4.

Chemical Thermodynamics
4.1 Introduction:
Thermodynamics arise from Greek words i) therme means "heat” and ii)
dynamis means "power" or “energy”.
Chemical thermodynamics is the study of the interrelation of heat and work
with chemical reactions.
E.g. Ice Cube Water Vapors

4.2 Term commonly used in Thermodynamics:

4.2.1 System and Surrounding:
1. System:- A part of the universe under thermodynamic investigation or
Anything which are kept in consideration.
2. Surrounding: - Everything external to the system or All other parts of the
universe outside the system.

4.2.2 Types of Thermodynamic System:

1. Open System:- A system that freely exchanges energy and matter with its
surroundings.
2. Closed System:- It can exchange energy (as heat or work) but not matter,
with its surroundings.
3. Isolated System:- A system that cannot exchange either energy or matter
outside the boundaries of the system.
 4.2.3 Properties of system:
1. Intensive Properties:-
These properties (physical or thermodynamic) do not depend on the
amount of matter that is present.
E.g. Boiling point, Melting Point, Density, Odour, Temperature, Pressure,
Surface Tension etc.
2. Extensive Properties:-
These properties (physical or thermodynamic) depend on the amount of
matter that is present.
E.g. Volume, Mass, Weight, Length, Enthalpy, Free Energy, Internal
Energy etc.

4.2.4 State Functions:-

If the system changes from one equilibrium state to another, the properties
have changes that depend only on the two states chosen and not on the process in
which the system changed from one to the other.
Or
If its value depends only upon the state of the system and does not depend
upon the path by which this state has been attained.
E.g. pressure, volume, temperature.

4.2.5 Path Functions:-

These are property or quantity whose values depend on the path of a system
from the initial state to the final state. E.g. heat and work

4.2.6 Thermodynamic Equilibrium:-

Thermodynamic equilibrium is the basic concept of thermodynamics.
Thermodynamic equilibrium of a thermodynamic system is defined as the system
whose properties do not change with time and can only be changed to another
condition with the expense of effects on other systems.
 For example, the gas in a cylinder with a movable piston will be at
equilibrium if the temperature and pressure inside are uniform and if the restraining
force on the piston is just sufficient to keep it from moving.

4.2.7 Process and its types:

1. Isothermal process is a process in which the Temperature of the system remain
uniform and constant. For a given constant temperature the internal energy (U)
of the system remains constant. Thus, ΔT = 0 and ΔU = 0.
2. Isobaric process is a process in which the Pressure of the system remain
uniform and constant. In the laboratory chemical reactions are carried out in open
containers at constant atmospheric pressure ΔP = 0.
3. Isochoric process is a process in which the Volume of the system remain
uniform and constant. A chemical reaction carried out in a closed container is
isochoric ΔV = 0.
4. Adiabatic process is one which there is no heat transfer across any portion of
the boundary (Q=0). In adiabatic process the system is completely insulated from
the surroundings.
5. Reversible process if the process can be turned back to such that both the
system and the surroundings return to their original states, with no other change
anywhere else in the universe. In reality, no such processes as reversible
processes can exist in nature.
Or
A process is said to be thermodynamically reversible when the driving force due
to System pressure (P) is little Smaller than the opposing force due to external
pressure (Pext).

Features of reversible process

i. The driving and opposing forces differ by an infinitesimal amount.
ii. The process can be reversed by an infinitesimal change in conditions.
iii. A reversible process proceeds infinitely slowly and takes place in infinite
number of steps.
iv. At the end of every step of the process, the system attains mechanical
equilibrium with the surroundings.
4.3 Nature of heat and work
4.3.1 Nature of work (W):
In mechanics the work is defined as the energy by which body is displaced
through a distance d with an application of force. Thus,

W=f×d
 In thermodynamics the type of work involved is pressure-volume or PV
work, that is, work is done when the system (gas) expands or contracts against the
external opposing force.

W = PV
𝑓
W= ×V
𝐴
In terms of distance, area and volume become d2 and d3.
𝑓
W= × 𝑑3
𝑑2
The Equation become

W=f×d

4.3.2 Nature of heat (Q)

Heat is a form of energy by which the system exchanges energy with its
surroundings. When the system and its surroundings are at different temperatures
heat either flows in or let out of the system.
Sign conventions of W and Q:
+Q : Heat is absorbed by the system from the surroundings. (Endothermic)
-Q : Heat is released by the system from the surroundings. (Exothermic)
+W : Work is done on the system by the surroundings.
-W : Work is done by the system on the surroundings.

