Types of systems

States of a system and state variables

Thermodynamic Processes

First Law of Thermodynamics

Internal Energy
Enthalpy
Heat Capacity
Specific Heat Capacity
Molar Heat Capacity

Relationship b/w Cp and Cv

Poisson's Ratio (V)
Thermochemistry
Enthalpy of Reaction
Thermodynamics Different types of enthalpy
reactions:
Hess's Law
Born-Haber Cycle

Limitations of First Law of

Thermodynamics
Non-spontaneous Reaction
Entropy
Effects of temperature on Spontaneity in terms of entropy
spontaneity of process change
Standard free energy change Gibb's Free Energy
∆
( Gº') of a reaction
Extras
Practice Problems
 Thermodynamics
The branch of science that deals with the study of different forms of energy
and the quantitative relationships between them is known as thermodynamics.

System: The part of the universe chosen for thermodynamics consideration is

called system.
Surroundings: The remaining part of the unit excluding the system is called
surrounding.

Universe = System + Surroudings

TYPES OF SYSTEMS:

Open System: If a system can exchange both matter and energy (heat) with
surroundings, it's called an open system. Eg: Animals and Plants are open
systems
Closed system: If a system can exchange energy only with the surroundings
not matter, it is called a closed system. Eg: Hot water placed in a metallic
container.
Isolated system: If a system can neither exchange matter nor energy with
the surroundings, it is called an isolated system. Eg: Hot water placed in a
thermos flask.

STATE OF A SYSTEM AND STATE VARIABLES:

The state of a system means the conditions of the system which are described
in terms of certain measurable properties such as temperature, pressure,
volume, etc of the system if any of these properties of the system change.
Therefore, these properties of the system are called state variables.

STATE FUNCTION:
A physical quantity is said to be state functioning its value depends only upon
state of the system and does not depends upon the path by which this state
has been attained . Examples: Temperature, Pressure, Volume, Internal Energy,
enthalpy, entropy, free energy etc.
MACROSCOPIC PROPERTIES

If a system contains a large number of chemical species (atoms or molecules) it

is called a macroscopic system. The properties of the macroscopic systems
are called macroscopic properties. There are two types:

Extensive properties: These properties which depend upon the quantity of

matter contained in the system are called extensive properties. Eg: mass,
volume, heat capacity, internal energy, enthalpy, entropy, Gibbs free energy,
etc.

Intensive Properties: These properties which depend only upon the nature
of the substance and are independent of the amount of the substance
present in the system are called intensive properties. Eg: temperature,
pressure, refractive index, viscosity, density, surface tension, specific heat,
freezing point, boiling point, emf of a cell, pH of a solution, etc.

Extensive properties are additive but intensive properties are not.

The ratio of extensive properties becomes intensive. Eg: Prssure=

(Force/Area)

Thermodynamic equilibrium

A system is said to be in thermodynamic equilibrium if its macroscopic

propertieslike temperature, pressure, etc do not change with time.
 THERMODYNAMIC PROCESSES

A thermodynamic process is said to occur when the system changes from

one state (initial state) to another (Final State).

Some important thermodynamic processes are as follows:

Isothermal process: It is a process during which the temperature of the
system is kept constant.
Adiabatic process: It is a process during which no heat can flow from the
system to the surroundings or vice-versa.
Isochoric process: It is a process during which the volume of the system is
kept constant.
Isoboric process: It is a process during which the pressure of the system is
kept constant.

Hint: Isothermal process occurs when the system has conducting walls (or an
open system). The container with conducting walls is called diathermic.
Adiabatic process occurs when it is a closed system and has non-conducting
walls ( called adiabatic walls)

Reversible and irreversible processes:

A reversible process is a process that is carried out infinitesimally slowly so

that all changes occurring in the direct process can be exactly reversed and
the system remains almost in a state of equilibrium with the surroundings at
every stage of the process.
A process that does not meet the above requirements is called an irreversible
process.
Internal Energy (E or U):

The energy stored within a system (or substance) is called internal energy.It is
represented by E or U. It is the sum of different types of energies associated
with atoms such as electronic energy (Ee), Nuclear energy (En), chemical bond
energy (Ec), potential energy (Ep) and kinetic energy (Ek)

U or E = Ee + En + Ec + Ep + Ek

Internal energy is a state function

The change in internal energy ( U): U2-U1
Where U1= Internal energy in the initial state
Where U2= Internal energy in Final State

Sign of U = △
if U2>U1 then △V=+ve (increase)
if U1>U2 then △V=-ve (decrease)

Heat:

Heat is another mode of energy exchanged between the system and the
surroundings as a result of the difference in temperature between them. It is
recognized by "Q".

