Second Law of Thermodynamics

SECOND LAW OF THERMODYNAMICS
ESSENCE OF SECOND LAW

First law deals with conservation and conversion of energy but fails to state the
conditions under which energy conversion is possible. The second law is
directional law which would tell if a particular process occurs or not and how
much heat energy can be converted into work.
THERMAL RESERVOIR
A thermal reservoir is the part of environment which can exchange heat energy
with the system. It has sufficiently large capacity and its temperature is not
affected by the quantity of heat transferred to or from it. The temperature of a heat
reservoir remains constant. The changes that do take place in the thermal reservoir
as heat enters or leaves are so slow and so small that processes within it are quasi-
static. The reservoir at high temperature which supplies heat to the system is called
HEAT SOURCE. For example: Boiler Furnace, Combustion chamber, Nuclear
Reactor. The reservoir at low temperature which receives heat from the system is
called HEAT SINK. For example: Atmospheric Air, Ocean, river.
HEAT ENGINE
A heat engine is a device that operates in a cycle in which
heat is transferred from heat source to heat sink, for
continuous production of work.
Both heat and work interaction take place across the
boundary of the engine. It receives heat Q1 from a higher
temperature reservoir at T1. It converts part of heat Q1 into
mechanical work W1. It rejects remaining heat Q2 to the sink
at T2. There is a working substance which continuously flow
through the engine to ensure continuous/cyclic operation.
Fig 1
PERFORMANCE OF HEAT ENGINE
It is measured by thermal efficiency which is the degree of useful conversion of
heat received into work.
ηth = Net work output/ Total Heat supplied = W/Q1 = (Q1 – Q2) / Q1
ηth = 1 – Q2/Q1 = 1 – T2/T1; Since Q1/Q2 = T1/T2
OR
Thermal efficiency is defined as the ratio of net work gained (output) from the
system to the heat supplied (input) to the system.
1
HEAT PUMP
Heat pump is the reversed heat engine which removes
heat from a body at lower temperature and transfers
heat to a body at higher temperature.
It receives heat Q2 from atmosphere at temperature T2
equal to atmospheric temperature. It receives power in
the form of work ‘W’ to transfer heat from low
temperature to higher temperature. It supplies heat Q1
to the space to be heated at temperature T1.
PERFORMANCE OF HP: It is measured by the

coefficient of performance (COP). Which is the ratio of
amount of heat rejected by the system to the
mechanical work received by the system.
Fig 2
(COP)HP = Q1/W = Q1/ (Q1 – Q2) = T1/ (T1 – T2)
REFRIGERATOR
The primary function of a heat pump is to transfer heat
from a low temperature system to a high temperature
system, this transfer of heat can be utilized for two
different purpose, either heating a high temperature
system or cooling a low temperature system. Depending
upon the nature of use. The heat pump is said to be acting
either as a heat pump or as a refrigerator. If its purpose is
to cause heating effect it is called operating as a H.P. And
if it is used to create cold effect, the HP is known to be
operating as a refrigerator.
(COP)ref = Heat received/ Work Input = Q2/W
= Q2/ (Q1 – Q2)
(COP)ref = Q2/ (Q1 – Q2) = T2/ (T1 – T2)
Fig 3
(COP)HP = (COP)ref + 1
COP is greater when heating a room than when cooling it.
2
KELVIN PLANK STATEMENT
It is impossible to construct such
a H.E. that operates in cycle and
converts all the heat supplied to it
into an equivalent amount of
work. The following conclusions
can be made from the statement.
1. No cyclic engine can convert
whole of heat into equivalent
work.
2. There is degradation of energy Fig 4
in a cyclic heat engine as
some heat has to be degraded
or rejected. Thus second law
of thermodynamics is called
the law of degradation of Fig 5
energy.
3. For satisfactory operation of a
heat engine there should be at
least two heat reservoirs
source and sink.
CLAUSIUS STATEMENT
It is impossible to construct such a H.P. that operates in a cycle and transfers heat
from a colder body to a hotter body without the aid of an external agency.
3
CARNOT CYCLE
Carnot, showed that the temperatures of heat source and
heat sink are the basis for determining the thermal
efficiency of a reversible cycle. He showed that all such
cycles must reject heat to the sink and efficiency is
never 100%. To show a non-existing reversible cycle,
Carnot invented his famous but a hypothetical cycle Fig 6
known as Carnot cycle.
Carnot cycle consists of two isothermal and two
reversible adiabatic or isentropic operations. The cycle
is shown on P-V and T-S diagrams.
Operation 1-2: T = C
Q1 = W1-2 = P1V1lnV2/V1 = mRT1lnV2/V1
Operation 2-3: PVγ = C Fig 7

Q=W=0
Operation 3-4: T = C
Q2 = W3-4 = P3V3lnV4/V3 = mRT2lnV3/V4
Operation 4-1: PVγ = C

Q=W=0
Net Work Done = mRT1lnV2/V1 – mRT2lnV3/V4
Since compression ratio = V3/V4 = V2/V1, T2 = T3
W = mRlnV3/V4(T1 – T3)
CARNOT THEOREM
No heat engine operating in a cycle between two given thermal reservoirs, with
fixed temperatures can be more efficient than a reversible engine operating
between the same thermal reservoirs.
 Thermal efficiency ηth = Work output/Heat supplied
 Thermal efficiency of a reversible engine (ηrev)
ηrev = (T1 – T2)/T1
 No engine can be more efficient than a reversible Carnot engine i.e. ηrev ≥
ηth
4
Condition:
1. If T1 = T2; No work, η = 0
2. Higher the temperature difference, higher the efficiency.
3. For the same degree of increase in source temperature or decrease in the sink
temperature, Carnot efficiency is more sensitive to change in sink
temperature.
CLAUSIUS INEQUALITY
When ever a closed system undergoes a cyclic process, the cyclic integral  dQ/T
is less than zero (i.e., negative) for an irreversible cyclic process, and equal to zero
for a reversible cyclic process.
So for a cyclic process,
 dQ/T ≤ 0
The equation for reversible cyclic process may be written as:
 dQ/T=0
The equation for irreversible cyclic process may be written as:
 dQ/T + I = 0
I = Amount of irreversibility of a cyclic process.

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SECOND LAW OF THERMODYNAMICS

ESSENCE OF SECOND LAW

PERFORMANCE OF HP: It is measured by the

COP is greater when heating a room than when cooling it.

Operation 2-3: PVγ = C Fig 7

Operation 4-1: PVγ = C

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