ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT.

TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
THERMODYNAMICS
SYNOPSIS AND FORMULAE SHEET
The branch of science which deals with the quantitative relationship between heat and other forms of
energies is called Thermodynamics.
Limitations of thermodynamics:
(i) Does not talk about rate of a chemical reaction.
(ii) Does not describe the system while the changes are taking place, it only deals with initial and final
state.
(iii) Does not deal with microscopic properties of a system, it only deals with macroscopic properties.

Thermodynamics terms:
(i) System: It refers to the part of universe in which observations are carried out.
(ii) Surroundings: The part of universe other than the system is known as surroundings.
(iii) Boundary: The wall that separates the system form the surroundings is called boundary. It can be real
or imaginary.
(iv) Thermodynamic equilibrium: A system in which the macroscopic properties do not undergo any
change with time is called thermodynamic equilibrium.
(v) Thermal equilibrium: If there is no flow of heat from one portion of the system to another, the system
is said to be in thermal equilibrium.
(vi) Mechanical equilibrium If no mechanical work is done by one part of the system on another part of the
system, it is said to be in mechanical equilibrium. Such a condition exists when pressure remains constant.

Types of Systems
(i) Open system: The system in which energy and matter both can be exchanged with the surroundings.
(ii) Closed system: The system in which only energy can be exchanged with the surroundings.
(iii) Isolated system: The system in which neither energy nor matter can be exchanged with the
surroundings.

State of System
When macroscopic properties have definite value, the conditions of existence of the system is known as
state of system.
State functions: (State variables) When values of system is independent of path followed and depend only
on initial and final state, it is known as state function, e.g. U, H, G etc.
Path functions: These depend upon the path followed, e.g work, heat, time etc.

Thermodynamic Properties
(i) Extensive Properties:
Properties of the system which are dependent on the quantity of matter are called extensive properties,
e.g. internal energy, volume, enthalpy, etc.
(ii) Intensive Properties:
Properties of the system which are dependent only on the nature of matter and not on the quantity of matter
are called extensive properties, e.g. pressure, temperature, specific heat, density etc. Whenever unit amount
of an extensive property is given then, the property becomes an intensive property.

Thermodynamic Process
It is the operation which brings change in the state of the system. Thermodynamic processes are
(i) Isothermal process In which temperature remains constant, i.e., (ΔT = 0, Δ U = 0).
(ii) Isochoric process In which volume remains constant, i.e., (ΔV = 0).
(iii) Isobaric process In which pressure remains constant, i.e., (ΔP = 0).
(iv) Adiabatic process In which heat is not exchanged by system with the surroundings, i.e., (q = 0).
(v) Reversible process A process that follows the reversible path, i.e., the process which occurs in infinite
number of steps in this way that the equilibrium conditions are maintained at each step, and the process can
be reversed by infinitesimal change in the state of functions.

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
(vi) Irreversible process The process which cannot be reversed and attains equilibrium only at the end of
the process. All natural processes are Irreversible.
(vii) Cyclic process It is a process in which system returns to its original state after undergoing a series of
change. For cyclic process ΔE = 0, ΔV = 0, ΔP = 0, ΔT = 0, ΔH = 0, i. e. change in all state function is zero.
W and q are not zero, they may either be +ve or –ve

Modes of Transference of Energy

Heat (q)
It occurs when there is a difference of temperature between system and surroundings. It is a random form of
energy and path dependent. Its units are joule or calorie.
Work (W)
If the system involves gaseous substances and there is a difference of pressure between system and
surroundings, work is referred as pressure-volume work (WpV).