Sign of Q: When heat is given out by the system to the surroundings, q is

negative. When heat is absorbed by the system from the surroundings q is
positive.

In the S.I. system, Heat is expressed in the terms of joule.

1 Joule: 0.239 calories
1 calorie: 4.184 Joules
Work:

Work is said to have been done whenever the point of application of a force (F)
is displaced (dl) in the direction of the force.

W = F x dl

The above type of work is called mechanical work.

Two main types of works used in thermodynamics are:

1.) Electrical work: Work (W) = Q (charge) * V (Potential)

W = nFE
nF = charge on "n" moles of electrons
E= Cell Potential
F= Faraday's Constant
n= No of electrons lose or gain in cell reactions.

2.) Pressure : Volume work or work of expansion/compression

This type of work is involved in systems consisting of gases. It is the work

done when the gases expand or contract against external pressure. It is a kind
of mechanical work.
Consider a gas enclosed in a cylinder fitted with a frictionless piston.
Suppose the area of the cross-section of a cylinder= a cm3 and pressure on
the piston = P (Which is slightly less than the internal pressure of the gas so
that the gas can expand)
Distance through which the gas expands= dl cm. Then:
P= F/a or F=P x a
Work done by gas= Force * Distance = F * dl = F*a*dl
But (a*dl=dV), a small increase in the volume of the gas. Hence the small
amount of work done (dw) by the gas can be written as:
dw=P.dv
If gas expands from initial volume V, to the final volume V2 against constant
external pressure then total work done will be given by:

Where △V = (V2-V1) is the total change in the volume of the gas

P is the external pressure and hence is written as Pext so that:

Sign of W:
if work is done on the system, w=(+)
if work is done by the system, w=(-)
Work done in isothermal/reversible reaction of ideal gases:

The small amount of work done (dw) when the gas expands through a small
volume (dV) against the external pressure is given by:

However for reversible expansion:

Total work done (W) when the gas expands from initial volume V1 to final
volume V2, will be:

For ideal gas:

Hence,
 For isothermal process,
T= constant
therefore,

Hints: Reversible Work of expansion (Wrev is the max work)

For reversible expansion,Pext should be slightly smaller than Pint. In other

words, Pext is the max possible value of the pressure, therefore, for a
given change of volume, W is the maximum.
For irreversible expansion, external pressure is much smaller than internal
pressure. Therefore,for a given change of volume, W is minimum

Similarly,reversible work of compression is less than irreversible work

of compression

Isothermal reversible
expansion

Isothermal irreversible
expansion
 First law of Thermodynamics

Energy can neither be created nor destroyed although it may be converted

from one form to another. or the energy of an isolated system is constant

Derivation of First law of Thermodynamics

The internal energy of a system can be increased by i) supplying heat to

the system and by doing ii) work on the system

Suppose the initial internal if the system is V1, if it absorbs heat (q) , it's
internal energy will be U1 + q.
If further work (W) is done on the system, the internal energy will become:
U1 +q + W
let's call this final energy V2, then:

U2 = U1 + q = W
U2-U1 = q + W
△U = q + W
The equation is the mathematical formulation of the first law of
thermodynamics.

Formula for numericals:

1.) Work done of the irreversible process

q = -w = pex(Vf-Vi)

2.) Work done for isothermal reversible process

Hints

a.) For isothermal isomers, △V=0

b.) For adiabatic process, q=0
c) Work done against vaccum or for isochoric process, W=0
d) For cyclic process, △V=0

Q.1) Express the change in internal energy of a system when:

(i) No heat is absorbed by the system from the surroundings, but
work (w) is done on the system. What type of wall does the system
have?
(ii) No work is done on the system, but Q amount of heat is taken out
from the system and given to the surroundings. What type of wall
does the system have?

Solution:
∴
(i) Here, q=0 ΔU=q+w=0 ∴ΔU=q+w=0
As no heat is absorbed by the system, the wall id adiabatic.
(ii) As heat is taken out, the system must be having thermally
conducting walls.

Q.2) Calculate the internal energy change when a system absorbs

15kJ of heat and does 5kJ of work.

