Thermodynamics

Literally meaning of thermodynamics means, thermo→heat and

dynamics → movement or flow. So, thermodynamics may be
defined as “a branch of science which deals with the study of
energy transfer and its effect on the properties of system”.
Some thermodynamics terms:-
Some commonly used terms in Thermodynamics are
System:- The part of the universe under consideration is called system.
Boundary:- The real or imaginary surface that separate the system and
surrounding is called boundary.
Surrounding:- The region outside the boundary of any system is called
surrounding.
Types of systems
Open system:-
An open system is one which exchange both matter and energy with
the surrounding. Example, a cup of tea
Closed system:-
A closed system is one which exchange energy with the surrounding but
not matter. Example, hot water in closed vessel.
 Isolated system:-
An isolated system is one which can neither exchange matter nor energy
with surrounding. Example hot water in thermos.
State function:-
The thermodynamic parameters of a system whose value depends only
on the state of the system but not on the path followed by the system are
called state function. Example, temperature, pressure, volume, internal
energy, enthalpy, entropy, Gibbs free energy etc.
[state:- current situation of a system]
State variable:-
Thermodynamics parameters that change the state of a system on
changing its values is called state variable example, entropy, enthalpy,
Gibb’s free energy, Temperature, Volume, Pressure, Work, heat etc.
Types of thermodynamics properties:-
Extensive properties:-
The Thermodynamics properties whose values depend on the quantity of
matter contained in the system is called extensive property. Example,
mass, volume, number of moles, heat capacity, entropy, internal energy,
enthalpy, free energy etc. [ depend on the mass] Intensive properties:-
The thermodynamic properties whose values depend on the nature of the
substance but not quantity of the matter contained in the system is called
intensive properties. Example, density, temperature, pressure,
concentration, viscosity etc. [ independent of mass]

Internal energy:-
The sum of all possible energies associated with a substance in a system
is called internal energy and is denoted by E or U
Mathematically,
E = K.E + P.E. + bond energy + heat energy + …………
First law of thermodynamics:- , the total energy of the system remain constant
i.e. energy can neither be created nor be destroyed but can be converted from
The first law of thermodynamics is also called the law of conservation of
energy and can be defined as one form to another form.
Mathematical formulation:-
Let us consider a system in its initial state having internal energy E1. If q amount
of heat is supplied to the system, this supplied heat is used to increase the internal
energy of the system or does some work or both. Let, E2be the internal energy in
the final state of the system. Then,
or, E- E1= q + W E2= E1+ q + W ∆E = -q + W ∆E = -q + W ∆E = q - W
or, ∆E = q + W
This is the mathematical formulation of 1st law of thermodynamics. But, if
the work done is the work done of expansion, then, W = -P∆V [ Work =
force x displacement ∆E = q - P∆V = pressure x area x ∆l Or, q = ∆E +
P∆V = P x ∆V W = P∆V ]
Sign convention for heat and work
If work is done on the system, then, w = +ve
If work is done by the system, then, w = -ve
If heat is absorbed or gain by the system, then, q = +ve
If heat is lost by the system, then, q = -ve
Q. A system does 200J of work and at the same time it absorbed 150 J
of heat. What is the change in internal energy?