Expression for Pressure-Volume Work

(i) Work of irreversible expansion against constant pressure p under isothermal conditions
W = - pext ∆V or W = - Δn(g) RT
(ii) Work of reversible expansion (max work done) under isothermal conditions
V 
Wrev = - 2.303 nRT log  2 
 V1 
P 
or Wrev = - 2.303 nRT log  1 
 P2 
(iii) Work of reversible expansion under adiabatic conditions
 nR 
Wrev =   (T2 – T1), where, γ = Poisson’s ratio
 γ-1 
(Under adiabatic conditions TV γ-1 = constant)
(iv) Work of irreversible expansion under adiabatic conditions
 P T -P T 
Wirrev = - pext × R  1 2 2 1 
 P1P2 
(v) When an ideal gas expands in vacuum, pext = 0, W = 0

Sign conventions of W and q:

+W 
ONTHE SYSTEM
 
ON THE SYSTEM
 +q
Surrounding SYSTEM Surrounding

 W 
BY THE SYSTEM
 
BYTHE SYSTEM
 -q

Units of ‘R’and Wmax are always same.

R = 8.314 JK1mol1
= 8.314 × 10-3 kJ K1mol1
= 2 cal K1mol1
= 0.08206 lit-atm K1 mol1

Units of energy and work

1J = 1 Kg m2s-2
The relation between joule and pascal is : 1 J = 1 Pa m3
1 atm = 101.3  103 kg m-1 s-2

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
Thus, 1 L.atm = dm3 101.3  103 kg m-1 s-2
= m3  10-3  101.3  103 kg m-1 s-2
= 101.3 kg m-1 s-2
= 101.3 J

Units:
Pressure: 1 atm = 76cm Hg = 760 mm Hg = 760 torr
= 1.013 × 105 Pascal = 1.013 × 105 N/m2 = 1.013 × 102 KPa
Volume: 1dm = 1 lit = 103 cm3 = 103 ml = 10-3 m3
3

Energy and work have same units:

1 lit-atm = 24.22 cal = 101.3J = 101.3 × 107 erg
1J = 107 erg = 0.239 cal
1 cal = 4.184 J

Increasing order of energy: erg < Joule < Cal < lit-atm

In W = -pex V
P V W
Pa(Nm ) m3
-2
J
Atm lit (dm3) lit atm
dyne cm-2 cm3 erg

Internal Energy (E or U)
It is the energy of the system.
U = U intermolecular + U intramolecular + U vibrational + U translation + U rotation + Uelectronic
Its absolute value cannot be determined but experimentally change in internal energy (U) can be
determined by U = U2 – U1 or ΣUP - ΣUR
U mainly depends on temperature.

Zeroth Law of Thermodynamics or Law of Thermal Equilibrium

The law states that if the two systems are in thermal equilibrium with a third system then they are also in
thermal equilibrium with each other. Temperature is used here to know, the system is in thermal equilibrium
or not.

First Law of Thermodynamics

Energy can neither be created nor destroyed although it can be converted from one form to the other.
Mathematically, ∆U = q + W.
1. Isothermal process: q = -W or -q = W
2. Adiabatic process: ∆U = W or -∆U = -W
3. Isochoric process: ∆U = qv or -∆U = -qv
4. Isobaric process: ∆U = qp - pext ∆V
Neither q nor W is a state function, yet (q + W) is a state function because q + W = U, and
U is a state function.

Enthalpy (H)
It is the sum of internal energy and PV-energy of the system. It is a state function and extensive property.
Mathematically,
H = U + PV
Like U. absolute value of H also cannot be known, ΔH is determined experimentally.
ΔH = H2 – H1
Exothermic reaction, ΔH = -ve
Endothermic reaction, ΔH = +ve.

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
Relationship between ΔH and ΔU
ΔH = ΔU + ΔPV (If pressure is not kept constant)
(Use this formula for gaseous expansion and compression)
ΔH = ΔU + PΔV (If pressure is kept constant)
ΔH = ΔU + Δn(g) RT (Use this formula incase of chemical reaction)
ΔH = qp, ΔU = qv
Here, Δn(g) = n(g)p – n(g)r
If Δn = +ve, ΔH > ΔU
If Δn = -ve, ΔH < ΔU
If Δn = 0, ΔH = ΔU
For Isothermal expansion of an ideal gas, ΔT = 0, ΔU = 0, ΔH = 0.
Process in which ΔH = 0 is called as an isoenthalpic process.

