(i) During isothermal process (n, T constant) of an ideal gas, change in enthalpy (∆H) is

zero because at constant temperature pV = constant, hence ∆H = ∆U + ∆(pV)  ∆H = ∆U

+ 0  ∆H = ∆U = 0 (or) ∆H = nCV ∆T = nCV (o) = 0
Work done in isothermal reversible expansion of ideal gas,
V2 p
Wrev  2.303nRT log  2.303nRT log 1
V1 p2
Note: All phase transitions are isothermal processes but ∆U ≠ 0 and ∆H ≠ 0.

(ii) Adiabatic process (n constant, q = 0):

In adiabatic process, work behaves as a state function since ∆U = w and ∆U is a state
function.
In adiabatic expansion of an ideal gas, temperature of the system decreases. So, adiabatic
expansion of an ideal gas is accompanied by decrease in internal energy (∆U).
In adiabatic compression of an ideal gas, temperature of the system increases. So, adiabatic
compression of an ideal gas is accompanied by increase in internal energy (∆U).
It is also called isotropic process, because there is no change of entropy during adiabatic
process.  ds  
dq 0
  0
 T T 
nR(T2  T1 )  Cp 
In adiabatic process, w    
 1  CV 
For adiabatic reversible expansion of ideal gas,
pVγ = Constant; TVγ - 1 = Constant; p1-γ Tγ= Constant

(iii) Isochoric process (or) Isovolumic process (n, V constant):

The process is termed as isochoric in which volume remains constant throughout the change,
i.e., ∆V = 0, pressure and volume are variable. The process in closed system is isochoric in
nature.
In isochoric process, work done, w = -pext ∆V = -pext (0) = 0  ∆U = q
In isochoric process, ∆V = 0, ∆U ≠ 0, q ≠ 0 and w = 0.

(iv) Isobaric process (n, p constant):

The process is known as isobaric in which the pressure remains constant throughout the
change, i.e., ∆p = 0, volume and temperature are variable. The process in open system is
isobaric in nature.

In an isobaric process (n, p constant), 1st law of thermodynamics changes to ∆U = q + w =

qP – p∆V = ∆H – p∆V (or) ∆H = ∆U + p∆V (or) ∆H = ∆U + ∆n(RT)
In isobaric process, during expansion of gas work done is negative and positive during
compression of gas.
In isobaric process, ∆p = 0, ∆U ≠ 0, q ≠ 0 and w ≠ 0.
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(v) 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.
In cyclic process, change in all state function will be zero, i.e., ∆T = 0, ∆U = 0, ∆H = 0 and
∆P = 0.
1st law of thermodynamics, ∆U = q + w  For a cyclic process, 0 = q + w, hence q = - w,
that means work done = - ve
1st law of thermodynamics, ∆U = q - w  For a cyclic process, 0 = q - w, hence q = -w,
that means work done = +ve

THERMODYNAMICS
Thermodynamics means flow of heat. Thermodynamics is the branch of chemistry and it
deals with quantitative relationship between heat and other forms of energy in physico-
chemical transformations. It does not deal with total energy of body.
Thermodynamics helps to predict the feasibility of a chemical reaction, i.e., the chemical
reaction occurs on its own or not.
(I) Thermodynamic terms:
(1) System, Surroundings and boundary:
System: A small part of universe chosen for thermodynamic study is called system.
Surroundings: The remaining part of the universe in contact with system is called
surrounds. So, Universe = system + surroundings
In a reversible process, the surroundings are always in equilibrium with the system.
Boundary (Wall): Anything which separates system and surroundings is called boundary.
The boundary may be real or imaginary. It may be rigid or non-rigid. It may be conductor or
a non-conductor of heat. The terms diathermic wall and adiabatic wall are used for
conductor and non-conductor of heat boundaries respectively.
(2) Types of systems:
(a) On the basis of composition, there are two types of systems:
(i) Homogeneous system: Homogenous system consisting of one phase only.
e.g., pure single solid or liquid or gas, a mixture of gases and a true solution.
(ii) Heterogeneous system: Heterogeneous system may consist of two or more phases.
e.g., ice in contact with water, two or more immiscible liquids, insoluble solid in
contact with a liquid, etc.,
(b) On the basis of exchange of matter and energy between system and surroundings:
Open system Closed system Isolated system
Exchange of Yes, ∆q ≠ 0 Yes, ∆q ≠ 0 No, ∆q = 0
energy between
system and
surroundings
Exchange of Yes No No
matter between
system and
surroundings
Internal energy ∆U or ∆E ≠ 0 ∆U or ∆E ≠ 0 ∆U or ∆E = 0
2
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change,
 Type of wall Diathermic wall (or) Diathermic wall (or) Adiabatic wall (or)
(boundary) Conducting wall Conducting wall non-conducting wall
Examples The presence of The presence of The presence of
reactants or liquid or reactants or ice or reactants or ice or hot
ice or hot water or hot water or hot tea water or hot tea or
hot tea or hot coffee or hot coffee in a hot coffee in a
in an open beaker, closed vessel made thermally insulated
lime-kiln, all living of conducting vessel (thermo flask),
systems (human material like copper etc.,
beings, plants and or steel, glowing
animals), earth, bulb (tube light), a
class-room, car satelite in an orbit,
engines, etc. etc.
Heating of solid iodine in a sealed container (solid iodine sublimes to iodine vapours, but
iodine vapours cannot escape from the container) is closed system.

(3) State of the system is the conditions of existence of a system when its macroscopic
properties have definite values. It is defined in terms of its state functions such as p, V, T,
etc.,
State variables (or) State functions: The thermodynamic property which depends only
upon the initial and final states of the system and independent on the path is called state
function. Examples: Pressure (p), volume (V), temperature (T), number of moles (n), energy,
enthalpy (H), internal energy (U), Gibb’s energy (G), entropy (S), etc.,
i.e., Short code:{(p, V, T, n, energy), (H, U, G, S)}
Path functions: The thermodynamic property which depends upon the path of
transformations is called path function. Examples: Work(w) and heat(q) are path functions
because they appear only at the boundary of a system.
Heat (q) is a path function but q P and qV are state functions since qP = H and qV = U.
Work (w) and heat (q) are path functions but q + w = ∆U and ∆U is a state function.