4.4 Expression for pressure-volume (PV) work:

 Consider a certain amount of gas at constant pressure P is enclosed in a
cylinder fitted with frictionless, rigid movable piston of area A. Let volume of the
gas be V1 at temperature T.
On expansion the force exerted by a gas is equal to area of the piston
multiplied by pressure with which the gas pushes against piston.
Force = Pressure (P) × Area (A)
F = -Pext × A (1)
This pressure is opposite in sign to the external atmospheric pressure that
opposes the movement.
If the piston moves out a distance d, then the amount of work done is equal
to the force multiplied by distance.
W=f×d (2)
Substitute equation 1 in equation 2
W = -Pext × A × d
The product of area of the piston and distance it moves is the volume change
(ΔV) in the system.
W = -Pext × ΔV
W = -Pext × (V2 – V1)

W = -Pext.ΔV
When gas expands i.e. V2 > V1 then work is done by the system (i.e. gas)
on the surrounding (i.e. piston). In that case W is negative.
When gas compressed i.e. V1 > V2 then work is done on the system (i.e.
gas) by the surrounding (i.e. piston). In that case W is positive.

4.4.1 Free expansion:

Free expansion means expansion against zero opposing force. Such expansion
occurs only in vacuum. When the gas expands in vacuum, there is no opposing
force that is Pext. Hence, W=0. In other words no work is done when the gas
expands freely in vacuum.
4.4.2 Units of energy and work:
SI Unit of Energy is Joule and Work is dm3 bar.

4.5 Concept of maximum work:

In vacuum, opposing force is zero therefor no work is involved. With an
increase of the opposing force from zero, more work will be needed by the system.
When the opposing force reaches its maximum the system performs maximum
work. With an opposing force being greatest more effort would be needed to
overcome it.
But when the opposing force (Pext) becomes greater than the driving force (P)
then process gets reversed. Hence opposing force should be maximum but cannot
be greater than driving force.
4.5.1 Expression for the maximum work:
Consider n moles of an ideal gas enclosed in a cylinder fitted with frictionless
movable rigid piston. It expands isothermally and reversibly from the initial
volume V1 to final volume V2 at temperature T. The expansion takes place in a
number of steps.

When the volume of a gas increases by an infinitesimal amount dV in a single

step, the small quantity of work done
dW = -Pext.dV (1)
We know that, dP= P-Pext
Pext = P-dP
Insert above equation in equation no. 1, We get
dW = -(P-dP).dV
dW = -P.dV + dP.dV
The product dP.dV which is very small, we get
dW = -P.dV (2)
The total work is obtained by integration of Eq. (2) between the limits of initial
and final states. This is the maximum work, the expansion being reversible.
𝐹𝑖𝑛𝑎𝑙 2𝑉
∫𝐼𝑛𝑖𝑡𝑖𝑎𝑙 dW = − ∫𝑉 P. dV
1

𝑉
WFinal – WInitial = − ∫𝑉 2 P. dV
1

Here Wmax = WFinal – WInitial

 𝑉
Wmax = − ∫𝑉 2 P. dV (3)
1

From ideal gas equation, PV= nRT

𝑛
Therefore P = RT (4)
𝑉
Insert above equation in equation 3
𝑉 𝑛
Wmax = − ∫𝑉 2 RT. dV
1 𝑉

