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CHEMICAL THERMODYNAMICS

INTRODUCTION

Thermodynamics is a science that deals with the relationship of heat and energy and their
inter conversion of one form into the other as heat energy, electrical energy, chemical
energy, mechanical energy etc.

Greek roots
therme meaning heat and
dynamics meaning power or strength or motion
A more elegant definition the power of heat. Or Flow of heat

Scope / Importance of thermodynamics

Most of the important generalizations of physical chemistry including Raoults


law, Vant Hoff law of dilute solutions, Vant Hoff isotherm, free energy, law of
chemical equilibrium, the phase rule, etc., can be derived from the laws of
thermodynamics

Thermodynamics helps to predict the spontaneity of a process under a given set of


conditions.

It helps to determine the extent to which a process can proceed before attainment
of equilibrium

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Terminology / Fundamental Thermodynamic Concepts


System - A system is defined as part of the universe which is under investigation and
separated from its surroundings by a boundary.
Surrounding - The part of the universe other than the system is called surrounding.
System + Surroundings = Universe
Boundary / walls The real or imaginary surface separating the system from the
surrounding is called boundary.

Types of System

Open system: A system which can exchange both matter and energy with its
surroundings is called open system.

Closed system: A system which can exchange energy but not matter with its
surroundings is called a closed system.

Isolated system: A system which cannot exchange both energy and matter with its
surroundings is called an isolated system.

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(a) Evaporation of water placed in an open beaker


(b) The beaker is closed with a lid
(c) The vessel is insulated

Homogeneous system: A system which consists of only one phase and uniform
throughout.
Example: Mixture of gases

Heterogeneous system: A system which consists of two or more phases and not
uniform throughout.
Example: A system consisting of two or more immiscible liquids, ice in water

Macroscopic properties
The properties of a system in bulk which are easily measurable and can be
Extensive or Intensive in nature.
Intensive Property
The properties which are independent of the quantity of matter present in the
system are called intensive property.
Extensive Property
The properties which depend on the amount or mass of matter in the system are
called Extensive property.
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Intensive Property

Extensive property

Temperature,

Volume

Boiling point

Mass

Density

Internal energy

Viscosity

Heat capacity

Refractive index

Free energy

Freezing point

Enthalpy

Thermal conductivity

Entropy

Specific heat

Number of moles

Surface tension

Process
A thermodynamic process is an operation carried out on the system to bring about a
desired change in the system. During a process the state of the system changes.
Different types of Process

Isothermal Process The process is carried out at constant temperature. dT=0 .


During the process heat transfer occurs between the system and surrounding.

Adiabatic Process During this process no heat enters or leaves the system. q=0
The process s carried out only in isolated system.

Isobaric Process - The process at which pressure is constant. dP=0

Isochoric Process A process which occurs when the system is at constant


volume. dV=0

Cyclic process- Cyclic process is an operation when the system returns to its
original state after undergoing series of changes. For a cyclic process dE=0 :
dH=0

Spontaneous Process A process which occurs on its own without any driving
force.

Non Spontaneous Process A process which occurs with the aid of driving force

Reversible Process The process is reversible if it is carried out slowly so that all
the steps is reversible and at equilibrium.

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Irreversible Process The process does not go back to its initial state. The driving
force and opposing force differ by large amount. The process is carried out
abruptly in non equilibrium conditions.
Reversible process
Reaction occurs in many steps

Irreversible process
It has only two steps, initial and
final step

It is a slow process

It is a rapid process

Driving force and opposing force

Driving force and opposing force

differ by a small amount

differ by a large amount

Occurs in both directions

Occurs only in one direction

The work obtained is maximum

The work obtained is minimum

It is an imaginary process

It is a real process

It can be reversed by changing

It cannot be reversed

thermodynamic variables

Exothermic & Endothermic Reactions


Exothermic reactions If heat is given by the system to the surrounding (q < 0 or ve)
Examples: Freezing, condensation.

