CHEMISTRY THERMODYNAMICS

What is Thermodynamics and why is it useful ?

Thermodynamics is the branch of science that describes the behaviour of
matter and the transformation between different forms of energy on a
macroscopic scale. Thermodynamics describes a system in terms of its
bulk properties. Only a few such variable are needed to describe the
system, and the variables are generally directly accessible through
measurements. A thermodynamic description of matter does not make
reference to its structure and behaviour at the microscopic level.

The laws of Thermodynamics : The law's of thermodynamics is the law of

observation. No one has ever observed that any thing goes in contrary to
thermodynamics law. So we elevate this observation to the status of
thermodynamic law. The real justification of this comes when things we
derive using this law turn's out to be true that is verified by experiments
Application of Thermodynamics :
(i) It provides relationship between heat, work and measurable properties
of matter. (ii) It predicts direction of natural change - like what
circumstances are best for rusting of iron. (iii) It predicts up to what
extent a chemical reaction can proceed in forward direction. Example :
How much ammonia (NH3) can be formed from N2 and H2 in a closed
container. (iv) It help in understanding why different phases of matter
exist - and provide simple relationship between various measurable
properties of system (thermodynamical variables) :

Salient featurs of Thermodynamics :

During study of this chapter you will observe that mostly you will be
dealing with macroscopic properties
(bulk properties) like pressure, volume, temperature density of system.
This is because thermodynamics
is macroscopic science and it do not concern's with detailed microscopic
make up of the system.
Limitations :
(1) It tells us whether a given chemical reaction will take place or not
under the given set of conditions
but doesn't tell us anything about the rate of reaction.
(2) It tells us about the initial and final properties of the system but
doesn't tell us anything about the path
or mechanism followed by the system.
Basic definitions :
(i) System : Part of universe under investigation is called system.
(ii) Surrounding : Anything out side the system is called surrounding.
Types of system :
(i) Closed system : A system which can exchange only energy with
surrounding.
(ii) Open system : A system which can exchange both energy and matter
with surrounding.
(iii) Isolated system : A system which cannot exchange matter or energy
with surrounding.
(iv) Homogeneous system : System consist of single phase. eg. Pure solid,
a pure liquid a solution, or a mixture of gases.
(v) Heterogenous system : A system consisting of many phases. eg.
System of two immiscible liquids, two or more solids, a liquid in contact
with its vapour etc. are example of heterogenous system.
(vi) Boundary : The interface between system and surrounding is called
boundary. Across boundary energy and mass are transferred between
system and surrounding. Boundary can be real or hypothetical.
(vii) Wall : A real boundary is called wall can be rigid,
Types of wall :
Rigid wall : The wall is immovable wPV = 0.
Non Rigid wall : The wall is movable wPV 0.
Adiabatic wall : The heat exchange across the wall is q = 0.
Dithermic wall : The heat can be exchanged across the wall q 0.
Phase : By the term phase we mean a homogeneous physically distinct
part of a system which is bounded
by a surface and can be separated out mathematically from the other
parts of the system.
The state of a system :
We specify the state of a system - say, a sample of material - by
specifying the values of all the variables
describing the system. If the system is a sample of a pure substance this
would mean specifying the values
of the temperature, T, the pressure, p, the volume, V, and the number
of moles of the substance, n.
State variables : To define a thermodynamics states of a system, we
have to specify the values of certain measurable quantities. These are
called thermodynamic variable or state variable.
A system can be completely defined by four variables namely pressure,
temperature, volume and composition. A system is said to be in a certain
definite state when all of its properties have definite value.. Between two
fixed state the change in the value of state function is same irrespective
of the path connection two states.
Differential of a state function integerated over a cyclic path returns
zero. In other words summation of change in state function in a cyclic
process is equal to zero.
Example : T, V, P and U (internal energy), H (enthalpy) are state
variables.
Path function or path dependent quantities : The value of path function
depends upon path connection two states . There can be infinite vaules of
path function between two states depending upon path or process. Path
functions are also called indefinite quantities since between two fixed
state the value of path function is not fixed. Heat and Work are two
important path dependent quantities with which we deal in this chapter.

