ENERGETICS OF

CHEMICAL REACTION
CHEMICAL ENERGETICS
The branch of chemistry which deals with change in
energy during a reaction is called chemical
energetics.
CHEMICAL THERMODYNAMICS
Thermodynamics deals with the study of energy
exchange between the system and surrounding and
flow of energy in or out of the system.
SOME THERMODYNAMIC TERMS
1. System : system is the part of universe which is under
consideration for the purpose of theoretical or
experimental study. Examples
a. Chemical in a test tube is a system.
b. Water in a beaker is a system
2. Surrounding : the remaining portion of the universe
which is not the part of system is called surrounding. It
represents that portion of universe with which a system
interact. Example
a. Water in a beaker is system, while the rest of the part is
surrounding.
3. Boundary : anything that separate system from
surrounding is called boundary. It is the portion of universe
through which system and surrounding can interact each
other.
TYPES OF SYSTEM
depending upon the mode of exchange of heat and energy, a
system can be classified into following types.
a. Open system : A system which can exchange matter
and energy between system and surrounding is called
open system. Hot water in a open beaker is an example
of open system.
b. Closed system : A system which can exchange energy
but not a matter with the surrounding is called closed
system. The total content of matter remain constant in
closed system. Hot tea taken in a closed metallic vessel
is an example of closed system heat can be exchanged
but not the matter.
3. Isolated system : when a system can neither
exchange matter nor energy is said to be isolated
system. The boundaries of this system are closed and
insulated. Eg.
a. Hot water in a thermos flask.
b. Hot things in a closed container having insulated
walls.
Extensive and intensive properties of a system
a. Extensive properties:
The property whose value depends upon the quantity
of matter contained in the system is called extensive
property. Eg. Mass, volume, area, internal energy, heat,
capacity, enthalpy, entropy, free energy etc.
b. Intensive property:
The property whose value does not depends upon the
amount of substance in the system is called an intensive
property. Eg. Density, temperature, pressure, concentration,
viscosity, refractive index, surface tension, boiling point,
melting point etc.
State variables
The properties or parameters which determines the
state of a system are called a state variable. Any
change in these properties also changes the state of a
system. The values of state variable depends on the
state of system. i. e. initial state and final state and
not how the state has been reached. For example-
temperature, pressure, volume, concentration etc.
State function:
A physical quantity is said to be state function if
its value depends on initial and final state of the
system only but not on the path followed by the
change of state is called state function. For example:
internal energy, enthalpy, free energy etc.
Internal
  energy ( E or U)
The total energy contained in a system is called it’s
internal energy. It is made up of translational energy,
rotational energy, vibrational energy, bond energy,
electronic energy and the interaction energy of constituent
particles.
It is state function because it depends upon the state of
system and not upon how the system attains the state. The
absolute value of internal energy cannot be determine but
change in internal energy can be determine.
If the internal energy of a system in the initial state is E1
and final state is E2 then change in internal energy is E =
E2 – E1. Similarly for chemical reaction, E = Ep – Er.
Thermodynamic
  process
An operation which brings about changes in the state of any system
is called thermodynamic process. Various types of thermodynamic
processes are as follows:
1. Isothermal process:
When the temperature of the system remain constant the process is
called isothermal process. In this process heat can flow from system
to surrounding and vice-versa. To keep the temperature constant, here
change in temperature is zero i.e. T = 0
2. Adiabatic process:
When there is no exchange of heat between system and surrounding
then the process is called adiabatic process. In this process the system
is completely insulated from the surrounding. Here, change in heat is
zero. i.e. = 0
3.  Isobaric system:
When the pressure on a system remains constant during any operation then the
process is called isobaric process. Here, the change in pressure is zero. i.e. P=0
4. Isochoric system:
when there is no change in volume of the system during any operation then the
process is called isochoric process. Here, the change in volume is zero.i.e V = 0
5. Cyclic process:
If a system undergoes various changes and ultimately returns into initial state then
the process is called cyclic process. Here, the change in energy and enthalpy is zero
i.e. E=0, =0
6. Reversible process:
When a process is carried out so slowly so that all the changes occurring in direct
process can be reverse and the system and the surrounding are always in
thermodynamic equilibrium then the process is called reversible process.
7. Irreversible process:
When a process is carried out rapidly such that the system
does not get a chance to attain equilibrium between initial and
final state, then it is called irreversible process. Such type of
process is carried out in single process or in few steps. All
natural processes are irreversible processes.
Exchange of energy between system and surrounding ( Heat and
Work)
1. When system and surrounding are at different temperatures, then
energy is transfer in the form of heat. If system is at higher
temperature than surrounding, heat is lost by system. If surrounding
is at higher temperature than system the heat is absorbed ( gained) by
system.
Sign convention
a. If heat is absorbed (gained) by the system then heat i.e. q is +ve.
b. If heat is lost from the system then heat q is –ve.
2.  Transfer of energy in the form of work
If system and surrounding are at two different pressure then energy is
transfer in the form of mechanical work.
For example- if a gas enclosed in a cylinder fitted with air tight piston
has higher pressure than external pressure. The piston will moves
outward until pressure inside and outside are equal. In this process
work is done by the system.
On the other hand, if the pressure inside is lower than pressure outside
then the piston will move inward in this process work is done on the
system. Now, this work is measured as,
work = force x change in distance (displacement)
= displacement x area
W = PV
W=P
(a)If
  work is done on the system then internal energy of system is
increased and the work done on the system is taken as positive.
Therefore for compression we write W= PV.
(b) If work is done by the system then internal energy of system is
decreased then the work done by the system is taken as negative.
Therefore for expansion we can write W= -PV.