(4) Macroscopic (or) bulk properties of system: “The properties of the system which arise
from the bulk behavior of matter are called macroscopic properties”.
The measurable properties of a system can be divided into 2 types.
(i) Extensive property: The property of a substance that depends on its mass or quantity or
size of matter present in the system is called extensive property.
Examples: Enthalpy (H), Internal energy (U), Gibbs energy (G), entropy (S), heat capacity
(C),
mass (m), volume (V), no. of moles (n), work (w), energy, heat, length, force, conductance,
resistance, etc.,
i.e., (H, U, G, S, C), (m, V, n, w, energy, heat, length, force, conductance, resistance)
(ii) Intensive property: The property of a substance that does not depends on its mass or
quantity or size of matter present in the system is called intensive property.
Examples: Pressure (p), temperature (T), density (d), concentration (like molarity, molality,
mole fraction),
viscosity, surface tension, refractive index, specific heat (s or c), specific gravity, dielectric
constant, dipole moment, EMF of a dry cell, pH value, freezing point (F.P.), boiling point
3
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(B.P.), vapour pressure, etc.,

 x = extensive property x = extensive property x = intensive property
y = extensive property y = intensive property y = intensive property
x + y = Ext. (q + w=∆U) x + y = Ext. x + y = Int.
x – y = Ext. (∆U – w = q) x – y = Ext. x – y = Int.
x.y = Ext.(force × length = x.y = Ext.(m×c = C) x.y = Int.
work or energy)& (Mass ×
Acceleration = Force)
𝑥 𝑚 x x
= 𝐼𝑛𝑡. ( = d) &  Ext.  Int.
𝑦 𝑉 y y
𝐹𝑜𝑟𝑐𝑒
( = Pressure)
𝐴𝑟𝑒𝑎
dx  H 
 Int.  T  
dy  S 
The sum, subtraction and product of two extensive properties will be extensive. But ratio
of them will be intensive. Examples: (q + w=∆U), (∆U – w = q), .(force × length = work or
energy)& (mass × acceleration = force)
𝐹𝑜𝑟𝑐𝑒
m, V are extensive properties but m/V = d is an intensive property. Similarly, =
𝐴𝑟𝑒𝑎
𝛥𝐻
Pressure and = T.
𝛥𝑆
If extensive property expressed per gram or per mole, it becomes intensive. e.g.,
(a) Mass and volume are extensive but mass per unit volume (i.e., density) is intensive.
(b) Heat capacity is extensive property but heat capacity expressed per gram is called
specific heat which is intensive property.
(c) Force is extensive property but force per unit area (i.e., pressure) is intensive.
(d) Similarly, molar volume, molar entropy, molar heat capacity, molar enthalpy, molar
internal energy, molar conductivity, etc., are intensive properties.
The sum, subtraction, product and ratio of two intensive properties is also intensive.

(5) Thermodynamic processes or operations:

When the thermodynamic system changes from one state to another, the operation is called a
process. The various types of the processes are: Isobaric (dP = 0), Isothermal (dT = 0),
Adiabatic (dq = 0), Isochoric (dV = 0) and Polytropic (PV X = C) process. 4
Page
The area under the curve of the PV diagram gives the work done to, or by, the system.
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.

Reversible process: A process which occurs infinitesimally slowly, i.e., opposing force is
infinitesimally smaller than driving force and infinitesimal increase in the opposing force
can reverse the process, it is said to be reversible process.

Irreversible process: The process goes from initial to final state in a single step or finite
number of steps in finite time and cannot be reversed exactly by small changes in p, V, T, etc.

(II) Nature of work and heat:

(a) Heat: Heat is the quantity of energy which flows between a system and its surroundings
on account of temperature difference. Heat is a path function.
Heat absorbed or evolved, q = ms ∆T (or) mc∆T
Where, m = mass of substance, s (or) c = specific heat, ∆T = temperature difference.
Units: It is measured in calories. SI unit of heat is Joule.
By conventions of IUPAC in chemical thermodynamics;
Case-1: q is positive when heat is transferred from surroundings to the system and internal
energy of the system increases.
Case-2: q is negative when heat is transferred from system to the surroundings and internal
energy of the system decreases.

(b) Work: Work is a path function.

Work is a mode of energy transfer to or from a system with reference to the surroundings.
Work done on a system increases the energy of the system and work done by the system
decreases the energy of the system.
Definition: If an object is displaced through a distance ‘l’ against a force ‘F’, work is to be
done. Mechanical work (or) p-V work = w = Force × Displacement = F × l
Force
But, pext   Force  pext .A ; Therefore, w = pext. A. l
Area
According to IUPAC system,
Work done on the system, w = + ve & Work done by the system, w = - ve
Units: work is measured in Joules (J), kilo Joules (kJ), ergs, Calories, etc.
1 Joule  107 ergs  1Nm  1kgm2 s 2 ; 1 Joule = 0.2390 cal; 1 Cal = 4.18 J;
1 L atm = 101.3 J = 1.013 x 109 erg = 24.2 Cal.
Energy increasing order: 1 L atm > 1 Calorie > 1 Joule > 1 erg

(III) (a) Internal energy, (E) or (U):

Every substance or system possesses a fixed quantity of energy which depends upon its
chemical nature and its state of existence. This energy is known as internal energy or
intrinsic energy and it is denoted by U or E. (or) The total energy stored in a substance at
constant temperature and volume is called internal energy.
The absolute value of internal energy cannot be determined exactly because it includes all
types of energies, i.e., E  Etranslational  Erotational  Evibrational  Ebonding  Eelectronic  ......... . But the change
5
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in internal energy can be determined by using bomb calorimeter.

It indicates internal energy is a state function and depends only on initial and final states of
the system. Internal energy is independent of the path. ∆U will be same even if the change is
brought about differently.
∆U = U2 – U1 (or) UProducts – UReactants
Where, U2 = internal energy of the system at final state; U1 = internal energy of the system at
initial state.
∆U is positive if UP > UR and ∆U is negative if UP > UR.
Characteristics of internal energy:
(i) When matter enters into a system, its internal energy increases and matter leaves from a
system, its internal energy decreases. This indicates internal energy is an extensive property.
(ii) When heat passes into a system, its internal energy increases and heat passes from a
system, its internal energy decreases.
(iii) When work is done on the system, its internal energy increases and work is done by the
system, its internal energy decreases.
(iv) There is no change in internal energy of a cyclic process, i.e., ∆Ucyclic = 0.
(v) In isothermal (∆T = 0) process, change in internal energy is zero, i.e., ∆Uisothermal = 0.
(vi) The internal energy of an isolated system cannot change according to first law of thermodynamics.

