Basic Terminologies

System, Surroundings and Boundary

Suppose you want to understand the effect of increase in temperature on air inside a
balloon.

Outer surface of
balloon will be the
boundary.
Air inside the
balloon will be our
system.

Everything outside the boundary is surroundings.

Basic Terminologies
Types of Boundaries

A real boundary is also called as wall. The types of wall are as follows :

Rigid wall: Non-Rigid wall: Adiabatic wall: Diathermic wall:

The wall (boundary) The wall is The heat can’t be The heat can be
is immovable. movable. exchanged across the exchanged across the
wall. wall.
Basic Terminologies
Types of System
 Basic Terminologies

● ●
State Function Path Function

Property of a system which is dependent only on the Quantities which are dependent on the path/way
state of the system. It is independent of the path

●
adopted to attain a particular state.
Changes in state function are not state function.
●
the system has achieved a particular state.
These quantities are defined when there is a
process going on.
Example: ΔT, ΔV, ΔP etc. are not state functions.

Heat Work
Temperature Volume

Distance
Pressure travelled
 Basic Terminologies

●
Extensive Properties

Depend upon the quantity of the

● Intensive Properties
Independent of the amount of
the substance present in the
matter contained in the system.

● ●
system.

●
Additive in nature.

Examples - Volume, mass, total energy etc.

● Non additive in nature.
Examples - Temperature, pressure, density,
concentration, vapour pressure, B.P., F.P.,
Viscosity, pH, specific heat etc.
IMPORTANT!
Ratio of two extensive properties is an intensive property.

For example,

Mass
Mass Volume = density
Volume

Extensive Extensive Intensive

Thermodynamic Processes
The operation by which a system changes from one state to another state is called a
process.

Isothermal Isobaric
Process: Process:
dT = 0 dP = 0
T = constant P = constant

Isochoric Adiabatic
Process: Process:
dV = 0 dQ = 0
V = constant Q=0
Thermodynamic Processes
Graphical Representation

Isobaric process

Pressure
Isothermal process

Adiabatic process
Isochoric process
Volume
Thermodynamic Processes
Cyclic Process

● When a system undergoes a number of different states by different processes and

finally returns to its initial state, it is said to have completed a cycle and the process is

● called a cyclic process.

For a cyclic process, the change in state function is zero, i.e., ΔT = 0, ΔV = 0, ΔP = 0.
Zeroth Law of Thermodynamics
Zeroth Law

If two systems are in thermal equilibrium with a third system, then they are
also in thermal equilibrium with each other.

A
Thermal Thermal
equilibrium equilibrium

B C
also in thermal
equilibrium

(All three are in thermal equilibrium with each other)

Work(w)

P-V Work

= pex . (–ΔV) = –pex ΔV = –pex (Vf – Vi)

First Law of Thermodynamics

Mathematical form of first law

∆U = q + w

heat transfer work interaction

change in
between system between system
internal energy
and and surroundings
of the system
surroundings
First Law of Thermodynamics

The following sign conventions are to be followed:

Quantity Positive Sign (+) Negative Sign (–)

q means system gains heat means system loses heat

means work done on means work done by

w
system system

means net gain of energy means net loss of energy

ΔU
by system by system
Calculation of Work (W)

Air Air

Compression Expansion
△V = –ve △V = +ve
W = +ve W = –ve
Work is done on Work done by
the system the system
Calculation of Work (W)

Work in Isochoric process

V = constant
dV = 0 P
W=0
From first law of thermodynamics
ΔU = qv
isochor

Heat exchanged at constant

volume
V1 V
Calculation of Work (W)

Work in Isobaric process

Pgas = constant
Since pressure of gas is defined during whole of the process
and hence the process must be reversible

Isobar
So dw = -PextdV

Pressure
= -Pgas dV

W = -P(Vf - Vi)
Volume
Isothermal Process
When a system undergoes an isothermal change, ΔU = 0
Then, according to First law of thermodynamics,
ΔU = q + w ⇒ q = –w

