Thermodynamics

The branch of science which deals with the quantitative relationship

between heat and other forms of energies is called thermodynamics.
Thermodynamic Terms
(i) System It refers to the part of universe in which observations
are carried out.
(i) Surroundings The part of universe other than the system is
known as surroundings.
iii) Boundary The wall that separates the system from the
surroundings is called boundary.
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
matter both
0) Open system The system in which energy and
can be exchanged with the surroundings,
can be
le (i) Glosed system The system in which only energy
exchanged with the surroundings.
nor
(iii) Lsolated system The system in which neither energy
matter can be exchanged with the surroundings.
 88 Handbook of Chemistry
State of System
value, the conditions t
When microscopic properties have definite system.
existence of the system is known as state of
State functions (State variables) Whenonly values of a system ar
on initial and final
independent of path followed and depend
AU,AH, AG etc.
state, it is known as state function, e.g.
followed, e.g. work
Path functions These depend upon the path It
heat, etc.
e
Thermodynamic Properties It
Intensive Properties in
on the nature of matter
Properties of the system which depend only intensive properties, e.g
but not on the quantity of matter are called F
pressure, temperature, specific heat, etc.
Extensive Properties ar
Properties of the system which are dependent on the quantity of
matter are called extensive properties, e.g. internal energy, volume,
enthalpy, etc.
Thermodynamic Process TI
It is the operation which brings change in the state of the system.
Thermodynamic processes are ot

(i)Isothermal process In which temperature remains th

constant, i.e. (dT= 0, AU=).
F
(ii) Isochoric process In which volume remains constant,
ie. (AV = 0). E
CO
(iii) Isobaricprocess In which pressure remains constant,
M
i.e.(Ap = 0).
W
(iv) Adiabatic process In which heat is not exchanged by system
with the surroundings, i.e. (Aq = 0).
(v) Cyclic process It is a process in which system returns to
its originalstate after undergoing a series of change,
i.e. AUyelie =0; AH cvcie = 0.
(iv) Reversible process A process that follows the reversible
path, i.e. the process which occurs in infinite number of stepsin2
way that the equilibrium conditions are maintained at each step.
and the process can be reversed by infinitesimal change in the
state of functions.
 Thermodynamics 89

Irreversible process The process which cannot be reversed

(rii) processes are
AII natural
and amount of energy increases.
irreversible.

InternalEnergy (E orU)
substance. It is the sum of many types
Tt is the total energy within the translational energy, etc. It is an
of energies like vibrational energy,
function.
extensive property and state change in
but experimentally
Its absolute value cannot be determined
determined by
internal energy (AU)can be
mat AU =U, -U, or ZUp - ZUR
exothermic process, AU =- ve whereas for endothermic process
For
AU= +ve.
volume and quantity of matter
U depends on temperature, pressure, which state has been attained.
and is independent of the method by
City
Zeroth Law of Thermodynamics or Law of
Thermal Equilibrium
in thermal equilibrium with
The law states that if the two systems are with each
sten a third system then they are also in thermal equilibrium
whether the system is in
other. T'emperature is used here to know
nains thermal equilibrium or not.

First Law of Thermodynamics

it can be
Energy can neither be created nor destroyed although
converted from one form to the other.
Mathematically, AU= q+ W
sten
where, AU = internal energy change
q= heat added to system
W= work added to system
Sign convention
(0) qis+ ve = heat is supplied to the system
ible
) qis-ve = heat is lost by the system
(0) Wis +ve = work done on the system
tel (iv) Wis ve = work done by the system
the
90 Handbook of Chemistry
Modes of Transference of Energy
Work (W)
If the system involves gaseous substances and there is a to
pressure between system and surroundings, work is difference o
referred.
pressure-volume work (Wav).
Expression for Pressure-Volume Work
i)) Work done in irreversible expansion against constant pressu It
punder isothermal conditions
q=- WpV = Pext AV
W
(i) Work done in reversible expansion under isothermal conditions
q=- W,ey = 2.303 nRT log M

or rey = 2.303 nRT log re

P2
(üi) Work done in reversible expansion under adiabatic conditions
nR
Wrey =
Y-1 -(T, -T,)
where, y= Poisson's ratio
(Under adiabatic conditions T Vò-=constant)
(iv) Work done in irreversible expansion under
adiabatic conditions
Wirrey = Pot XnR A - P,T,
(v) When an ideal gas
expands in vacuum then
Pext = 0
Work done is
maximum in reversible conditions.
Units CGS system - erg
SI
system - joule
I Work and heat both
appear
during achange in state. only at the boundary of the system
Heat (g)
It occurs when
and there is a difference of
Its unitS are joule or random form of temperature
surroundings. It is a between system
energy and path dependent.
calorie.
 Thermodynamics 91