FIRST LAW OF THERMODYNAMICS:

The first law of thermodynamics is also known as law of
conservation of energy. “It can be stated as the total energy in the
universe remains constant although or may undergo transformation
from one form to another.”
Let us consider a system in it’s initial state having internal energy E 1,
if q amount of heat is supplied to the system then work equal to W is
done by the system. Then the internal energy of the system in the final
stage is E2 is given by,
 E2 = E1 + q - W ( W is -ve, since work is done by the system)

Or, E2 – E1 = q - W
E= q - PV ( W = )
So that, q = E + PV (2)
This shows that heat supplied to the system is converted into internal
energy and work done. Hence, the energy remain conserved.
 SPECIAL CASES:

1. If no mechanical work is done then P V=0, in this case all the heat
supplied to the system is utilize to raise the internal energy.
Therefore, q = E
2. If no heat is utilized to raise the internal energy then, E = 0, in this
case all the heat supplied to the system is utilized in doing mechanical
work. Therefore, q= PV

Limitaions:
The first law of thermodynamics doesn’t tell us
1. The extent and direction convertibility of one form of energy into
another.
2. Why natural processes are unidirectional.
3. Why the chemical reaction do not proceed to completion.
4. Weather the reaction will occur or not in the given sets of
conditions.

Exothermic and Endothermic reactions

Exothermic reaction
The reaction in which heat is liberated to the surrounding is called
exothermic reaction. For example, the reaction between active metal
and dilute acid heat is evolved.
Zn (s) + 2 HCl (dil) → ZnCl2 + H2 (g) + heat
The enthalpy change ∆H is given by,
∆H = HP – HR
 Since, HR HP, ∆H is negative in exothermic reaction.
 Endothermic reaction
The reaction during which heat is absorbed form
surrounding is called endothermic reaction. For example,
dissolution of NH4Cl in water.
NH4Cl (s) + H2O NH4Cl (aq) – heat
The enthalpy change is given by,
H = HP – HR
Since, HP HR, H is positive in endothermic reaction.
Heat content or Enthalpy (H)
In an open system, mechanical work (PV) done against
expansion or contraction is to be added to internal energy.
Therefore, the term Internal energy is replaced by another
thermodynamic term Enthalpy or Heat content in an open
system to express total energy if system. The function
enthalpy is denoted by H and is therefore defined by the
relation:
H = E + PV
The enthalpy of a system can be defined as the sum of the
internal energy and the product of pressure and volume of
the system.
Enthalpy is a state function.
 Suppose, a system changes from one state to another state at
a constant pressure. Let, H1, E1, V1 be enthalpy, internal
energy and volume of a system at initial state respectively
and H2, E2 and V2 be enthalpy, internal energy and volume