(b) Enthalpy (H):

Heat content of a system at constant temperature and constant pressure is called enthalpy.
(or) The amount of heat exchanged by a system with its surroundings at constant temperature
and constant pressure is called enthalpy. (or) The sum of the internal energy and the
pressure-volume energy of the system is called enthalpy. H = U + pV
Enthalpy is extensive property. Its value depends upon the amount of the substance,
chemical nature of the substance and conditions of temperature and pressure.
Enthalpy of a system is a state function that means depends upon the initial and final states
of the system. So, the absolute value of ‘H’ cannot be determined exactly and therefore its
change can be determined. Its change can be given as ΔH = H2 – H1 (or) HProducts - HReactants
Where, H2 = Enthalpy of the system in final state, H1 = Enthalpy of the system in initial state.
Reactions with ΔH value being negative are exothermic reactions and reactions with ΔH
value being positive are endothermic reactions.
(c) Zeroth law of thermodynamics:
It states that if two systems are in thermal equilibrium with a third system, the two original
systems are in thermal equilibrium with each other. Basically, if system ‘A’ and ‘B’ are in
thermal equilibrium with system ‘C’, then the systems ‘A’ and ‘B’ will also be in thermal
equilibrium with each other.
A B

C
(d) First law of thermodynamics: It is another form of law of conservation of energy.
“Energy cannot be created or destroyed but it can be converted from one form to another”.
Whenever energy of particular form disappears in a process, exactly an equivalent quantity
of another form of energy must appear that means energy not be created. The total energy of
6
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an isolated system remains constant though it may change from one form to another.
Consider a system whose internal energy is U1. If ‘q’ amount of heat is supplied to the
system, then the internal energy of the system increases and become U1 + q. Now if work ‘w’
is also done on the system, the internal energy further increases and becomes U 2. Thus, U2 =
U1 + q + w  U2 - U1 = q + w c ∆U = q + w
Case-(1): If work done on the system (i.e., during compression of a gas) and heat is absorbed
by system, ∆U = q + w, i.e., the net energy change of a closed system is equal to heat
absorbed plus the work done on the system.
Case-(2): If work done on the system (i.e., during compression of a gas) and heat is released
by system, ∆U = – q + w
Case-(3): If work done by the system (i.e., during expansion of a gas) and heat is absorbed
by system, ∆U = q – w, i.e., the net energy change of a closed system is equal to heat
absorbed minus the work done by the system.
Case-(4): If work done by the system (i.e., during expansion of a gas) and heat is released by
system, ∆U = – q – w

Some useful conclusions from first law of thermodynamics: ∆U = q + w is the general case.
(i) In an isolated system, no transfer of energy as heat or as work, i.e., q = 0 and w = 0, then
∆U= 0. This indicates, the energy of an isolated system is constant.

(ii) During isothermal process (n, T constant) of an ideal gas, change in internal energy is
zero, i.e., ∆U = 0 since ∆T = 0 and internal energy depends on temperature {∆U = nC V∆T =
nCV(0) = 0}.
Then first law of thermodynamics reduces to 0 = q + w  q = – w, i.e., heat absorbed from
surroundings = work done by the system (or)
– q = w, i.e., heat given to surroundings = work done on the system

(iii) In an adiabatic process (n constant, q = 0), there is no exchange of heat between the
system and surroundings, i.e., q = 0 then first law of thermodynamics reduces to ∆U = w (or)
– ∆U = – w.
It shows that if work is done on the system, its internal energy increases (or) if work is done
by the system its internal energy decreases.
In adiabatic process, work behaves as a state function since ∆U = w and ∆U is a state
function.

(iv) In an isochoric process (or) Isovolumic process (n, V constant), change in volume is
zero, i.e., ∆V = 0, then w = –p∆V = 0.
If no work is done, w = 0 at constant volume, then the first law of thermodynamics reduces
to ∆U = q (or) –∆U = –q (or) ∆U = qV. {Here, qV = heat change at constant volume}
It shows that increase in internal energy of the system is equal to the heat absorbed by the
system and decrease in internal energy of the system is equal to the heat lost by the system.
In isochoric process, ∆V = 0, ∆U ≠ 0, q ≠ 0 and w = 0.

(v) In an isobaric process (n, p constant), 1st law of thermodynamics changes to ∆U = q + w

= qP – p∆V = ∆H – p∆V (or) ∆H = ∆U + p∆V (or) ∆H = ∆U + ∆n(RT)
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In isobaric process, during expansion of gas work done is negative and positive during
compression of gas.
In isobaric process, heat behaves as a state function since qP = ∆H and ∆H is a state
function. In isobaric process, ∆p = 0, ∆U ≠ 0, q ≠ 0 and w ≠ 0.

(vi) In cyclic process, change in all state function will be zero, i.e., ∆T = 0, ∆U = 0, ∆H = 0
and ∆P = 0.
1st law of thermodynamics, ∆U = q + w  For a cyclic process, 0 = q + w, hence q = - w,
that means work done = – ve
1st law of thermodynamics, ∆U = q – w  For a cyclic process, 0 = q - w, hence q = -w,
that means work done = +ve

(e) Relation between ΔH and ΔU: (i) ΔH = ΔU + pΔV (ii) ΔH = ΔU + ΔngRT (iii) ΔH =
ΔU + Δ(pV) (or) ΔH = ΔU + (p2V2 – p1V1)
Here, Δng refers to the number of moles of gaseous products minus the number of moles of
gaseous reactants. The difference between ΔH and ΔU is not usually significant for systems
consisting of only solids and / or liquids. Solids and liquids do not suffer any significant
volume changes upon heating.
Case-(1): If Δng = 0, then ΔH = ΔU.
Examples: (i) H2 (g)  C 2 (g)  2HC (g) (ii) C(s)  O2 (g)  CO2 (g)
(iii) In case of reactions that do not involve any gaseous components, Δng = 0
HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l)
(iv) In case of reactions that carried out in closed vessels of fixed volume (i.e., ΔV = 0) or in
bomb calorimeter, Δng = 0
Case-(2): If Δng = – ve then ΔH < ΔU
Examples: (i) N2 (g)  3H2 (g)  2NH3 (g) (ii) 2SO2 (g)  O2 (g)  2SO3 (g) (iii) PC 3 (g)  C 2 (g)  PC 5 (g)
Case-(3): If Δng = +ve then ΔH > ΔU