THERMOCHEMISTRY:
The standard state of a substance is the form in which it is most stable at a pressure of 1 bar
(105 Pa = 0.0987 atm) or 1 atm at a particular temperature (usually 25oC).
Standard states of element: H2(g), Hg(l), Na(s), C(graphite), S8 (Rhombic)
Standard state of compound: i) H2O(l), CaCO3(s), CO2(g)
ii) First four Alkanes, Alkenes, Alkynes- Gases
iii) Alcohols, Aldehyde (Except- HCHO: Gas), Ketones, Esters, Acids- Liquids
iv) Solvents like C6H6, CS2, Toluene- Liquids
Guidelines for writing of thermochemical equations:
i) The equation must be balanced for the number of moles of reactants and products.
ii) The numerical value and appropriate sign of enthalpy change must be shown on the right hand side of the
equation.
iii) The physical states (s, l, g, aq) of reactants and products must be specified.
iv) Ho for the reverse reaction is equal in magnitude and opposite in sign to the value corresponding to the
forward reaction.
v) If the coefficient indicating the number of moles of all the substances in the thermochemical equation are
multiplied or divided by a numerical factor, the value of Ho must also be multiplied or divided by the same
factor

Various Forms of Enthalpy of Reaction

1. Enthalpy of Formation (ΔfH⊝):
It is heat change when one mole of compound is obtained from its constituent elements in their standard
states.
Enthalpy of formation at standard state is known as standard enthalpy of formation Δ fH°.
It also gives the idea of stability of the compound formed. [ΔfH⊝ (If exothermic) α Stability]
Standard enthalpy of formation of an element from itself is zero.
ΔH = ΣH(f)p - ΣH(f)R
2. Enthalpy of Combustion (ΔCH⊝):
It is the Enthalpy change taking place when one mole of a compound undergoes complete combustion in the
presence of oxygen (ΔCH⊝)
ΔHc is always negative, except for combustion of nitrogen to form nitric oxide and Flourine to OF2, which
are positive.
Calorific value: Is the amount of heat in calories produced from the complete combustion of one gram of
food or fuel. Units in SI are calg-1 or kJ kg-1.
3. Enthalpy of Neutralisation (ΔnH⊝):
It is the enthalpy change (usually heat evolved) that takes place when 1 g-equivalent of an acid is neutralised
by 1g-equivalent of a base in dilute solution.
Enthalpy of neutralisation of strong acid and strong base is always constant, i.e., -57.32 kJ/mol or
-13.7Kcal/mol.
[Enthalpy of neutralisation of strong acid and weak base or weak acid and strong base is not constant and
numerically less than 57.1 kJ due to the fact that here the heat is used up in ionisation of weak acid or weak
base. This is known as enthalpy of ionisation of weak acid or weak base.]

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
Heat of neutralisation of weak acid = Heat of neutralisation of strong acid + Heat of ionisation of weak acid
Heat of neutralisation of weak base = Heat of neutralisation of strong base + Heat of ionisation of weak base

Heat of neutralisation of HF is about -68kJ, i.e. more than -57.1kJ. This is due to very high hydration energy
of fluoride ions.

4. Enthalpy of Fusion(ΔfusH⊝):
The enthalpy change that accompanies the fusion of one mole of a solid, converting solid to liquid without
change in temperature at constant pressure is called its enthalpy of fusion.
It is always endothermic.
5. Enthalpy of Vaporisation (ΔvapH⊝):
The enthalpy change that accompanies the vaporization of one mole of a liquid without changing its
temperature at constant pressure is called enthalpy of vaporization.
It is always endothermic.
6. Enthalpy of Sublimation (ΔsubH⊝):
The enthalpy change that accompanies the conversion of one mole of solid directly into its vapour at
constant temperature and pressure is called its enthalpy of sublimation.
It is always endothermic. ∆subH = ∆fusH + ∆vapH
8. Enthalpy of Atomisation (ΔaH⊝)
The enthalpy change accompanying the dissociation of one mole of given substance into gaseous atoms is
called enthalpy of atomization.
9. Enthalpy of Solution (ΔsolH⊝):
The enthalpy change accompanying the formation of one mole of a crystalline solid from its constituent ions
in the gaseous state.
solnH = LH (Endothermic) + hydraH (Exothermic)