Here n, R and T remain constant

𝑉 𝑑𝑉
Wmax = −𝑛𝑅𝑇 ∫𝑉 2
1 𝑉

Wmax = −𝑛𝑅𝑇. 𝑙𝑛𝑉2 − 𝑙𝑛𝑉1

𝑉2
Wmax = −𝑛𝑅𝑇. 𝑙𝑛
𝑉1

Convert ln into Log10

𝑽𝟐
Wmax = −𝟐. 𝟑𝟎𝟑𝒏𝑹𝑻. 𝒍𝒐𝒈𝟏𝟎 (5)
𝑽𝟏

At constant temperature, P1V1 = P2V2

𝑃1 𝑉2
=
𝑃2 𝑉1
𝑷𝟏
Wmax = −𝟐. 𝟑𝟎𝟑𝒏𝑹𝑻. 𝒍𝒐𝒈𝟏𝟎 (6)
𝑷𝟐

4.6 Internal energy (U):

A system in a fixed state has a definite and constant amount of energy known as
Internal Energy U. It is sum of Kinetic energy (motion of the system) and Potential
energy (position & arrangement of the system) of the system.
∆U= U2 – U1
Where U1 and U2 are internal energy of the initial and final states. U is a state
function and extensive property.
E.g.
i. The energy transferred to the system by heating it or performing work on
it is added to the system. Therefor ∆U become positive.
ii. The energy transferred from the system by cooling or by performing work
on the surroundings is removed from the system. Therefor ∆U become negative.
4.7 First law of thermodynamics:
The law is stated in different ways as follows.
i. Energy of the universe remains constant
ii. The total internal energy of an isolated system is constant
iii. Energy is neither created nor destroyed and can only be converted from
one form to another.
All above statements are equivalent.
∆U= Q + W
Where ∆U= Change in internal energy
Q = Heat
W = Work
For infinitesimal changes.
dU= dQ + dW
4.7.1 First law of thermodynamics for various processes:
i. Isothermal process: Temperature is constant in such process, internal
energy is constant. Hence, ΔU = 0
For isothermal process
Q + W= 0
Q = -W
When work is done on the system by the surroundings it results in release of
heat.

ii. Adiabatic process: In adiabatic process, there is no exchange of heat

between system and its surroundings that is, Q = 0. Then
∆U= + W
Thus an increase in internal energy of the system is the work done on it.

iii. Isochoric process:

From first law of thermodynamics, ∆U= Q + W
But we know that, W = -Pext.ΔV
Therefore, ∆U= Q + (-Pext.ΔV)

As the reaction is carried out in a closed container, volume of the system is

constant or ΔV = 0
∆U= QV (7)
 Equation shows a change in internal energy of the system is due to heat
transfer at constant volume.

iv. Isobaric process: Usually chemical reactions are carried out in the open
containers under constant atmospheric pressure. In such reactions, ΔV ≠ 0
∆U= Q + (-Pext.ΔV)
∆U= Q - Pext.ΔV
QP = ∆U + Pext.ΔV (8)
The reactions carried out in open containers under constant atmospheric
pressure indicate heat changes occurring during reaction and it is denoted by a
special symbol ΔH i.e. enthalpy change

4.8 Enthalpy (H):

Enthalpy of a system is sum of internal energy of a system and the energy
equivalent to PV work
H = U + PV
Change in enthalpy, ΔH, is also state function given by
ΔH = H2 - H1
Where H1 and H2 are the enthalpies of initial and final states, respectively.
Now H1 = U1 + P1V1
H2 = U2 + P2V2

Therefore ΔH = U2 + P2V2– (U1 + P1V1)

ΔH = U2 + P2V2– U1 - P1V1
ΔH = U2 + P2V2– U1 - P1V1
ΔH = (U2 - U1) + (P2V2 - P1V1)
ΔH = ΔU + Δ(PV)
But reaction is carried out at constant pressure Hence ΔP= P

ΔH = ΔU + PΔV (9)

Compare Equation 8 and 9, we get

ΔH = QP
Change in enthalpy of a system is equal to heat transferred from it at the
constant pressure. H and QP are state functions.

4.8.1 Relationship between ΔH and ΔU for chemical reactions:

At constant pressure, ΔH and ΔU are related as
ΔH = ΔU + PΔV
 i. For reactions involving solids and liquids, ΔV usually is very small
because solids or liquids do not show volume change with change of
pressure and Hence ΔH = ΔU
ii. For reactions involving gases, ΔV cannot be neglected
ΔH = ΔU + PΔV
ΔH = ΔU + P.(V2 – V1)
ΔH = ΔU + PV2 – PV1 (10)

Ideal gas equation form initial and final state

PV1= n1RT
PV2= n2RT
Insert above equation in equation no. 10
ΔH = ΔU + n2RT – n1RT
ΔH = ΔU + (n2 – n1) RT
ΔH = ΔU + Δng RT
Where Δng = Change in no. of moles in gaseous state
4.8.2 Work done in chemical reaction:
The work done by a system at constant temperature and pressure is given by
W = -P.ΔV where Pext = P
W = -P. (V2 – V1)
W = -P.V2 + P.V1
W = - Δng .P
The above equation gives the work done by the system in chemical reactions.

