CHEMISTRY PUC – I YEAR

CHEMICAL THERMODYANMICS
The word Thermodynamics ‘is derived from the Greek words thermo(heat)
dynamics(movement).
Thermodynamics is the branch of science which deals with the study of inter conversion of
heat and other forms of energy during physical and chemical processes.

TERMS USED IN THERMODYNAMICS

1) System : It is a specific portion of the universe which is under thermodynamic study and
which is separated from the rest of the universe with a definite boundary.
Ex. 1) All plants and animals are living systems
2) A beaker containing a liquid.

2) Surrounding : It is The portion of the universe excluding system and capable of

exchanging matter and energy with the system.
Ex: IF a beaker containing a liquid is kept in a water bath, then water bath is considered as
surrounding. Therefore, system + surrounding =universe

3) Boundary : If is real or imaginary surface which separates the system from the
surroundings.
Ex: In a beaker containing liquid, the wall of the beaker is the boundary.

Types of system :On the basis of movements of matter and energy in or out of the system,
the system are classified into 3 types

i) Open system : A system which can exchange both matter and energy with its
surrounding is called an open system.
Ex. A) All living things are open systems b) Hot liquid in an open beaker water evaporates
and water vapour goes into the surroundings. Heat energy is also radiated to surroundings.

ii) Closed system : A system which can exchange energy nut not matter with the
surrounding is called closed system.
Ex: a) Hot water in a closed vessel b) Pressure cooker.

iii) Isolated system : A system which cannot exchange matter and energy with the
surrounding is called isolated system.
Ex: a) Hot coffee in a thermo flask. B) Hot water in a closed and insulated vessel.

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State of a system:
State of a system indicates the position of the system and can be explained by defining
definite values for its properties like temperature, Volume pressure etc.
In other words, a system at a given state has all its property values fixed.

Properties of a system :
Thermodynamic properties of a system are of two kinds

a) Extensive properties :
These properties depend on the amount of the substance present in the system.
Ex : Mass, Volume, Enthalpy, Heat capacity etc.

b) Extensive properties :
These properties do not depend on the amount of substance present in the system.
Ex: pressure temperature, density, Surface tension viscosity, Refractive index, mole
fraction. etc.

State inductions :
The properties which depends only on the state of a system and not on the path taken by it
to reach that system are called state functions.
Ex: Pressure, temperature, volume enthalpy, entropy and energy

Standard state :
The state of a system at 298K and 101. 3k Pa pressure is known as standard state of system.
Ex: Liquid state is the std state of water.

Internal energy (U) :

The total amount of energy possessed by a fixed amount of a substance under a given set of
conditions is called internal energy or intrinsic Energy. In a chemical reaction, the change in
the energy is given by
∆U= U2-U1 OR ∆U = UPRODUCT - UREACTANT

Change in the internal energy is defined as the amt of heat liberated or absorbed during a
chemical reaction at constant volume.
i.e. ∆U = qV

FIRST LAW OF THERMODYNAMICS (LAW OF CONSERVATION OF ENERGY)

This law states that ‘’ Energy can neither be created nor be destroyed but can be transformed
from one form into another’’

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Mathematical form of 1st law of Thermodynamics :

When a system with internal energy U1 absorbs heat q, the total energy of the system
becomes
U1 + q. If is the work done on the system, the total energy of the system, the total energy of
the system is said to be in a new state with internal energy U2.
U2 = U1 + q + w
U2 - U1 = q + w
U = q + w
Therefore change in internal energy = heat absorbed by the system + work done on the
system.

Sign convensions of heat (q) and work (w)

1) Heat absorbed by the system is indicated by positive sign(+H)
2) Heat liberated by the system is indicated by negative sign (-H)
3) Work is done on the system is indicated by positive sign (+W)
4) Work and done by the system is indicated by negative sign.(-W)

THERMODYNAMIC PROCESS

A series of operations carried out on the system to change its initial state to final state is
called process.