Effect of temperature on solubility/Calculation of enthalpy of solution:

If the solubility of a substance is known at two different temperatures, the mean molar enthalpy of solution
over this temperature range can be calculated by applying an equation,
S  Δ H  1 1 
log  2   sol   
 S1  2.303R  T1 T2 
where S1 and S2 are solubilities at temperatures T1 and T2 respectively.

10. Enthalpy of Dilution (ΔdilH⊝):

The enthalpy of dilution is defined as the enthalpy change that occurs when a solution of one concentration
is diluted to form the solution of another concentration.
11. Bond Enthalpy (bondH⊝/ B.E)
The enthalpy change necessary to break particular covalent bond in one mole of gaseous molecules to
produce gaseous atoms and/or radicals is called bond enthalpy.
The bond enthalpy is always positive because energy is always needed to break a bond.
In case of polyatomic molecules, average bond enthalpy of a particular bond is considered.
∆Ho (reaction) = ∑ B.E (reactant bonds)  ∑ B.E (product bonds)

Laws of Thermochemistry
1. Lavoisier Laplace Law:
The enthalpy change during a reaction is equal in magnitude to the enthalpy change in the reverse process
but it is opposite in sign.
2. Hess’s Law of Constant Heat Summation
The standard enthalpy of a reaction. which takes place in several steps, is the sum of the standard enthalpies
of the intermediate reactions into which the overall reactions may be divided at the same temperature.
According to Hess’s law:ΔH = ΔH1 + ΔH2 + ΔH3
Main application of Hess’s law is to determine the enthalpy of any reaction, which cannot be calculated in
laboratory

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
3. Trouton’s Rule:
According to this law, “The ratio of enthalpy of vaporization and normal boiling point of a liquid is
approximately equal to 88 J per mol per kelvin. i.e.,
H vap
 88 J / mol / K
T
4. Dulong and Petit Law:
This law states “The product of specific heat and molar mass of any metallic element is equal to
6.4 cal/ mol/ °C. i.e.,
Specific heat × molar mass = 6.4 cal/ mol/ °C
5. Kirchhoff’s Equation:
H 2 – H1
ΔCp =
T2 – T1
U 2 – U1
and ΔCv =
T2 – T1
6. Clausius – Clapeyron Equation:
P Δ H     T2 – T1 
– 2.303 log 1 = vap   where, ΔvapH = molar heat of vaporisation.
P2 R  T1 T2 

Heat Capacity of a System

Heat Capacity (C) of a system is defined as the amount of heat required to raise the temperature of a system
by 1° C/1o K.
q = C × T
1. Molar Heat Capacity
It is the heat capacity 1 mole of substance of the system.
q = n CT
2. Specific Heat Capacity
It is the heat capacity of 1 g of substance of the system
q = m CΔ T.
where, m = mass of substance, c = specific heat or heat capacity
 dq   dH 
Cp =   =  
 dT  p  dT  p
 dq   dU 
Cv =   =  
 dT  v  dT  v
Cp - Cv = R

3
CV =   R
2
3 5
Cp =   R + R =   R
2 2
 Cp  5
Poisson’s ratio, γ =  =   = 1.66
 CV  3
γ = 1.66 for monoatomic gas
γ = 1.40 for diatomic gas
γ = 1.33 for triatomic gas

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
MEASUREMENT OF U AND H (CALORIMETRY)
We can measure energy changes associated with chemical or physical processes by an experimental
technique called calorimetry. In calorimetry, the process is carried out in a vessel called calorimeter.
For chemical reactions, heat absorbed at constant volume, is measured in a bomb calorimeter.