Consider the following cases:

1. If no. of moles of product is greater than no. moles of reactant i.e. n 2 > n1
then Δng is Positive and W < 0 i.e work is done by the system.
2. If no. of moles of reactant is greater than no. of moles of product i.e. n2 < n1
then Δng is negative and W > 0 i.e work is done on the system.
3. If n1 = n2, ng = 0 and W = 0 i.e. No work is done when number of moles of
reactants and products are equal.
4.9 Enthalpies of physical transformations:
4.9.1 Enthalpy of phase transition: In phase transition, one phase of a
substance is converted into another at constant temperature and pressure without
change in chemical composition.

i. Enthalpy of fusion (ΔfusH):

When one mole of a solid is converted into liquid without change in
temperature at constant pressure is enthalpy of fusion.
E.g. H2O(s) (Ice) H2O(l) ΔfusH = + 6.01 kJ/mol
Above reaction is endothermic. If you reverse the above reaction then it
became exothermic reaction and same amount of energy release by reaction.
H2O(l) H2O(s) (Ice) ΔfusH = - 6.01 kJ/mol
ii. Enthalpy of vaporization (ΔvapH) :
The quantity of heat that needs to be absorbed to vaporize a particular quantity
of liquid at a constant temperature.
E.g. H2O(l) H2O(v) ΔvapH= +45.07 kJ/mol
When one mole of water is vaporised at 1 atm presure, the enthalpy change
is and +44 kJ at 25°C. The condensation to vapour is accompanied with a release
of heat.
H2O(v) H2O(l) ΔfusH = - 45.07 kJ/mol
iii. Enthalpy of sublimation (ΔsubH ):
The enthalpy change when one gram of a solid directly converts into vapor at
a constant temperature
E.g. H2O(s) (Ice) H2O(1) ΔfusH = + 51.08 kJ/mol
The conversion of solid to vapour occurs in one or two steps, first melting of
solid into liquid and second its vaporization.
First Step
H2O(s) (Ice) H2O(l) ΔfusH = + 6.01 kJ/mol
Second Step
+ H2O(l) H2O(v) + ΔvapH= +45.07 kJ/mol

H2O(s) (Ice) H2O(1) ΔfusH = + 51.08 kJ/mol

 4.9.2 Enthalpy for the atomic / molecular change:
i. Enthalpy of ionization (ΔionH) :
The minimum amount of energy that is required to remove electrons present in
the outermost shell from an isolated gaseous atom.
E.g. Na(g) Na+(g) + e- ΔionH = 494 kJ/mol

ii. Electron gain enthalpy (ΔegH) :

When one mole of gas-phase atoms of an element accept electron to form
gaseous anion is called as electron gain enthalpy.
E.g. Cl(g) + e- Cl-(g) ΔegH = -349 kJ/mol

iii. Enthalpy of atomization (ΔatomH):

The enthalpy change during dissociation of one mole of gaseous molecule into
atoms are called as enthalpy of atomization.
E.g. Cl2(g) 2Cl-(g) ΔatomH = 242 kJ/mol

iv. Enthalpy of solution (ΔsolnH):

The enthalpy change in a process when one mole of a substance is dissolved in
specified amount of solvent is called enthalpy of solution.
E.g. Nacl(s) + H2O NaCl(aq) ΔsolnH = 4 kJ/mol

4.10 Thermochemistry:
It is the Branch of physical chemistry which deal with energy changes during
chemical or physical process. When reaction take place, energy may be absorbed
or released. Thermochemistry helps to measure this energy change.