Work done in isothermal irreversible process:

w = – pex ΔV

Work done in isothermal reversible process:

dV V2
P1
w = – nRT ∫ V = –2.303nRT log 1 = –2.303nRT log P
V
2
Free expansion: Expansion of a gas in vacuum (pex = 0) is called free
expansion. No work is done during free expansion of an ideal gas.
Cyclic Process
In a cyclic process, where initial and final states are the same,
U2 = U1, then ΔU = 0
i.e, q = –w
Calculation of work for cyclic process:
Work done = Area enclosed in PV-diagram
For clockwise it is –ve.
For anti-clockwise it is +ve.
Enthalpy of a System
Enthalpy is the total energy content of a system that consists of internal energy plus the
pressure–volume energy.

H = U + PV

Internal Product of
Enthalpy
Energy pressure and
volume
Relationship between ΔH and ΔU

We know that,
H = U + PV
dH = dU + d(PV)

Case – 1: If pressure is constant Case – 2: If volume is constant

dH = dU + PdV dH = dU + VdP
or ΔH = ΔU + PΔV or ΔH = ΔU + VΔP
Relationship between ΔH and ΔU
Case – 3: If pressure and volume Case – 4: For ideal gas expansion or
both change compression
dH = dU + d(PV) dH = dU + d(PV)
or ΔH = ΔU + Δ(PV) or ΔH = ΔU + Δ(PV)
or ΔH = ΔU + P2V2 – P1V1 or ΔH = ΔU + Δ(nRT)
or ΔH = ΔU + nRΔT
Case – 5: For chemical reactions of ideal gases (at constant temperature)
ΔH = ΔU + Δ(nRT)
or ΔH = ΔU + (Δng)RT
Δng = Number of moles of gaseous product – Number of moles of gaseous reactants
Enthalpy of a System
Temperature variance of ΔH and ΔU

Heat change at constant volume, qv = ΔU

Heat change at constant pressure, qp = ΔH
Now, using the concept of molar heat capacity,
qv = nCvΔT and qp = nCpΔT
Cp and Cv are the molar heat capacities at constant pressure and constant volume
respectively.
Thus, we can conclude,
ΔU = nCvΔT ΔH = nCpΔT
Second Law of Thermodynamics
Modified statement with the concept of entropy: For a spontaneous process, the
entropy of the universe increases; for a reversible process, the entropy of the
universe does not change.

Mathematically
For a spontaneous/irreversible process:
ΔS universe = ΔS system + ΔS surroundings > 0
For a reversible process:
ΔS universe = ΔS system + ΔS surroundings = 0

When a system is in equilibrium, the entropy is maximum, and the change in

entropy, ∆S = 0.

We can say that entropy for a spontaneous process increases till it reaches
maximum and at equilibrium the change in entropy is zero.
Entropy

Entropy is the measure of randomness or disorder of the system.

Mathematically
1
∫ dS = T ∫ δqrev

qrev
ΔSr = T
It is a state function.

Units: cal K-1 mol-1 or JK-1mol-1

Entropy
Factors influencing entropy

The thumb rule is -

More the disorder, more is the
entropy.

Entropy depends on the mass/moles of the system. Thus, it is an extensive

property.

2 moles of 4 moles of
Oxygen Oxygen

Less
entropy More
entropy
Entropy
Factors influencing entropy

As the number of gas molecules increases during a chemical reaction, entropy

increases.
If Δng > 0, then ΔS of the reaction is positive.
If Δng < 0, then ΔS of the reaction is negative.
If Δng = 0, then ΔS of the reaction may be positive or negative.
Heat Capacity

Total Heat Capacity (CT)

Heat required to raise the temperature of system by 1oC under the given process is
known as total heat capacity.

Heat ÷ Change in
temperature = Total heat
capacity
(q) = (ΔT) × (CT)
Heat Capacity
Specific Heat Capacity (s)

Heat required to raise temperature of unit mass (generally 1 g) of a substance by 1 oC.

Specific
Heat ÷
=
Change in
temperature
÷× Mass =× Heat
capacity
(q) (ΔT) (m)
(s)
Heat Capacity
Molar Heat Capacity (Cm)

Heat required to raise temperature of 1 mole of a substance by 1 oC.