Solution: 10KJ

Q.3) Calculate w, q & ΔU when 0.75mole of an ideal gas expands

isothermally & reversibly at 27∘C from volume 15L to 25L.

Solution: W = -955.5J, q =+955.5J , ΔU = 0

Q.4) Calculate the amount of work done in each of the following
cases:
1. One mole of an ideal gas contained in a bulb of 10-litre capacity at
1 atm is allowed to enter into an evacuated bulb of 100-litre
capacity.
2. One mole of a gas is allowed to expand from a volume of one litre
to a volume of 5 litres against the constant external pressure of 1
atm (1 litre atm = 101.3J). Calculate the internal energy change in
each case if the process were carried out adiabatically

Solution: 1.) W=0, ΔU=0 2.) W=-405.2J, ΔU=-405.2J

Internal Energy

According to the first law of thermodynamics:

△U = q + W
△U = q - P△V
q = △U + P△V
at constant volume (△V=0)
Qv = △U

Internal energy change is the heat absorbed or evolved at constant volume.

Enthalpy (H):

The thermodynamic quantity (U + PV) is called the heat content or enthalpy

of the system and is represented by the symbol H.
H = U + PV

Enthalpy is a state function. Therefore,

△
Enthalpy change ( H) = H2 - H1
where H1: initially enthalpy of the system H2: Final enthalpy of system
 △
Enthalpy change ( H) Qr = △H
Enthalpy change of a system is equal to the heat absorbed or evolved by
the system at constant pressure
or ΔH=ΔU+ΔPV
Enthalpy change may be defined as the sum of the increase in internal
energy of the system and pressure-volume work done.

Relation between heat of reaction at constant temperature and that at

constant volume
Derivation: Qp = qv + ΔRT
We know that: qp=ΔH and qV=ΔU --------------(I)
At constant pressure: ΔH=ΔU+ΔPV --------------(II)

Where ΔV= change in volume

The second equation can be rewritten asl ΔH=ΔU+P(V2-V1)-----------(III)
where V2= Final volume of the system V1=Initial volume of system

For ideal gas, pV=nRT so that we have

pV1 = n1RT
pV2 = n2RT
Where n1 and n2 are no. of moles of gaseous reactants and products
respectively.

From equation (iii), ΔH=ΔU+n2RT - n1RT

ΔH = ΔU + (n2-n1)RT
ΔH = ΔU + ΔngRT
Where Δng=n2-n1 is the difference between the number of moles of
gaseous products and gaseous reactants.
From equation (i),we get:
qp = qv + ΔngRT
Conditions:

(a) if ng = 0, then qp = qv
(b) if Δng>0, then qp>1v
(c) if Δng<0, then qp<qv
(d) When the reaction is carried out on a closed vessel so that volume
remains constant (ΔV=0)

Formula for Numericals:

Qp = Qv +ngRT or ΔH=ΔU + ΔngRT

Q.1) The heat of combustion of benzene in a bomb calorie meter (at

constant volume) was found to be 3263.9 KJ/mol at 25 degrees Celsius.
Calculate the heat of combustion of benzene at constant pressure.
Solution: -3267.67 KJ/mol

Q.2) If water vapor is assumed to be a perfect gas, the molar enthalpy

change at 1 bar and 100 degrees celsius is 41 KJ/mol. Calculate the
internal change when:
(a) 1 mol of water is vaporized at 1bar pressure and 100-degree celsius
(b) 1 mole of water is converted into ice

Solution:
(a) 37.9 KJ/mol
(b) 41 KJ/mol

→
Q.3) Find out the internal energy change for the reaction A(l) A(g) at 373
K. Heat of vaporization is 40.66 kJ/mol and R=8.3 Jmol−1K−1.

Solution:
(a) 37.56 KJ/mol
Q.4) When 0.532 g of benzene is burnt with an excess of oxygen at a
constant volume 22.3 kJ of heat is given out. Calculate ΔH for the
combustion process.(R=8.314 J/K/mol, boiling point 353K)

Solution: −3273.52 kJ/mol

Heat Capacity (C):

The heat capacity of a system is defined as the amount of heat required to

raise the temperature of the system through 1 degree celsius.