Types of process
i) Adiabatic process : In this process the system does not exchange heat with its
surroundings
(q = 0), U= q+w becomes U = w.
ii) Isothermal process : In this process temperature of the system remains constant. T=0,
E=0, U=q+w becomes q=-w

iii) Reversible process : This process takes place (very slow) slowly the process which can
be reversed by changing the driving forces of system called reversible process . Reversible
processes attain equilibrium state.

iv) Irreversible process : The process which cannot be reversed by changing the driving
force of the system is called irreversible process. An irreversible process takes place very
fast. Irreversible process do not attain equilibrium state.

v) Isobaric process : This process takes place at constant pressure.

vi) Isochoric process: This process takes place at constant volume

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Mechanical Work:
In a chemical system involving gases, work is said to be done when they undergo
expansion or contraction. Such work is called pressure- volume work.
When a gas subjected to isothermal expansion, from an initial volume V1 to final volume
V2, the change in volume is denoted by V the work done is the product of external
pressure and the change in volume.
i.e. w=-P
The negative sign indicates work is done by the system .

WORK DONE DURING REVERSIBLE ISOTHERMAL EXPANSION

For extremely small expansion of an ideal gas the small amount of work done dw is given
by
dw=--pdv
If can ideal gas (system) expands from an initial volume V1 to the final volume V2 the total
workdone is
2
W=-∫1 𝑝𝑑𝑣
For one mole of an ideal gas PV= RT,  P= RT/V
𝑉 𝑑𝑣
 W=-RT∫𝑉 2
1 𝑣
On integration
W=-2.303n RT log V2 /V1
For ’n’ moles, w=-2.303 n RT log V2/V1.....(1)
For an ideal gas, P1V1= P2 V2
 P1 / P2 = V2 /V1
 w=- 2.303nRT log P1 /P2........(2)
W = work done during reversible isothermal expansion, n= no. Of moles, T = absolute
temp.
V1 & V2 are initial volume and final volume. P1 & P2 are initial and final pressure .

WORK DONE DURING REVERSIBLE ADIABATIC EXPANSION

In an adiabatic process, heat neither enters nor leaves the system. Hence there is no net heat
change. The work done in an adiabatic expansion can be obtained from the change in
internal energy is the product of molar heat capacity at constant volume (CV) and the
change in temperature T.
w = n CV (T2-T1)
Where Cv-> molar heat capacity at constant volume.
T1 - > initial temperature of the system , T2 -> Final temperature of the system

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Free expansion :
Expansion of a gas in vacuum (Pex=0) is called free expansion. No work is done during free
expansion of an ideal gas whether the process is reversible or irreversible.

Isothermal and free expansion of an ideal gas :

For isothermal expansion of an ideal gas into vacuum, w=0 since Pex =0 U = q+w can be
expressed for isothermal irreversible and reversible changes as follow
a) For isothermal irreversible change,
q=-w= Pex (V2 – V1)
b) For isothermal reversible change
q=-w = nRT in V2/V1 = 2.303n RT log V2/V1
c) For adiabatic change, q=0
U=Wad

Enthalpy (H) :
Most of the chemical reactions are carried out at constant pressure. The heat change
occurring in reactions carried out at constant pressure is expressed using a
thermodynamics function called Enthalpy of the system. it is represented by the symbol H.
Therefore enthalpy is the total heat content of the system under the given set of
thermodynamic conditions.

Mathematically, H= U + PV
i.e Enthalpy is the sum of internal energy and product of pressure and volume.

Enthalpy is an extensive property and state function. In chemical reactions, change in

enthalpy can be calculated by using the equation.
H=Hproducts -Hreactants
This equation is also called energy equation.

Enthalpy change H is defined as ‘’the heat change occurring when reaction is carried out
at constant pressure’’
H = qp

Relation Between H and U : Mathematically, Enthalpy is defined as H= U+ PV

for an ideal gas PV = n RT, therefore the above equation becomes H = U + n RT
where,
n = No. Of moles of gaseous products- No.Of moles of gaseous reactants.
If n = 0 then H = U
If n = +ve thenH >U
If n = -ve then H <U

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Exothermic reaction :
A reaction in which heat is evolved when reactants are converted into products is known as
exothermic reaction.
Example : C(s) +O2(g)  CO2(g),H=-393.5 kJ

Endothermic reaction :
A reaction in which heat is absorbed when reactants are converted into products is known
as endothermic reaction.
Example : C(graphite) +2H2 (g) --> C2 H4 (g) H=+52.3 kJ

Note: 1) In an exothermic reaction, Hreactants>Hproducts’H is negative

2) In an endothermic reaction, Hreactants<Hproducts’H is Positive

Thermo chemical equations :

A balanced chemical equation which indicates the enthalpy change and physical states of
reactants and products is called a thermo chemical equation. In a thermo chemical
equation, H indicates whether the reaction is exothermic(-) or endothermic (+) .