Spontaneous Process
Spontaneous process is defined as a process that takes place on its own under the given set of conditions
once it has been initiated if necessary without the continuous external influence.
All natural processes are spontaneous process.
Spontaneous process where no initiation is needed
(i) Sugar dissolves in water.
(ii) Evaporation of water.
(iii) Nitric oxide (NO) reacts with oxygen.
Spontaneous process where some initiation is required
(i) Coal keeps on burning once initiated.
(ii) Heating of CaCO3 to give calcium oxide and CO2 is initiated by heat.

CaCO3(s)   CaO(s) + CO2(g)
CRITERIA FOR SPONTAINEITY:
1. Energy and spontaneity:
Chemical reaction must be exothermic in order to take place spontaneously.
Although, the spontaneous changes are exothermic, the exothermicity is not the sufficient criterion for the
spontaneity of the process. There are many processes that are endothermic but spontaneous.
2. Entropy (S)
It is the measurement of randomness or disorder of the molecules. It is a state function and extensive
property.
Units : JK-1 mol-1
The change in entropy during a process is mathematically given as
q H
ΔrS° = Σ S° (products) – Σ S° (reactants) = rev 
T T
ΔS > 0, Increase in randomness.
ΔS < 0, Decrease in randomness.
Order of entropy: Gas > Liquid > Solid
Entropy of even elementary substances are not zero.
For an adiabatic reversible process, q=0, at all stages. Hence, ΔS = 0. Such processes are called as
Isoentropic.

Entropy change of an ideal gas is given by

T2 V T P
ΔS = Cv ln + R ln 2 = Cp ln 2 + R ln 1
T1 V1 T1 P2
V2 P
At constant temperature (isothermal process): ST = R ln =R ln 1
V1 P2
T2
At constant volume (isochoric process): SV = Cv ln
T1
T
At constant pressure (isobaric process): SP = CP ln 2
T1
∆Stotal = ∆Ssys + ∆Ssurr
A process is a spontaneous if and only if the entropy of the universe increases.
For a process to be Spontaneous: ∆Stotal > 0 or ΔSsyst + ΔSsurr > 0
At equilibrium state, ΔS = 0,
As spontaneous processes are thermodynamically irreversible, and reversible processes attain equilibrium,
∆Ssys + ∆Ssurr > 0 for the irreversible process and ∆Ssys + ∆Ssurr = 0 for reversible process

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
Limitations of ΔS criterion and need for another term We cannot find entropy change of surroundings
during chemical changes. So we need another parameter for spontaneity viz Gibbs’ energy of system (G).

Second Law of Thermodynamics

The entropy of the universe is always Increasing in the course of every spontaneous or natural change.
Or
All spontaneous processes or natural change are thermodynamically irreversible without the help of an
external work. i.e., heat cannot flow itself from a colder to hotter body.

Joule-Thomson Effect
The phenomenon of cooling of a gas when it is made to expand adiabatically from a region of high pressure
to a region of extremely low pressure is known as Joule-Thomson effect. This effect is zero when an ideal
gas expands in vacuum.
[When an ideal gas undergoes expansion under adiabatic condition in vacuum, no change takes place in its
 E   E 
internal energy, i.e.,   = 0 where,   is called the Internal pressure.]
 V T  V T

Joule-Thomson Coefficient
The number of degrees of temperature change produced per atmospheric drop in pressure at constant
enthalpy when a gas is allowed to expand through a porous plug is called Joule-Thomson coefficient. It is
given as
 dT 
μ=  
 dp 
where, μ = Joule-Thomson coefficient
dT = change in temperature
dp = change in pressure.