Extensive and Intensive variables : Propterties which depend on the

amount of the substance (or substances) present in the system are called
extensive propterties. e.g. Mass, volume, heat capacity, internal energy,
entropy, Gibb's free energy (G), surface area etc. These properties will
change with change in the amount of matter present in the system. It is
important to note that the total value of an extensive property of a
system is equal to the sum of the values of different parts into which the
system is divided.
Intensive properties : Properties which are independent of the amount of
substance (or substances) present in the system are called intensive
properties, e.g. pressure, density, temperature, viscosity, surface tension,
refractive index, emf, chemical potential, sp. heat etc, These are intensive
properties. An extensive property can be converted into intensive
property by defining it per unit of another extensive property. E x .
Concentration = mole / volume Density = mass / volume heat capacity =
heat absorbed / rise in temperature While mole, mass, heat are extensive
properties, concentration, density and heat capacity are intensive
properties.

Thermodynamic equilibrium : Thermodynamic generally deals the

equilibrium state of the system in which the state variable are uniform
and constant throughout the whole system. The term thermodynamic
equilibrium implies the existence of three different types of equilibria in
the system.
These are : (i) Mechanical equilibrium : When there is no macroscopic
movement within the system itself or of the system with respect to
surroundings, the system is said to be in a state of mechanical
equilibrium.

(i i) Chemical equilibrium : When the system consists of more than one

substance and the composition of the system does not vary with time,
the system is said to be in chemical equilibrium. The chemical
composition of a system at equilibrium must be uniform and there should
be no net chemical reaction taking place.
(iii) Thermal equilibrium : When the temperature throughout the entire
system is the same as that of the surroundings then the system is said to
be in thermal equilibrium.
Equation of state : An equation that relates the variables T, p, V, and n
to each other is called the "equation of state." The most general form for
an equation of state is. f (p, V, T, n) = 0.

The ideal gas equation of state : The best known equation of state for a
gas is the "ideal gas equation of state". It is usually written in the form,
pV = nRT This equation contains a constant, R, called the gas constant.

The vander Walls equation of state for real gases : The vander Walls
equation of state is, 2 2 n (p a ) V + (V – nb) = nRT Notice that the
vander Walls equation of state differs from the ideal gas by the addition
of two adjustable parameters, a, and b (among other things). Note :
Equation of state for liquid and solids are also defined empirically.

Process : Anything which changes state of system is called process.

Usually as a result of heat and work interactions change of state take
place. e.g. isothermal process Path of a process : The exact sequence of
steps through which system changes state is called path of a process.e.g.
reversible or irrervisible path

Some thermodynamic processes : (1) Isothermal process : A process in

which temperature of the system remains constant is called isothermal
process.
(2) Isobaric process : A process in which pressure of the system remains
constant is called isobaric process. Temperature and volume of the
system may change. E x . All the reactions or processes taking place in
open vessel like boiling of water in open vessel, burning of charcoal,
melting of wax take place at contant pressure (1 atm.)

(3) Adiabatic process : A process in which no heat exchange takes place

is called adiabatic process. Adiatatic process occurs in isolated systems.

(4) Isochoric process : The process for which volume of the system
remains constant is called isochoric process i.e., Heating of gas in closed
vessel.

(5) Cyclic process : If a system after completing a series of different

process returns to its initial state then overall process is called cyclic
process. In cyclic process all the state variables remains constant because
initial state becomes final state in cyclic process. E x . H = 0, E = 0,
P.E. = 0

Polytropic processes : It is defined as a process in which PVn =constant

=k All of the above mentioned processes can be performed in two ways ,
reversibly and irreversibly  Reversible process : When the difference
between driving force and opposing force is very small and the process is
carried out infinitesimally slowly, then the process is called reversible
process. The reversible process is carried out in such a manner that at
any moment of the change the directon of process can be reversed by
making a small change in driving force.A reversible process is also called
quasi static process.

During a reversilbe process, the system and surrounding remain in

equilibrium throught the process. The reversible proceses are idealized
processes which cannot be actually carried out, but neverthless they are
very important because they help in calculation of change in state
function in the process.In other words the reversible processes are
hypothetical processes.

A quasi static process is the one in which system remain infinitesimally

closer to the state of equilibrim through out the process.  Irreversible
process : Any process which does not take place in the above manner
and difference between driving force and the opposing force is quite
large is called irreversible process.

All natural processes are example of irreversible process.