EX : 2H2 (g)+O2(g) --> 2H2 O(1) H =-572 KJ

Heat capacity :
The quantity of heat liberated or absorbed by a system can be measured. The heat supplied
to a system appears as a rise in temperature. The increase in temperature is directly
proportional to the heat supplied to the system.
qT
q=C.T
where ‘c’ is heat capacity, T is rise in temperature . ifT is 1C or 1K then q=C.

Heat capacity is defined as ‘’ quantity of heat required to raise temperature by 1C or

1K”.
Heat capacity is an extensive property.

Specific heat capacity (C) or specific heat :

It is defined as the quantity of heat required to raise the temperature of 1 gram of a
substance by 1C or 1K.
Specific heat capacity (C) = heat capacity /mass = C/m
𝑞 𝑞
 Specific heat capacity (C) = 𝑚𝑇 (∵ 𝐶 = 𝑇)
Or
Q= C x m x T
Thus quantity of heat liberated (or absorbed) by a system is given by the product of mass,
specific heat capacity and change in temperature.

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The unit of specific heat capacity is Jg-1 K-1

Molar heat capacity ‘C’M

It is defined as the quantity of heat required to raise the temperature of one mol of a
substance by one degree celcius or one Kelvin.
The unit of molar heat capacity is Jmol-1 K-1

The relation between Cp and CV for an ideal gas :

The heat capacity at constant volume is denoted by CV and at constant pressure is denoted
by CP.
q=C.T , qv =Cv.T=U , qp =Cp.T=H
For 1 mole of an ideal gas, H = U+PV , H= U+RT
But H = Cp.T, U= CV. T
 Cp.T, = CV. T + RT
CpT - CVT = R.T
(Cp-Cv)T= R.T
Cp-Cv = R

MEASUREMENT OF U AND H

Calorimetry : we can measure energy changes associated with chemical or physical process
by an experimental technique called calorimetry. In calorimetry the process is carried out
in a vesal called calorimeter, Which is immersed in a known volume of a liquid. Knowing
the heat capacity of the liquid in which calorimeter is immersed and the heat capacity of
calorimeter , it i9s possible to determine the heat liberated in the process by measuring
temperature changes. Measurements are made under two different conditions. I) at
constant volume, qv ii) at constant pressure, qp
i) U measurement :

For chemical reactions, heat absorbed at constant volume is measured in a bomb

calorimeter. Here, a steel vessel (the bomb) is immersed in a water bath. The steel vessel is

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immersed in water bath to ensure that no heat is lost to the surroundings. A combustible
substance is burnt in pure dioxygen supplied in the steel bomb, heat evolved during the
reaction is transferred to the water around the bomb and its temperature is monitored since
the bomb calorimeter is sealed. its volume does not change. i.e. the energy changes
associated with reaction are measured at constant volume. Under these conditions, no work
is done as the reaction is carried out at constant volume in the bomb calorimeter. Even for
reactions involving gases. There is no work done as V=0. Temperature change of the
calorimeter produced by the completed reaction is then converted to q. By using the known
heat capacity of the calorimeter with the help of the equation.
Q=c x m x T=C.T

ii) H measurements :
Measurement of heat change at constant pressure (generally under atmospheric pressure)
can be done in a calorimeter shown in the figure. We know that H=qp (at constant p) and
therefore, heat absorbed or evolved, at constant pressure (qp)is also called the heat of
reaction or enthalpy of reaction rH.
In an exothermic reaction, heat is evolved and system loses heat to surroundings. Therfore,
qp will be negative and r H will also be negative . Similarly in an endothermic reaction,
heat is absorbed, qp is positive and r H will be positive.