Examples: (i) PC 5 (g)  PC 3 (g)  C 2 (g) (ii) CaCO3 (s)   CaO(s)  CO2 (g)

(iii) NH4HS(s) 
NH3 (g)  H2S(g)

(f) Heat capacity:

The amount of heat required to raise the temperature of substance through one degree celsius
(or one kelvin) is called heat capacity of a substance. It is denoted by ‘C’.
q q
q = coeff × ΔT  q = C ΔT (or) C  (or) C 
T T2  T1
The coefficient, C is called the heat capacity. The magnitude of the coefficient depends on
the size, composition and nature of the system.
Molar heat capacity: The amount of heat required to raise the temperature of one mole of a
substance through one degree celsius (or one kelvin) is called molar heat capacity of a
C
substance. Molar heat capacity of a substance, Cm 
n
Molar heat capacity of a substance, Cm  c  M
Where, M = molar mass of substance, c = specific heat capacity
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Specific heat capacity: The amount of heat required to raise the temperature of unit mass
(i.e., one gram) of a substance through one degree celsius (or one kelvin) is called specific
heat capacity of a substance. Specific heat capacity,
Heat capacity C q
c  
m m m T
 q  m.c. T (or) q  m.s. T
Units of specific heat capacity: J g 1 K1 (or) J g 1 oC1
Specific heat of water = 1Cal g 1K1 (or) 4.18 Jg 1 K1
Molar heat capacity of water = 18 Cal mol1K1 (or) 4.18×18 = 75.24 J mol1 K1
Dulong and Petit rule: A metallic element with higher atomic mass has lower specific heat.
Atomic mass × specific heat (Cal/gm) ≈ 6.4
6.4
Atomic mass 
Specific heat (Cal / gm)
This rule is valid for solid elements except Be, B, C and Si.
The relationship between Cp and CV for an ideal gas:
The amount of heat at constant volume is given by, qv = CVΔT = ΔU for one mole (or) ΔU =
n CV ΔT for ‘n’ moles
The amount of heat at constant pressure is given by, qp = CPΔT =ΔH for one mole (or) ΔU =
n Cp ΔT for ‘n’ moles
For a mole of an ideal gas, CP - CV = R and for n moles, CP - CV = nR
Here R = p∆V= work done by 1 mole of an ideal gas in expansion at constant pressure when
heated through 10 C  1.987 Cal K1 mol1  8.314 J K1 mol1
∆CP (or) ∆CV =0 for solids because molar heat capacities of solids are nearly same. Hence,
ΔH of a reaction involving solids does not change much with temperature.
5
Cp R
CP 2 5
Ratio of molar heat capacities (or) ratio =      1.66 for mono atomic gas;
CV CV 3 R 3
2
5 7 5 3
RR R R R
CP 2 7 C 2  4R  4  1.33 for triatomic
   2   1.4 for diatomic gas;   P  2
CV 3 R  R 5 R 5 CV 3 R  3 R 3R 3
2 2 2 2
gas
CP   CP Pr oducts   CP Reac tan ts & C V   C V Pr oducts   C V Reac tan ts

(IV) Applications of work:

Work done in isothermal irreversible process, wirr = – pex (Vf – Vi)
Case-(1): During compression, Vi > Vf. So, ΔV = Vf – Vi = – ve
 Work done in isothermal irreversible compression = w = p exΔV
Case-(2): During expansion, Vf > Vi. So, ΔV = Vf – Vi = + ve
 Work done in isothermal irreversible expansion = w = – pexΔV
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Work done in isothermal reversible expansion,
Vf
dV V V p
wrev    nRT  nRT ln f  2.303nRT.log f  2.303nRT.log i
Vi
V Vi Vi pf

Free expansion of gas:

Expansion of a gas in vacuum (pex = 0) is called free expansion. No work is done during free
expansion of an ideal gas whether the process is reversible or irreversible because no
opposition from external pressure. Therefore, w = 0.
We know, ΔU = q + w  ΔU = q − pexΔV
If a process is carried out at constant volume (ΔV = 0), then
ΔU = qV the subscript ‘V’ in qV denotes that heat is supplied at constant volume.

Isothermal and free expansion of an ideal gas:

For isothermal (T = constant) expansion of an ideal gas into vacuum; w = 0 since p ex = 0.
Also, Joule determined experimentally that q = 0; therefore, ΔU = 0
ΔU = q + w can be expressed for isothermal irreversible and reversible changes as follows:
(i) For isothermal irreversible change, q = – w = pex (Vf – Vi)
𝑉𝑓
(ii) For isothermal reversible change, q = – w =−2.303 𝑛𝑅𝑇. log
𝑉𝑖
(iii) For adiabatic change, q = 0, ΔU = wad
 w = nCV ∆T, that means work done is positive and work is done at the expenditure of
internal energy.
wrev > wirr in isothermal expansion of a gas since pin > pext
wirr > wrev in isothermal compression of a gas since pext > pin
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(V) Measurement of ∆U and ∆H: Calorimetry
Measurement of ∆U and ∆H by Calorimetry:
U  qV  c  m T  CT (or)
q  c  (W  m)  (T2  T1 )
Here, q = heat of the reaction (given out), W= water equivalent of the calorimeter, m = mass
of the liquid in the calorimeter, c = specific heat, T2= final temperature and T1= initial
temperature.
Heat of combustion at constant volume =
 Heat capacity of calorimeter   rise in  Molar mass of compound
    Calories
 and its components   temperature  Mass of compound
M
i.e., U  (W  m)  c  (T2  T1 )  Calories
w1
This is converted into joules by multiplying with 4.184
Note: Specific heat of water = 1Calg 1 K1 (or) 4.18 Jg 1 K1
Here, M = molecular mass of the substance, w1 = mass of the substance taken

(VI) Thermo Chemistry:

(1)The standard enthalpy of reaction is the enthalpy change for a reaction when all the
participating substances are in their standard states.
*The reference state or standard state of an element is its most stable state of aggregation at
25°C and 1 bar pressure. For example, the reference state of dihydrogen is H2 gas and those
of dioxygen, carbon and sulphur are O2 gas, Cgraphite and Srhombic respectively.
By convention, standard enthalpy of formation, Δ fHΘ of an element in reference state or
standard state, i.e., in its most stable state of aggregation is taken as zero (actually cannot be
determined).
(a) Gases (H2, O2, N2, F2, Cl2, inert gases) (b) Liquids (Br2, Hg, water, methanol, ethanol,
benzene, etc.) (c) Solids (all metals except Hg, iodine, naphthalene, anthracene, etc.)
(d) If an element exhibits allotropy, the enthalpy is zero for the most stable and most
abundant allotrope of the element. For example, carbon(graphite), sulphur(α-rhombic),
phosphorous(white), arsenic(grey) are stable allotropes.
Entha py of reaction(rH)
Enthalpy of formation (∆fH) =
Number of mo es of product formed

(2) Types of reactions based on enthlpy change:

(i) Exothermic or Exorgic reactions: A chemical reaction, which occurs with the evolution
of heat is called exothermic reaction. Exothermic reaction can be represented as:
Reactants– Q→Products (or) Reactants→ Products +Q (or) Reactants→ Products; ∆H = – Q
At constant pressure, ∆H = HProducts – HReactants = – ve (or) ∆H < 0, i.e., HP < HR
At constant volume, ∆U = UProducts – UReactants = – ve, (or) ∆U < 0, i.e., UP < UR
Examples: N2 (g) + 3H2 (g) → 2NH3 (g); ΔrHΘ = -91.8 kJ
C (graphite )  O2 (g) CO2 (g)  393.5 k.J
(ii) Endothermic or Endorgic reactions: A chemical reaction, which occurs with the
11

absorption of heat from the surroundings is called endothermic reaction. Endothermic

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reaction can be represented as:

Reactants +Q→Products (or) Reactants→ Products –Q (or) Reactants→ Products; ∆H = + Q
At constant pressure, ∆H = HP – HR = +ve (or) ∆H > 0, i.e., HP > HR
At constant volume, ∆U = UP – UR = +ve (or) ∆U > 0, i.e., UP > UR
Examples: N2 (g)  O2 (g)  2NO(g) 180.8 kJ
C (graphite) 2S(g) CS2 (g)  91.9 kJ
(2) The compounds which have negative enthalpies of formation are called exothermic
compounds and are more stable than reactants. The compounds which have positive
enthalpies of formation are called endothermic compounds and are less stable than reactants.
*(3) Calculation of enthalpy of reaction:
(i) The enthalpy change of a chemical reaction, ΔrH = (sum of enthalpies of products) – (sum
of enthalpies of reactants)   aH
i Pr oducts   bH
i Re ac tan ts
i i

(Here symbol Σ (sigma) is used for summation and a i and bi are the stoichiometric
coefficients of the products and reactants respectively in the balanced chemical equation.
(ii) Standard enthalpy of reaction, ΔrHΘ = [Sum of standard enthalpies of formation of
products] – [Sum of standard enthalpies of formation of reactants]
  ai fH (products)   bi fH (reactants)
i i

(iii) Standard enthalpy of reaction, ΔrHΘ = [Sum of standard enthalpies of combustion of

reactants] – [Sum of standard enthalpies of combustion of products]
   CH (reactants)    CH (products)
Influence of temperature on the enthalpy and internal energy of reaction by Kirchhoff’s
equation:
dH  H2  H1
Kirchhoff’s equation at constant pressur is given a: CP    (or) CP  T  T
 dT P 2 1

dH  U2  U1

Kirchhoff’s equation at constant volume is given as CV    (or) : C V  T  T
 dT V 2 1

*(4) Applications of bond enthalpy:

(i) The standard enthalpy of reaction, ΔrHΘ = [Sum of bond energies of gaseous reactants -
Sum of bond energies of gaseous products]
  bond enthalpies of reac tan ts –  bond enthalpies of products
= [Energy required to break all the bonds in reactant molecules] – [Energy required to break
all the bonds in the product molecules]
(ii) The standard enthalpy of reaction, ΔrHΘ = [Sum of enthalpies of bond formation of
gaseous products - Sum of enthalpies of bond formation of gaseous reactants]

  fHbonds of products –  fHbonds of reac tan ts
Enthalpy of bond formation, (ΔfHbondΘ) is the enthalpy change when one mole of a particular
type of bond is formed from gaseous atom.
In case of atomic species, bond enthalpy is replaced by enthalpy of atomisation.
Bond entha py of mo ecu e
Mean bond entha py 
Number of bonds per mo ecu e
(iii) Resonance energy = Experimental or actual heat of formation – Calculated heat of
12

formation.
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(5) Enthalpy of solution for an ionic compound:
solH  latticeH  hydH = latticeH  hydHof cation  hydHof anion
(5) Enthalpy of hydration of anhydrous salt = [Enthalpy of solution of anhydrous salt] –
[Enthalpy of solution of hydrated salt]

(6) Enthalpy of neutralization: If the acid or base or both are weak, the heat of
neutralization is less than 57.3 kJ or 13.7 k cal.
The difference between 57.3 kJ and actual heat of neutralization is equal to the heat of
ionization of weak acid or weak base (or) both, involved in the neutralization reaction. For
example,
Enthalpy of ionization of weak acid = {Heat of neutralization of weak acid with a strong
base} – {– 57.3 kJ (or) 13.7 k cal}
Enthalpy of ionization of weak base = {Heat of neutralization of weak base with a strong
acid} – {– 57.3 kJ (or) 13.7 k cal}
 q 
 T  
Note: The rise in temperature  ms  remains the same when volumes of same acid and
base are increased by the same factor; nm mass will produce nq heat.
(7)
Θ
Lattice enthalpy can be determined indirectly by Na ( s )  Cl2 ( g )  Δ H
 NaCl ( s ) f

using Born-Haber cycle which depends upon the

Hess’s law. Hess’s law: The energy released or +s 1
 D
absorbed in a reaction is same whether the reaction 2
takes places in a single step or several steps. Na ( s ) Cl ( g )
Born-Haber cycle for the formation of NaCl:
According to Hess’s law of constant heat summation,  I1  e   E. A.1 U