Reversible process VS Irreversible process
(1) Driving force is infinitesimally small.
(1) Driving force is large and finite.
(2) PV work is done across pressure difference
(2) PV work is done across pressure difference d P P
(3) A reversible heat transfer take place across
(3) Irrerversible heat transfer take place across temperature difference
dT temperatur difference T
(4) It is an ideal process. (4) It is a real process.
(5) It takes infinite time for completion of process. (5) It takes finite time
for completion of process..
(6) It is an imaginary process and can not be (6) It is a natural process
and occurs in realised in actual practice. particular direction under given
set of conditions.
(7) Throughout the process , the system remain (7) The system is far
removed from state of infinetesimelly closer to state of equilibrium
equilibrium and exact path of process is and exact path of process can
be drawn indeterminate.

Heat and Work : Heat and work both are mode of energy transfer
between system and surrounding. Heat flows due to temperature
gradient while work is done due to imbalance of generalized force. Due
to imbalance of generalized force(intersive property) generalized
displacement (extensive property) is produced. The product of
generalized force and generalized displacement is work. Work done on
the system can reversible and irrervisible depending on magnitude of
imbalance of generalized force.
Heat is also transfered between system and surrounding in two ways –
reversible and irreversible. Reverssible heating means heating an object
from Ti to Tf using infinite heat reservoirs. Irreverssible heat transfer
means heat transfer across temp difference T. Heating an object from
100 K to 1000 K by using heat reservoir of temperature 1000 K is an
example of irreverssible heating. While heating an object from 100 to
1000 K using reservoir of temp 100 + dT, 100 + 2dT, ......... 1000 –
dT, 1000 K is an example of reversible heating. You can clearly see
reversible heating is hypothetical concept. Work can be of many types :
The following table show different kinds of work.
PV-WORK Consider a clylinder fitted with a frictionless piston, which
enclosed n mole of an ideal gas.
Let an external force F pushes the piston inside producing displacement
in piston.Let distance of piston
from a fixed point is x and distance of bottom of piston at the same
fixed point is . This means the volume
of cylinder = ( – x)A where A is area of cross section of piston.

For a small displacement dx due to force F , work done on the system.

dw = F.dx
Also P =F.A
F = PA
dW = PA.dx
V = ( – x) A
dV = – A . dx
dW = – Pext. dV
: During expansion dV is +ive and hence sign of w is -ive since work is

done by the system and -ive sign

representing decrese in energy content of system. During compression,

the sign of dV is -ive which gives +ive

value of w representing the increase in energy content of system during

compression.

SIGN CONVENSIONS :

According to latest sign conventions

(a) Work done is taken negative if it is done by the system since energy

of system is decreased.

Ex. Expansion of gas.

(b) Work done is taken positive if it is done on the system, since energy

of system is increased.

W = – Pex. V

Q . Find the work done in each case :

(a) When one mole of ideal gas in 10 litre container at 1 atm. is allowed

to enter a vaccuated bulb of

capacity 100 litre.

(b) When 1 mole of gas expands from 1 litre to 5 litre against constant

atmospheric pressure.

A . (a) W = – P V

But since gas enters the vaccum bulb and pressure in vaccum is zero. This

type of expansion is called

free expansion and work done is zero.

Heat : Heat is defined as the amount of energy which flows between

system and surrounding because of
temperature difference.
Note : Heat always flows from high temperature to low temperature .
Sing convention :
Heat is taken negative when it goes out of the system.
 Heat is taken positive when it comes inside the system.

Difference bet ween heat a nd work :

When a gas is supplied some heat, its molecules move faster and with
greater randomness in different directions.
But when work is done on the same system gas molecules are compressed
and move initially in direction of
force as they get condensed.
So heat is random form of energy while work is organised from of energy.

The internal energy and the first law of thermo dynamics :

The first law of thermodynamics is based on experience that energy can be

neither created nor destroyed,
if both the system and the surroundings are taken into account.
Suppose a blocks of mass 'M' is moving in
gravitational field with velocity v. The total energy of blocks (in ear th
frame of reference) is given as :
E = K + V + U : (K = kinetic energy, V = potential energy, U = internal
energy)
A thermodynamic system is studies generally at rest so K = 0. If effect of
gravitation field (or other fields are
ignored) is also ignored then we left with E = U. Thus U (internal energy) is
energy of system.
If a system is present in particular thermodynamic state say 'A' it has fixed
amount of internal energy UA.
Suppose by a process the system is taken from state A to state B. In the
process 'q' heat is absorbed by
system and w work is done on the system. Thus in the state 'B' total
internal energy of system become

First law of thermodynamics states that energy is conserved. Direct

consequence of this statement is U
is state function. This implies between any two fixed state, there can be
infinite process or path, but
U in all process will remain the same.(Property of a function of state)
Consider a system taken from state A to B by nth different paths.
from first law
UB – UA = q1 + w1 = q2 + w2 = .... qi + wi
Here qi, wi are heat and work involve in respective processes.
Note that heat and work involve in all the process are different but U
is same. This mean heat and work are indefinite quantities while U is a
definite quantity.