Molar
Heat ÷
=
Change in
temperature
÷× Moles =
× Heat
capacity
(q) (ΔT) (n)
(Cm)
Heat Capacity
Relation between Heat Capacities

Total
Heat
Capacity

Molar Specific
Heat Divide by molar mass Heat
Capacity Capacity
Multiply by molar mass
Relationship between Cp and Cv
Since heat capacity is a path function. For an ideal gas, two different types of
molar heat capacities are defined.

Molar Heat Capacity

Molar heat capacity at

Molar heat capacity at
constant pressure
constant volume (CV)
(Cp)
Relationship between Cp and Cv

C p = Cv + R
Molar heat Molar heat
capacity at Universal
capacity at
constant gas
constant
pressure constant
volume

NOTE: This expression is valid only for an ideal gas.

Relationship between Cp and Cv
Table for CP and CV for different types of gases

CP
Atomicity CV CP = C V + R 𝜸= C
V

Monoatomic 3 5
R R 𝜸 = 1.66
2 2
Diatomic or linear 5 7
R R 𝜸 = 1.40
polyatomic
2 2
Non - linear polyatomic
3R 4R 𝜸 = 1.33

NOTE: These values are applicable at low or moderate temperatures.

Work in Adiabatic Process

There is no heat exchange between system and surrounding, q = 0

From first law of thermodynamics, ΔU = q + W
Expansion
W = -ve
ΔU < 0
ΔT < 0
ΔU = W T2 <T1
Temperature decreases,
cooling occurs

W = +ve
Compression
ΔU > 0
T2 >T1
Temperature increases,
heating occurs
Calculation of Adiabatic Work
Operation of a Adiabatic Reversible Process

T2V2𝜸–1 = T1V1𝜸–1
or T V𝜸–1 = constant
PV𝜸 = constant
Calculation of Adiabatic Work
Operation of a Adiabatic Reversible Process

Thus, for an adiabatic reversible process:

PV𝜸 = constant
P

PV𝛾 = C 1

V
Comparison of Isothermal and Adiabatic Process

Isothermal
P

Adiabatic
Adiabatic slope = 𝜸 × isothermal slope
V
Since 𝜸 is always >1, slope of P-V curve is more negative in case of adiabatic
process.
Graph Transformation
If a graph is parallel to a certain axis (let’s say x–axis), then the quantity plotted
on y–axis(the other axis) is constant for that process. For example–

P T

V
V
Here the graph is parallel to Here the graph is parallel to
the volume axis. Thus, the temperature axis. Thus,
pressure is constant. volume is constant.
Graph Transformation
If a graph is a straight line passing through origin, then there is a direct
proportion between the quantities on Y and X axis.

Here the graph is a straight

line passing through origin.
Thus, V ∝ T
Graph Transformation
If a graph is hyperbolic, then there is inverse relationship between the quantities
plotted on Y and X axis.

Here the graph is hyperbolic.

Thus, P ∝ 1/V
Graph Transformation
Let’s take an example to understand graph transformation:
A cyclic process ABCD is shown in P–V diagram for an

●
ideal gas. Convert this into a V–T diagram.

●
AB is a line parallel to V–axis. Thus, pressure
is constant for this process.
At constant pressure, V ∝ T B

Thus, V–T graph for this process will be a straight line A

passing through origin. Also, since VB > VA, the
temperature TB > TA.
Graph Transformation
●
● BC is a hyperbolic curve. Thus, P ∝ 1/V
Thus, temperature will be constant for this process.

Thus, V–T graph for this process will be a straight line parallel to V axis.
Also, VC > VB,.

C
B

A
Graph Transformation
●
● CD is a line parallel to P axis.
Thus, volume will be constant for this process.

Thus, V–T graph for this process will be a straight line parallel to T axis.
Also, since PD < PC, TD < Tc.

D C
B

A
Graph Transformation
●
● DA is a hyperbolic curve. Thus, P ∝ 1/V
Thus, temperature will be constant for this process.

Thus, V–T graph for this process will be a straight line parallel to V axis.
Also, VD > VA.

