DAV PUBLIC/MODEL SCHOOL

MLL
SUBJECT: CHEMISTRY CLASS:XI
CHAPTER: THERMODYNAMICS

Relevant Concepts & Basic Ideas:

Thermodynamics deals with the relationship between various forms of energy in
a process. Thermodynamics deals with macroscopic properties. This chapter introduces a
major subsidiary thermodynamic property, the Gibbs free energy which lets us express
the spontaneity of a process in terms of the properties of the system. This chapter helps to
explain why gases expand or diffuse.

System and Surrounding

1. System: A system can be defined as where the observations were made, it is the part of the
universe.
2. Surroundings: Surrounding can be defined as the part other than the system is, surrounding.
The system and surroundings can be differentiated by a wall called a boundary.
Types of System:
1. Open system: System can be open if it can exchange both energy and matter with
surroundings.
2. Closed system: System can be closed if it can exchange energy but not matter with
surroundings.
3. Isolated system: System can be isolated if it can neither exchange energy nor matter
with surroundings.
Extensive Properties
The properties which depend upon mass of the substance is known as extensive
properties i.e., mass, volume, internal energy, enthalpy etc.
Intensive Properties
The properties which are independent of mass of the substance is known as intensive
Properties i.e., temperature, pressure, density, refractive index.

Extensive properties Intensive Properties

Volume Molar volume

Number of Moles Density

Mass Refractive index

 Free Energy (G) Surface tension

Entropy Viscosity

Enthalpy Free energy per mole

Internal Energy (E & U) Specific heat

Pressure, Temperature, Boiling point, freezing Point. Etc.

Heat Capacity

Thermodynamic State of a System

A state is the condition of a system as specified by its physical 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.
State Functions
The thermodynamic parameters which depends only on initial and final states of system
is known as state function. i.e., internal energy(E), Enthalpy (H), entropy (S), Gibb's freeenergy
(G).
Path Functions
The thermodynamic parameters where value does not depend merely on initial and final
state but depends upon the path followed is known as path function. i.e., heat (q), work
done (W).

Thermodynamic Process
The sequence followed to change one thermodynamic state of a system into another is
called thermodynamic process. The types of thermodynamic processes are:
1. Isothermal process: It is the process in which temperature is kept constant means
temperature of initial and final state of system along with entire path of process is
same.
2. Isobaric process: It is the process in which pressure is kept constant for entire
process.
3. Isochoric process: It is the process in which volume is kept constant.

4. Adiabatic process: The process in which heat transaction across boundary is not
allowed.
5. Reversible process and Irreversible process: In thermodynamics, a process is
said to be reversible when energy change in each step of the process can be
reversed by changing the variables such as pressure, volume or temperature
acting on them. In such a process, the driving and opposing forces differ
infinitesimally and the process can be reversed completely by increasing the
opposing force by an infinitesimally small amount.
Any process which does not take place in the above mentioned manner is said to
be an irreversible process. In an irreversible process the driving and opposing
force differ by a large amount.

6. Cyclic process: It is the process which runs in close loop, means process in which initial and
final states are identical.
Internal Energy :
Every substance is associated with definite amount of energy that is called internal
energy. It is an extensive property and a state function. Internal energy of ideal gases is a
function of temperature only.
Pressure-Volume Work :
It is the work done when the gas expands or contracts against the external pressure.
Consider a cylinder containing one mole of an ideal gas fitted with a frictionless and
Weightless piston having an area of cross-section A. The total volume of the gas is Vi and the
initial pressure of the gas inside P.

Let the external pressure acting on the piston is Pex. If the external pressure Pex is slightly greater
than P piston moves downward till the pressure inside the cylinder becomes equal to Pex. Let this
change be achieved in a single step and the final volume be Vf. During this
compression, suppose the piston moves a very small distance Δl. Thus, the work done on
the gas is given by,
ω=−∫ Pexdv
dv= Vf-Vi
Heat
The change in internal energy of a system can be brought about by the transfer of heat
from the surroundings to the system or vice-versa. This exchange of energy between the
system and surroundings is possible as a result of the temperature difference between
them. This energy called heat is represented by Q.
Zeroth Law of Thermodynamics
When two different system are in thermal equilibrium with 3rd system separately then will also in
thermal equilibrium with each other.