First Law of Thermodynamics Equation

The equation for the first law of thermodynamics is given as;

ΔU = q + W

Where,

• ΔU = change in internal energy of the system.

• q = algebraic sum of heat transfer between system and

surroundings.

• W = work interaction of the system with its surroundings.

T he microscopic nature of Fir st law of t her mo dynamics:

The internal energy of the gas confined in a container is defined relative
to a coordinate system fixed
on the container. Viewed at a microscopic level, the internal energy can
take on a number of forms
such as.
 The kinetic energy of the molecules ;
The potential energy of the constituents of the system ; for example, a
crystal consisting of dipolar molecules
will experience a change in its potential energy as an electric field is
applied to the system ;
The internal energy stored in the form of molecular vibrations and
rotations;
The internal energy stored in the form of chemical bonds that can be
released through a chemical
reaction.
The total of all these forms of energy for the system of interest is given
the symbol U and is called
the internal energy.
Hence total internal energy of a system can be written as
U = Utranslat ional+Urotational+Uvibrat
ional+Uintermolecular+Uelectronic+Urelativistic
of these Urelativistic and Ueletronic is unaffected by ordinary heating. So
basically the kinetic energy terms
and intermolecur accommodate heat provided to the system . Hence
heat capacity of a sample depends
upon these four terms.
For an ideal gas, intermolecular is equal to zero, because of absence of
intermolecular force of attractionin ideal gas. Uintermolecular have large
and negative value in solids and liquids.
For an ideal gas U is only function of temperature e.g. U=F(T) +Constant
Due to absence of pressure or volume terms in ideal gas internal energy,
U is independent of pressure
and volume of theoretical ideal gas.
Enthalpy :

Chemical reactions are generally carried out at constant pressure

(atmospheric pressure) so it has been
found useful to define a new state function Enthalpy (H) as :
H = U + PV (By definition)
o r H = U + (PV)
o r H = U+ P V (at constant pressure) combining with first law.
Equation (1) becomes
H = qp
Heat excha nge at consta nt volume a nd consta nt pre ssure (qp a nd
qv) :
For an isochoric process in a system involving only PV work,
U = qV
This result is valid for all the substance under isochoric conditions (when
only PV work is involved) Also
from the previous article it is clear that
H = qp
This result is valid for all the substance involving isobaric process(when
only PV work is involved)
Hence heat exchanged at constant pressure and volume are important
Definite quantities
Heat capacity :
The heat capacity of a system may be defined as the amount of heat
required to raise the temperature of the
system by one degree.
If q is the small quantity of heat added to the system, let the
temperature of the system rises by dT, then
heat capacity C of the system is given by
Heat Capacity and Specific Heat
Different substances respond to heat in different ways. If a metal chair
sits in the bright sun on a hot day, it may become quite hot to the
touch. An equal mass of water in the same sun will not become nearly as
hot. We would say that water has a high heat capacity (the amount of
heat required to raise the temperature of an object by 1oC ). Water is
very resistant to changes in temperature, while metals in general are
not. The specific heat of a substance is the amount of energy required to
raise the temperature of 1 gram of the substance by 1oC . The table
below lists the specific heats of some common substances. The symbol for
specific heat is cp , with the p subscript referring to the fact that
specific heats are measured at constant pressure. The units for specific
heat can either be joules per gram per degree (J/goC) or calories per
gram per degree (cal/goC) .
In case of gases we have two types of heat capacity i.e. heat capacity at
constant volume and heat capacity at constant pressure.
It is the rate of change of enthalpy with temperature at constant
pressure.
Hence heat capacity of a system at constant volume Cv is equal to the
increase in internal energy of the
system per degree rise of temperature at constant volume. Similarly heat
capacity at constant pressure Cp is
numerically equally to the increase in enthalpy of the system per degree
rise of temperature.
For 1 mole of an ideal gas, heat capacity at constant pressure i.e. Cp is
greater than the heat capacity at
constant volume i.e., Cv
Cp > Cv

