Thermodynamics

By Er. Kabita Ojha

 Thermodynamics
⚫ It is the Branch of physics that deals with work, heat, and
temperature and their relation to energy, physical
properties of matter, radiation etc.
⚫ Thermodynamics deals with the inter-relationship
between heat and work.
⚫ It is concerned with the inter conversions of one kind of
energy into another without actually creating or
destroying the energy.
Importance of Thermodynamics:
⚫ It helps to predict whether any given chemical reaction
can occur under the given set of conditions.
⚫ It helps in predicting the extent of reaction before the
equilibrium has attained.
⚫ It helps to reduce some important laws of chemical
equilibrium, distribution law.
Terms Used in Thermodynamics:
System:
⚫ It is a part of the universe which is separated from the rest
of the universe by real or imaginary boundaries.
⚫ There are main three types of system based on the nature of
the movement of energy and matter in or out of the system.
1) Open System
2) Closed System
3)Isolated System
Surroundings:
⚫ Everything in the universe that is not the part of the
system and can interact with it is called as surroundings.
⚫ The rest of the universe constitute the surrounding.
Boundary:
⚫ Anything (fixed or moving) which separates the system
from its surroundings is called boundary.
⚫ The boundaries of a system can be fixed or movable.
⚫ Mathematically, the boundary has zero thickness, no
mass, and no volume.
Open System:
⚫ A system is said to be open if it can change both energy
and mass with its surroundings.
⚫ For eg. a open beaker containing an aqueous salt solution
represents open system. Here, matter and heat can be
added or removed simultaneously or separately from the
system to its surroundings.
⚫ All living things (or systems) are open systems because
they continuously exchange matter and energy with the
surroundings.
Closed System:
⚫ A system which permits the exchange of energy but not
mass, across the boundary with its surroundings is called
a closed system.
For Eg: When we keep a closed bottle of water in the
fridge, the quantity of water in the bottle remains the
same. However, it loses energy to the surrounding as a
result of which the temperature of the water inside it
goes down.
Isolated System:
⚫ A system which can exchange neither energy nor
matter with its surroundings is called an isolated
system.
⚫ For example, a sample in a sealed thermos flask with
walls made of insulating materials represents an
isolated system.
⚫ According to Physical State of matter, system are of
two types:
1) Homogeneous System:
⚫ A system is said to be homogeneous if the physical
states of all its matter are uniform.
⚫ For eg. mixture of gases, completely miscible mixture
of liquids etc.
2) Heterogeneous System
⚫ A system is said to be heterogeneous, if its contents
does not possess the same physical state.
⚫ For eg: immiscible liquids, solid in contact with an
immiscible liquid, solid in contact with a gas, etc.
⚫ Macroscopic properties of system
⚫ The properties which are associated with bulk or macroscopic
state of the system such as pressure, volume, temperature,
concentration, density, viscosity, surface tension, refractive index,
colour, etc. are called as macroscopic properties.
⚫ Types of Macroscopic Properties:
⚫ Extensive properties:
⚫ The properties that depend on the mass or size of the system are
called as extensive properties.
⚫ Examples: volume, number of moles, mass, energy, enthalpy,
internal energy etc.
⚫ The value of the extensive property is equal to the sum of
extensive properties of smaller parts into which the system is
divided.
Intensive Properties:
⚫ The properties that are independent of the mass or
size of the system are known as intensive properties.
⚫ For eg: mass, volume, heat capacity are extensive
properties while density, pressure, temperature,
specific volume, specific heat are intensive properties.
⚫ For eg. refractive index, surface tension, density,
temperature, boiling point, freezing point, viscosity
etc., of the system.
⚫ These properties do not depend on the number of
moles of the substance in the system.
Thermodynamic Equilibrium
⚫ A system is said to be in equilibrium if its macroscopic
properties like temperature, pressure do not change with
time.
Thermodynamic Process:
⚫ A thermodynamic process is said to occur when the system
changes from one state to another.
⚫ Isothermal process:
⚫ When a process is carried out in such a manner that the
temperature remains constant throughout the process, it is
called isothermal process.
⚫ Heat can flow from the system to the surrounding and vice
versa in order to keep the temperature of the system
constant.
Adiabatic process:
⚫ When a process is carried out in such a manner that no
heat can flow from the system to the surrounding or
vice versa i.e. the system is completely insulated from
the surrounding, it is called adiabatic process.
Isochoric process:
⚫ It is a process during which the volume of the system is
kept constant.
⚫ Isobaric Process:
⚫ It is a process during which the pressure of the system
is kept constant.
Reversible process:
⚫ 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 surrounding at every
stage of the process.
⚫ A process which is not carried out infinitesimally
slowly so that the successive steps of the direct process
cannot be retracted and any change in the external
condition disturbs the equilibrium.
 Laws of Thermodynamics
Zeroth Law of Thermodynamics:
⚫ This law states that when two bodies are in thermal equilibrium
with a third body, they are also in thermal equilibrium with each
other.
⚫ When two systems are each in thermal equilibrium with the third
system, then the two systems are also in thermal equilibrium with
one another.
⚫ Eg: Consider three bodies A, B, C, if A and B are individually in
thermal equilibrium with a third body C, then, the bodies A and B
also will be in thermal equilibrium with each other.
⚫ If two bodies are in thermal equilibrium then they will have same
temperature, here all bodies are in thermal equilibrium with each
other, hence the value of temperature for three bodies is same.
First Law of Thermodynamics:
⚫ This law states that the heat and mechanical work are
mutually convertible. According to this law, a definite
amount of mechanical work is needed to produce a
definite amount of heat and vice versa.
⚫ This law also states that the energy can neither be
created nor destroyed, though it can be transformed
from one form to another.
⚫ According to this law, the energy due to heat supplied
(Q) must be balanced by the external workdone (W)
plus the gain in internal energy (E) due to rise in
temperature. In other words,