4.10.1 Enthalpy of chemical reaction (ΔrH):

Consider General chemical reaction,
aA + bB cC + dD

The enthalpy change for the reaction is

ΔH = H2(product) - H1(reactant)
ΔH = [cHC + dHD] – [aHA + bHB]
Where HA and HB = Molar enthalpies of A and B i.e. reactant
HC and HD = Molar enthalpies of C and D i.e. Product
ΔrH = ΣHproduct - ΣHreactant
 Enthalpy of a chemical reaction is the difference between the sum of
enthalpies of products and that of reactants.
4.10.2 Exothermic and endothermic reactions:
i. When ΣHproduct < ΣHreactant, ΔrH is positive indicates the reaction is
endothermic.
ii. When ΣHproduct > ΣHreactant, ΔrH is negative indicates the reaction is
exothermic.

4.10.3 Standard enthalpy of reaction (ΔrH°):

Standard states of pure element or compound is the most stable form of the
pure substance at a pressure of 1 atm or 1 bar (101325Pa) at 25°C or 298K. When
reactants and products are in their standard states, the word standard is placed
before the term and the superscript ΔrH° is used.
E.g. Gas at 1 atm for H2, O2, CO2
Liquid for H2O, C2H5OH
Crystalline for NaCl, Urea, Dextrose
Solid state for metals
Sometimes substance existing in different polymorphic form
E.g. Carbon (graphite and diamond)
4.10.4 Standard Enthalpy of Formation (∆H°f):
The enthalpy change that accompanies a reaction in which one mole of pure
compound in its standard state is formed from its elements in their standard states.
E.g. the formation of one mole of CH4 in its standard state from the elements
carbon and hydrogen in their standard states is represented by
C(graphite) + 2H2(g) CH4(g) ΔfH°(CH4) = -74.6 kJ/mole
4.10.5 Standard Enthalpy of Combustion (∆H°c):
The standard enthalpy change accompanying a reaction in which one mole of
the substance in its standard state is completely oxidised or burn.
E.g. C(graphite)+ O2(g) CO2(g) ∆cH(298)(Cgraphite)=-393.5 kJ/mole
4.10.6 Standard enthalpy of reaction from standard enthalpies of
formation:
Calculations of ΔrH° from ΔfH° of compounds are based on the following.
i. Standard enthalpies of formation of an element is zero.
E.g. ΔfH°(H2)= ΔfH°(Cl2)= ΔfH°(C)= 0
ii. Standard enthalpy of formation of a compound is equal to its standard
enthalpy.
ΔfH° (compound) = H°(compound)
 Consider the reaction,
aA + bB cC + dD

Standard enthalpy of the reaction is given by

ΔfH° = [cH°C + dH°D] – [aH°A + bH°B]
ΔfH° = [cΔH°C + dΔH°D] – [aΔH°A + bΔH°B]
ΔfH° = ΣΔH°product - ΣΔH°reactant

4.10.7 Thermochemical equation:

It is the balanced chemical equation in which the enthalpy change, physical
states and the number of moles of reactants and products, have been specified.
Here follow the guidelines for writing thermochemical equations:
1. The value and appropriate sign of enthalpy change is given on the right hand
side. This value is ΔrH°.
2. The physical states of reactants and products are specified by letter. Such as
S for solid, l for liquid and g for gas.
3. If forward reaction is endothermic reaction then backward reaction became
exothermic reaction.
4. If coefficients which indicating the number of moles of all substances in
thermochemical equation are multiplied or divided by a certain numerical
factor then standard enthalpy of reaction (ΔrH°) need to be multiplied or
divided by the same.
E.g. CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ΔrH° = -890 kJ
4.10.8 Bond enthalpy:
The enthalpy change required to break particular covalent bond in one mole
of gaseous molecule to produce gaseous atoms and/or radicals, is called bond
enthalpy.
E.g. The H-H bond in one mole of H2(g) is decomposed producing gaseous 2H
atoms. The enthalpy change of the reaction is 436.4 kJ
H2(g) H(g) ΔrH° = 436.4 kJ
 Average bond enthalpy in polyatomic molecules:
In CH4 molecule there are four identical C-H bonds. The bond enthalpy of
all the 4 C-H bonds are different. The breaking of C-H bonds in CH4 occurs in four
steps as follows
CH4(g) CH3(g) + H(g), ΔrH°= 427 kJ
CH3(g) CH2(g) + H(g), ΔrH° = 439 kJ
CH2(g) CH1(g) + H(g), ΔrH° = 452 kJ
CH1(g) C (g) + H(g), ΔrH° = 347 kJ
CH4(g) C (g) + 4H(g), ΔrH° = 1665 kJ
Average C-H bond enthalpy 1665/4 = 416 kJ

4.10.9 Hess’s law of constant heat summation

The law states that, “Overall the enthalpy change for a reaction is equal to sum of
enthalpy changes of individual steps in the reaction”.