C = q/ T △
Where △T=T2-T1

Specific heat capacity (C):

The heat capacity of a system is defined as the amount of heat required to

raise the temperature of one gram of a substance through 1 degree celsius.

m=mass of substance in grams

Molar Heat Capacity:

the heat capacity of a system is defined as the amount of heat required to

raise the temperature of one mole of substance through 1-degree celsius.

Cp= q/nΔT
Cp= C/nm
where "n" = number of moles
Types of heat capacities or molar heat capacities

Heat Capacity at Constant Volume:

The heat is supplied to a system to raise its temperature by 1 degree celsius

keeping the volume of the system constant is called heat capacity at
constant volume.

Cv = △U/△T
At constant volunme

Heat Capacity at Constant Pressure:

The heat is supplied to a system to raise its temperature by 1 degree celsius

keeping external pressure constant is called heat capacity at constant
pressure.

Cp= qp/ΔT
Cp= qH/ΔT
At constant pressure
Relationship between Cp and Cv:

At constant volume heat capacity is denoted by Cv and at constant pressure,

heat capacity is denoted by Cp. Let us find the relationship between the two,
we can write that expression for heat (q):

(I) At constant volume: qV = n CV ∆T = ∆U ---------------(I)

(ii) At constant pressure: qP = n CP∆T = ∆H ------------(ii)

We know that for 1 mole of an ideal gas,

∆H = ∆U + ∆(pV )
∆H = ∆U + ∆(RT )
∆H = ∆U + R∆T

From eq.1 and 2, we get,

CP ∆T = CV∆T + R ∆T
CP = CV + R
CP – CV = R (For 1 Mole of gas)
or CP – CV = nR (For n Mole of gas)

Measurement of ∆U:
Internal energy change is measured experimentally using an apparatus called
Bomb Calorimeter. It can be calculated using the formula:

∆U = C x ∆t x (M/m)

Where:
C= Heat capacity of the bomb calorimeter
∆t= rise in temperature
m= mass of substance in grams
M= Molar mass of the substance
 Measurement of ∆H:
Enthalpy change is measured experimentally using an apparatus called coffee-
cup calorimeter.

The value of ∆H can be calculated as follows:

Assuming that the density of the solution is the same as that of water (1g/mol)
and the specific heat of the solution is equal to that of water (4.184 Jk-g-) and
neglecting the heat capacity of the polythene bottle.

Suppose the initial temperature of the acid and base = t

The final temperature of the solution after mixing= t2
The rise in temperature ( ∆t): t2-t1
The total mass of the solution(m): mass of acid + mass of the base
The heat produced: m x c x ∆t
(where c = specific heat of the solution)

The heat produced by neutralization of 1litre of 1N HCl

△H= [(m * c * △t * 1000)/V] * (1/N)
Where N= Normality of acid
V = Volume of acid in ml

Exothermic reaction:

Reactions in which heat is released are called exothermic reactions.

For exothermic reactions:
∆H: negative (Hp < Hr)

Endothermic reaction:

Reactions in which heat is absorbed are called exothermic reactions.

For exothermic reactions:
∆H: positive (Hp > Hr)
Poisson's Ratio (V)

The value of V depends upon the atomicity of the gaseous molecules. This is
because some additional energy is required for vibrational and rotational
motions of the polyatomic molecules in addition to the translational motion.
The heat capacity of gaseous molecules increases with atomicity.

Cp = Cv + R
Cp/cv = 1 + (R/Cv)
or V = 1 + R/Cv

The 'Cv' increases with the atomicity of the gas and hence V decreases with
increasing atomicity of the molecules.

For monoatomic gases like He, Ne, Ar, Kr, Xe etc:

V=1.66
For diatomic gases like H2,O2,N2,CO etc
V=1.40
For Triatomic gases like CO2
V=1.30
Extra: The internal energy associated with any molecule depends upon its
degree of freedom which means different modes of transitional, rotational and
vibrational motion. Monoatomic gases like He,Ne etc have only transitional
degree of freedom whereas a polyatomic molecule consisting of N atoms has
degree of freedom as follows:

Transational Rotational Vibrational

Linear molecules 3 2 3N-5

Non-Linear
3 3 3N-6
Molecules

Each translational and rotational degree of freedom contributes energy =0.5kT

and each vibrational degree of freedom contributes energy = kT (Where
k=Boltzmann constant and equal to: R/Na)

However vibrational degrees of freedom contributes only at high temperatures

and do not contribute at ordinary temperature.