Endothermic reactions If heat is taken by the system from surrounding (q > 0 or +ve)
Examples: Melting, evaporation, sublimation.

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STATE AND THERMODYNAMIC EQUILIBRIUM


Equilibrium: It is a state of balance.

A system in which the macroscopic properties do not undergo any change with
time is said to be in thermodynamic equilibrium. During this state three types of
equilibrium exists within the system. They are

Mechanical equilibrium

No mechanical work is done by one part of the system on other part. At this state
the pressure is constant throughout the system.

Chemical equilibrium

No chemical change occurs at any part of the system. At this stage the
composition is same throughout the system.

Thermal equilibrium

No heat flow from one part of the system to other part. The temperature remains
same throughout the system.

STATE of the SYSTEM: The state of the system is the conditions of existence of
system and is described by macroscopic properties.
State Function or State Variables
The macroscopic properties of the system ( Temperature, pressure, surface tension,
viscosity, internal energy, enthalpy ) which changes with the change in the state of the
system is called state variables or state function. Change in the value of state function
depends only on the initial and final state of a system and not on the path through which
the system attains the final state. Ex. U, H, G, S
Path function or path variables
The property which depends on the path through which a system attains the final state is
called path function.

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Ex. Heat, work

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Work, Heat & Energy


Heat
Heat is defined as the form of energy that is transferred across a boundary by
means of difference of temperature.

Heat and temperature are different


Temperature - Intensive property
Heat

- Extensive property

Sign Convention - Heat

Heat absorbed by the system q +ve (q >0)

Heat released by the system q -ve (q < 0)

Work: Product of force and displacement


Energy is transferred by work to an object or system when a force is exerted through a
distance on that object or system
Sign convention - Work
Work done on the system by surroundings +ve (compression) (w >0)

Work done by the system on surroundings -ve (Expansion)

WORK DONE IN CHEMICAL / MECHANICAL PROCESS

Expansion work : w = Pext V

Compression work : w = + Pext V

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Energy Energy is ability to do work. All forms of energy can be divided into the two
following categories:
Kinetic Energy or Energy in action or The energy of motion
Potential Energy or Stored energy or The energy of position
Many systems we encounter will contain both kinetic and potential energy
Energy is a state function.

Internal Energy - ( E) or (U) The total amount of energy associated with the given
substance.
Internal energy = kinetic + potential energy of the molecules or atoms of a body
Kinetic energy = translation, rotation, vibration of the molecules or atoms
E = Ev + Er + Ee + Et
Change in internal energy can be easily measured by applying first law of
thermodynamics.
E = q w
Enthalpy (H) It is the heat content of a system.
H= E + PV

Most Chemical processes takes place at constant P

Amount of heat that passes between the system and the surroundings is given by

qp = E +PV

This heat flow is given the term Enthalpy H

At const P, H = E+ P V --- I LAW

Energy of a system at constant V , E = qv (w=0)

-state function

LAWS OF THERMODYNAMICS
The Zeroth law of thermodynamics : If a system A is in thermal equilibrium with system
B , and system B is in thermal equilibrium with system C , then systems A and C are in
equilibrium with each other.

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First Law of Thermodynamics / Law of conservation of energy

Energy can neither be created nor destroyed, but it can be converted from one
form to another form.

Total energy of the universe is constant

Mathematical Expression of I Law

In general, if in a given process the quantity of heat transferred from the


surrounding to the system is q and work done by the system in the process is w,
then the change in internal energy,
E = q - w (1)

Compression: I law: E = q + w
Expansion : I law: E = q + (- w)
If the process has undergone infinitesimal change, the I Law expression becomes
dE = dq dw

or

dE = dq PdV

Limitations of I Law

No restriction on the direction of the flow of heat

Does not specify the feasibility of the reaction

It is not possible to convert heat energy into an equivalent amount of work.

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