two boys Motu and Chotu are standing at the top of a building. Motu
used the lift to come down and Chotu used the steer case to come down from
the building. The work done among them are different while they are at the
top and bottom of the building. This shows that it considered the initial floor
and final floor as well as the path of them.
Thermodynamic properties:
There are two types of thermodynamic properties they are,
i) Intensive property
ii) Extensive property

Intensive property:
The property of the system which does not depend on the amount or size
or mass of the system is called as intensive property. It does not depend on the
quantity of a system. If the amount of the substance is fixed then it is known as
intensive property.
Example: I) Temperature
ii) Refractive index
iii) Density
iv) Molar heat
v) Specific heat
vi) Surface tension
vii) Viscosity
viii) Pressure

Extensive property:
The property of the system which depend on the amount or size or mass
of the system is called as extensive property. It depends on the quantity of a
system not on the quality. If the amount of the substance is not fixed, then it is
known as extensive property.
Example: i) Mass
ii) Volume
iii) Internal energy
iv) Entropy
v) Enthalpy
vi) Free energy
vii) Heat capacity
viii) Force
Note:
 Density = mass/volume = extensive / extensive = intensive.
 The ratio of extensive properties indicates the intensive property.

Thermodynamics processes:

The path followed to change the state of the system.

Isothermal process:

 An isothermal process refers to a process that takes place at a constant

temperature. In other words, during an isothermal process, the
temperature of the system remains constant throughout the entire
process.
Or
The system change its state in constant temperature is known as
isothermal process.

T = Constant
ΔT=0
P, V = variable
 Heat is exchanged with surroundings.
 Volume (V) and pressure (P) are constant.

Isobaric process
 Pressure of the system during entire process remains constant.
P = constant
ΔP=0
V, T = variable

Isochoric process:
Volume remains constant.
V = constant
ΔV = 0
P, T = variable

Adiabatic process:
No exchange of heat between system and surroundings takes place during
entire process.
q=0
T, P, V = variable

Cyclic process:
  A cyclic process is one in which the starting and ending stages are the
same. It is a series of actions that conclude with the system in its initial
state. The internal energy of a system are equal at the beginning and end
of a cyclic process.
 Change in all state functions in cyclic process will be zero. i.e. ΔE=0,
ΔH=0, ΔP=0, ΔT=0.

Reversable process:
 System reaches the initial state along the same path.
 No work has to be done by the surroundings on system to reach initial
state.
 It is a slow process.
 Driving force is much lesser than the opposing force.
 It is imaginary.
Irreversable process:
 System does not reaches the initial state along the same path.
 Work has to be done by the surroundings on system to reach initial
state.no
 It is a fast process.
 Driving force is much greater than the opposing force.
 It is real.

Work and Heat

Heat (q):
 Heat is a mode of transfer of energy. It flows due to temperature
difference.
 Heat always flows from high temperature to low temperature.
 When heat is released from the system then, q=negative.
 When heat is absorbed by the system then, q=positive.
 dq = Small amount of heat.
 ∫dq=q = Total amount of heat.

Work (w):
  The transfer of energy from one form to another form by applying force
is known as work.

Consider a gas enclosed in a cylinder fitted with a piston:

 Work is done when the piston moves up or down.

let the pressure of gas be p1 and the external pressure gas be p2. Initial volume
of gas be v1 and the final volume of the gas be v2.
Two cases arises.
Case i):
 if p1 > p2 (piston moves upward)
 v2 > v1 (expansion)
 work is done BY the system.
 Δv = positive and w = negative
Case ii):
 If p2 > p1 (piston moves downward)
 V1 > v2 (compression)
 Work is done ON the system.
 Δv = negative and w = positive

Mathematical representation:
W = -p2 (Δv) (∴discussed deep in upcoming topics)

Units of energy:
 SI unit = joule (j) CGS unit = erg 1j = 10^7 erg
1 atm-L = 101.3 j 1 bar-L = 100 j 1 cal = 4.2 j
1 atm = 24.2 cal

Internal energy: (E/U)

 The sum of total of all possible kinds of energies present in the system at
rest is known as internal energy.
U = Utrans + Urot + UP.E +UK..E +….
 It is an extensive property.
 Absolute value of internal energy cannot be found instead change in
internal energy (ΔU) can be found using Bomb calorimeter.
 It is a state function.
ΔU = Ufinal – Uinitial
ΔU = Uproduct – Ureactant (in reaction)
 For example,
A = SF B = PF
dA = small change in A dB = small amount of B
∫dA = ΔA = Large change in A ∫dB = B = Total amount of B

U (internal energy) = SF W (work) = PF

dU = small change in U dW = small amount of W
∫dU = ΔU ∫dW = W
 Internal energy is depends upon volume and temperature for real gas
U = f (V,T).
 Internal energy is depends upon temperature for ideal gas
U = f (T).
 dU = ncvdT where cv = molar heat capacity
Total change in internal energy = ∫dU = ∫ncvdT
ΔU = ncv(T2 – T1)

 ΔU =ncvdT
For isothermal process (T=constant) => ΔT=0 => ΔU=0
 If ΔU = -ve => ncv(T2 -T1) = -ve => T2<T1 (temperature of the system
decreased). ΔU < 0.
 If ΔU = +ve => ncv(T2 -T1) = +ve => T2>T1 (temperature of the system
increased). ΔU > 0.
 f