Na  ( g ) Cl  ( g )

(8) The amount of heat produced in calorie or joule when one gram of a substance (food or
fuel) is completely burnt or oxidized is called calorific value.
S tan dard entha py of combustion of subs tan ce CH
Calorific value  
Mo ar mass of subs tan ce M
In a homologous series of organic compounds, higher members have higher heat of
combustion, i.e., heat of combustion increases with increase in molecular weight and
number of moles of O2 consumed by one mole of substance, but calorific value decreases.
Examples:
Enthalpy of combustion values of alkanes: CH4 (g)  C2H6 (g)  C3H8 (g)  C4H10 (g)  .....
Methane Ethane Pr opane Butane
Calorific values of alkanes: CH4 (g)  C2H6 (g)  C3H8 (g)  C4H10 (g)  .....
Methane Ethane Pr opane Butane
Enthalpy of combustion values of hydrocarbons: CH4 (g)  C2H2 (g)  C2H4 (g)  C2H6 (g)
Methane Acety ene Ethy ene Ethane
Calorific values of hydrocarbons: CH4 (g)  C2H2 (g)  C2H4 (g)  C2H6 (g)
13

Methane Acety ene Ethy ene Ethane

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The following are different types of enthalpies of reaction.

 Standard Definition Examples
enthalpy
change
(1) Standard It is the enthalpy 1
(1) H2 (g)  O2 (g)  H2O( );  fH  285.83 kJ / mol
molar change for the 2

enthalpy of formation of one mole (2) C(graphite, s)  2H2 (g)  CH4 (g); fH  74.81 kJ / mol
formation of a compound from its (3) 2C(graphite, s)  3H2 (g)  ½O2 (g)  C2H5OH( );
(ΔfHΘ) elements in their most  fH  277.7 kJ / mol
stable states.
(2) Standard It is the amount of heat (1) H (g)  1 O (g)  H O( );  H  285.83 kJ / mol
2 2 2 f
enthalpy of released when one 2
combustion mole of a substance (2) C(graphite, s)  O2 (g)  CO2 (g); fH  393.5 kJ / mol
(ΔcHΘ) burns in excess of (3) CH4 (g)  2 O2 (g)  CO2 (g)  2H2O( ); cH  890.3 kJ / mol
oxygen in their Enthalpy of combustion is generally exothermic
standard states at and redox reaction.
specified temperature.
(3) Standard It is the enthalpy (1) Melting of ice, H2O(s)→H2O(l); ΔfusHΘ =
enthalpy of change that 6.0 kJ mol−1
fusion accompanies melting
(ΔfusHΘ) of one mole of a solid
substance in standard
state. It is endothermic
(4) Standard It is the amount of heat (1) H2O(l)→H2O(g); ΔvapHΘ = + 40.79 kJ mol-1
enthalpy of required to vaporize
vaporization one mole of a liquid at
(ΔvapHΘ) constant temperature
and under standard
pressure.
(5) Standard It is the enthalpy (1) Solid CO2 or ‘dry ice’ sublimes at 195 K
enthalpy of change when one mole with ΔsubHΘ=25.2 kJ mol-1
sublimation of a solid substance (2) Naphthalene sublimes slowly and for this
(ΔsubHΘ) sublimes at constant ΔsubHΘ = 73.0 kJ mol-1
temperature and under
standard pressure.
Standard enthalpy of fusion, vaporization and sublimation are called
standard enthalpy of phase transition.
(6) Enthalpy It is the enthalpy (1) H2(g) → 2H(g); ΔaHΘ = 435.0 kJ mol-1
of change on breaking (2) CH4(g) → C(g) + 4H(g); Δa HΘ = 1665 kJ
atomization one mole of bonds mol-1
(ΔaHΘ ) completely to obtain (3) Na(s) → Na(g) ; ΔaHΘ = 108.4 kJ mol-1
atoms in the gas phase.
(7) Bond It is the change in (1) H2(g) → 2H(g); ΔH-HHΘ = 435.0 kJ mol-1
dissociation enthalpy when one (2) Cl2(g) → 2Cl(g) ; ΔCl-ClHΘ = 242 kJ mol-1
enthalpy mole of a gaseous (3) O2 (g) → 2O(g) ; ΔO=OHΘ = 428 kJ mol-1
(ΔbondHΘ) covalent compound is Bond energy (dissociation) of a molecule is
14

broken to form always endothermic (positive).

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products in the gas

 phase.
Mean bond Mean bond enthalpy is CH4(g)→C(g)+4H(g);ΔaHΘ=1665 kJ mol-1
enthalpy also bond dissociation Mean bond enthalpy of C—H bond, ΔC-HHΘ =
enthalpy but used only 1
¼(ΔaHΘ) = (1665 kJ mol1 )  416 kJ mol1
for poly atomic 4
molecules.
(8) Enthalpy It is the enthalpy (1)NH4NO3 (s)  H2O( )  NH4NO3 (aq);  solH  25.69 kJ / mol
of solution change when one mole (2)KOH( )  H2O( )  KOH(aq);  SolH  57.61 kJ / mol
(ΔsolHΘ) of a solute/substance
dissolved in excess of
solvent so that further
dilution produces no
enthalpy change.
(9) Enthalpy The enthalpy change KC (200H2O) 180 H2O  KC (380H2O);  H  2.68 kJ
of dilution that take place when a
(or) Heat of solution having one
dilution: mole of solute is
diluted from one
concentration to
another concentration
is called heat of
dilution.
(10) It is the enthalpy (1) CuSO4 (s)  5H2O( )  CuSO4 .5H2O(s); hydH  78.2 kJ
Enthalpy of change when of one
hydration mole of an anhydrous
(Δ Hyd H) substance combine
with required number
of moles of water
molecules to form
hydrated salt. It is
always exothermic.
(11) Lattice It is the enthalpy (1) Na+Cl-(s) → Na+(g) + Cl-(g);
Enthalpy change when one mole ΔlatticeHΘ = +788 kJ mol-1
(ΔlatticeHΘ): of an ionic compound
dissociates into its ions
in gaseous state.
(12) The enthalpy change (i) S (rhombic, s)  S (monoclinic, s);
Enthalpy of when one mole of the H  2.5 kJ / mol
allotropic substance undergoes Transition from rhombic sulphur to monoclinic
transition: transition from one sulphur is endothermic indicates rhombic
allotropic form to sulphur is more stable than mono clinic.
another allotropic (ii) C(graphite, s)  C(diamond, s)
form. H  1.9 kJ / mol
Transition from graphite to diamond is
endothermic indicates graphite is more stable,
15