1) Enthalpy change of a reaction (rH) or enthalpy of reaction :

It is defined as the change in enthalpy that occurs when the number of moles of reactants
indicated by the balanced chemical equation have completely reacted under the given
conditions.
Ex: 1) N2(g) O2 (g) 2NO(g) ; H = + 180.8kJ
1) C (graphite)+O2 (g) 
2) CO2 (g) ; H = + 180.8kJ

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2) Standard enthalpy of reaction (rH) :

It is defined as enthalpy change that occurs when the number of moles of reactants
indicated at one bar pressure at a specified temperature (generally 298K)
Ex : C(s)+O2 (g) CO2(g) rH = + 393.5kJ

3)Enthalpy changes during phase transformations :-

i) Standard enthalpy of fusion (fusH) :

It is defined as the change in enthalpy that occurs when one mole of a solid substance in its
standard state melts at its melting point & standard pressure (1 bar).
Ex : H2O (s)  H2O (1)fus H=+6.0 kJ mol-1.
Enthalpy of fusion of Ice is 6 kJ mol-1.

ii) Standard enthalpy of vaporisation or molar enthalpy of vaporisation :

It is defined as ‘’the change in enthalpy that occurs when one mole of as liquid is converted
into its vapour at its boiling point & under standard pressure (1 bar)
Ex : H2O (1)  H2O (g)vap H=+40.6 kJ mol-1.
Enthalpy of vaporization of water is 40.6 kJ mol-1.

iii) Standard Enthalpy of Sublimation (subH) :

It is defined as ‘’the change in enthalpy that occurs when one of a solid substance is
converted into its gaseous state at a constant a temperature under standard pressure (1 bar).
Ex : i) CO2 (s)  CO2 (g) ; sub H=+25.2 kJ mol-1.
ii) I2 (s)  I2 (g) ; sub H=+62.4 kJ mol-1.

4) Enthalpy of formation :
It is defined as the change in enthalpy that occurs when one mole of a compound is formed
from its elements.
Standard Enthalpy of formation : (fH)
It is the enthalpy change that occurs when one mole of the compound is formed in its
standard state from its elements in their standard states, under 1 bar pressure, at specified
temperature.
Ex : C(s) +O(g) CO2 (g) fH=-393.5 kJ mol-1.
a) Standard enthalpy of formation of elements in their standard state are zero.
Ex: fH for carbon (graphite)=O , fH for Sulphur (rhombic)=O, fH for phosphorus
(white)=O

b) Standard enthalpy of formation of a compound = standard enthalpy of the compound

itself.
Ex: Enthalpy of formation of CO2 = enthalpy of CO2 itself.

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c) The stability of compounds can be related to their enthalpies. Lower the enthalpy of
formation of a compound the more stable is the compound.
Ex : CO2 (f H=-393.5 kJ) is more stable than CO(f H=-110.5 kJ)

5) Standard enthalpy of combustion :( cH)

It is defined as the enthalpy change that occurs when 1 mole of a substance is burnt
completely in excess of oxygen, provided all of the reaction & products are in their
standard states.
Ex. C (graphite)+O2 (g) CO2 (g) c H=-393.5 kJ mol-1
Standard enthalpy of combustion of CO2 (g) is- 393.5 kJ mol-1
6) Enthalpy of atomization :
It is defined as the enthalpy change that occurs when the breaking of all of the bonds in one
mole of the given substance takes place to form constituent gaseous atoms.
Ex. a) H2 (g) 2H(g) aH=+435 kJ mol-1
In this case of diatomic molecules like H2 , the enthalpy of atomisation is same as the bond
dissociation energy.
b) Na(s) Na(g) aH=+108.4 kJ mol-1
In this case the enthalpy of atomisation is same as the enthalpy of sublimation.
c) CH4 (g) C(g) +4H(g) aH=+1665 kJ mol-1

7) Bond enthalpy : (bondH)

It is defined as the enthalpy change in enthalpy that occurs when one mole of covalent
bonds of a gaseous covalent compound is broken to form products in the gaseous phase.

H2 (g) 2H(g) ; H-HH=+435 kJ mol-1

Here 435 kJ mol-1 is the bond dissociation enthalpy of H-H bond. This is applicable for
homo diatomic molecules.