For Monoatomic gases, energy (U) per mole: 3RT/2

Diatomic gases have translational, rotational, and vibrational motion. At
moderate temp, contribution by vertical motion is negligible but it has two
rotational degrees of motion. Hence total energy per mole of diatomic gas+
2.5RT

Solve:
Q.1) Calculate the heat necessary to raise the temperature of 60g of
aluminum from 35∘C to 55∘C. Molar heat capacity of al is 24 J.mole −1
K−1.

Q.2) Calculate the enthalpy change on freezing of 1.0mol of water at

10.0oC to ice at −10.0oC.
ΔfusH=6.03kJmol−1at 0oC
​
Cp(H2O(I)]=75.3Jmol−1K−1
​
​
​
Cp[H2O(s)]=36.8Jmol−1K−1
​
​
​
 Thermochemistry

Thermochemical equations: When a balanced chemical equation not only

indicates the quantities of different reactants and products but also indicates
the amount of heat involved or absorbed, it is called thermochemical equation

Enthalpy of reaction

The amount of heat evolved or absorbed in a chemical reaction when the

number of moles of the reactants as represented by the chemical equation has
completely reacted, is called the heat of reaction or enthalpy of reaction.

The heat of the reaction depends upon a number of factors:

Quantities of the reactants involved
The physical state of the reactants and products
Allotropic modification
Concentration of solution
Temperature
Condition of constant: Volume or constant pressure

Standard enthalpy change of reaction (ΔrH):

The standard enthalpy of reaction is the enthalpy change for a reaction when all
the participating substances are in their standard states. The standard state of a
substance at a specified temperature is its pure form at 1 bar.
EXTRA:

Quantitatively, the effect of temperature on the heat capacity of a reaction is

given by Kirchoff's equation:

∆H2 - ∆H1 = ∆Cp (T2-T1)

∆U2 -∆U1 = ∆Cv (T2-T1)

Different types of enthalpy reactions:

Standard enthalpy change of vaporization (ΔvapH):

Amount of heat required to vaporize one mole of a liquid substance at constant

temperature and under standard pressure (1 bar) is called its standard enthalpy
of vaporization.
Eg: H20(l) --------------> H20(g) ΔvapH = 40.79 KJ/mol

Standard enthalpy change of Fusion (ΔfusH):

The amount of heat required to melting of one mole of a solid substance in a

standard state is called its standard enthalpy of fusion
Eg: H20(s) --------------> H20(l) ΔfusH = 6.00 KJ.mol

Standard enthalpy change of sublimation (ΔsubH):

It is the change in enthalpy when one mole of a solid substance sublime at a

constant temperature and under standard pressure.
Eg: CO2(s) --------------->CO2(g) ΔsubH = +73.0 KJ/mol

Standard enthalpy change of Formation (ΔfH):

The enthalpy change for the formation of one mole of a compound from its
elements in their stable states is called standard enthalpy change of formation.
→
Eg: H2(g) + 1/2O2(g) H2O(l) (ΔfH)= -258.8 KJ/mol
Standard enthalpy change of Combustion (ΔcH):

The enthalpy change of combustion is the amount of heat evolved when one
mole of substance under standard conditions (298K,1 bar pressure) is
completely burnt to form the products also under standard conditions.
Eg: CH4(g) + 2O2(g) ----------> CO2(g) + 2H2O(l) (ΔcH) = -890.4 KJ/mol

Hints:

(a)Combustion reactions are exothermic in nature i.e the enthalpy change is

negative.
(b) Calorific amount: The calorific value of s fuel or food is the amount of heat in
calories or joules produced from the combustion of one gram of thee fuel or
food.

Enthalpy change of neutralization (ΔneutH):

It is defined as the heat evolved when one gram equivalent of the acidic
neutralized by a base, the reaction is carried out in a dilute aqueous solution.