D C
B

A
Irreversible Processes
Isothermal Free Expansion Adiabatic Free Expansion

T = constant (ΔU = 0) and w = 0 w = 0 and q = 0

From first law of thermodynamics, From first law of thermodynamics,
ΔU = q + w ΔU = q + W
So, q = 0 So, ΔU = 0
An isothermal free expansion of ΔU = nCVΔT ⇒ ΔT = 0
an ideal gas is adiabatic as well. T1 = T 2
Adiabatic free expansion of an ideal
gas is isothermal as well.
Entropy Calculation in different Processes

T2 V2
ΔS = nCv In + nR In
T1 V1

For isothermal process (T2 = T1)

V2
ΔSsys = nR ln V1
For isochoric process (V2 = V1)
T2
ΔSsys = nCv ln T1
For isobaric process (V2/V1 = T2/T1)
T2
ΔSsys = nCp ln T1
Entropy Calculation in different Processes

Entropy change in phase transition

Phase transition at constant temperature and pressure are reversible.Thus,

ΔSTotal = 0
ΔSSystem + ΔSSurrounding = 0
– ΔH
ΔSSurrounding =
T
ΔH
ΔSSystem =
T
Entropy Calculation in different Processes
Entropy change in phase transition

Entropy of fusion Entropy of vapourisation Entropy of sublimation

ΔHfusion ΔHvap ΔHsub

ΔSfusion= ΔSvap = ΔSsub =
Tf Tb Tsub

Tf = Freezing point Tb = Boiling point Tsub = Sublimation point

Gibbs Free Energy (G)
Thus for the purpose of finding out the feasibility of a process, a new function,
Gibbs free energy (G) was defined.

G = H – TS
Gibbs Enthalpy Product of
energy or absolute
Gibbs temperature and
function entropy
Criteria for Spontaneity
Role of temperature in spontaneity

ΔG = ΔH + (–TΔS)
ΔH ΔS ΔG Remarks

–ve +ve –ve Spontaneous at all

temperatures

–ve –ve –ve (at low temperature) Spontaneous

+ve (at high temperature) Non–spontaneous

+ve +ve +ve (at low temperature) Non–spontaneous

–ve (at high temperature) Spontaneous

+ve –ve +ve Non–spontaneous at all

temperatures
Third Law of Thermodynamics
The entropy of a perfectly crystalline solids may be taken as zero at the absolute
zero temperature

T=0K
S=0
Third Law of Thermodynamics
It helps in calculation of the absolute entropy of a substance at any temperature T
Let S0 = entropy at 0 K
S = entropy at T K

T CpdT
ΔS = S – S0 = T
0

But S0 = 0 at 0K by third law of thermodynamics

T CpdT
S= T
0

S = CplnT = 2.303 Cp logT Cp is assumed to be

constant in range of 0 to T
Reaction Enthalpy
The enthalpy change accompanying a reaction is called the reaction enthalpy.
The enthalpy change of a chemical reaction, is given by the symbol ∆rH.

Sum of Sum of
∆ rH = enthalpies of enthalpies of
products reactants
–
∆rH = ∑ ai Hproducts – ∑ bi Hreactants

ai and bi are the stoichiometric coefficients of the products and reactants respectively
in the balanced chemical equation.
Reaction Enthalpy
Standard Enthalpy of Reactions (ΔH°)

Element Reference State

Hydrogen H2 (g)

Oxygen O2 (g)

Carbon C (graphite)

Sulphur S (rhombic)

Phosphorus P4 (white)

Metals M(s) except Hg(l)

Bromine Br2 (l)

Iodine I2 (s)
Standard enthalpy of formation
The standard enthalpy change for the formation of one mole of a compound from its
elements in their most stable states of aggregation (also known as reference states).
Its symbol is ∆fH0.

Elements in
their One mole
standard compound
state.
Standard enthalpy of formation
Let’s learn how to write thermochemical equations corresponding to standard enthalpy
of formation -
Ex. 1 Enthalpy of formation of water:

H2 (g) + ½O2 (g) → H2O(l); ∆fH0 = –258.8 kJ mol–1

Hydrogen in Oxygen in One mole of

its reference its reference water is
state state formed.
Enthalpies for Different Types of Reactions
Standard enthalpy of combustion

Standard enthalpy of combustion is defined as the enthalpy change per mole (or per
unit amount) of a substance, when it undergoes complete combustion and all the
reactants and products being in their standard states at the specified temperature. It is
denoted as ΔcH°.