In case of poly atomic molecules, Bond dissociation enthalpy is different for different bonds
within the same molecule. For example ; the enthalpy change for the atomisation of
methane i.e,. enthalpy change when all of C-H bonds in 1 mole of methane break is 1665 kJ
mol-1 CH4 (g) C (g) +4H(g) aH=+1665 kJ mol-1

All the four C-H bonds in methane are identical in bond length & energy but the energies
reguired to break the individual C-H bonds in each successive step differ.
CH4 (g) CH3 (g) +H(g) ; bond H = +427 kJ mol-1
CH4 (g) CH2(g) + H(g) ; bond H = +439 kJ mol-1
CH2 (g) CH(g) + H(g) ; bond H = +452 kJ mol-1
CH (g) CH2(g) + H(g) ; bond H = +347 kJ mol-1

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 CH4 (g)  C (g) + 4H(g) ; bond H = +1665 kJ mol-1

In such cases mean bond enthalpy is used.
1
The mean bond enthalpy of C-H bond = 4 (1665)= 416.25 kJ mol-1

8) Standard enthalpy of solution : (solH)

It is defined as the enthalpy change when one mole of a substance dissolves in specified
amount of solvent under standard conditions.

Enthalpy of solution at infinite dilution :

It is defined as the enthalpy change when one mole of a substance dissolved in such a large
quantity of solvent such that further addition of solvent does not cause any more change in
enthalpy.

Ex. (1) KCI (s) +aqKCI (aq) ; sol H = 18.5 kJ

Enthalpy of solution KCI is +18.5 kJ
2) H2SO4 (1) +aqH2SO4 (aq) ;sol H = -75 kJ
The enthalpy of solution H2SO4 is -75 kJ

Hess’law of constant heat Summation :

The law states that , the total enthalpy change of a reaction remains the same whether the
reaction occurs in a single step or series of several steps.
Or
The standard enthalpy of a reaction is algebraic sum of Hvalues of intermediate reactions
into which the overall reaction may be split.
Ex: C(s) +O2(g) ; fH-393.5 kJ mol-1

This reaction occurs in two steps.

1
Step 1. C(S) + 2 𝑂2 (g)  CO (g) H = -283 kJ mol-1
1
Step 2.CO(g)+ 2 𝑂2(g)  CO (g) H = -110 kJ mol-1
The net reaction is , C(s) +𝑂2 (g) CO2 (g) H=-393.5 kJ mol-1

Note : The application of Hess’s law is that the thermo chemical equations may be added
or subtracted like algebraic equations.

Lavosier&laplacelaw :
It states that ‘’ the quantity of heat evolved when a reaction amt of a compound is formed is
equal to the heat that must be supplied to decompose it.
Ex : C (S) +O2 (g) CO2 (g) H=- 393.5kJ mol-1
CO2 (g)  C(s) + O2 (g) H=+393.5kJ mol-1

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9. Lattice Enthalpy (L H)

It is the enthalpy change taking place when one mole of ionic compound dissociates into
gaseous ions of opposite charge at the standard conditions.
NaCl (s)  Na+ (g) +Cl-(g) L H=+788 kJ mol-1.

Enthalpy of hydration of ions :

It is defined as the energy released by hydration of ions furnished by one mole of ionic
compound.
When ionic salt is dissolved in water it involves two energy changes.
1. Lattice enthalpy ((L H)
2. Enthalpy of hydration (Hyd H)

According to Hess’s law,

sol H = L H+Hyd H
sol H may be +ve or –ve
i) if heat liberated during hydration of the ions is more than the heat absorbed to break the
lattice, Then sol H will be –ve .
ii) If heat liberated during hydration of ions is less than the heat absorbed to break the
lattice, Thensol H will be –ve
If sol H is very high and hyd H is very low then dissolution of salt may not occur.

Lattice enthalpy and Born- Haber cycle :

It is not possible to determine lattice enthalpy of an ionic crystal by experiment. It can be

calculated by applying born-Haber cycle, in which the principle of Hess’s law is applied.
Consider the energy changes involved in the formation of sodium chloride crystal from
metallic sodium chlorine gas and calculated lattice enthalpy of NaCl(s).

The reaction involves the following steps :

I. Sublimation of metallic sodium

Na(s) Na(g) ; sub H=108.4 kJ mol-1.