Capacity of a System required

Heat is defined as the amount of heat
(C) ofa system
Heat capncitytemperature of a system by 1°C.
to raise the
rele Molar Heat Capacity
It is the heat capacity
of 1 mole of'
system.
substance of the

nt pres Specific Heat Capacity

system.
heat capacity of 1g of substance of the
It is the q= mc AT.
capacity
substance, c = specific heat or specific heat
where, mn = mass of
Conditi Molar heat capacity, at
constant pressure, C = C XM
capacity, at constant volume, Cy = Gy XM
Molar heat pressure and constant volume
heats at constant
(C, and cy are specific molecular weight of gas)
respectively and M is C p R (R= Molar gas constant)
R
onditis M

constant volume, Cy =R
The molar heat capacity at
constant pressure,
The molar heat capacity at
nditios c,-G)R+R-(G)R
Poisson's ratio, Y==1.66
Cy
Y= 1.66 for monoatomic gas
Y= 1.40 for diatomic gas
Y= 1.33 for triatomic gas

Measurement of AH and AU: Calorimetry

gaseous reactions Reactions involving gases are carried
(a) For constant volume.
out in a bomb calorimeter at
calorimeter)
tem
AU =- (Heat absorbed by bomb
reaction in solution Reactions involving solution are
(b) For
out at constant pressure inside a coffee-cup calorimeter.
carried
ystem
A,H = (mc AT)oalorimeter t (me A7 )solution:
ent.
92 Handbook of Chemistry
Enth
Enthalpy (H) It is t
It is the sum of internal energy and pV-energy of the system. It is large
state function and extensive property. Mathematically, chan
H=U+ pV So,
Like U, absolute value of H also cannot be known, AH is determinei Enth
experimentally. It is
AH = H,- H, or AH = EHp- EHR hydr
For exothermic reaction (the reaction in which heat is evolved) a sp
AH =-ve, whereas for endothermic reaction (the reaction in which proo
heat is absorbed), AH =+ve.
Ent
Relationship between AH and AU
It is
AH =AU+ pAV or AH= AU+ An(gRT
sub
Here, An, = change in the number of gas moles.
En
Enthalpy Change or Reaction Enthalpy (A,H) It i
It is the change in enthalpy that accompanies a chemical reaction liq
represented by a balanced chemical equation.
En
A,H =H) H R)
It
Enthalpy of reaction expressed at the standard state conditions is
ac
called standard enthalpy of reaction (AH°) di
Factors affecting enthalpy of reaction are
) Physical state of reactants and products. Co
(i) Allotropic forms of elements involved.
(iii) Chemical composition of reactants and
products.
(iv) Amount of reactants.
(v) Temperature.

Various Forms of Enthalpy of Reaction

Enthalpy of Formation (A,H)
It is the heat change when one mole of
compound is obtained from is
constituent elements. Enthalpy of formation at standard state 5
known as standard enthalpy of formation (AH°) and is taken a5
zero by convention.
Enthalpy of Combustion (AçH°)
It is the enthalpy change taking place when one mole of a
compound
undergoes complete combustion in the presence of oxygen (AcH)
ArH is always negative, because process of combustion is exothermic
 Thermodynamics 93

(AsHo)
Enthalpy of Solution
mole of a substance is dissolved in
enthalpy change when onefurther
It is the of solvent, so that on dilution noappreciable heat
large excess
change occur.
So,
AsolH°= Ajattice H° + Ahvd H°

mine Enthalpy of Hydration (Ahyd H°) anhydrous or partially

Tt is the enthalpy change when one mole ofof moles of water to fornm
hydrated salt combines with required number
combustion. It is an exothermic
lhived,ch a specific hydrate undergoes complete
process.

Enthalpy of Fusion (A hs Ho)

mnelting of one mole of solid
It is the enthalpy change that accompanies
substance.