Q. During a process, a system absorbs 710 J of heat and does work. The
change in internal energy for the process is 460 J. What is the work
done by the system?
Q. During a process, the internal energy of the system increased by 240
KJ while the system performed 19 KJ of work on its surrounding. How
much heat was transferred?
Advantages of first law of thermodynamics:- 1.
It gives the concept of conservation of energy. 2.
It makes the use of key concept of internal energy,
heat and work.
Limitations of first law of thermodynamics:-
1. It could not explain the direction of heat flow.
2. It could not explain about the spontaneity of the
process.
3. If total heat is converted into useful work,
efficiency of the system is 100% which is not
 possible.
Enthalpy:-
The amount of heat content by the system at constant pressure is called enthalpy. It is
denoted by H.
Mathematically,
H = E + PV ------------------ (1)
Where, E = Internal energy of the system
P = Pressure
V = Volume
Since, E, P, and V are state function, H also be a state function.
If H1 and H2 be the enthalpies of initial and final state, then,
H1= E1+ PV1-------------------- (2)
H2= E2+ PV2---------------------(3)
Substracting eqn(2) from eqn(3)
H2– H1= (E2+ PV2) – (E1+ PV1)
Or, ∆H = (E2– E1) + P(V2– V1)
⸫ ∆H = ∆E + P∆V -------------------- (4)
From 1st law of thermodynamics,
q = ∆E + P∆V ------------------(5)
From eqn(4) and (5)
∆H = q
 Hence, enthalpy change is the heat evolved or heat absorbed by the system at constant
pressure
Types of thermodynamics process:-
Thermodynamic process is the operation by which a system changes from one state to
another state. Some thermodynamic process are,
Isothermal process:- Any process carried out under constant temperature is called
isothermal process.
i.e. ∆T = 0
Adiabatic process:- Any process in which heat is remain constant is called adiabatic
process i.e. no exchange heat between system and surrounding.
i.e. ∆q = 0
Isobaric process :- Any process which is carried out at constant pressure is called
isobaric process.
i.e. ∆P = 0
Isochoric process:- Any process which is carried out at constant volume is called
isochoric process.
i.e. ∆V = 0
Cyclic process:- Thermodynamic process which starts from certain state and finally
return back to the same state after a series of change is called cyclic process. In cyclic
process,
Change in internal energy (∆E) = 0
Change in enthalpy (∆H) = 0
 Enthalpy of reaction heat of reaction:-
It can be defined as, “the amount of heat absorbed or released
when all gram moles of reactants converted into the
product”. it is denoted by ∆H and is given by,
R
∆H = ΣHP- ΣH Where, HP = enthalpy of product HR
= enthalpy of reactant
E.g, C + O2 CO2, ∆H = - 94.1kcal. Types of
enthalpy of reaction:-
Enthalpy of formation:-
It can be defined as, “the amount of enthalpy change when 1
mole of a compound is formed from its constituent
element”. It is denoted by ∆Hf.
Enthalpy of formation of elements and homoatomic molecules
(H2, Cl2, O2, N2) is zero.
E.g, H2 + Cl2 2HCl , ∆H = - 44kcal Heat of
formation of HCl (∆Hf) = -44/2 = -22kcal.
Enthalpy of combustion:-
It is defined as, “the amount of enthalpy change when 1 mole of element or
 compound is completely burnt in excess of air”. It is denoted by ∆HC
and is given by.
∆HC = Σ∆HC Product - Σ∆HC Reactant
E.g, C + O2 CO2; ∆HC = -94.1 kcal
CH4 + 2O2 CO2 + 2H2O ; ∆HC = -212.7 kcal
Exothermic and Endothermic reaction:
Exothermic reaction :-
The reaction is said to be exothermic, if heat energy released during the chemical
reaction.
In exothermic reaction, the enthalpy of product must be less than that of
reactant. So enthalpy change must be negative.
i.e. ∆H = HP – HRis –ve. Where, HP > HR
Diagrammatically exothermic reaction can be shown as,
 Endothermic reaction:-
The reaction is said to be endothermic, if heat energy is absorbed during
the chemical reaction.
In endothermic reaction, the enthalpy of product must be higher
than that of reactant. So enthalpy change must be positive.
i.e. ∆H = HP – HRis +ve, where HP > HR
Diagrammatically endothermic reaction can be shown as.

y gr e
,

Hess’s law of constant heat summation:-

Hess’s law of constant heat summation can be defined as, the enthalpy change
for a chemical reaction is same, no matter whether the reaction occurs in a
single step or in a multiple steps.
Let us consider, a process involving the conversion of A to B in one step,
say path(I). Let, the enthalpy change of the process is ∆H. Suppose, the same
process is carried out in two steps involving a change from A to C and C to
B, say path(II). Let ∆H1and ∆H2 be the enthalpy change from A to C and C
to B respectively.
 Applications of Hess's law of constant heat
summation:-
1. It is applicable for the determination of heat of
formation.
2. It is applicable for the determination of heat of
transition.
3. It is applicable for the determination of bond
energy.
Spontaneous process:-
A natural phenomenon which takes place itself is known as spontaneous process.
E.g. Heat flows from hot body to cold body.
Water flows from top to bottom.
Rusting of iron when iron is left over moist air.
Driving force:- The force required to make a process spontaneity is called driving
 force.
Entropy:- The thermodynamic parameter which measures the degree of randomness or
disorderness of the molecule of the system is called entropy. It is denoted by S. It is
very difficult to determine so, it is always expressed in term of entropy change ∆S. i.e.
∆S = Sfinal - Sinitial
Mathematically,