less energetic than diamond. Diamond is

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endothermic compound.
 (13) It is the heat evolved, (1) HC (aq) NaOH(aq  NaC (aq)  H2O( ); nH  57.3 kJ
Strong acid Strong base
Standard when 1 mole of H+ (2) CH COOH(aq) NaOH(aq)  CH COONa(aq)
enthalpy of ions react with 1 mole
3
Weak acid Strong base
3

neutralizatio of OH- ions in aqueous  H2O( ); nH  55.22 kJ

n solutions to form one (3) HC (aq) NH4OH(aq)  NH4C (aq)  H2O( );
(Δ n H Θ ) Strong acid Weak base
mole of water. The nH  51.46 kJ
maximum value of heat
(4) CH3COOH(aq)  NH4OH(aq)  CH3COONH4 (aq)
of neutralization is Weak acid Weak base
-1
57.3 kJ mol (or) 13.7  H2O( ); nH  49.3 kJ
-1
k cal mol

Ionization energy and Electron affinity:

Ionization energy and electron affinity are defined at absolute zero. At any other
temperature, heat capacities for the reactants and the products have to be taken into account.
Enthalpies of reactions for M(g) → M+(g) + e- (for ionization) and M(g) + e- → M-(g) (for
T
electron gain) at temperature, T is rH (T)  rH (0)   rCPdT
0
The value of Cp for each species in the above reaction is 5/2 R (CV = 3/2 R)
5 5
So, ΔrCpΘ = + R (for ionization) and ΔrCpΘ = – R (for electron gain)
2 2
5
Therefore, ΔrHΘ (ionization enthalpy) = E0 (ionization energy) + RT
2
5
ΔrHΘ (electron gain enthalpy) = – A (electron affinity) – RT
2

(VII) Spontaneity:
Spontaneity means ‘having the potential to proceed without the assistance of external
agency’. The natural tendency of a process to occur on its own in a particular direction
under a given set of conditions is called spontaneous process.
Driving force for a spontaneous process:
(A) Is decrease in enthalpy a criterion for spontaneity?
Exothermic reactions occur readily and spontaneously. Therefore we can say that decrease in
energy (∆H = - ve) is a criterion/driving force for spontaneity of a reaction.
For example: (i) 1/2 N2(g) + 3/2 H2(g) = NH3(g); ΔrHΘ= – 46.1 kJ mol-1
(ii) 1/2 H2(g) + 1/2 Cl2(g) = HCl (g) ; ΔrHΘ = – 92.32 kJ mol-1
(iii) H2(g) + 1/2 O2(g) → H2O(l) ; ΔrHΘ = - 285.8 kJ mol-1
But, many endothermic reactions (∆H = + ve) occur spontaneously.
For example: (i) 1/2 N2(g) + O2(g) → NO2(g); ΔrHΘ= +33.2 kJ mol-1
(ii) C(graphite, s) + 2 S(l) → CS2(l); ΔrHΘ = +128.5 kJ mol-1
(iii) Evaporation of water from an open container is an endothermic process but occurs
spontaneously. H2O( )  H2 O(g); H  44 kJ mol1
(iv) Melting of ice takes place by absorption of heat from surrounding and occurs
spontaneously. H2O(s)  H2 O( ); H  6.0 kJ mol1
16
Page
(B) Entropy and spontaneity:
Entropy (S): It was introduced by Clausius.
"The degree of randomness or disorder of molecules in a system may be expressed by a
thermodynamic property is known as entropy". It is denoted by symbol ‘S’.
Entropy is a state function (it depends on the state variable T, p, V, n of the state) and
extensive property (depends on the mass of the system). The change in entropy, ∆S = S (final
state) – S (initial state) = S (products) – S (reactants)
At any given temperature, the molecules in a gaseous state are more disorderly than those in
the liquid state and the molecules in the liquid state are more disorderly than those in the
solid state. Sgas > Sliquid > Ssolid
For this reason a liquid goes into vapour state easily and spontaneously.
Therefore spontaneous reactions are accompanied by an increase in entropy. That means ∆S
= +ve, i.e., ∆S > 0.
When entropy of one mole of a substance is expressed at 298K and 1atm pressure it is called
standard entropy of that substance. It is denoted by S0.
S0   S0(Pr oducts)   S0(Re ac tan ts) = [Sum of the standard entropies of products] - [Sum of the
standard entropies of reactants]
Mathematical formula of entropy:
qrev
ΔS is related with q and T for a reversible reaction as: S 
T
Here, qrev = heat absorbed by the system isothermally and reversibly at ‘T’
T = temperature during state change.
Units of entropy and entropy change:
qrev
Entropy change, S 
T
 Unit of change in entropy is Cal K-1. In SI system, J K-1.
Entropy is an extensive property, i.e., it depends on the mass of the substance. Hence, unites
of entropy are expressed as Cal K-1 mol-1. In SI system, J K-1 mol-1.
Spontaneity in terms of entropy change:
(i) In a non-isolated system, the total entropy change is sum of the change in entropy of the
system and the change in entropy of the surroundings. ∆Stotal = ∆Ssystem + ∆Ssurroundings (∆Stotal
is also termed as ∆Suniverse)
For a spontaneous process, ∆Stotal must be positive, i.e., ∆Stotal = ∆Ssystem + ∆Ssurroundings > 0. If
17

∆Stotal is negative, the direct process is non-spontaneous whereas the reverse process is
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spontaneous.
For natural processes and irreversible processes, entropy of universe is increasing, ∆Suniverse >
0. This means that there is increase in entropy of universe in spontaneous changes.