Enthalpy of Vaporisation (A yap Ho)

conversion of one mole of
It is the enthalpy change that accompanies
ion lhquid substance completely into vapours.
Enthalpy of Neutralisation (A, Ho)
g-equivalent of an
is It is the enthalpy change that takes place whenof1a base (or acid) in
acid (or base) is neutralised by l g-equivalent
dilute solution.
is always
Enthalpy of neutralisation of strong acid and strong base
constant, i.e. 57.1 kJ.

weak acid
Enthalpy of neutralisation of strong acid and weak base or57.1
less than kJ due
and strong base is not constant and numerically weak acid or
to the fac that here the heat is used up in ionisation of
weak base. This is known as enthalpy of ionisation of weak acid/or
base.

Enthalpy ofTransition (A,H)

substance undergoes
It is the enthalpy change when one mole of the
transition from one allotropic form to another.

Enthalpy of Atomisation (A,H°)

mole of the molecule
t 1s the enthalpy change occurring when one
breaks into its atoms.

I:
94 Handbook of Chemistry
Enthalpy of Dilution
It is the enthalpy change, when one mole of a substance is diluted fro
one concentration to another.
wh
Enthalpy of Sublimation (A,ubH®)
It is the enthalpy change, when one mole of a solid substance sublimes In
Lattice Enthalpy Th
kn
It is the enthalpy change, when one mole of an ionic compound
dissociates into its ions in gaseous state.

Bond Enthalpy (A bonaHe)

Enthalpy is required to break a bond and energy is released when A
bond is formed. For this, two different terms are used in th
thermodynamics.
(a) Bond dissociation enthalpy The enthalpy change, is the
change in enthalpy when one mole of covalent bonds of a gaseous
covalent compound is broken to form product in the gas phase.
(b) Mean bond enthalpy The average value of dissociation
energies of polyatomic molecule.
Some factors affecting the bond enthalpy:
(i) Size of atoms (ii) Electronegativity
(iüü) Bond length (iv) Number of bonding electrons
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 internal energy, i.e.
where,
), is called the internal pressure. J
Joule-Thomson Coefficient
The number of degrees of temperature change produced pe
atmospheric drop in pressure at constant enthalpy when a gas
allowed to expand through a porous plug is called Joule-Thomson
coefficient. It is given as
 Thermodynamics 95

dp
where, 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. It is given as
2a
T;= Ri
where, aand b= van der Waals' constant.
At inversion temperatureTi, the Joule. Thomson coefficient = 0, i.e.
the gas is neither heated nor cooled.
Laws of Thermochemistry
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.

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
AH =AH, + AH, + AH,
Applications of Hess's law are
(a) In determination of heat of formation.
(b) In determination of heat of transition.
(c) In determination of heat of hydration.
(d) To calculate bond energies.
Trouton's Rule
According to this rule, "The ratio of enthalpy of vaporisation and
hormal boiling point of a liquid is approximately equal to 88 J per mol
per kelvin, i.e..
AH vap- 88 J/moVK
T
 96 Handbook of Chemistry
Increase in
AS> 0,
Dulong and Petit Law AS<0, Decrease in
This lawstates "The product of specific heat and molar mass of anu ele
metallic element is equal to 6.4 cal/mol/°C, i.e. Entropy of even
Entropy change of
Specific heat x molar mass =6.4 cal/mol/°C
Kirchhoff's Equation
AH, -AH and ACy = AE,- AE,
T,-T T, -T Entropy Change
The change of ma
Clausius-Clapeyron Equation transition.

- 2.303log PAHy(2-T
The entropy chan
AR TT;
where, AH, =molar heat of vaporisation.
Spontaneous Process
The physical or chemical process which proceeds by its own in a AS,
particular direction under given set of conditions without outside help
is called spontaneous process. It cannot be reversed.
All natural processes are spontaneous process.
Spontaneous process where no initiation is needed
(1) Sugar dissolves in water.
(i) Evaporation of water.
(ii) Nitric oxide (NO) reacts with oxygen. Enthalpy Crit
Spontaneous process where somne initiation is required All the proces:
(1) Coal keeps on burning once initiated. (exothermic
(ii) Heating of CaCO, to give calcium oxide and CO, is initiated by spontaneously.
heat. spontaneously.
CaCO,(s) CaO(s)+ CO,(g) Entropy
A
Crite
process 1s s
Entropy (S)
It is the measure of degree of randomness or disorder of the
increases.
For a process
It is a state function and extensive property. molecules.
Units :JK-' mo! At equilibrium
The change in entropy during a process is mathematically given as
A,S° =ES° (products) - ES°(reactants) =re AH
Limitations
cannot fnd e
So we need
T
where, dwow = heat absorbed by the system in reversible manner system (G).
T= temperature
 Thermodynamics 97
absorbed.
AS> 0, Increase in randomness, heat is
AS<0, Decrease in randomness, heat is evolved.
Entropy of even elementary substances are not zero.
Entropy change of an ideal gas is given by
AS = nCy In +nRIn2