Eg: NaOH +HCl------------->NaCl + H2O

(ΔneutH) = -57.1 KJ/mol

Hints: Enthalpy change of neutralization of any strong acid (HCl, HNO3,

H2SO4) and a strong base (LiOH, KOH,NaOH, CsOH) is always the same
(-57.1 KJ)
In the case of a weak acid or weak base or both are weak, the enthalpy
change of neutralisation is 57.1KJ)
Enthalpy change of solution (ΔsolH):

It is defined as the enthalpy change when 1 mole of a substance is dissolved in

a specified amount of the solvent.
Eg: KC(s) l + aq. ------------> KCl(aq) (ΔsolH) = +18.6 KJ/mol
CuSO4(s) + aq. ------------> CuSO4(aq) (ΔsolH) = -66.5 KJ/mol

Enthalpy change of atomisation (ΔaH):

It is the enthalpy change when 1 mole of substance dissociates into gaseous

atoms.
Eg: H2(g) ------------> 2H (g) (ΔaH)=+435.0 kJ/mol
GH4(g) -----------> C(g) + 4H(g) (ΔaH)=+1665 kJ/mol
Na(s) -------------> Na(g) (ΔaH)=+108.4 kJ/mol

Enthalpy of allotropic transformation (ΔHtransform):

It is the enthalpy change when 1 mole of an allotropic modification changes to

another.
Eg: C(graphite) --------------> C(diamond) (ΔHtransform)
S(monosilic) ------------> S(Rhombic) (ΔHtransform)
Bond enthalpy or bond energy:

It is the amount of energy released when one mole of bonds is formed from
isolated atoms in the gaseous state, or, The amount of energy required to
dissociate one mole of bonds present between the atoms in gaseous
molecules.

For diatomic molecules like H2O2, N2, Cl2, HCl, etc the bond energies are
equal to their dissociation energies. These may be also called their
enthalpies of atomization.

Eg. H2(g) ------------> 2H(g) (ΔbH) = +436 KJ/mol

Cl2(g) ------------> 2Cl(g) (ΔbH) = +242 KJ/mol

For polyatomic molecules, the bond energy of a particular bond is not the
same when present in different types of compounds or in the same
compound. The bond energy for the first, second, third, and fourth C-H
bonds is not equal. Their values are +427,+439,+452, and +347 KJ/mol
respectively. Their total sum gives the enthalpy of the atomization of CH4

∆H: 427 + 439 + 452 + 347 = 1665 KJ/mol

In such cases, we use mean(average) enthalpy of C-H bond: 416.25 KJ/mol

In case of bond energy:

ΣrH = ΣB.E (reactants) - ΣB.E (products
Hess's Law:

It states as follows "the total amount of heat evolved or absorbed in a reaction

is the same whether the reaction takes place in one step or in a number of
steps.
Eg. When carbon(graphite) burns to form CO2 directly in one step, 393.5
KJ/mol of heat is produced.
C(s) + O2(g) -------------------> CO2(g) ∆
H: -393.5 KJ/mol

If carbon burns to form CO first which then burns to form CO2, the heats
involved in the two steps are as follows:

C(s) + 0.5O2(g) ----------> CO(g) ΔrH∘=−110.5kJ ​

CO(g) + 0.5O2(g) -------------> CO2(g) ΔrH∘=−283.0kJ
​
The total evolved in the two steps will be -393.5 KJ/mol which is the same when
reaction takes place directly in one step.

Q.1) Calculate the enthalpy change of methane from the following data.
→CO2(g); ΔrH∘=−393.5kJ
C(s)+O2(g)
2H2(g)+O2(g)→2H2O(l); ΔrH∘=−571.8kJ
​
​
​
CH4(g)+2O2(g)→CO2(g)+2H2O(l); ΔrH∘=−890.3kJ
​
​
​
​
​
​
​
​
​
Solution: -74.8 KJ/mol

Q.2) Calculate the standard heat of the formation of carbon-di-sulfide (l).

Given that the standard heat of combustion of CS2 are 110.2 KJ/mol and
those of carbon and sulfur are 297.4 and 394.5 respectively:

Solution: -879.1 KJ/mol

Q.3) The enthalpies of formation of methane, carbon dioxide, and water
are -74.8, -393.5, and -286.2 kJ/mol respectively. Calculate the enthalpy
of combustion of methane/

Solution: -891.1 KJ/mol

The standard enthalpy change for elements in standard state is taken

as zero.

Q.4) Calculate the enthalpy of the reaction:

C(s) + H2O(g) ------------> CO(g) + H2(g)
Given the enthalpies of the formation of carbon monoxide ad steam are
-110.5 and -243.0 KJ/mol respectively.