Q= W + E
Disadvantages of First Law of Thermodynamics:
⚫ 1st law says that " All the amount of heat is converted into
work." But it is impossible to convert all the heat into work,
there will be always some losses to surroundings, only
particular quantity of heat is converted into work, remaining
heat is wasted to sink.
⚫ It does not define the direction of energy transfer i.e. whether
the energy is conserved from hot body to cold or cold body to
hot body.
⚫ Due to the above reasons, the second law of thermodynamics
was developed.
Second Law of Thermodynamics:
⚫ This law states that there is a definite limit to the amount
of mechanical energy, which can be obtained from a given
quantity of heat energy.
⚫ There are two sub laws in second law to overcome all the
disadvantages of first law, they are:
1) Kelvin-Plank Statement
2) Clausius Statement
Kelvin-Plank Statement
⚫ It is impossible to construct an engine working on a cyclic
process, whose sole purpose is to convert heat energy into
work. According to this statement, the second law of
thermodynamics is sometimes called as law of
degradation of energy.
⚫ All the heat energy given to an engine cannot be
converted into useful work, some amount of heat
energy will be rejected to the surroundings or sinks.
Clausius Statement:
⚫ It is impossible for a self acting machine working in a
cyclic process, to transfer heat from a body at a lower
temperature to a body at a higher temperature without
the aid of an external agency.
⚫ Heat can not flow from cold reservoir to hot reservoir
without any external work, but heat can flow from hot
reservoir to cold reservoir without any external work.
Otto Cycle
⚫ The cycle in which heat is added at constant volume is
the prototype of the actual cycle used in engines with
spark ignition (automobiles, aircraft, etc.)
⚫ Such engines are distinguished by compression of the
fuel mixture (mixture of fuel vapour with air).
⚫ It is also known as constant volume cycle.
⚫ Pressure-volume and temperature-entropy diagram of
otto cycle is shown below:
Otto Cycle
⚫ This cycle consists of two isentropic processes and two
constant volume processes.
⚫ The isentropic line 1-2 corresponds to compression of the
combustible mixture, constant volume line 2-3 to
combustion of mixture (addition of heat), resulting in a rise
in pressure to P3.
⚫ After this the products of combustion expand isentropically
(process 3-4), and during constant volume (process 4-1)
heat is removed from the gas.
Heat and Work corresponding to each process:
⚫ Process 1-2: Isentropic Compression process:
⚫ Heat Input: 0
⚫ Work Output: -Cv (T2-T1)
Process 2-3: Constant Volume Process
⚫ Heat Input: Cv (T3-T2)
⚫ Work output: 0
Process 3-4: Isentropic Expansion Process
⚫ Heat Input: 0
⚫ Work Output: -Cv (T4-T3)
Process 4-5: Constant Volume Process
⚫ Heat Input: Cv (T1-T4)
⚫ Work Output: 0
⚫ Heat Addition at constant volume is given by
Q (A)= m*Cv (T3-T2)
if m= 1 kg
Q (A)= Cv (T3-T2) .......KJ/Kg
Heat rejection at constant volume is given by:
⚫ Q (R)= m*Cv(T4-T1)
⚫ if m=1 kg
⚫ Q (R)= m*Cv(T4-T1).....KJ/Kg
⚫ Work developed or work done by the engine:
⚫ W.D.= Heat Added-Heat Rejected = Qa- Qr
⚫ W.D.= Cv [(T3-T2)-(T4-T1)]
⚫ Efficiency of Otto Cycle is given by:
⚫ η = W.D/Q(A)
⚫ We know for reversible adiabatic compression process
1-2:

⚫ Similarly for reversible adiabatic expansion process 3-4,

⚫ Finally, Efficiency is:

Diesel Cycle
⚫ The cycle in which heat is added at constant pressure
is known as Diesel cycle. It consists of two isentropic,
one constant pressure and one constant volume.
⚫ This cycle is typical of heavy fuel engines referred to as
Diesel.
⚫ Air is compressed along isentropic lines 1-2, resulting
in a rise of temperature to that required for
self-ignition of fuels.
⚫ The fuel is injected into the compressed air and
combustion takes place during constant pressure
process 2-3 (addition of heat).
⚫ Next are the processes of isentropic expansion 3-4 and
constant-volume exhaust 4-1 (removal of heat).
Heat added at constant pressure is given by:
⚫ Q (A)= m Cp (T3-T2)
⚫ Q (A)= Cp (T3-T2) [m=1 kg]
⚫ Heat Rejected at constant volume is given by:
⚫ Q (R)= m Cv (T4-T1)
⚫ Q (R)= Cv (T4-T1) [m=1 kg]
⚫ Workdone= Cp (T3-T2)-Cv (T4-T1)
Therefore, ideal efficiency or air standard efficiency of DIESEL cycle
can be calculated as:
⚫ η = Work output/ Heat absorbed

⚫ where CP/ Cv = γ (Ratio of specific heats at constant

pressure and constant volume)
⚫ We know that for reversible adiabatic compression process 1-2.
⚫ T2 = T1rγ-1
⚫ For constant pressure process 2-3,
⚫ T3 = ρT1rγ-1
⚫ From reversible adiabatic expansion process 3-4,