Entropy Change During Phase Transition

phase
The change of matter from one state to another state is called
transition.
The entropy changes at the time of phase transition:
AS melting AH fusion
T
T, =melting point of substance
AH.vaporisation
ASyaporisation
T, = boiling point of substance
ASaublimation AHsublimation
Tsub
Th = Sublimation temperature
Enthalpy Criterion of Spontaneous Process
All the processes which are accompanied by decrease of energy
(exothermic reactions, having negative value of AH) OCCur
spontaneously. It fails when some endothermic reactions occur
spontaneously.
Entropy Criterion of Spontaneous Process
the universe
A process is spontaneous if and only if the entropy of
increases.
For a process to be spontaneous
(ASuniverse >0or ASsvst t ASgurr >0)
At equilibrium state, AS = 0.
Limitations of AS criterion and need for another term We
cannot find entropy change of surroundings during chemical changes.
S0 we need another parameter for spontaneity viz Gibbs' energy of
8ystem
(G).
98 Handbook of Chemistry
No
Second Law of Thermodynamics
ter
enc
course of
The entropy of the universe is always increasing in the every ma

spontaneous or natural change.

Or St
All spontaneous processes or natural changes are thermodynamicallu It
irreversible without the help of an external work, 1.e., heat cannot fo are
itself from a colder to hotter body. 29

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
W
Mathematically, G= H- TS
St
Change in Gibbs energy during the process is given by Gibbs
Helmholtz equation. G
(AG =G-G = AH - TAS) C
where, AG= Gibbs free energy, H =enthalpy of system
TS =random energy,
AGsystem =-TAStotal [In hypothetical system where AH = 0]
The Gibbs energy criterion of spontaneity
AG> 0, process is non-spontaneous
AG<0, process is spontaneous
AG = 0, process is in equilibrium state.

Effect of Temperature on Spontaneity

S.No. Sign of AH Sign of AS AG= AH-TAS 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 Non-spontaneous
temperature at low temperature
|Negative at high Spontaneous at high
temperature temperature
4. |Negative Negative Spontaneous'at low
Negative at low
temperature temperature
Positive at high Non-spontaneous
temperature at high
temperatures
 Thermodynamics S99
exothermic reaction which is non-spontaneous at high
Now an temnperature. Similarly,
temperature may become spontaneous at low temperature
ondothermic reactions which are non-spontaneous at low
high temperature.
very may become spontaneous at
Standard Free Energy Change (AG)
takes places when the reactants
Tt is the change in free energy which
caliowly are converted into products at the standard states, i.e. (1 atm and
298 K)
AG° = AH° TAS
AG° = EAG Products) - 2AGf r(Reactant)
hich
arty. formation
where, AG, = standard energy of
elements is zero.
Standard energy of formation of all free
Gibbs Energy Change and Equilibrium
Criterion for equilibrium,
A+ B C+D
AG =0
Now, relation AG= AG°+ RT In Q
0= AG° + RT In K
AG° =- RT lnK
Or

AG° =- 2.303 RT log K

’ We also know that
AG° = AH° -TAS° =- RT In K
Relationbetween AG° and EMF of the Cell
all
AG° =- nFEgell
where, n= number of electrons lost or gained
F=Faraday or 96500 C
re Ecell = standard electrode potential

Third Law of Thermodynamics law,

oW This law was formulated by Nernst in 1906. According to this absolute
The entropy of a perfectBy crystalline substance at zero K cr
zero is taken to be zero.
100 Handbook of Chemistry
We can fnd absolute entropies of pure substances at
temperature. different
AS = C,d In T=2.303 0 Cp d log T
where, C, = heat capacities
T= temperature between 0.K and T K.
This law is only applicable for perfectly crystaline substances. If there
is imperfection at 0 K, the entropy willbe larger than zero.

Carnot Cycle
It is an imaginary cycle which
demonstrates the maximum
of heat into work. It involves four conversion
processes
(i) isothermal reversible
expansion;
(iü) adiabatic reversible expansion;
(ii) isothermal reversible compression;
(iv) adiabatic reversible
compression.
The efficiency of a heat engine in a Carnot
cycle,
n2-
F= 92-41 w
T, 92