Reversible and Irreversible process :

Reversible process : Process which is carried out in such a manner that it
could be reversed by an infinitesimal
change. A reversible process takes infinitesimally small, infinite steps to
complete and
time taken to complete the process is infinite. So, it is a theoretical
process and it sets
a ceiling on the processes carried out practically.
Irreversible process : Process which doesn’t satisfy the reversible criteria.
Examples of irreversible process :
1. Fee expansion of gas
2. Melting of ice in warmer liquid
3. Anything that is real.
We can also define the reversible and irreversible process in a more of
mathematical sense as follows :
Reversible process : Process in which there is an infinitesimally small
difference between the driving
force and opposing force.
Irreversible process : Process in which there is a finite difference between
the driving force and opposing
force.
Cha nge i n i nter nal energy a nd ent halpy i n chemical react ions :
Enthalpy and
i nternal energy
change in chemical reaction involve change in potential energy due to
chemical change. During chemical
change transformation of bonds take place. If the bonds in product are
more stable, leading to decrease
in potential energy of atom and molecules, the enthalpy and internal
energies decreases . In the process
surplus energy is librated and process is called exothermic process.
During endothermic chemical process which take place absorbing energy
from surrounding, the potential
energy of system of chemical substance increases.
Consider a chemical reaction
aA + bB ---> cC + dD
The internal energy change can be given as (Theoratically)
U= cUc + dUd – aUa – bUb
where Ua , Ub , Uc , Ud etc. are molar internal enegy of respective
species.
since absolute internal energies cannot be determine, Ui are determined
with respect to internal energy
of elements in their most stable state. The internal energies of elements
in their most stable allotropic
modification is arbitary taken as zero at 298K and 1 atm pressure.
also, rU = qv for reaction taking place under constant volume and
temperature condition. For the
similar reaction occuring at constant pressure and temperature,
enthalpy change, H is given by
H = cHc + dHd – aHa – bHb
where H are enthalpies of respective species
however H is equal to heat exchange during chemical process at
constant pressure and temperature.
rH =qp for reaction taking place under constant pressure and
temperature conditions
Relationship between rH and rU in chemical reactions : For a general
chemical reaction given by
aA + bB ---> cC + dD
rH = cHc + dHd – aHa – bHb .......... (1)
but Hi = Ui +PVi
substituting the value of molar enthalpies of substance in equation (1) we
get
rH = cUc + dUd – aUa – bUb + P(cVc+ dVd – aVa – bVb)
rH = rU+ P(Vf – Vi) ................ (2)
(a) If all the reactant and products are ideal gases Vc ,Vd ,Va andVb all
are equal to molar volume of ideal
gas e.g. V= RT/P which on substitution in previous equation gives
rH = rU + (d + c – a – b)RT
rH = rU+ ngRT ...................(3)
Where ng is difference of stoichiometric cofficient of gaseous products
and gaseous reactants.
(b) In case of liquid and solids present in chemical equations , their molar
volumes can be ignored in
comparison to molar volume of ideal gases and hence do not count
stoichiometric cofficient of solid
and liquids in ng.
(c) In case of non ideal behaviour of gases, equation (2) should be used.
Cha nge i n i nter nal energy and ent halpy i n phase tra nsit ion : At
cer tai n temperature under one
atmospheric pressure, one phase changes into other phase by taking
certain amount of Heat. The temperatrue
at which this happens is called transition temperature and heat absorbed
druing the process is called
Enthalpy of phase transition. Heat absorbed during transition is
exchanged at constant pressure and
temperatrue and it is significant to know that the process is reversible.
Fusion : Solid ice at 273K and 1 atm pressure reversibly changes into
liquid water. Reversibly, isothermally
and isobarically, absorbing heat know as latent heat of fusion.or enthalpy
of fusion.
Vaporisation : Water at 373K and 1 atm pressure changes into its
vapors absorbing heat known as
latent heat of vaporisation.The latent heat of vaporisation is heat
exchanged isothermally , isobarically
and reversibly to convert water into its vapour at boiling point.
Internal energy change of phase transitions involving gas phase has no
practical significance because it
is not possible to carry out U of phase transition directly through an
experiment. However U of phase
transition can be determined theoretically from experimentally obtained
value of H of phase transition.
H2O( ) H2O(g)
Hvaporisation = Uvaporisation + P(Vf – Vi)
Hvaporisation = Uvaporisation + {RT/V}{Vg}
ignoring volume of liquid as compared to molar volume of gas
Hvap. = Uvap. + RT
where R is gas constant and T absolute temperature for condensed phase
transitions like solid liquid transitions
 Hvap. ~ Uvap.
Second law : There are two types of processes reversible process or quasi
static process in which system
remains in equilibrium with surrounding through out the process.
However reversible processes can not take place on it's own - and are
not natural process. Reversible
process do not lead to production of disorder.
On the other hand most of the processes taking place around us is
example of irreversible process. Irreversible
process also natural processes or spontaneous processes.