of a system at final state respectively. From the definition of
enthalpy,
H1 = E1 + PV1 (at initial state) (1)
H2 = E2 + PV2 ( at final state) (2)
Subtracting 1 from 2 we get,
(H2- H1) = (E2- E1) + P ( V2- V1)
H=E+PV
 Enthalpy change of reaction
Enthalpy change of reaction is the amount of heat absorbed
or evolved in a process under constant pressure condition.
From the first law of thermodynamics, q = E + PV.
Since, we have H = E + P V
So that, q = H
1. When heat is absorbed q is positive, therefore H is also
positive and the process is called endothermic process.
2. When heat is evolved q is negative. Therefore H is also
negative and the process is called exothermic process.
 Standard enthalpy change of reaction
The enthalpy change of a reaction when the reactant and product are
in their standard states at 250C or 298 K and under a pressure of one
atmosphere is known as the standard enthalpy change. It is
represented by H0 or H298.

Enthalpy of reaction or heat of reaction

Enthalpy of reaction is amount of heat absorbed of released when all
gram moles of the reactant convert into products.
Factors affecting enthalpy of reaction
1. Amount of substance: Since, enthalpy is an extensive
property, enthalpy change during a reaction depends on amount of
substance taken or formed.
 2. Physical state : If the substances involved in the reaction are in
different physical or allotropic forms, the enthalpy change differs.
a) H2 (g) + ½ O2 (g) H2O (l), H = -68.3 K cal
H2 (g) + ½ O2 (g) H2O (g) , H = -57.8 K Cal
b) C (graphite) + O2 (g) CO2 (g), H = -94.1 K Cal
C (diamond) + O2 (g) CO2 (g), H = -94.5 K Cal
3. Temperature and pressure: Enthalpy change is affected by
change in temperature and pressure. Enthalpy change measured at
250C and 1 atm pressure is called standard enthalpy change and for a
chemical reaction, the change is called standard enthalpy of
reaction(H0).
  Different types of enthalpy of reaction
A. Enthalpy change in chemical changes
1. Enthalpy of formation (Hf):
It is defined as the enthalpy change when 1 mole of compound is formed
from its elements. The enthalpy of formation of elements is zero.
H2 (g) + ½ O2 (g) H2O (l), H = -68.3 K cal
The standard enthalpy of formation of water is -68.3 K Cal.
H2 (g) + I2(s) 2HI (g), H = +12.4 K cal
The enthalpy of formation of hydrogen iodide is not 12.4 K Cal because
2 mol of hydrogen iodide is formed. Therefore, the standard enthalpy of
formation of hydrogen iodide is = + 6.2 Kcal.
2. Enthalpy of neutralization :
enthalpy of neutralization of an acid or base is defined as enthalpy
change when 1 gm equivalent of acid or base is neutralized by 1 gm
equivalent of base or acid, when both are in aqueous solution.
Neutralization reaction is exothermic reaction.
 HCl (aq) + NaOH (s) NaCl (aq) + H2O (l), = -13.7 K cal.

So that, enthalpy of neutralization is -13.7 Kcal.