Combustion
Products in
of one mole
their
of the standard
substance state.
Enthalpies for Different Types of Reactions
Enthalpy of reaction in terms of enthalpy of combustion

Sum of enthalpies Sum of enthalpies

Enthalpy of
reaction = of combustion of
reactants
– of combustion of
products

Δr H = ∑a ΔcH – ∑b ΔcH
(reactants) (products)
Enthalpies for Different Types of Reactions
Enthalpy of Hydration (for substances forming hydrated salts)

Enthalpy change when one mole of an anhydrous (or partly hydrated) compound
combines with the required number of moles of water to form a specific hydrate at the
specified temperature and pressure
For example -
CuSO4(s) + 5H2O(l) ⟶ CuSO4⋅5H2O; ΔhydH = -78.20 kJ mol-1
Enthalpies for Different Types of Reactions
Enthalpy of Neutralisation

The amount of heat released when one gram equivalent of an acid is neutralised by one
gram equivalent of a base.

1 eq. 1 eq. Salt +

acid + base = water
Enthalpies for Different Types of Reactions
Enthalpy of Neutralisation
The amount of heat released when one gram equivalent of an acid is neutralised by one
gram equivalent of a base.

H+(aq) + OH-(aq) ⟶ H2O(l) ΔH = -57.1 kJ/mole = -13.7

kcal/mol

● For Strong Acid + Strong Base the heat of neutralisation is always equal to -13.7
kcal/mole or -57.1 kJ/mole.

● For any other combination of acid and base, heat released is less than 13.7
kcal/mol or 57.1 kJ/mole. This is because some of the released heat is used in
dissociation/ionisation.
Enthalpies for Different Types of Reactions
Enthalpy of Ionisation/Dissociation

Weak acids, weak bases, and their salts are not completely dissociated/ionised by
themselves in the solvent. The amount of heat required to ionise acid/base is known as
enthalpy of ionisation.
AB → A+ + B–; ΔH = enthalpy of ionisation
Enthalpies for Different Types of Reactions

Enthalpy of Ionisation/Dissociation

Enthalpy of Enthalpy of
Enthalpy of
neutralisation for neutralisation for
weak acid/base + = ionisation for
weak acid/base
+ strong acid +
strong base/acid strong base
Enthalpies for Different Types of Reactions

Enthalpy of Atomisation

It is the enthalpy change on breaking bonds in one mole substance completely to

obtain atoms in the gas phase. It is denoted as ΔaH°.

For example - H2(g) ➝ 2H(g) ; ΔaH° = 435.0 kJ mol-1

H H For diatomic
molecules,
enthalpy of
atomisation is
equal to bond
energy.
Enthalpies for Different Types of Reactions

Enthalpy of Atomisation

CH4(g) ➝ C(g) + 4H(g) ; ΔaH = 1665 kJ mol-1

C H H H H

Let’s see one more example -

Na(s) → Na(g); ΔaH° = 108.4 kJ mol-1
Here enthalpy of atomisation is same as the enthalpy of sublimation.
Enthalpies for Different Types of Reactions
Lattice Enthalpy

The lattice enthalpy of an ionic compound is the enthalpy change which occurs
when one mole of an ionic compound dissociates into its ions in gaseous state. It
is denoted by ΔlatticeH°
For example - NaCl(s) → Na (g) + Cl (g); ΔlatticeH° = +788 kJ mol–1
Enthalpies for Different Types of Reactions

Enthalpy of Hydration (for ions)

Enthalpy change when one mole of ions undergoes hydration. It is denoted as

ΔhydH. If solvent is other than water, it can also be called enthalpy of solvation.
For example -

Na+(g) Na+(aq.); ΔhydH = –405 kJ mol-1

Bond Dissociation Enthalpies
The bond dissociation enthalpy is the change in enthalpy when one mole of
covalent bonds of a gaseous covalent compound is broken to form products in the
gas phase. It is denoted by ∆bondH∘.
AB(g) → A(g) + B(g); ∆A–BH∘.