Solution: +132.5 KJ/mol

Q.5) Calculate the enthalpy of the reaction for the following reaction:
H2(g) + I2(g) ------------> 2HI(g)

Bond Bond energy

H-H 433

I-I 151

H-I 299

Solution: -14 KJ
Lattice Enthalpy:

It is the enthalpy change that occurs when one mole of ionic compound
dissociates into its ions in gaseous state.
→
NaCl Na+(g) + Cl−(g)

Born-Haber Cycle:

It is impossible to determine lattice enthalpies directly by experiment, we use

an indirect method where we construct an enthalpy diagram called a Born-
Haber cycle.

Let us now calculate the lattice enthalpy of Na+ Cl-(s) by following steps
given below:

1.) Sublimation of Na metal:

Na (s) →
Na (g),
Sublimation energy ΔHsub = + 108.4kJ/mol

2) Ionisation of Na atoms:
Na(g) → Na+(g) + 1e– ,
Ionization energy ∆HIE = +496kJ/mol

3) Dissociation of chlorine gas into atoms:

Cl2(g) →2Cl(g) (1/2)
Hdiss= (1/2) 242 = +121kJ/mol

4) Electron gained by chlorine atom:

Cl(g) + 1e– →
Cl– (g)
∆
Electron affinity = HEA = -348.6kJ/mol

5) Gaseous sodium ion and gaseous chloride ion combine to form solid
sodium chloride molecule.
Na+(g) + Cl– (g) → Na+ Cl– (s)
Lattice energy = ∆HLE = U = ?

The heat of formation of NaCl(s) is found to be: -411.2 KJ/mol

Na(s) + 0.5 Cl2(g) →
NaCl(s)
The complete process involving the formation of one mole of NaCl(s) directly
and through a series of steps indirectly may be represented by a cyclic
process as shown:

Applying Hess's Law:

The lattice energy of the NaCl solid = U = ΔHf0 – (ΔHsub + ∆HIE + ½ ∆Hdis +
∆HEA).
= -411.2 -108.4 -496 -121 +348.6
= – 788kJ/mol

Limitations of first law of thermodynamics:

It provides no information about the spontaneity or feasibility of the process.

Spontaneous process: A process that under some given conditions may take
place by itself or by initiation is called a spontaneous process.
Eg: The flow of water down a hill.

Non-Spontaneous process: A process that can neither take place by itself nor
by initiation is called a non-spontaneous process.
Eg: Flow of water up a hill
Driving force: The force which is responsible for the spontaneity of a process is
called the driving force.

For a spontaneous process, there are two forces:

Non-Spontaneous process: In order to acquire max stability, every system
tends to have minimum energy. Therefore the exothermic process is called
spontaneous or feasible.
N2(g) + 3H2(g) ⇌ 2NH3(g)
​
​
​
The tendency for maximum randomness: The second factor which is
responsible for the spontaneity of a process is the tendency to acquire
maximum randomness.

Extra: The overall intensity for a process to occur depends upon the resultant
of the following two tendencies:
1. The tendency for minimum energy represented by E
2. Tendency for max random represented by R

FOR A PROCESS A---------->B

Type 1: When the net driving force is in the forward direction.

E ---------->
R ---------->
Driving force(D) = ( E + R) (Spontaneous)

E --------------------> E <-------
R <------- R -------------------->
Driving force(D) ---------> Driving force(D) --------->
D = (E -R) Spontaneous D = (R-E) Spontaneous

Type 2: When the net driving force is in the backward direction.

E <---------- E ---------->
R <---------- R <-----------------
Driving force(D) <----------------- Driving force(D) <----------

Non-spontaneous reaction
Entropy

Entropy is a measure of randomness or disorder of the syste

The greater the randomness, the higher the entropy. The increasing order
of entropy of solid, liquid, and gas is :
Solid < Liquid < Gas
Entropy is a state function. The change in its value during a process called
entropy change ( △S) is given by:
△S=S2-S1 = Σ S(Products) - Σ S(Reactants)
Quantitatively, △S is related to q and T for a reversible process as
follows.

Entropy change during a process is defined as the amount of heat (q)

absorbed isothermally and reversibly divided by the absolute
temperature (T) at which the heat is absorbed.
Units of enthalpy change are called cal/Kmol in C.G.S and J/Kmol in SI
units.

Entropy change during phase Transformations:

Entropy change of fusion: It is the change in entropy when 1 mole of a solid

substance changes to liquid form at the melting temperature.

