5.

THERMODYNAMICS
It is a branch of science that deals with the relationship between heat and work. Chemical thermodynamics is a
branch of chemistry that deals with the heat changes associated with chemical reactions.
Some definitions:
System and Surroundings
System is the part of the universe which is under observation or investigation. The part of the universe except
system is called surroundings. The system and surroundings are separated by a boundary which may be real or imaginary.
System + surroundings → Universe
Types of systems
Depending on the ability to exchange energy and matter with the surroundings, systems are classified into three
types:
1. Open system: It is a system that can exchange both energy and matter with the surroundings.
E.g. Hot water taken in an open vessel.
2. Closed system: It is a system that can exchange only energy and not matter with the surroundings.
E.g. Hot water taken in a closed vessel.
3. Isolated system: It is a system that cannot exchange both energy and matter with the surroundings.
E.g. Hot water taken in a thermo flask.
Depending on the number of particles, systems are of two types:
1. Microscopic system: It is a system containing a few number of particles.
2. Macroscopic system: it is a system contains a large number of particles.
The properties of a macroscopic system are called macroscopic properties. The important macroscopic properties
are: Temperature (T), Pressure (P), Volume (V), length (l), breadth (b), height (h), internal energy (U), enthalpy (H), entropy
(S), Gibb’s energy (G) etc.
Macroscopic properties can be divided into two:
1. Extensive properties: These are properties which depend on the amount of matter present in the system. Or,
these are the properties which change when a system is divided.
E.g.: Volume (v), length (l), breadth (b), height (h), internal energy (U), enthalpy (H), entropy (S), Gibb’s energy (G), heat
capacity etc.
2. Intensive properties: These are properties which are independent of the amount of matter present in the
system. Or, these are the properties which do not change when a system is divided.
E.g. : Temperature (T), Pressure (P), Volume (V), density, refractive index, molar heat capacity, viscosity, surface tension etc.
State and Path functions
A function or a property that depends only on the initial and final state of a system and not on the path followed is called a
state function.
E.g. for state functions: T, P, V, U, H, S, G etc.
Path functions: These are properties which depend on the path followed also.
E.g. heat (q) and work (w)
Thermodynamic process
A process is the method (path) by which a state change occurs in a system. The different types of thermodynamic
process are:
1. Isothermal process: It is a process that occurs at constant temperature. For this process ΔT = 0 but Δq ≠ 0
2. Isobaric process: It is a process that occurs at constant Pressure. For such a process ΔP = 0
3. Isochoric process: It is a process that occurs at constant volume. For such a process ΔV = 0
4. Adiabatic process: It is a process that occurs at constant heat energy. Here no heat enters into or leaves from the
system. For such a process Δq= 0 but ΔT ≠ 0
5. Cyclic process: It is a process that takes place in a cyclic manner. Here the system undergoes a series of changes and
finally returns to its initial state. For such a process ΔU=0 and ΔH = 0
6. Reversible process: Every process is associated with two types of forces – driving force and opposing force. Driving
force favours the process while opposing force opposes it. If the driving and opposing forces are differed by an
infinitesimally small quantity the process takes place in both directions. Such a process is called reversible process.
 7. Irreversible process: If the driving and opposing forces are differed by a large quantity, then the process takes place
in only one direction. Such a process is called irreversible process.
Internal Energy (U)
Every body is associated with a definite amount of energy. This energy is called internal or intrinsic energy. It is the
energy possessed by a body. It is the sum of different types of molecular energies like translational kinetic energy, rotational
kinetic energy, vibrational kinetic energy, electronic energy, nuclear energy etc.
Internal energy of a body is an extensive property and state function. We cannot calculate the exact value of
internal energy, but we can calculate the change in internal energy (ΔU) during a process by using an apparatus called Bomb
Calorimeter.
The change in internal energy (ΔU) = U2-U1, where U1 and U2 are the initial and final internal energies respectively.
The unit of internal energy is kJ/mol.
The internal energy of a system can change in mainly by two ways:
1. By the transfer of heat
2. By doing work
First law of thermodynamics: It is the same as law of conservation of energy. It states that energy can neither be
created nor be destroyed. Or, the total energy in the universe is always a constant. Or, the total energy of an isolated system
is always a constant.
Let the initial internal energy of the system be U1
The final internal energy of the system U2= U1 + q + w
The change in internal energy ΔU = U2-U1 = (U1 + q + w) - U1
Mathematically ΔU = q + w (1)
Where q is the amount of heat absorbed by the system and w is the amount of work done on the system.