CH3COOH (aq) + NaOH (aq) CH3COONa(aq) + H2O(l) H =
-12.3Kcal.
The enthalpy of neutralization of strong acid and strong base is -13.8
Kcal. Whereas that of weak acid or weak base is lower because some
part of heat is absorbed for the complete ionization for dissociation.
Therefore, heat of dissociation of CH3COOH above = 13.7 – 12.3 =
1.4 Kcal.
3. Enthalpy of combustion (Hc):
Enthalpy of combustion of any substance is defined as amount of
heat released when 1 mole of substance is completely combusted in
excess of air.
 CH4(g) + O2 CO2 (g) + 2H2O (l), Hc = -212.8 Kcal.

Since 212.8 Kcal heat is released when 1 mol of methane is

completely combusted therefore enthalpy of combustion of methane
is 212.8 K cal.
C (s) + ½ O2 CO Hc = 26.4 Kcal
C (s) + O2 CO2 Hc = -94 Kcal
The standard enthalpy of combustion of carbon is -94 Kcal but not
26.4 Kcal.
B. Enthalpy change in physical change.
1. Enthalpy of solution (Hs) :
The change on enthalpy when 1 mol of solute is dissolved in a
specified quantity of solvent at a given temperature is called enthalpy
of solution.
 2. Enthalpy of vapourization :
The enthalpy of vaporization of any substance is defined as the
amount of heat absorbed when one mole of liquid is converted into
it’s vapour form at it’s boiling point.
H2O (l) H2O (g), H = +40.6 KJ
Hence enthalpy of vapourization of H2O is +40.6 KJ.
3. Enthalpy of fusion:
Enthalpy of fusion of a substance is defined as the amount of
heat absorbed when 1 mole of the solid substance is converted into its
liquid form at its melting point.
H2O (s) H2O (L), H = +6 KJ
Therefore, 6KJ heat is needed to convert 1 mole of ice into water at
273K. Hence, enthalpy of fusion of H2O is +6 KJ.
 4. Enthalpy of transition:
Enthalpy of transition of a substance is defined as enthalpy
change when 1 mole of the substance is converted into its other
allotropic form.
S() S(), H = -0.6 Kcal.
Hence, enthalpy of transition of -sulphur is -0.6 Kcal.
5. Enthalpy of Hydration:
The amount of heat evolved or absorbed when one mole of the
anhydrous salt combines with the required number of moles of water
so as to change into the hydrated salt, is called the heat of hydration.
Eg. CuSO4 (s) + 5H2O CuSO4.5H2O (s) H = -78.2 KJ.
 Bond energy:
When ever chemical bond is formed, energy is released and if same
amount energy is supplied to the bond, it should get broken therefore
bond energy or bond dissociation energy is the energy required to
break one mole of bond of gaseous covalent compound to produce the
product in gaseous state. It is expressed in KJmol-1.
Bond energy of a particular bond is defined as the average amount of
energy released when 1 mole of bond is formed from isolated gaseous
atoms or the amount of heat required when 1 mole of bonds are
broken so as to get the separated gaseous atoms.

H0 = bond energy of reactant- bond energy of product

 Hess’s law of constant heat summation
G.H. Hess, a Russian chemist, in 1840, gave a law about
the heat of reactions on the basis of experimental
observations.
This law states that “Total amount of heat evolved or absorbed in a
reaction is the same whereas the reaction takes place in one step or in
a number of steps. This can be illustrated by the following example.
If the reaction
A B takes place in the steps as shown below.

A B

C D
 Then, H = H1 + H2 + H3 + ……….

