UNIT -4: CHEMICAL THERMODYNAMICS
Basic thermodynamic terms:
System: A system is defined as the specified part of the universe that is separated from the rest
of the universe by a boundary.
Surroundings: Anything outside the system is called the surroundings. The system is separated
from the surroundings by the boundary. The boundary may be either fixed or moving.
Types of system:
1. Closed system: There is no mass transfer across the system boundary. Energy transfer may be
there.
2. Open system: There may be both mass and energy transfer across the boundary of the
system.
3. Isolated system: There is neither mass nor energy transfer across the boundary of the system.
State of the system and state variable: The state of a system means the conditions of the
system. It is described in terms of certain observable properties which are called the state
variables, for example, temperature (t), pressure (p), and volume (v).
State function: Its value during the process depends only upon the initial state and final state of
the system and does not depend on the path by which the change has been brought about.
Macroscopic system and its properties: If as system contains a large number of chemical
species such as atoms, ions, and molecules, it is called macroscopic system.
Extensive properties: These properties depend upon the amount of matter contained in the
system. Examples are; mass, volume, heat capacity, internal energy, enthalpy, entropy, Gibb's
free energy.
Intensive properties: These properties don’t depend on the amount of the substance present in
the system, for example, temperature, refractive index, density, surface tension, specific heat,
freezing point, and boiling point.
Thermodynamic processes: The route by which the change of state of a system is brought
about is called a process. Thermodynamic process can be occurred when the system changes
from one state (initial) to another state (final).
Types of thermodynamic processes:
1. Isothermal process: When the temperature of a system remains constant during a process,
we call it isothermal. Heat may flow in or out of the system during an isothermal process.
1
2. Adiabatic process: No heat can flow from the system to the surroundings or vice versa.
3. Isochoric process: It is a process during which the volume of the system is kept constant.
4. Isobaric process: It is a process during which the pressure of the system is kept constant.
5. Reversible processes: A process which is carried out infinitesimally slowly so that all
changes occurring in the direct process can be exactly reversed and the system remains almost in
a state of equilibrium with the surroundings at every stage of the process.
INTERNAL ENERGY (E)
Each substance is associated with a certain quantity of energy that depends upon the factors such
as temperature, pressure, volume and chemical nature. This energy is known as internal energy.
Characteristics of internal energy (E)
1. E is not measurable quantity. Only ∆E is measurable (∆E = Efinal – Einitial).
2. It is an extensive property.
3. E for cyclic process is zero.
4. It is a state function.
SPECIFIC HEAT AND HEAT CAPACITY
Specific heat is the quantity of heat energy required to raise the temperature of one gram of a
substance through one degree Celsius. It is an intensive property.
Heat capacity of a substance is defined as the quantity of heat energy required to raise the
temperature of the given quantity of substance from lower temperature to the higher
temperature.
ENTROPY (S)
Entropy is a measure of disorder or randomness in a system. It is expressed in Cal/K or J/K. It is
expressed by the equation
∆S = q/T
Where, ∆S is the change in entropy
q is the amount of heat exchanged
T is the temperature.
Entropy changes in physical transformation:
2
The general formula for entropy changes in physical transformation is written as
∆S = ∆H/T = molar heat of reaction/Temperature of physical transformation
If ∆H is expressed in heat of reaction per gram, then
∆S = ∆H/T = (heat of reaction x molecular weight of substance)/Temperature of physical
transformation
Example:
1. Solid to liquid state (Fusion)
∆Sf = ∆Hf/Tf
2. Liquid to Vapor (Vaporization)
∆Sv = ∆Hv/Tb
Tb = boiling point.
3. Sublimation reaction
∆Ss = ∆Hs/Ts
4. Phase transformation (tr):
∆Str = ∆Htr/Ttr
FREE ENERGY (G) AND WORK FUNCTION (A)
G and A are state functions. Since G and A depends on the quantity of matter, they are extensive
properties. They are defined by following equations.
G = H – TS
A = E – TS
Significance of free energy (G)
1. It helps in calculating net work done by the system.
2. It helps in predicting the spontaneity of a process.
3. It is applicable to equilibrium system also.
___________________________________________________________________________