∆S = ��������
=
�� ∆����
Where, qrev = Heat absorbed by reversible process
T = Absolute temperature
∆H = Enthalpy change of a system
Greater the randomness of the molecules in the system, larger will be the
value of entropy. So, entropy of solid liquid and gas is in the sequence
of Ssolid > Sliquid > Sgas
The unit of entropy is JK-1
Molar Entropy change:- The entropy change for one mole of the substance is
called Molar Entropy change and its unit is JK-1mole-1.
 Entropy of a reaction:- The amount of Entropy change when certain molar
quantity of reactants react to form product under a particular condition is
called entropy of reaction. It is denoted by ∆Srand is given by ∆Sr =
∑Sproducts - ∑ Sreactants
Effect of temperature on entropy of a substance:-
Entropy is the measure of randomness of the molecules of a substance. As
the temperature is increased, kinetic energy of the molecules of a substance
will be also increase, so that molecular arrangement is disturbed and hence
molecular randomness increased. So, with increase in temperature, entropy
of a substance is increased and vice versa .
Criteria of spontaneity( spontaneity in term of Entropy):-
For isolated system,
a. ∆Ssys > 0 → process is spontaneous i.e. +ve
b. ∆Ssys < 0 → process is non-spontaneous i.e. –ve
c. ∆Ssys = 0 → process is equilibrium.
For open system, both system and surrounding should be
consider. ∆Stotal = ∆Ssys + ∆Ssurr > 0 → spontaneous i.e. +ve
∆Stotal < 0 → non-spontaneous i.e –ve
∆Stotal = 0 → equilibrium
Second law of thermodynamics
Second law of thermodynamics can be stated as,
1. a spontaneous process is always accompanied by an increase of
entropy.
i.e. ∆Stotal = ∆Ssys + ∆Ssurr > 0 i.e. +ve
2. There is no heat engine that can convert all the heat into useful work
i.e. no heat engine has 100% efficiency.
3. Heat cannot transferred spontaneously from cold to hot body without use
of external agency.
Explanation:-
Total entropy of the universe is given by
∆Stotal = ∆Ssys + ∆Ssurr -------------------- (1)
When a system absorbs q amount of heat, equal amount of heat lost by the
surrounding,
i.e. qsys = -qsurr
-ve sign indicate the loss of heat by surrounding
Dividing both sides by T
��������
��
��= - ��������
��
 ⸫ ∆Ssys = - ∆Ssurr --------------------(2)
From this relation, we come in conclude that, entropy change of the system is greater
than that of surrounding.
i.e. ∆Ssys > ∆Ssurr Then, eqn(2) becomes
∆Ssys + ∆Ssurr >0 ----------------- (3)
From eqn (1) and (3)
∆Stotal = ∆Ssys + (-∆Ssys) >0
⸫ ∆Stotal > 0 i.e, +ve
Hence, a spontaneous process is always accompanied by an increased of entropy.
Gibb’s free energy:- The amount of energy available for doing useful
work at constant temperature is called Gibb’s free energy or simply
free energy. it is denoted by G and is given by,
G = H – TS -----------------(1)
Where, H = Enthalpy of a system
T = Absolute tempr
S = Entropy of a system
If G1and G2 be the Gibb’s free energy of initial and final state
respectively, then,
G1 = H1 – TS1-----------------(2)
 G2 = H2 – TS2-----------------(3)
Substracting eqn(2) from (3)
G2 – G1 = (H2 – TS2) – (H1 – TS1)
∆G = (H2 – H1) – T(S2 – S1)
∆G = ∆H – T∆S
This equation is the Gibb’s free energy change with enthalpy change,
entropy change, at constant temperature. This equation is also
known as Gibb’s – Helmholtz eqn
Criteria of spontaneity with respect to free energy change:-
i. If ∆G = -ve, then, ∆Stotal = +ve, so, the process is spontaneous.
ii. If ∆G = +ve, then, ∆Stotal = -ve, so, the process is non-spontaneous.
iii. If ∆G = 0, then ∆Stotal = 0 , so the process is equilibrium.

Criteria of spontaneity of exothermic and endothermic reaction on the basis of free energy
change, entropy change and temperature:-
We have Gibb’s Helmholtz equation,
∆G = ∆H + T∆S
Where, ∆G = free energy change
∆H = enthalpy change
T = Absolute Temperature
∆S = entropy change
a. For exothermic reaction, ∆H = -ve.
i. If ∆S is +ve, then ∆G = -ve, so, the process is spontaneous.
ii. If ∆S is -ve, and ∆H = T∆S then, ∆G = 0, so the process is in
equilibrium.
iii. At high tempr, if ∆S is –ve,
∆H < T∆S
⸫ ∆G = +ve, then, the process is non-spontaneous.
iv. At low tempr, ∆S is –ve
∆H > T∆S
∆G = -ve, then, the process is spontaneous.
b. For endothermic reaction, ∆H = +ve,
i. If ∆S is -ve, then ∆G = +ve, so, the process is non-spontaneous.
ii. If ∆S is +ve, and ∆H = T∆S then, ∆G = 0, so the process is in
equilibrium.
iii. At high tempr, if ∆S is +ve,
∆H < T∆S
⸫ ∆G = -ve, then, the process is spontaneous.
r
iv. At low temp , ∆S is +ve
∆H > T∆S
∆G = +ve, then, the process is non-spontaneous.
Relationship between standard free energy and equilibrium constant (keq):-
If the reaction takes place in non-standard condition, then the free energy
change(∆G) of reaction is different from the standard free energy
change(∆Go). So, ∆G and ∆Goare related as,

∆G = ∆Go + RTlnKeq --------------- (1)

Where, R = Universal gas constant(8.314Jmol-1k-1) T = Absolute tempr
Keq = Equilibrium constant At equilibrium, ∆G = 0. So,
eqn (1) becomes
∆Go = − RTlnKeq

∆Go = −2.303 RTlogKeq