Where H be the heat released for the reaction A to B and H1, H2, H3 be
the heat released in each steps.
The example below is the experimental verification of Hess’s law.
C (s) + ½ O2 CO (g), H1 = -26.4 Kcal
CO (g) + ½ O2 (g) CO2 (g), H2 = -67.6 Kcal
C (g) + O2 (g) CO2 (g), H = H1 + H2
= -26.4 - 67.6
= -94 Kcal
 Theoretical representation of Hess’s law
Suppose a reaction A to B takes place as below,
Fig

H is the heat released on going from A to B and H1, H2, H3 are heat
released in each states then according to Hess’s law, H = H1 + H2 +
H3.
Say, H H1 + H2 + H3
Then, H H1 + H2 + H3,
On going form B to A, H amount of heat is absorbed.
On completing a cycle by the reaction (H1 + H2 + H3) - H
 amount of heat will be released and on completing several cycle
large amount of heat will be released by the system without
performing any work which is against first law of thermodynamics.
On the other hand when H is greater than H1 + H2 + H3. Then the
system will gain large amount heat after many cycles which is also
impractical therefore the reaction H = H1 + H2 + H3 must be true.

Application of Hess’s law

1. It helps us to determine the enthalpy of many chemical reaction.
2. Calculation of heat of formation.
3. Calculation of heat of allotropic transformation.
Chemical thermodynamics
 Spontaneous process
The process which takes place by itself without help of any external agency
until they attend a state of equilibrium are called spontaneous process. All the
natural process are spontaneous process. Spontaneous process is feasible. For
example: rusting of iron, flow of water form higher level to lower level, transfer of
heat from hot object to cold object etc.

Characteristics of spontaneous process:

I. It takes place itself.
II. It can be occurred very fast or slow.
III. All spontaneous process are continuous until state of equilibrium.
IV. Some spontaneous process may need initiation i.e. some amount of energy is
required to start the process, when the process is started it continuous of its
own. For example: lighting of a candle involving burning of wax (initiated by
ignition), heating of calcium carbonate to give calcium oxide and
carbondioxide.
  Entropy and its physical concept.
Entropy is defined as the measure of degree of randomness of a
system. Greater is the randomness larger would be the value of
entropy and more ordered is the molecular arrangement, lower is the
value of entropy. It is denoted by ‘S’.

The entropy of gaseous state is higher than that of liquid state and
entropy of liquid is higher than that of solid state.

Sgas SliquidSsolid
 Entropy is state function and is extensive property. So entropy change
is defined as,
S = S2 - S1 = Sp - SR
Mathematically entropy is defined as, S=
Where q rev is the amount of heat supplied to the system reversibly.
for entropy change, S=
 Unit of entropy
The unit if entropy in CGS system is calorie per Kelvin (cal K-1). It is
also known as entropy unit. In S.I. system the unit of entropy is joule
per Kelvin ( JK-1).

Entropy change for one mole of substance is called molar entropy

change and it’s unit is JK-1mol-1.

Entropy change in phase transformation

1. Entropy of fusion:
The entropy of fusion is the change in enthalpy when 1 mole of a
solid substance changes into liquid at its m.pt.
 Mathematically,

S=
At melting point, =
S = Sliq – Ssol =
Since, Tm= melting point
Ssol = molar entropy of the solid
Sliq = molar entropy of liquid
Hfus = enthalpy of fusion per mole
H melting is always positive so that S during melting will also be
positive.
  2. Entropy of vaporization:
Entropy of vaporization is the entropy change when 1 mole of a
liquid changes into vapours at its boiling temperature.
Mathematically,
S=
At boiling point, = Hvaporization
So that, S =
S during vaporization is always positive.
  3. Entropy of sublimation:

The entropy change when 1 mole of the solid changes into vapour at
a particular temperature is called entropy of sublimation.
Ssublimation =

4. Entropy of freezing
Sfreezing =
  Entropy and spontaneity
1. If Stotal = Ssystem + Ssurrounding 0, Stotal will be positive, the
process will be spontaneous.
2. If Stotal = Ssystem + Ssurrounding 0, Stotal will be negative, the
process will be non-spontaneous.
3. If Stotal = Ssystem + Ssurrounding = 0, then the process will be in
equilibrium.