II Ionisation of Na atoms
Na(s) Na+(g) +𝑒̅ ; i H=495.6 kJ mol-1.
i H is ionisation enthalpy of Na

III. Dissociation of Cl2.

Cl2 (g) 2Cl (g) ;a H=242 kJ mol-1

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1
Cl2 (g) Cl (g) ;a H=121 kJ mol-1
2
a H enthalpy of atomisation or dissociation.

iv. Conversion of Cl(g) ; e H=-348.6 kJmol-1

e H is electron gain enthalpy.

v. Combination of Na+ (g) and Cl (g) ions to form one mole of NaCl(s)
Na+ (g) Cl (g) NaCl(g) ; LH=?
Applying Hess’s law we get
1
fH=subH +iH+2dissH+eH+LH
LH=- 411.2 -108.4-121-495.5+348. =-787.6 kJ mol-1

Thus lattice enthalpy of NaCl(s) is -787.6 kJ mol-1

SPONTANEOUS PROCESS

A process which takes place on its own accord without any external aid is called
spontaneous process. It takes place only in one direction.

Examples :
1. Water flows from higher to lower level.
2. Flow of heat from a hot body to a cold body.
3. Melting of ice at room temperature.
4. Reaction between nitric oxide and oxygen to form nitro dioxide.
2NO + O2 2NO2
5. Vaporisation of water in an open vessel.
6. Dissolution of sugar in water to form a solution.
7. Hydrogen reacts with oxygen to form water. 2H2 +O22H2O

NON- SPONTANEOUS PROCESS

A process that does not take place on its own and requires the help of external agency is
called non-spontaneous process.
Examples :
1. Water does flow lower level to higher level.
2. Decomposition of water into hydrogen and oxygen. 2H2O  2H2 +O2

Criteria for Spontancity of a Reaction

There are two causes of spontaneity of a process.

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1) Tendency of a system to acquire a state of minimum energy.

2) Tendency of a system to acquire a state of maximum disorder.

Driving Force :
The overall tendency of a system to occur by itself is a resultant of these two tendencies and
is called driving force. I may be noted that

Entropy (S) :
‘’Entropy is the quantity which measures the disorder or randomness of a system’’ It is
denoted by ‘S’.

Physical significance of Entropy :

1. Entropy is the property of a substance which measures the disorder or randomness in a
system.
2. The more is randomness, the larger is the value of entropy.
3. It is also a measure of the unavailable energy.
During expansion of a gas or diffusion of a gas.Disorderincrease.Entropy increases.
Gaseous sate has maximum disorder. Liquid state has more order. Solid state is still more
ordered state. Thus, entropy is highest in the gaseous state and least in solid state. Thus.

Gas > Liquid > Solid

The change in the entropy depends on entropy values at initial states and not on the
method in which the process is carried out. Hence entropy is thermodynamics quantity i.e.
., It is state function and it is and it is an extensive property.
The change in entropy during a process is calculated using expression

𝑄 𝐻𝑒𝑎𝑡𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑑𝑞
∆𝑆 = = 𝐴𝑏𝑠𝑜𝑙𝑢𝑡𝑒𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒or ds = 𝑇
𝑇

Unit of entropy : The unit of entropy is joules per Kelvin i.e. JK-1

1. Spontaneity and entropy change :

Consider melting of ice room temperature and dissolution of ammonium chloride in water.
These reactions are spontaneous accompanied by increase in an isolated system it becomes
spontaneous, if entropy increases during the process

e.g. In a process, A >B

If S1 is the initial entropy and S2 is the final entropy, then S2> S1 for a spontaneous process.

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S = S2 –S1 is positive quantity for a spontaneous process.

If the process is carried out in an open system, STotal represents the total entropy change in
system and surroundings.

i.e, STotal = system + S Surounding

If S Total is positive , the process is spontaneous. If STotal is negative the process is non-
spontaneous. Thus entropy is increases in spontaneous process. It becomes maximum at
equilibrium.
Thus, entropy criterion about the spontaneity of a process can be summarized as follows.
STotal> 0. The process is spontaneous.
STotal< 0. The process is non- spontaneous.
STotal = 0. The process is at equilibrium.