Inversion Temperature
The temperature below which a gas becomes cooler on expansion is known as the inversion temperature.
 2a 
It is given asTi =  
 Rb 
where, a and b = van der Waals’ constant
At inversion temperature Ti, the the Joule Thomson coefficient μ = 0, i.e., the gas neither heated nor cooled.

Gibbs Energy or Gibbs Free Energy

It is the energy available for a system at some conditions and by which useful work can be done.
It is a state function and extensive property.
Mathematically,
G = H – TS
ΔG = ΔH – TΔS
ΔGsystem = – TΔStotal
The Gibbs energy criterion of spontaneity
ΔG > 0, process is non-spontaneous
ΔG < 0, 0, process is spontaneous (Exoergonic process)
ΔG = 0, process is in equilibrium state (Endoergonic process)

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 ABHISHEK, VINAY & ARUN’S CHEMISTRY PVT. TUTORIALS
ABHISHEK SIR: 9833395472 VINAY SIR: 9867442504 ARUN SIR: 9870577035
Effect of Temperature on Spontaneity
SR.NO Sign of ΔH Sign of ΔS ΔG = ΔH – TΔS Remarks
1. Negative Positive Always negative Spontaneous at all temperatures
2. Positive Negative Always positive Non-spontaneous at all
temperatures
3. Positive Positive Positive at low temperature Non-spontaneous at low
Negative at high temperature temperature Spontaneous at high
ΔH < TΔS temperature
4. Negative Negative Negative at low temperature Spontaneous at low temperature
Positive at high temperature Non-spontaneous at high
ΔH > TΔS temperatures
Standard Free Energy Change (ΔG°)
ΔG° = ΔH° - TΔS°
ΔG° = ΣG f (Products) - ΣΔG f (Reactant)
Gibbs Energy Change and Equilibrium
G =G° + RT In Q
0 = G° + RT In K (At equilibrium)
or G° = - RT In K
or G° = -2.303 RT log K

Relation between G° and EMF of the cell

G° = -nFE °cell

Third Law of Thermodynamics

This law was formulated by Nernst in 1906. According to this law, “The entropy of a perfectly crystalline
substance at zero K or absolute zero is taken to be zero”. We can find absolute entropies of pure substances
at different temperature.
T
S = ST - So= ST = 0
CpdT = 2.303 Cp log T, where, Cp = Heat capacity
T = temperature between 0 K and T K
This law is on1y applicable for perfectly crystalline substances. If there is imperfection at 0 K, the entropy
will be larger than zero.

Residual entropy: There are certain substances which possess some entropy even at absolute zero.
The entropy possessed by a substance at absolute zero is called its residual entropy.
Residual entropy can be calculated using the formula: S R = k ln W
Where W represents the number of possible orientations of the molecule that are equally probable, i.e., have
nearly same energy and k is Boltzmann constant. (W is called thermodynamic probability).
For example in case of CO there are two orientation that are equally probable hence if there are N molecules of
CO
W = 2N  SR = k ln W = k ln 2N = kN ln 2
For 1 mole kN = R.
Hence, SR = R ln 2 = 2.303 R log 2 = 2.303  8.314  0.3010 JK-1 mol-1 = 5.85 JK-1 mol-1

Instant cold and hot packs:

These are plastic bags containing a pouch of water and a suitable solid solute.
In cold instant pack: The solid solute taken is such whose dissolution is endothermic.
Generally, ammonium nitrate is taken. When the pack is squeezed, the pouch breaks. Water mixes into the
solute. Dissolution being endothermic, the pack cools down and can be used for giving a cooling sensation.
NH4NO3 (s) + water → NH4+(aq) + NO3-(aq); ∆H =+26.2kJ
In hot instant pack: The solid solute taken is such whose dissolution is exothermic. Generally, CaCl2 or
MgSO4 is used. These packs are used for giving heating sensation.
CaCl2(s) + water → Ca2+(aq) + 2 Cl-(aq). ∆H = - 82.2kJ (These packs are generally used for giving first aid to
the athletes for treatment of injuries. They give instant relief in 15-20mins)
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