Entropy change in reaction

Entropy change in reaction is defined as the difference of the
entropy of formation of product and entropy of formation of
reactants and depends upon the stoichiometric coefficients of
the reaction. For reaction which is given as,
S = Sf(product) - Sf(reactant)
 Let us consider a reaction of following type

aA + bB cC + dD
Entropy change for reaction is given as,
S = [cSC + dSD ] – [aSA + bSB]

Standard entropy change

The entropy change at standard condition, they are 298K temperature
and 1 atm pressure is called standard entropy and is denoted by S0 and
it’s change is given as
S0 = S0product - S0reactant
  Second law of thermodynamics:
There are many forms of stating second law of
thermodynamics. Some of them are as follows,
i. The entropy of universe is continuously increasing
where as the energy of the universe is always constant.
ii. Heat cannot be completely converted into work without
producing changes of giving some effect in some part of
the system.
iii. All the spontaneous processes are accompanied by the
increase in entropy of the universe.
iv. No heat engine has 100% efficiency i.e. thermodynamic
efficiency = 1
 Second law of thermodynamics can be defined on the basis
of entropy change. For this consider a spontaneous flow of
heat from a system at higher temperature to the
surrounding at lower temperature.
let, Tsys and Tsur are the temperature of system and
surrounding respectively where TsysTsur and system evolve
Q amount of heat spontaneously to the surrounding, the
entropy of system is decreased which is given as
Ssys = -
On the other hand the entropy of surrounding increases
which is given as
Ssur = +
 So that, total entropy change of the universe is given as
universe = Ssys + Ssur
=- +
Since, TsysTsur , the numerical value of is less than
therefore Suniverse is positive. Where total energy of the
universe i.e. system + surrounding = -Q + Q.
= 0.
Hence total entropy of universe is increasing whereas total
energy of the universe remains constant. This is the second
law of thermodynamics.
Gibbs free energy (G)
Gibbs free energy can be defined as the energy available for doing
useful work at constant temperature and pressure.
It is denoted by G and mathematically it is defined as,
G = H – TS.
Where, H = enthalpy
T = absolute temperature
S = entropy
It is also known as free energy function or Gibbs free energy function.
It is state function and extensive property.
Derive Gibb’s-Helmholtz equation.
let G1, H1 and S1 be free energy, enthalpy and entropy of system at
initial state and G2, H2 and S2 be free energy, enthalpy and entropy of
system at final state.
 Initially, G1 = H1 – TS1 ………………(i)

Finally, G2 = H2 – TS2………………..(ii)
On subtracting equation (i) from equation (ii) we get,
G2 – G1 = (H2 – H1) – T(S2 – S1)
G = H - T S……………………….(iii)
Equation (iii) is also known as Gibb’s- Helmholtz equation. It is very
useful equation in chemical thermodynamics.

Free energy change of reaction

The free energy change of reaction is defined as the difference in the
sum of free energy of formation of products and that of reactants.
G = Gf(products) - Gf(reactants)
Free
  energy of formation of an element is taken as zero.

Criteria of spontaneity in terms of Gibbs free energy

change
We have from Gibbs Helmholtz equation,
G=H-TS
where, G = free energy change
= enthalpy change
S = entropy change
T = absolute temperature
For a process to be spontaneous, Suniverse should be positive. The relation is,
Suniverse = Ssys + Ssur
 Suppose heat is lost by the surrounding and gained by the system.

