Thermodynamics

The word thermodynamics is derived from

the Greek word
Therme – heat
Dynamics – flow (or) motion

Thermodynamics is the study of the

interconversion of heat , work and various
other kinds of energy.
Thermodynamic
Terms
 System
A system is defined as any specified portion
of matter under study which is separated
from the rest of the universe with a
bounding surface
 Surroundings
The rest of the universe which might be in a
position to exchange energy and matter with
the system is called the surroundings

Surrounding include everything other than

system

Universe = system + surrounding

 Boundary

Anything which separates system from the

surroundings is called boundary
Types of the system
 Open System
There is exchange of energy and matter between system
and surroundings .
The presence of reactants in an open beaker is an example
of an open system.
Here the boundary is an imaginary surface enclosing the
beaker and reactants.
 Closed System
There is no exchange of matter, but exchange of
energy is possible between system and the
surroundings.

The presence of reactants in a closed vessel

made of conducting material e.g.copper or steel
is an example of a closed system.
 Isolated System
There is no exchange of energy or matter between the system and
the surroundings .
The presence of reactants in a thermos flask or any other closed
insulated vessel is an example of an isolated system.
 The State of the System
The system must be described in order to make any
useful calculations by specifying quantitatively each of
the properties such as its pressure (p), volume (V), and
temperature (T ) as well as the composition of the
system.
The state of a thermodynamic system is described by its
measurable or macroscopic (bulk) properties.

We can describe the state of a gas by quoting its pressure

(p), volume (V), temperature (T ), amount (n) etc.
Variables like p, V, T are called state variables or state
functions because their values depend only on the state of
the system and not on how it is reached.
 INTERNAL ENERGY AS STATE
FUNCTION

 Internal energy of a system is defined as U

 This internal energy may be electrical chemical or
mechanical. the internal energy, U of the system, which may
change, when:-
 • heat passes into or out of the system,
 • work is done on or by the system,
 • matter enters or leaves the system.
 Work
We take a system containing some quantity of water in a thermos

flask or in an insulated beaker.

This would not allow exchange of heat between the system and

surroundings through its boundary and we call this type of system

as adiabatic and process is adiabatic process.

Adiabatic process is a process in which there is no transfer of

heat between the system and surroundings.

Here, the wall separating the system and the surroundings is called

the adiabatic wall.

The change in internal energy of the system is

observed by doing some work on it

(+w = Work done on the system

- W = Work done by the system)

Initial state:

Temperature is TA .

The internal energy of the system is UA .

We do some mechanical work on the system,

The final state of system is B

Its temperature, is TB .

It is found that TB > TA and

the change in temperature, ∆T = TB–TA.

Change in internal energy, ∆U =UB– UA .

 Heat

We can also change the internal energy of a system by transfer of

heat from the surroundings to the system or vice-versa without

expenditure of work.

This exchange of energy, which is a result of temperature difference

is called heat, q.
Unit of Heat :

(i) Calorie (Cal) or kilo calories (kcal).

(ii) 1 J = 107 ergs = 0.2390 cal

1 cal = 4.184 J, and 1 kcal = 4.184 kJ.

In case of Diathermic wall (thermally conducting wall)
We take water at temperature, TA in a container having thermally
conducting walls, say made up of copper and enclose it in a huge
heat reservoir at temperature, TB .
The heat absorbed by the system (water), q can be measured in
terms of temperature difference , TB – TA .
In this case change in internal energy, ∆U= q, when no work is done
at constant volume.
When heat is transferred from the surroundings to the system and

q is positive,

When heat is transferred from system to the surroundings.

q is Negative,
 First Law of Thermodynamics
Let us consider the general case in which a change of state is

brought about both by doing work and by transfer of heat.

We write change in internal energy for this case as:

∆U = q + w
For a given change in state, q and w can vary depending on how

the change is carried out.

q & w are path functions

However, q +w = ∆U will depend only on initial and final state.

Internal energy is state function

If there is no transfer of energy as heat or as work(isolated system)

i.e., if w = 0 and q = 0, then ∆ U = 0.

The equation, ∆U = q + w is mathematical statement of the first law

of thermodynamics, which states that

The energy of an isolated system is constant.

It is commonly stated as the law of conservation of energy i.e,

energy can neither be created nor be destroyed.

(i) No heat is absorbed by the system from the surroundings,

but work (w) is done on the system. What type of wall does the

system have ?
∆ U = wad, wall is adiabatic
(ii) No work is done on the system, but q amount of heat is taken out

from the system and given to the surroundings. What type of wall does

the system have?

∆ U = – q,

Thermally conducting walls (Diathermic wall)

(iii) w amount of work is done by the system and q amount of heat is
supplied to the system. What type of system would it be?