Example of natural processes :

(i) Water flowing down hill
(ii) Heat flowing from hot body towards cold body on it's own
(iii) mixing of two gases.
(iv) Rusting of iron
(v) Evaporation of water at room temperature.
(vi) Formation of NH3(g) from N2(g) and H2(g) gas in a closed
container.
(vii) Expansion of ideal gas in vacuum
(viii) Burning of coal in O2
Ever y natural process leads to production of disorder. (During
irreversible process system moves from
ordered state to disordered state).
The second law of thermo dynamics :
The second law of thermodynamics predict's direction of natural change.
It do so with the help of state
function 'S' - called entropy of system. But for predicting direction of
natural change another quantity

Since
Ssystem is state function - If a system make transition from state A to
state B - by infinite paths in
few of them may be reversible and other may be irreversible. SAB will
be same irrespective of path
(A direct consequence of Ssystem being a state function).
Prediction of spontaneit y of proce ss : If total entropy change in a
process is positive the process
must be spontaneous.
Ssystem + Ssurrounding > 0 for spontaneous change.
The second law of thermodynamics was developed during course of
development of cyclic engines.
2nd law statement :
It is impossible for a system to undergo cyclic process whose sole effects
are the flow of heat from a
heat reservoir and the per formance of an equivalent amount of work by
the system on surrounding.
The key term in above statement is cyclic engine. If the first part of it's
operation when engine do work
heat is absorbed and expansion on take place in second par t, it must
return to it's original state and
to contract, it must loose heat to a cold object (sink).

• Entropy is the loss of energy available to do work.

• Another form of the second law of thermodynamics states that the total
entropy of a system either increases or remains constant; it never decreases.

• Entropy is zero in a reversible process; it increases in an irreversible process.

• The ultimate fate of the universe is likely to be thermodynamic equilibrium,

where the universal temperature is constant and no energy is available to do
work.

• Entropy is also associated with the tendency toward disorder in a closed system.

Third law of thermodynamics :

Third law of thermodynamics helps in determining absolute entropy of
substances. It is based on an assumption
that entropy of every per fectly crystalline substance is zero at zero
Kelvin. This is justified because , at absolute zero every substance is in
state of lowest energy and position
of every atom or molecule is defined in solid. Hence at T=0 S(T=0)=0

Gibbs Free Energy Equation

Gibbs free energy is equal to the enthalpy of the system minus the product of the temperature
and entropy. The equation is given as;

G = H – TS

Where,

G = Gibbs free energy

H = enthalpy

T = temperature

S = entropy

Gibbs free energy is a state function hence it doesn’t depend on the path. So change in Gibbs
free energy is equal to the change in enthalpy minus the product of temperature and entropy
change of the system.

ΔG=ΔH-Δ(TS)

If the reaction is carried out under constant temperature{ΔT=O}

ΔG=ΔH-TΔS

This equation is called the Gibbs Helmholtz equation

ΔG>0; the reaction is non-spontaneous and endergonic

ΔG<0; the reaction is spontaneous and exergonic

ΔG=0; reaction is at equilibrium

Note:
 1. According to the second law of thermodynamics entropy of the universe always
increases for a spontaneous process.
2. ΔG determines the direction and extent of chemical change.
3. ∆G is meaningful only for reactions in which the temperature and pressure remain
constant. The system is usually open to the atmosphere (constant pressure) and we
begin and end the process at room temperature (after any heat we have added or
which is liberated by the reaction has dissipated).
4. ∆G serves as the single master variable that determines whether a given chemical
change is thermodynamically possible. Thus if the free energy of the reactants is greater
than that of the products, the entropy of the world will increase when the reaction
takes place as written, and so the reaction will tend to take place spontaneously. ΔS
universe = ΔS system + ΔS surroundings
5. If ΔG is negative, the process will occur spontaneously and is referred to as exergonic.
6. Therefore spontaneity is dependent on the temperature of the system.