At constant temperature and pressure, Ssurr =-

So that, Suni = Ssys -
or, TSuni = TSsys - H
or, TSuni = - (H - TSsys )
or, TSuni = - Gsys
1. If Gsys is positive then Suni will be negative, the process is non-
spontaneous.
2. If Gsys is negative then Suni will be positive, the process is
spontaneous.
3. If Gsys is zero then Suni will be zero the process is equilibrium.
 Standard free energy change.
The free energy change of a system at 298K temperature and 1
atmospheric pressure is called standard free energy change. It is
denoted by G0 is given as,
G0 = H0 - T0
For a reaction it is given as,
G0 = f(product) - f(reactant)

Standard free energy change and equilibrium constant:

Free energy change in standard and non-standard state are related as,
G = G0 + RTlnQ
Where, R = universal gas constant , Q= reaction quotient
 At equilibrium,

G = 0,
So, G0 = -RTlnK ( K = equilibrium constant)
G0 = -2.303RTlogK ( ln = 2.303log)
This is the relation between standard free energy change and
equilibrium constant.
free energy change and useful work (net work)

The work other than mechanical work i.e. pressure-volume

work is called as useful work. It is also called as net work and
is denoted as Wnet.
If W be the total work and P∆V be the mechanical work, then,
net work Wnet is measured as,
Net work = Total work – mechanical work
or Wnet = W - P∆V ……(1)
From Gibbs free energy change,
∆G = ∆H – T∆S ……….(2)
For constant pressure, the enthalpy change is,
∆ H = ∆E + P∆V ……….(3)
Then,
 

G=E+PV-TS
If qrev amount of heat is exchanged reversibly, then
S=
i.e. G = + P V – T
From first law of thermodynamics,
qrev = E + Wrev
where, Wrev is work done reversibly
Now,
G = E +P V - E - Wrev
  = P V – Wrev
= - ( Wrev - P V )
G = - Wnet

Hence, decrease in free energy change of a system (-

∆G) is equal to the useful work done by the system under
constant temperature and pressure.
DIFFERENCE BETWEEN INTERNAL ENERGY
AND ENTHALPY
Internal energy
1. The internal energy of a system is
an intrinsic value of the sum of the
potential and kinetic energy possessed
by a system.
2. It is represented as the sum of work
and heat done to the system.
ΔE=W+Q
enthalpy
1. It is defined as the energy of a
system, taking into account its internal
energy as well as any additional energy
required to displace environment.
2. . It is denoted by ΔH = E + pΔV.
 Numerical problems
1. Calculate S and G for conversion of ice into water when they are
equilibrium at 00C (H = 4KJ/mole).
2. Enthalpy and entropy change of a reaction are 40.63KJ/mole and
108.8KJ/mole respectively. Predict the feasibility of the reaction at
270C.
3. Calculate the standard free energy changes for the reaction
4NH3 (g) + 5O2 4NO (g) + 6H2O (l)
Given that the standard free energies of formation for NH3 (g), NO(g)
and H2O(l) are -16.8, +86.7 and -237.2 KJ/mole respectively. Predict
the feasibility of the reaction at the standard data.
4. For the equilibrium
PCl5(G) PCl3(g) + Cl2(g)
AT 298K, K = 1.8 10-7. what is standard free energy change for the
reaction?
 
Criteria of spontaneity, non spontaneity and
equilibrium of exothermic and endothermic reactions
on the basis of free energy and entropy change.
Criteria of spontaneity, non spontaneity and equilibrium of
exothermic and endothermic reactions can be predicted on
the basis of free energy and entropy change and enthalpy
change.
According to Gibb’s Helmholtz equation

= H -T S
Where, G = free energy change
H = enthalpy change
S = entropy change
 a) For exothermic reaction:
H is always negative.
i) If is positive, the value of is –ve and the process is
spontaneous at all temperature.
ii) If is negative, the value of is –ve at low temperature
therefore process will be spontaneous and and +ve at higher
temperature and the process is non spontaneous.
b) For endothermic process
H is always positive.
i) If is negative, the value of is +ve and the process is non-
spontaneous .
ii) If is positive, the value of may be +ve or –ve

At high temperature, T therefore is negative and the process

is spontaneous.
At low temperature, T therefore is positive and the process is
non spontaneous.
 Henceexothermic reaction is favoured at low temperature but
endothermic reaction is favoured at high temperature.

c) When value of is zero the process is in equilibrium.