Consider the synthesis of NH3

i. 2H2(g) + N2(g) N2H4(g), ΔrH1° = +95 kJ
ii. N2H4(g) + H2(g) 2NH3(g) ΔrH2° = -187 kJ
3H2(g) + N2(g) 2NH3 ΔrH° = -92.2 Kj

The sum of the enthalpy changes for steps (i) and (ii) is equal to enthalpy change
for the overall reaction. To determine the overall equation of reaction, reactants
and products in the individual steps are added or subtracted like algebraic entities.

Application of Hess’s law

The Hess's law has been useful to calculate the enthalpy changes for the reactions
with their enthalpies being not known experimentally.

4.11 Spontaneous (irreversible) process:

Process which takes place itself, without any external factor under the given
condition is called spontaneous process.
Features of spontaneous process:
i. A process that occurs on its own without outside intervention.
ii. It proceeds in one direction and cannot take place in the opposite direction
unless the external stimulant is present.
iii. The spontaneous processes can be rapid or slow or spontaneity is not
concerned with the rate of the reaction.
iv. The process continues till equilibrium is reached.
4.11.1 Energy and spontaneity :
The spontaneous reaction takes place in a direction in which energy of the
system is lowered. It is only possible when energy is release. Hence exothermic
reaction are spontaneous.
But In other hand,
a. Ice melts spontaneously above 0 °C by absorbing heat from the surroundings.
It is endothermic.
b. NaCl dissolves spontaneously in water with the absorption of heat from the
surroundings.
Both these reactions are spontaneous It is therefore, clear that the exothermicity
is not the sufficient criterion for deciding of spontaneity.
4.11.2 Entropy :
i. In solid state water i.e. in ice, Molecules are arranged in a definite order.
ii. When ice melts, this highly crystalline arrangements of water molecules
collapse. The molecules become free in liquid state. An ordered state thus
tends to become more disordered.
iii. When liquid water vaporizes, gaseous water molecules move freely and
randomly in the available space. A less disordered state becomes highly
disordered.

These disorderness and randomness is measured by Entropy, denoted by S.

Greater the disorder of a system larger is its entropy.
Definition of entropy:-
It is a measure of molecular disorder or randomness. An entropy change of a
system is equal to the amount of heat transferred (Qrev) to it in a reversible manner
divided by the temperature in kelvin T.
𝑄𝑟𝑒𝑣
ΔS =
𝑇
The ΔS is thus expressed in J K-1.

4.11.3 Entropy and spontaneity (Second law of Thermodynamics) :

1. Consider the spontaneous reaction at room temperature
2H2O2(l) 2H2O(l) + O2(g) ΔS= +126 kJ
Entropy increases due to the formation of O2 gas. Entropy of the system
increases in spontaneous reaction.
2. 2H2(g) + O2(g) 2H2O(l), ΔS= - 327 kJ
The entropy of the system decreases. Note the reaction is spontaneous.

4.11.4 Second law of thermodynamics:

The second law of thermodynamics states that, “total entropy of a system and
its surroundings increases in a spontaneous process.” For the process to be
spontaneous
ΔStotal = ΔSsys + ΔSsurr > 0

E.g. Determine the following reaction type is spontaneous or not

2H2(g) + O2(g) 2H2O(l)
Where ΔS= -327 J/K and ΔH = 572 kJ at 298 K.
Given Data-
ΔSsys = -327 J/K
𝑄𝑟𝑒𝑣 𝛥𝐻 572×103
ΔSsurr = = = = 1919 J/K
𝑇 𝑇 298
We know, ΔStotal = ΔSsys + ΔSsurr
= -327 + 1919
ΔStotal = +1592 J/K i.e ΔStotal > 0
Reaction is Spontaneous

Sign Convention for ΔStotal

i. ΔStotal = 0 i.e. Process is at Equilibrium
 ii. ΔStotal < 0 i.e. Process is non-spontaneous
iii. ΔStotal > 0 i.e. Process is Spontaneous