2. Spontaneity and enthalpy change :

Generally a substance has a tendency to attain a lower energy state, as lower energy state is
more stable. In spontaneous processes there is a decrease in energy. In a reaction,
A B
If H1 is the enthalpy of a reactants and H2 is enthalpy of products, H2< H1 for a
spontaneous process, H = H2 – H1 = a negative quantity for a spontaneous processes.
In other words. Exothermic reactions are spontaneous. However this is not always true.

There are many endothermic reactions, which are spontaneous.

e.g. Melting of ice, evaporation of alcohol in which H is positive. Even some endothermic
chemical reactions are spontaneous.
e.g, NH4Cl + Water NH4Cl(aq) ;H = + 35 kJ
thus the energy factor alone cannot predict the spontaneity of process.

Second law of thermodynamic can be stated as follows

1. All naturally occurring process are spontaneous and irreversible
2. without the help of external energy the spontaneous process can not be reversed.
3. ‘’The entropy of the universe is continuously increasing’’
i.e., Stotal = Ssystem + S surroundings
4. Nature tends to pass from a less probable to a more probable condition.

Free Energy (G)

Free energy is defined as ‘’ The maximum amount of energy available to a system during a
process that can be converted into useful work’’.
OR
It is the capacity of any system to do useful work

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Mathematically, It is defined by the following expression

G=H- TS This equation is known as Gibbs free energy equation.

Where G=Free energy H=Enthalpy of the system S= Entropy T= Temperature in

Kelvin

Gibb’s free energy is a state function i.e. Change in free energy during the process depends
only on initial and final states and not on the path chosen

Relation among G, H and S

The change in free energy G at constant temperature and pressure is given as

G = H- T  S
This equation is known as Gibbs- Helmholtz equation.

Criterion for Spontaneity of a system :

Free energy change i.e. G, provides the overall criterion for the spontaneity of a chemical
process. For a reaction carried out at constant temperature and pressure
If G =-ve (negative i.e, <0), the reaction is spontaneous i.e. fesible.
G =+ve (positive > 0), the reaction is non-spontaneous
G= zero, the reaction is at equilibrium.

Standard free energy Change : (G)

‘’It is defined as free energy change of a reaction when the reactants and products are in
their standard state i.e 298 K and 1 atmosphere’’.

Relation Between Standard Free Energy Change And Equilibrium Constant

The standard free energy change of a chemical reaction is related to its equilibrium constant
by the relation.
G=-2.303 RT log10Kp
Where G= Standard free energy Change R= gas constant Kp = Equilibrium constant T=
temperature in Kelvin.

Predicting the feasibility using Gibbs- Helmholtz equation

Gibbs- Helmholtz equation is as follows :

G = H-TS

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The spontaneity of a process depends on both energy factor H, and randomness factor i.e
TS. Depending upon the signs of H and TS and their relative magnitudes, the following
different possible arise.

Case-I When both H and TS are negative

i.e. energy factor favours the process but randomness factor opposes it. Then,
i) If H > TS in magnitude, G is negative and the process is spontaneous.
ii) If H < TS in magnitude, G is positive and the process is non-spontaneous.
iii) If H = TS, G is zero and the process is in equilibrium
Case- II When both H and TS are positive
i.e. energy factor opposes the process but randomness factor favours it. Then,
i) If H > TS, In magnitude, G is positive and the process is non-
spontaneous.
ii) If H > TS, In magnitude, G is negative and the process is spontaneous.
If H = TS, G is zero and the process is in equilibrium.
Case-III When H is negative but TS is positive
i.e. energy factor as well as the randomness factor favour the process.
G will be highly negative and the process will be highly spontaneous.
Case –IV When H is positive but TS is negative
i.e. energy factor as well as the randomness factor favour the process.
The process will be highly non-spontaneous andG will be highly positive.