⚫ ∵V4 = V1 = Total volume and V2 =clearance volume

⚫ T4 = ρ γ T1
⚫ Now putting the values of equation (ii), (iii) & (iv) in (i):-

⚫ This is air standard efficiency of DIESEL cycle and from

⚫ Form the expressions of efficiency of OTTO & DIESEL
cycles it is clear that as the value of ρ & r each is always
more than 1.
⚫ So for same compression ratio, the efficiency of an
OTTO cycle is more than that of DIESEL cycle.
⚫ But in actual practice, due to practical reasons, the
compression ratio of an OTTO cycle is limited between
7 to 9.
⚫ While for a Diesel cycle, it is not limited and varies in
the higher range of 16 to 22.
⚫ Therefore practically, a Diesel engine is more efficient
than a Petrol Engine, due to higher value of
compression ratio.
Difference Between Otto & Diesel Cycle
Otto Cycle
Otto cycle is given by the Nicolas Otto in
1876.
It has low thermal efficiency.
It is also called Constant Volume Cycle.
It is ideal cycle for petrol engine.
Otto cycle engine used spark plug to ignite
the air fuel mixture.
This cycle has comparatively low
compression ratio. It compresses the
mixture up to 11:1 ratio.
A mixture of air and fuel is entered in
Diesel Cycle
Diesel Cycle is given by Dr. Rudolph Diesel
in 1897.
It has high thermal efficiency.
It is also called a Constant Pressure Cycle.
It is ideal cycle for diesel engine.
Fuel automatically ignites due to high
temperature of compressed gas.
Diesel cycle has high compression ratio. It
compresses the mixture up to 22:1 ratios.
Only air is entered in suction stroke.
1. Otto cycle is a........
a) Constant pressure cycle
b) Constant volume cycle
c) Constant temperature cycle
d) Constant entropy cycle
b) Constant volume cycle
2. An actual engine is to be designed having same efficiency
as the Carnot Cycle. Such a proposition is
a) Feasible
b) Impossible
c) Possible
d) Possible, but with lot of sophistications
d) Possible, but with lot of sophistications
3. For the same compression ratio, the efficiency of diesel
cycle is........ Otto cycle
a) Greater than
b) Less than
c) Equal to
d) None of the above
b) Less than
4. For the same maximum pressure and temperature
a) Otto cycle is more efficient than Diesel cycle
b) Diesel Cycle is more efficient than Otto cycle
c) Dual cycle is more efficient than Otto and Diesel cycles
d) Dual cycle is less efficient than Otto and Diesel cycles.
b) Diesel Cycle is more efficient than Otto cycle
5. measurement of a thermodynamics property called as
temperature, that based on the..........
a) Zeroth law of thermodynamics
b) First law of thermodynamics
c) Second law of thermodynamics
d) Third law of thermodynamics
a) Zeroth law of thermodynamics
6. Second law of thermodynamics is defined the....
a) Enthalpy
b) Entropy
c) Internal energy
d) Pressure
b) Entropy
7. Zeroth law of thermodynamics.
a) Deals with Reversible and irreversible process.
b) It states that if two system are equilibrium with third system and
they also thermal equilibrium with each other.
c) Deals with heat and work transfer
d) Deal with conservation of energy.
b) It states that if two system are equilibrium with third system and
they also thermal equilibrium with each other.

8. Heat transfer take place according to ......

a) Zeroth law of thermodynamics
b) First law of thermodynamics
c) Second law of thermodynamics
d) Third law of thermodynamics
c) Second law of thermodynamics
9. Refrigeration is working on......
a) Zeroth law of thermodynamics
b) First law of thermodynamics
c) Second law of thermodynamics
d) Third law of thermodynamics
c) Second law of thermodynamics
10. The state of a thermodynamic system is represented by
a) Pressure, volume and temperature
b) Volume only
c) Pressure only
d) Number of moles
a) Pressure, volume and temperature
11. Which of the following is incorrect regarding first law of
thermodynamics?
a) It introduces the concept of entropy
b) It introduces the concept pf internal energy
c) It is applicable to cyclic processes
d) It is a restatement of principle of conservation of energy
a) It introduces the concept of entropy
12. Kelvin-Planck’s law deals with
a) Conservation of work
b) Conservation of heat
c) Conservation of work into heat
d) Conservation of heat into work
d) Conservation of heat into work
13. According to Clausius statement....
a) Heat is flow from hot body to cold body.
b) Heat is flow from cold body to hot body
c) Heat is not flow
d) None of these
a) Heat is flow from hot body to cold body.
14. The system that does not allow the heat to pass through its
boundary between the system and surroundings is called as
system.
a) adiabatic
b) open
c) isothermal
d) Close
a) adiabatic