4.11.5 Gibbs energy:

American theoretician J. W. Gibbs introduced a new thermodynamic
property called Gibbs energy usually denoted by G. It. is, therefore convenient to
consider the criterion of spontaneity in terms of the thermodynamic properties of
a system.
The Gibbs energy is defined as
G = H - TS (1)
Where H = Enthalpy
S = Entropy
T = Temperature
Since H, T and S are state functions, G is state function.
The change in Gibbs energy at constant temperature and constant pressure is
given by
ΔG = ΔH – TΔS (2)
4.11.6 Gibbs energy and spontaneity:
The total entropy change is given by,
ΔStotal = ΔSsys + ΔSsurr (3)
The subscript sys that refers to the system is dropped hereafter.
ΔStotal = ΔS + ΔSsurr
According to second law of thermodynamics for a process to be spontaneous,
Δ Stotal > 0
If reaction was endothermic then enthalpy change of surrounding became
negative i.e. – ΔH
−Δ𝐇
ΔSsurr = (4)
𝑇
Substitute above equation in equation no. 3
Δ𝐇
ΔStotal = ΔS -
𝑻
Multiply by T on Both side, we get
T. ΔStotal = T.ΔS – ΔH
 Multiply by minus sign (-),
-T. ΔStotal = -T.ΔS + ΔH
-T. ΔStotal = ΔH -T.ΔS (5)
From Equation no. (2),
-T. ΔStotal = ΔG

∴ ΔG = -T. ΔStotal (6)

Spontaneity in terms of Gibbs free energy is given by

i. ΔG = 0 i.e. Process is at Equilibrium
ii. ΔG > 0 i.e. Process is non-spontaneous
iii. ΔG < 0 i.e. Process is Spontaneous

4.11.7 Spontaneity and ΔH or ΔS:

From ΔG = ΔH - T ΔS (at constant T and P)
 Relation of ΔH and ΔS to ΔG
i. If ΔH and ΔS are both negative, ΔG is also negative only if ΔH is
more negative than TΔS at low temperatures
ii. If ΔH and ΔS are both positive, ΔG is also negative only if TΔS >
ΔH at high temperature.
iii. If ΔH positive and ΔS is negative, ΔG is positive at any temperature.
iv. If ΔH negative and ΔS is positive, ΔG is negative at any
temperature.

4.11.8 Temperature of equilibrium:

We know, ΔG = ΔH - TΔS
If reaction is at equilibrium then ΔG = 0
ΔH – TΔS = 0
ΔH = TΔS

𝚫𝐇
∴ T=
𝚫𝐒

T is the temperature at which the change over from spontaneous to

nonspontaneous behavior occurs.
 4.11.9 Gibbs function and equilibrium constant :

Gibbs energy change for a chemical reaction is given by,

ΔG = ΔG° + RT ln Q
Where ΔG = Gibbs Free Energy Change
ΔG° = Standard Gibbs Free Energy Change
Q = Quotient

Consider
aA + bB cC + dD

Quotient in terms of Concentration Quotient in terms of Pressure

ΔG = ΔG° + RT ln QC ΔG = ΔG° + RT ln QP
[𝐶]𝑐 [𝐷]𝑑 𝑃𝐶 𝑐 𝑃𝐷 𝑑
Where QC = Where QP =
[𝐴]𝑎 [𝐵]𝑏 [𝑃𝐴 𝑎 𝑃𝐵 𝑏

[𝑪]𝒄 [𝑫]𝒅 𝑷𝑪 𝒄 𝑷𝑫 𝒅
ΔG = ΔG° + RT ln (i) ΔG = ΔG° + RT ln (ii)
[𝑨]𝒂 [𝑩]𝒃 [𝑷𝑨 𝒂 𝑷𝑩 𝒃

The reaction reaches equilibrium, ΔG= 0 and Qc and Qp become Kc and Kp,
0 = ΔG° + RT ln KC 0 = ΔG° + RT ln KP
ΔG° = - RT ln KC ΔG° = -RT ln KP
Convert ln into Log10 Convert ln into Log10
ΔG° = -2.303 RT log10 KC ΔG° = -RT log10 KP