A
A B
+ B

For diatomic molecules, bond enthalpy is equal to the enthalpy of atomisation.

For example,
H2(g) → 2H(g); ∆H = ∆H–HH∘ = ∆aH∘
Bond Dissociation Enthalpies
It is possible to relate heat of reaction to changes in energy associated with
breaking and making of chemical bonds.

Sum of bond Sum of bond

Enthalpy of
reaction = enthalpies of
reactants
– enthalpies of
products

Δr H = ∑a ΔbondH – ∑b ΔbondH
(reactants) (products)

This relationship is approximate and is valid when all substances (reactants

and products) in the reaction are in gaseous state.
Resonance Energy

CH2 = CH – CH = O

Energy of most stable canonical form

Resonance Energy

δ+CH CH CH Oδ–
2

Energy of resonance hybrid

Resonance Energy
When a compound shows resonance, there is considerable difference between the
heat of formation as calculated from bond energy and that determined
experimentally.

Experimental or
Resonance
Energy = actual heat of
formation
– Calculated heat
of formation

Experimental or
Resonance
Energy = Calculated heat
of combustion – actual heat of
combustion

Since resonance stabilizes a molecule, resonance energy is

always with negative sign.
Hess’s Law of Constant Heat Summation
Statement
Hess’s law states that if a reaction is carried out in a series of steps, ∆H
for the overall reaction equals the sum of the enthalpy changes for the individual steps.

CH4(g) + 2O2(g)

–802 kJ
–890 kJ
Enthalpy CO2(g) + 2H2O(g)

–88 kJ

CO2(g) + 2H2O(l)
Hess’s Law of Constant Heat Summation
If a chemical reaction can be made to take place in a number of ways in one or
in several steps, the total enthalpy change is always the same.

>
∆H4

A D
∆H1 ∆H3

B ∆H2
C

According to Hess’s law, ∆H4 = ∆H1+ ∆H2 + ∆H3

Born Haber Cycle
Let’s understand how we can use Born Haber cycle to find lattice energy of NaCl -

Step What it represents?

1 Enthalpy of formation of NaCl(s)

2 Enthalpy of sublimation of Na

3 ½ (Enthalpy of atomisation of Cl2)

4 Enthalpy of ionisation of Na

5 Electron gain enthalpy of Cl

6 – ΔlatticeH° (NaCl)

*For chlorine, the enthalpy of atomisation

is equal to its bond energy.
Born Haber Cycle
Let’s understand how we can use Born Haber cycle to find lattice energy of NaCl -

Since enthalpy is a state function,

ΔH5 + ΔH6 = ΔH1 – ΔH2– 1/2ΔH3– ΔH4
ΔH5 – ΔlatticeH = ΔH1 – ΔH2– 1/2ΔH3– ΔH4
ΔlatticeH = ΔH5 – ΔH1 + ΔH2+ 1/2ΔH3+ ΔH4
Temperature Dependence of Enthalpy
On rearranging the equation, we get

∆HT2 – ∆HT1
= ∆CP
T2 – T1

This equation is called

Kirchhoff’s equation and is
used to find heat of reaction at
a temperature when it is
known at another temperature.
Temperature Dependence of Enthalpy
Similarly,

∆UT2 – ∆UT1
= ∆CV
T2 – T1

This equation is also another

form of the Kirchhoff’s
equation.
Relation b/w Gibbs energy, entropy & enthalpy change

ΔG = ΔH – TΔS

Free energy change of a reaction

ΔGr = ΔHr – TΔSr

ΔGr = ∑(ΔGf)product – ∑ (ΔGf)reactant

ΔHr = ∑(ΔHf)product – ∑ (ΔHf)reactant

ΔSr =∑ (ΔSf)product – ∑(ΔSf)reactant

ΔG = (–ve) Spontaneous
ΔG = (+ve) Non spontaneous
ΔG = 0 Equilibrium