Point To Remember

Free energy change criteria for predicting spontaneity is better than entropy change
criteria because the former requires free energy change of system only whereas the
latter requires entropy change of system and surroundings.

Second Law of Thermodynamics

Based on concepts of entropy and spontaneity. The second law of thermodynamics is defined
on the following basis;

1. All spontaneous processes are thermodynamically irreversible.

2. It is impossible to convert heat completely into work without wastage.
3. The entropy of the universe is continuously increasing.
4. The total entropy change i.e, entropy change of the system + entropy change of
surroundings is positive.

5. ∆H<0 ∆H>0
 ∆S>0 Spontaneous at all Spontaneous only at high temperature (when
temperatures T∆S is high)
(∆G<0)

∆S<0 Spontaneous at low Not spontaneous at any temperature

temperature (∆G>0)
(when T∆S is small)

● Spontaneous – is a reaction that is considered to be natural because it is a reaction that

occurs by itself without any external action towards it.

● Non-spontaneous – needs constant external energy applied to it in order for the process to
continue and once you stop the external action the process will cease.

Standard-state free energy of reaction (∆G°)

The free energy of reaction at standard state conditions:

∆G°=∆H°-T∆S°

Standard-state Conditions

1. The partial pressure of any gases involved in the reaction is 0.1 MPa.
2. The concentrations of all aqueous solutions are 1 M.
3. Measurements are also generally taken at a temperature of 25C (298 K).
4. pure liquids: the liquid under a total (hydrostatic) pressure of 1 atm.
5. solids: the pure solid under 1 atm pressure.

The change in the free energy of the system that occurs during a reaction measures the
balance between the two driving forces that determine whether a reaction is spontaneous. As
we have seen, the enthalpy and entropy terms have different sign conventions.

Favourable Unfavourable

∆H°<0 ∆H°>0

∆S°>0 ∆S°<0
Calculating The Change in Gibbs Free Energy
Even though ∆G is temperature-dependent, we assume to take ∆H and ∆S are independent
of temperature when there is no phase change in the reaction. So if we know ∆H and ∆S, we
can find out the ∆G at any temperature.

Methods

1. Estimating ∆H reaction using bond enthalpies

2. Calculating ∆H using standard heats of formation ∆fH°
3. Calculating ∆H and ∆S using standard values

Tips:

● Unit of ∆G is equal to ∆H

● Unit of ∆H is (KJ) /(mole reaction)

● Unit of ∆S is (KJ) /(mole reaction)K

Examples

The rusting of iron is an example of a spontaneous reaction that occurs slowly, little by little,
over time. Melting of ice also another example.

Relationship Between Free Energy and Equilibrium Constant

The free energy change of the reaction in any state, ΔG (when equilibrium has not been
attained) is related to the standard free energy change of the reaction, ΔG° (which is equal to
the difference in the free energies of formation of the products and reactants both in their
standard states) according to the equation.

ΔG = ΔG° + RT InQ

Where Q is the reaction quotient.

At equilibrium,

∆G=0 and Q become equal to the equilibrium constant. Hence the equation becomes,

ΔG° = –RT In K(eq)

ΔG° = –2.303 RT log K(eq)

● R = 8.314 J mol-1 K-1 or 0.008314 kJ mol-1 K-1.

● T is the temperature on the Kelvin scale

In a reversible reaction, the free energy of the reaction mixture is lower than the free energy
of reactants as well as products. Hence, free energy decreases whether we start from
reactants or products i.e, ∆G is -ve in backward as well as forward reactions.

Relationship Between Gibbs Free Energy and EMF of a Cell

In the case of galvanic cells, Gibbs energy change ΔG is related to the electrical work done by
the cell.

ΔG = -nFE(cell)

Where, n = no. of moles of electrons involved

F = the Faraday constant

E = emf of the cell

F=1 Faraday =96500 coulombs

If reactants and products are in their standard states,

ΔG°= –nFE°cell

∆G°and equilibrium

∆G° Reaction Keq

+ Non-spontaneous <<1

– Spontaneous >>1

0 At equilibrium 0