First Law of Thermodynamics

The first law of thermodynamics states that energy can neither be created nor destroyed.
According to first law of thermodynamics,
ΔU = q + W
Where, Q = Heat change
W = Work done
ΔU = Change in internal energy.
The sign conventions are given as;
Work done by the system = – W
Work done on the system = + W
Heat flows into the system = + Q
Heat flows out of the system = – Q

Enthalpy (H)
The total heat content of a system at constant pressure is known as its enthalpy.
Mathematically it is the sum of internal energy and pressure-volume energy
ΔH = ΔU + PΔV
It is an extensive property and a state function. Increase in enthalpy H is equal to heat
absorbed at constant pressure.
Heat Capacity
Heat capacity is amount of heat require to raise the temperature of a system by unity. It is
represented as "C". It is an extensive property and temperature dependent
Types of heat capacity
1. Specific heat: For 1 gram system the heat loose or gained by system to bring one
unit change in temperature is called specific heat denoted by 's'. specific heat is
the intensive property.
S= C/ m
2. Molar heat capacity: It is heat capacity for a system having 1 mole of material. It is
represented as Cm. It is an intensive property.
Cm= C/m
3. Heat capacity at constant volume: Heat capacity of a system in isochoric condition
is called heat capacity at constant volume, it is represented as Cv means molar
heat capacity at constant volume.
Cv= dU/dT
4. Heat capacity at constant pressure: Heat capacity of a system in isobaric
condition. It is represented by Cp means molar heat capacity at constant pressure.
Cp= dH/dT
Relation between Cp and Cv
We know that,
ΔH = ΔU + PΔV .....(i)
As per ideal gas equation
PΔV = RΔT .....(ii)
From (i) and (ii)
ΔH = ΔU + RΔT
ΔH/ΔT= ΔU/ΔT+R
Cp = Cv + R
Cp – Cv = R
Hess’s Law
According to Hess's law, If a reaction takes place in several steps then its standard
reaction enthalpy is the sum of the standard enthalpies of the intermediate reactions into
which the overall reaction may be divided at the same temperature.
1st method: C(s)+O2(g)→CO2(g)=ΔH
2nd method: C(s)+1/2O2(g)→CO(g)=ΔH1
CO(s)+1/ 2O2(g)→CO2(g)=ΔH2
According to Hess's law,
ΔH=ΔH1+ΔH2
Application of Hess's Law
1. Calculation of enthalpy of formation.
2. Determination of standard enthalpies of reactions.
Bond Dissociation Energy
The energy required to break one mole bond of a particular type in gaseous molecule is
known as bond dissociation energy. For example, we consider the dissociation of water,
H−OH(g)→H(g)+OH(g) ΔH =498 kJ/mol
Second Law of Thermodynamics
This states that the entropy of the universe always increases in every spontaneous
(natural) change.
Enthalpy Changes During Phase Transformation Enthalpy of fusion: Enthalpy of fusion is the
heat energy or change in enthalpy when one mole of a solid at its melting point is converted into
liquid state.
Enthalpy of vaporisation: It is defined as the heat energy or change in enthalpy when one mole of
a liquid at its boiling point changes to gaseous state.
Enthalpy of Sublimation: Enthalpy of sublimation is defined as the change in heat energy or
change in enthalpy when one mole of solid directly changes into gaseous state at a temperature
below its melting point.
Standard Enthalpy of Formation Enthalpy of formation is defined as the change in enthalpy in
the formation of 1 mole of a substance from its constituting elements under standard conditions of
temperature at 298K and 1 atm pressure.
Enthalpy of Combustion: It is defined as the heat energy or change in enthalpy that accompanies
the combustion of 1 mole of a substance in excess of air or oxygen. CO (g) + ½ O2 (g) CO2(g)
ΔHO = -283 KJ
Hess’s Law of Constant Heat Summation The total amount of heat evolved or absorbed in a
reaction is same whether the reaction takes place in one step or in number of steps
Born-Haber Cycle It is not possible to determine the Lattice enthalpy of ionic compound by direct
experiment. Thus, it can be calculated by following steps. The diagrams which show these steps is
known as Born-Haber Cycle.

• Spontaneity Spontaneous Process: A process which can take place by itself or has a tendency to
take place is called spontaneous process. Spontaneous process need not be instantaneous. Its actual
speed can vary from very slow to quite fast.
A few examples of spontaneous process are: (i) Common salt dissolves in water of its own. (ii)
Carbon monoxide is oxidised to carbon dioxide of its own.
• Entropy (S) The entropy is a measure of degree of randomness or disorder of a system. It is an
extensive property and a state function.. Its value depends upon the amount of substance
present in the system.
Entropy of a substance is minimum in solid state while it is maximum in gaseous state. The change
in entropy in a spontaneous process is expressed as ΔS

• Gibbs Energy and Spontaneity

A new thermodynamic function, the Gibbs energy or Gibbs function G, can be defined as
G = H-TS ΔG = ΔH – TΔS Gibbs energy change = enthalpy change – temperature x entropy
change ΔG gives a criteria for spontaneity at constant pressure and temperature,
i If ΔG is negative (< 0) the process is spontaneous.
ii (ii) If ΔG is positive (> 0) the process is non-spontaneous.
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