ΔrHΘ ΔrsΘ ΔrGΘ Description*

- + - Reaction spontaneous at all temperature

- - -(at low T) Reaction spontaneous at low temperature

+(at high Reaction nonspontaneous at high

- -
T) temperature

Reaction nonspontaneous at low

+ + +(at low T)
temperature

+ + -(T high T) Reaction spontaneous at high temperature

Reaction nonspontaneous at all

+ - +(at all T)
temperature

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QUESTIONS APPEARED IN PREVIOUS YEAR QUESTION PAPERS& MODEL QP

MARCH-2013
1. (a) Define enthalpy of formation.
(b) Given that : C(s) + O2(g)→CO2(g)∆G=-393.5KJ
H2(g) + 1/2O2(g)→H2O(-1)∆H=-285.0KJ
CH4(g) + 202(g)CO2(g)+2H2O(-1)∆H=-890KJ
Calculate the enthaphy of formation of methane .
2. a) ∆H and ∆𝑆 for a certain chemical reaction at 298J are 1684x103 J mol-1 and 549.4 JK-
1mol-1 calculate ∆𝐺 for the reaction. Is the reaction spontaneous?

b) Define enthalphy of solution.

FEB-2014
1. a) Molar enthalpy change for Vaporisation of one mole of water at 1 bar pressure is 41KJ
mol-1. calculate internal energy change when one mole of water is vapourised at 1 bar
pressure and 1000C(R= 8.314J/K/mol)
b) What is thermo chemical equation ?one mole of ethanol liquid is completely burnt
with air produ ce 1367 KJ/mol energy. Write the thermo chemical equation for this process.

2. a) State Hess law of constant heat of summation .

b) Write the Gibb’s equation . How the Gibb’s free energy change helps to decide the
spontaneity of the process.
MAY - 2014
1. a) Define entropy, what happens when liquid changes to vapour?
b) Calculate the enthalpy of formation of liquid benzene from the following data
C(s) + O2(g)→CO2(g)∆H=-393.5KJ
H2(g) + 1/2O2(g)→H2O(-1)∆H=-285.0KJ
C6H6 + 15/2 O2→ 6CO2 + 3H2O ∆H= -3267KJ/mol
2. a) Define the terms a) open system b) closed system c) Isolated system
b) what is extensive property? Give an example.
MARCH – 2015
1. a) What is extensive property ? give an example.
b) One mole of an ideal gas undergoes a reversible and isothermal expansion from a
volume of 2L to 20L at 300K . calculate the maximum work done . (R= 8.314J/K/mol)
2. a) Define entropy of a system. Give its SI unit.
b) Given that : C(s) + O2(g)→CO2(g)∆G=-393.5KJ
H2(g) + 1/2O2(g)→H2O(-1)∆H=-285.0KJ
CH4(g) + 202(g)CO2(g)+2H2O(-1)∆H=-890KJ
Calculate the enthaphy of formation of methane .

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MODEL PAPER – I
1. a) 2 mol of an ideal gas undergoes a reversible and isothermal expansion from volume of
2.5L to 10L at 270C . Calculate the work done by the gas in this expansion. (R=
8.314J/K/mol)
b) What is intensive property of a system? Pick the intensive property among Mass,
internal energy , density and volume.
2. a) Write Gibb’s equation. Using ∆G , how do you decide whether a reaction at a given
temperature is spontaneous or non spontaneous.
b) State Hess’s law of constant heat summation.
MODEL PAPER-II
1. a) Define Entropy . Give its SI unit.
b) What is intensive property? give an example.
c) State Hess’s law of constant heat summation
MODEL PAPER-III
1. a) What are extensive properties? Give an example.
b) Define enthalpy of combustion.
c) State First law of thermodynamics.
2. a) Calculate the enthalpy of formation of methanol, given that enthalpy of combustion of
methanol, carbon and hydrogen are -726KJ/mol, -393KJ/mol and -286KJ/mol respectively.
b) Define entropy.
MODEL PAPER-IV
1. a) Calculate the enthalpy of formation of methane . Given that enthalpies of combustion
of carbon, hydrogen and methane are -393.5KJ , -286KJ and -890KJ respectively.
b) State Hess’s law of heat summation.
2. a) Define lattice enthalpy. Write Born Haber cycle for the lattice enthalpy of NaCl.
b) Define the term Entropy. What happens to entropy when ice melts to liquid water.
MAY – 2016

1. a) State and illustrate Hess’s law of heat summation with an example.

b) Define standard enthalpy of combustion. Give an example.
2. a) Derive an expression for the mechanical work done in an isothermal reversible
expansion of an ideal gas.
b) State First law of thermodynamics.

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