Enthalpy (H)
It is the total heat content of a system. It is the sum of internal energy and pressure-volume energy of a system.
i.e. H = U + PV
It is a state function and an extensive property. i.e, whenever there is a change in enthalpy, it depends only on the
initial and final values and not on the path followed. If H1 is the enthalpy of a system in the initial state and H2 is that in the
final state, then the change in enthalpy, ΔH = H2 – H1.
The unit of enthalpy is kJ/mol. ΔH is determined by using an apparatus called calorimeter.
For a chemical reaction, if HP is the enthalpy of products and HR is that of reactants, then
ΔH = HP – HR.
If HP > HR, ΔH is positive and heat is absorbed during the process. Such a process is called endothermic process.
If HP < HR, ΔH is negative and heat is evolved during the process. Such a process is called exothermic process.

Spontaneous Process
It is a process that takes place without the help of any external agency. All natural processes are spontaneous. E.g.
flow of water from high level to low level, flow of heat from hot body to cold body, inter mixing of gases, burning of fuels,
melting of ice, evaporation of water etc. A spontaneous process cannot reverse its direction by its own.
Spontaneous chemical reactions are also called feasible or probable reactions.
e.g. N2 + 3H2 2NH3; ΔrH0 = - 46.1kJ/mol
2H2 + O2 2H2O; ΔrH0 = - 285.8 kJ/mol
A process that takes place with the help of an external agency is called non-spontaneous process. E.g. flow of water
from low level to high level.
Criteria for spontaneity
During spontaneous processes like burning of fuels, flow of heat from hot body to cold body, flow of water from
high level to low level etc, energy of the system decreases. So one of the criteria for spontaneity is decrease in energy.
But for some spontaneous processes like melting of ice, evaporation of water etc, heat is absorbed. i.e. the energy of
the system increases during the process. The above processes are accompanied with increase in disorder (entropy) of the
system. Thus another criterion for spontaneity is increase in disorderness or randomness of the system.
Entropy (S)
It is a measure of degree of disorderness or randomness of a system. As the disorderness increases, entropy also
increases. It is an extensive property and state function.
If S1 is the initial entropy of a system and S2 is its final value, then the change in entropy ∆S = S2 –S1.
For a given substance, the solid state has the least entropy and the gaseous state has the most. When temperature
increases entropy also increases.The unit of entropy and entropy change is J/K/mol.
If a system absorbs ‘q’ amount of heat reversibly at a temperature T, then the change in entropy,
∆S = qrev.
T Where qrev. is the amount of heat absorbed reversibly.
Entropy and spontaneity
During a spontaneous process, disorderness of the system increases. Thus entropy increases and hence ∆S becomes
positive.
The total entropy change for the system and surroundings is given by ∆STotal = ∆Ssyst. + ∆Ssurr.
For a spontaneous process, ∆STotal > 0
When a system attains equilibrium, the entropy becomes maximum and there is no further change in entropy. So ∆S
Total = 0
If ∆S Total < 0, the process is non-spontaneous.
Gibb’s energy (G)
It is defined as the maximum amount of available energy that can be converted to useful work. It is given by the
equation, G = H – TS
It is an extensive property and a state function. If G1 is the initial Gibb’s energy and G2 is its final value, then the change in
Gibb’s energy (∆G) = G2 – G1
The unit of Gibb’s energy is kJ/mol.
Relation between ∆G, ∆H and ∆S (Gibb’s Equation)
We know that G = H- TS
So ∆G = ∆H - ∆(TS)
= ∆H – (T∆S + S∆T)
At constant temperature, ∆T = 0. So,∆G = ∆H – T∆S
The change in Gibb’s energy for a system can be written as
This equation is known as Gibb’s Helmoltz equation.
For a spontaneous process, ∆STotal is positive. So ∆Gsyst. is negative. (or, ∆Gsyst. < 0)
For a non-spontaneous process, ∆STotal is negative, so ∆Gsyst. is positive. (or, ∆Gsyst. > 0)
For a process at equilibrium, ∆STotal = 0. So ∆Gsyst. = 0
Conditions for ∆G to be negative
We know that for a spontaneous process, ∆Gsyst. is negative. Also ∆G = ∆H - T∆S.
1) If ∆H is negative and ∆S is +ve, ∆G is always –ve and the process is always spontaneous.
2) If both ∆H and ∆S are positive, ∆G will be –ve when T∆S > ∆H. This is possible at high temperature.
3) If both ∆H and ∆S are negative, ∆G will be –ve when T∆S < ∆H. This is possible at low temperature.
Note: If ∆H is +ve and ∆S -ve, then ∆G will be always +ve and the process will be always non- spontaneous.