(ii) In an isolated system like mixing of gases, there is no exchange of energy or matter
between the system and surroundings. However, the mixing of gases is accompanied by
increase in randomness, i.e., there is increase in entropy. Therefore, it can be stated that “for
a spontaneous process in an isolated system, the change in entropy is positive” i.e., ∆S = +ve,
i.e., ∆S > 0.
During the spontaneous process, the entropy of the system increases gradually until the
system attains equilibrium state and at equilibrium the change in entropy is zero. So, the
mathematical condition for an isolated system at equilibrium is ∆S = 0.

(iii) In a reversible process, ∆Suniverse (or) ∆Stotal = 0, therefore ∆Ssys = - ∆Ssurr

qsys, rev
The change in entropy of a reversible process  Ssys 
T

(iv) For reversible and irreversible expansion of an ideal gas, under isothermal conditions,
ΔU = 0, but ΔStotal i.e., ΔSsys + ΔSsurr is not zero for irreversible process. Thus, ΔU does not
discriminate between reversible and irreversible process, whereas ΔS does.

(v) The entropy change for a cyclic process is zero, ∆S = 0.

(vi) The entropy change for reversible adiabatic process is zero, ∆S = 0 since dq rev = 0.

(vii) Entropy changes during phase transitions:

Hfusion Hvapourisation H
S fusion  ; Svapourisation  ; Ssub lim ation  Svapour  Ssolid  sub lim ation
Melting po int (K) Boiling po int (K) T

(viii) Entropy change of a system in reversible process,

T2 p T2 p
 sys S  nCP n  nR n 1  or   sys S  2.303nCP og  2.303nR og 1
T1 p2 T1 p2
Case-1: Entropy change for reversible isothermal process:
V2 V p p
 sys S  nR n  2.303nR og 2 (or)  sys S  nR n 1  2.303nR og 1
V1 V1 p2 p2
T2 T
Case-2: Entropy change in an isobaric (∆p = 0) process: sys S  nCp n  2.303 nCp og 2
18

T1 T1
Page
 T2 T
Case-3: Entropy change in isochoric (∆V = 0) process: sys S  nCv n  2.303 nC v og 2
T1 T1

(ix) Entropy change in mixing of ideal gases:

Let n1 moles of gas A and n2 moles of gas B are mixed, then total entropy can be calculated
as S  2.303R [n1 log x1  n2 log x 2 ]
n1 n2
Here, x1 and x2 are mole fractions of gases A and B, i.e., x1  ; x2 
n1  n2 n1  n2
(n1  n2 )
 S  2.303R [n1 log x1  n2 log x 2 ]
(n1  n2 )
 n n2 
 S  2.303R(n1  n2 )  1 log x1  log x 2 
 n1  n2 n1  n2 
S  2.303ntotal R  x1 log x1  x 2 log x 2 

(C) Second law of thermodynamics: It is stated in various forms proposed by various

scientists. Some of them are as follows:
(i) Clausius statement: It is impossible to construct a perpetual motion machine of second
kind which transfers heat from a lower temperature region (colder body) to a higher
temperature region (hotter body) without without expenditure of work or an external agent.
(or) It is not possible to convert heat into work without compensation (or) All forms of
energy can be converted into heat energy but heat cannot be converted into other forms of
energy fully by any process.
(ii) Heat cannot flow from a colder body to a hotter body on its own.
(iii) Heat cannot be converted into work completely without causing some permanent
changes in the system or in the surroundings.
(iv) All spontaneous processes are thermodynamically irreversible and entropy of the system
increases in all spontaneous processes.

(D) Overall tendency as the driving force for a process:

(i) Tendency for minimum energy (∆H = - ve) (ii) Tendency for maximum randomness (∆S
= + ve)
The resultant of above two tendencies is Gibbs free energy.

(E) Gibbs energy (G) and spontaneity:

The maximum amount of energy available to a system to do useful work is called Gibbs
energy. Gibbs function, G is an extensive property and a state function.
G = H – TS (or) ΔG = –wuseful (by the system)
Gibbs energy change of a system at constant temperature, ΔGsys = ΔHsys − TΔSsys
This equation is called Gibbs Helmholtz equation.
ΔG has units of energy because, both ΔH and the TΔS are energy terms, since TΔS = (K)
19

(J/K) = J.
Standard Gibbs energy change of a reaction, ∆rG0 =   f G0(Pr oducts)    f G0(Reac tan ts)
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= [Sum of the standard Gibbs energy formation of products] - [Sum of the standard Gibbs
energy formation of reactants]
Standard Gibbs energy formation (∆fG0) of an element under standard conditions is zero.
ΔG gives a criteria for spontaneity at constant pressure and temperature.
(i) If ΔG is negative or (∆G)T, P < 0 (or) ΔH−TΔS < 0, then the process is spontaneous.
(ii) If ΔG is positive or (∆G)T, P > 0 (or) ΔH−TΔS > 0 then the process is non-spontaneous.
(iii) If ΔG = 0 or (∆G)T, P = 0, then the process is at equilibrium.
Effect of temperature on spontaneity of reactions:
rH r S r G Description
- + - Reaction spontaneous at all temperature
- - - (at low T) Reaction spontaneous at low temperature
- - +(at high T) Reaction non-spontaneous at high temperature
+ + +(at low T) Reaction non-spontaneous at low temperature
+ + - (at high T) Reaction spontaneous at high temperature
+ - +(at all T) Reaction non-spontaneous at all temperature
Gibbs energy change may also be represented as dG = Vdp – SdT

Gibbs energy change in reversible processes and equilibrium (Relation between

standard free energy change and equilibrium constant):
G  r G  RT n K; but at equilibrium G  0 means the reaction mixture has no tendency to
change in either direction.
 
 rG  –RT n K  2.303 RT ogK   H  T S   K  eG RT
 10G 2.303 RT

K < 1 when G  0 and K > 1 when G  0

(F) Absolute entropy and third law of thermodynamics:

This is also known as Nernst heat theorem.
It is stated as “The entropy of a pure and perfectly crystalline substance is zero at the
absolute zero temperature (-2730 C)”. Because at absolute zero temperature, there is a
perfect order in the crystal. The statement is confined to pure and crystalline solids because
theoretical arguments and practical evidences have shown that entropy of solutions and
super cooled liquids is not zero at 0 K temperature.
T T
Cp
Mathematically, Lim S  0 (or)S T   dT (or) S T  S0   Cpd nT
T0 T
0 0
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