∆ U = q – w, closed system.
Applications
 Work

(Pressure – Volume work)

 Work = Pext V

Work = Pext ( Vf – Vi )
Work done on the system = + W

W = + PV = P (Vf – Vi )

Work done by the system = – W

W = – PV = – P (Vf – Vi )
Reversible process Irreversible process
1.it is ideal process and takes infinite 1.it is a spontaneous process and takes
time finite time
All natural processes are irreversible.
2.the driving force is infinitesimally 2.the driving force is much greater than
greater than the opposing force the opposing force & it is unidirectional
process.
3.it is at equilibrium at all stages 3.equilibrium exists in the initial and final
stages only
4.it is difficult to realize in practice 5.it can be performed in practice
pV-plot when pressure is not constant and changes in finite steps
during compression from initial volume, Vi to final volume, Vf . Work
done on the gas is represented by the shaded area
pV-plot when pressure is not constant and changes in infinite steps
(reversible conditions) during compression from initial volume, V i to final
volume, Vf . Work done on the gas is represented by the shaded area.

Compression:
Pext = P in + dp
Expansion:
Pext = P in – dp
Isothermal
Expansion
or
Compression
Reversible process
Irreversible process
Free Expansion
Expansion of gas in vacuum [Pext =0] is called free expansion

No work is done during free expansion of an ideal gas whether the

process is reversible or irreversible

ENTHALPY
The heat absorbed at constant volume is equal to change in

the internal energy i.e., DU = qV.

But most of chemical reactions are carried out not at constant

volume, but in flasks or test tubes under constant atmospheric

pressure.

We need to define another state function which may be

suitable under these conditions.

DU = qp – pDV

qp is heat absorbed by the system

–pDV represent expansion work done by the system

HEAT CAPACITY
It is the amount of heat required to raise the temperature of
a system through 1ºC
If ‘q’ is the amount of heat supplied to a system and as a
result let the temperature rise from T1 to T2 ºC.
(a) Specific Heat and Molar Heat Capacity at Constant Volume
(CV)
Specific Heat : It is the amount of heat required to raise the
temperature of 1 gm of a gas through 1º at constant volume.
Molar heat capacity : It is the amount of heat required to raise
the temperature of one mole of a gas through 1º at constant
volume
(b) Heat Capacity at Constant Pressure (CP) : It is
defined as the amount of heat required to raise the
temperature of one mole
of gas through 10 keeping pressure constant.
* CP is always greater than CV.
MEASUREMENT OF ∆U AND ∆H:
CALORIMETRY
(a) ∆U measurements : It is measured in special
type of calorimeter called bomb calorimeter.
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 changei.e., the energy changes associated
with reactions are measured at constant volume
(∆V = 0).
The value of ∆U can be calculated using the
formula,
∆ U = q = c × m × ∆ T = C ∆T
∆H measurements : Measurement of heat
change at constant pressure (generally under
atmospheric pressure) can be done in a
calorimeter shown in Figure.
Heat absorbed or evolved, qp at constant
pressure is also called the heat of reaction or
enthalpy of reaction, ∆rH.
In an exothermic reaction, heat is evolved, and
system loses heat to the surroundings.
Therefore, qp will be negative and ∆rH will
also be negative.
Similarly in an endothermic reaction, heat is
absorbed, qp is positive and ∆rH will be
positive.
ENTHALPY
CHANGE
Enthalpy of Reaction : The difference between the enthalpies of
the products and the reactants when molar quantities of the
reactants, as indicated by the balanced chemical equation, react
completely. Thus :
Enthalpy of formation (∆Hf) : Enthalpy of heat of formation
of a compound is the change in heat content or enthalpy
(∆H) when one mol of the compound is formed from its
elements in their commonly occurring (or standard) states.
Enthalpy of Combustion (∆HC) : Heat of combustion
is the enthalpy of reaction when 1 mol the substance
is completely burnt in the excess of air or oxygen.
Heat of combustion is always negative, because heat
is always evolved
Importance of Heat of Combustion : It can be used to
calculate the calorific value of a fuel (i.e., amount of heat
produced when 1 g of the substance is completely burnt).
It is expressed in J/g or kJ/g or cal/g.
It may be employed to calculate the heat of reaction when
heat of combustion of every reactant and product is known.
Enthalpy (or heat) of solution : Enthalpy of solution is the
enthalpy change (∆Hsol) when 1 mol of the substance is dissolved
in a solvent so that further dilution does not give any change in
enthalpy.