∆fusS=∆fusH / Tm
Where:
∆fusS=Enthalpy change of fusion per mole
Tm= Melting point in Kelvin
 Entropy change of vaporization: It is the entropy change when 1 mole of
liquid changes into vapor at its boiling temperature

∆vapS=∆vapH / TS
Entropy change of sublimation: It is the entropy change when 1 mole of
solid changes into vapor at particular temperature.

∆subS=∆subH / T
Where:
∆subH= Enthalpy change of sublimation at temperature (T)

Q.) Calculate the entropy change of n-hexane when one mole of it

∆
evaporates at 341.7K ( vapH = 29 KJ/mol)

Solution: 84.87 J/Kmol

 Spontaneity in terms of entropy change

∆S total) = ∆system + ∆surrounding

Total entropy change: (
" For all spontaneous processes, the total entropy change (∆S total) must
be positive"
i.e: (∆S total) = ∆system + ∆surrounding > 0
Criterion for the spontaneity in terms of entropy charge is as follows:
if (∆S total) = +ve, spontaneous
if (∆S total) = -ve, non-spontaneous
if (∆S total) = 0, process in equilibrium

Statements of the second law of thermodynamics:

1. All spontaneous processes are thermodynamically irreversible.

2. The entropy of the universe is continuously increasing.
3. Without the help of an external agency, a spontaneous process cannot be
reversed.
4. The complete conversion of heat into work is impossible without leaving
some effect elsewhere.

Extra:

Zenoth's law of thermodynamics: States that if two systems "A" and "B" are
in thermal equilibrium with a third system "C" separately, then "A" and "B"
should also be in thermal equilibrium with each other.
Third law of thermodynamics: The entropy of all perfectly crystalline solid
may be taken as zero at the absolute zero of temperature.
 Gibb's Free energy (G)

This is a thermodynamic quantity that helps in predicting the spontaneity of

a process.
Gibb's function is defined by the equation: G = H-TS
Where:
T= Absolute temperature
H= Enthalpy
S= Entropy of the system

For isothermal process, we have:

G1= H1 - TS1
G2 = H2 - TS2
G2 - G1 = (H2 - H1) - T(S2 - S10

ΔG = ΔH – TΔS
Where:
ΔG = Change in Gibb's free energy of the system
ΔH = Enthalpy change of the system
ΔS = Entropy change of the system
The equation, ΔG = ΔH – TΔS is known as Gibb's energy equation or
Gibbs-Helmholtz equation.

Gibb's free energy and useful work

Gibb's free energy is that thermodynamic quantity of a system the decrease

in whose value during a process is equal to the max possible useful work
that can be obtained from the system.
-ΔG = Wuseful or Wmax
Spontaneity in terms of entropy charge is as follows:
if ∆G = +ve, spontaneous
if ∆G = -ve, non-spontaneous
if ∆G = 0, The process is in equilibrium
 Effects of temperature on spontaneity of process

ΔG = ΔH – TΔS

Standard free energy change ( ∆Gº') of a reaction

It is defined as the change in free energy which takes place when the
reactants in the standard state (1ATM and 298K) are converted into the
products in their standard state.
∆rGº' = ΣGº'(Products) - ΣGº'(Reactants)
or ∆Gº = ∆Hº - T∆Sº

Relationship between standard free energy and equilibrium constant:

∆Gº = -2.303RT log Kp

Q.1) Calculate ∆rGº for conversion of oxygen to ozone
Solution:
→
32O2(g) O3(g) at 298 K
If Kp is = 2.47×10−29(atm)−12
Answer: 163.2kJ/mol

⇌
Q.2) For the equilibrium, PCl5(g) PCl3(g)+Cl2(g) at 298K,
∆Gº for the reaction (R=8.314JK−1mol−1).
​
​
​
K=1.8×10^−7. Calculate

Solution:
+34.48kJ mol−1

Q.3) What will be the value of ∆Gº. If equilibrium constant for a

reaction is 10?
Solution:
–5.744 kJ mol−1.

→
Q.4) For the reaction, 2A(g)+B(g) 2D(g),ΔUo=−10.5kJ and
ΔSo=−44.10JK−1. Calculate ΔGo for the reaction and predict
whether the reaction may occur spontaneously:
Solution:
0.16 KJ and non-spontaneous

Q.5) △H and △S of a reaction are 40.63kJ/mol and 108.8J/k/mol

respectively. Predict the feasibility of the reaction at 270C.
Solution:
not feasible