In terms of lattice energy (∆HU) and heat of hydration (∆Hhyd) of

ions, the heat of solution can be expressed as :
Standard Enthalpy of Reaction :
* The enthalpy of reaction at 298 K and 1 atm. pressure
when the reactants and products are in their standard states
is called
standard enthalpy of reaction.
(a) Enthalpy (or heat) of Fusion : Enthalpy of fusion of a substance is
"the heat change in converting 1 mole of it from the solid
to the liquid phase at its melting point."
Heat of fusion is always positive, because heat is needed to overcome
the intermolecular forces between constituent particles of a solid.
heat of fusion of water, H2O(s) = H2O(l ), is + 0.6 kJ mol–1.
(b) Enthalpy (or heat) of vaporization : Enthalpy of vaporization is the
heat change in converting 1 mol of the substance from liquid to the
gaseous state at its boiling point.
Ex, heat of vaporization of water, H2O(l) = H2O(g), is 42.0 kJ mol–1.
Enthalpy or heat of sublimation : Enthalpy or heat of sublimation of a
solid is heat change in converting 1 mol of a solid directly into its
vapour at a given temperature, below its melting point.
Ex, heat of sublimation of iodine, I2(s) = I2(g), is 62.4 kJ/mol
(d) Enthalpy of transition (or heat of transition) : Enthalpy of
transition is the enthalpy change (∆H) when 1 mol of an element
changes from one allotropic form to another.
Ex: C(diamond) = C(amorphous) ; ∆H = + 3.3 kcal/mol
HESS’S LAW OF CONSTANT HEAT SUMMATION
Thermochemical equations :
* When a balanced chemical equation not only indicates the
quantities of the different reactants and products but also indicates
the amount of heat evolved or absorbed, is called as
thermochemical equation.
Application of Hess’s law :
It helps us in calculations of :
* Heat of formation (∆Hf) of many substances which
cannot be synthesized directly from their elements.
* Bond energies
* Enthalpy changes of slow reactions and
* Enthalpy of transformation, say from one allotropic
from to the other.
SPONTANEOUS AND NON-SPONTANEOUS PROCESSES
Spontaneous Process :
* The process which can take place by itself or after proper initiation, under the given set of
conditions, is called a spontaneous process.” the term “Spontaneous” simply means that given
process is feasible or possible. Therefore, Spontaneous processes are also called as feasible or
probable processes. Spontaneous process may or may not be instantaneous. But all
instantaneous process are spontaneous.
* e.g. (i) Processes which occur on their own without proper initiation.
(a) HCl(g) + NH3(g) = NH4Cl (s)
(b) H2O (l) = H2O(g)
Water keeps on evaporating from ponds and rivers etc.
(ii) Processes which require initiation
(a) In domestic oven, once coal (carbon) is ignited it keeps on burning C (s) + O2 (g) = CO2
(g)
(b) CH4(g) + 2O2(g) = CO2(g) + 2H2O(l)
Non-Spontaneous Process:A process which has no tendency to occur or
which is made to occur only if energy from outside is continuously supplied e.g.
(i) Decomposition of water into H2 and O2 is non-spontaneous. However, water
can be decomposed by passing an electric
current through it, in a process called electrolysis.
H2O (l) = 2H2 (g) + O2 (g)
The process will continue as long as electric current is supplied, and as soon as
the supply of electricity is cut off the
decomposition stops.
(ii) Water cannot be made to flow up the hill, without the help of a machine.
(iii) Gold ornaments do not get tarnished in air even after a number of years.
This shows that gold does not combine with
oxygen in the air.
 ENTROPY
It may be defined as the measure of degree of randomness in the
molecule. It is represented by the symbol S.
Characteristic of Entropy :
(i) It is a state of function (ii) It is an extensive property
The change in entropy during a process when a system undergoes
charge from one state to another is represented as ∆S.

Chemical reaction

Calculation of entropy change

Second law of thermodynamics
* According to it all forms of energy can be converted into heat, but
no process is available for converting the heat so obtained
completely to other forms of energy.
An other statement is : In a spontaneous process, the entropy of
universe increases and remains unchanged in an equilibrium process
Gibb’s free energy
* It is defined as, the energy available in the system for conversion into useful work.
* It is that thermodynamic quantity of a system, the decrease in whose value during a
process is equal to the useful work done by the system. G = H – TS
where H is the heat content, T is the absolute temperature and S is the entropy of the
system.
As before, for the isothermal processes, we have ∆G = ∆H – T ∆S (Gibb’s Helmotz
equation)
∆H = H2 – H1 is the enthalpy change of the system
* Deriving the criteria for spontaneity from Gibbs-Helmholtz equation. According to
Gibbs-Helmholtz equation ∆G = ∆H – T ∆S
* The equation combines in itself both the factor which decide the spontaneity of a process,
namely
(i) the energy factor, ∆H (ii) the entropy factor, T ∆S
* Depending upon the signs of ∆H and T ∆S and their relative magnitudes, the following
different possibilities arise.
Standard free energy change (∆G°) :
* The standard free energy change ∆G° is defined as the free energy change for
a process at a specified temperature in which the reactants in their standard
state are converted to the products in their standard state.
* It is denoted by ∆G°.
* Like the standard enthalpy of formation of an element “the standard free
energy of formation of an element in its standard
The standard free energy of formation of a compound (∆Gº)
* The standard free energy of formation of a compound is the free energy
change of the reaction when 1 mol of the compound is formed from its
constituent elements in their standard states.
Phase transitions :
* At the transition temperature, e.g., at the melting or the boiling point, the
system is at equilibrium, (∆G = 0), therefore, the equation ∆G = ∆H – T ∆S

H2O (s) = H2O (l) H2O (l) = H2O (g)