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The clausius statement of second law of thermodynamics
is the first corollary i.e. ‘It is impossible to construct a device
operating in a closed cycle that performs no effect other than
the transfer of heat from a cooler body to a hotter body.’
The mathematical statement of which is given by;
Q1 ‐ Q2 = W
Hot reservoir
Q1
Heat
W
engine
Q2
Cold reservoir
Corollary 2:
It is impossible to construct an engine operating between
only two heat reservoirs, which will have a higher efficiency
than a reversible heat engine operating between the same two
reservoirs.
Q1 Q1
X R
WX W R
Q1 ‐ WX Q1 ‐ WR
Suppose these conditions are true,
Let ηX > ηR
If the reversible engine also receives heat Q1 from the source, it
will do work WR. Let us convert that heat engine to a heat
pump, then we have, that R receives Q1 ‐ WR & receives WR
from the surroundings & rejects Q1 heat to high temperature
reservoir.
Coupling it to heat engine the net work done now becomes;
(Q1 ‐ WR) – (Q1 ‐ WX)
= WX ‐ WR
Thus of corollary 2 is true, then we have we have that following
condition is also possible.
‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐
Q1 Q1
WX ‐ WR X R
Q1 ‐ WX
Corollary 3:
All reversible heat engines operating between the same
two reservoirs have same efficiency.
Since the second corollary has been proved true then it is
impossible that one has higher efficiency.
Thus according to the Carnot theorem both heat engines have
same efficiency. i.e.
η = (Q1 + Q2) / Q1 = (T1 ‐ T2) / T1
Corollary 4:
A scale of temperature can be defined which is
independent of any particular thermometric substance and
which provides an absolute zero of temperature.
Hot reservoir
Q
Heat
W
engine
Q0
Cold reservoir
Let us suppose a heat engine as shown in figure above
Thus from corollary 3, the efficiency of that heat engine
depends only on the temperature of the reservoirs.
η = 1 – Q / Q0
Let the temperature of the heat reservoir be T0,
Now, if T be the temperature of cold reservoir,
Then since
η α (1 – Q / Q1)
Also η = 1 – T / T0 {Carnot’s efficiency}
T
0
Q0a Q0b Heat pump Q0n
(reversible)
Q1b
Q1a Q1n
b
a n
Q1b
Q1a Q1n
W
Heat
engine
Q2z Q2p
Q2q
Z p
q
Q 2p
Q2z
Q2q
Heat pump
(reversible)
Q0z Q0q Q0p
T 0
Total work done by original engine;
n z
∑ Q1 – ∑ Q2
a p
The work delivered in auxilliary engines;
z
∑ ( Q2 – Q0 )
p
And work applied to heat pump;
n
∑ ( Q1 – Q0 )
a
Net work done;
n z z n
∑ Q1 ‐ ∑ Q2 + ∑ ( Q2 ‐ Q0 ) ‐ ∑ ( Q1 ‐ Q0 ) ≤ 0
a p p a
Thus,
n z
∑ Q0 ‐ ∑ Q0 ≤ 0
a p
Thus,
n z
∑ Q1T0/T1 ‐ ∑ Q2T0/T2 ≤ 0
a p
Then;
T=T0Q / Q0
Thus, we have defined a temperature scale called as
thermodynamic scale & since it begins from T=0, it is an
absolute scale of temperature.
Corollary 5:
The efficiency of any reversible engine operating between
more than two reservoirs must be less than that of that of a
reversible engine operating between two reservoirs which have
temperatures equal to the highest and lowest temperature of
the reservoirs in original engine
Corollary 6:
Whenever a system under goes a cycle, ∫ (dQ/T) is zero if
the cycle is reversible and negative if irreversible i.e. in general
∫ (dQ/T) < 0 . It is also called as Clausius inequality.
Proof:
Let us consider an engine operating between a finite
numbers of reservoirs
b
a n
Q1b
Q1a Q1n
Heat
engine
Q2z Q2p
Q2q
Z p
q
Let quantity of heat Q1a , Q0b ‐‐‐‐‐‐‐‐‐‐ Q1n be supplied from finite
number of reservoirs at temperatures T1a‐‐‐‐‐‐‐‐‐‐T1n.
Let the heat rejected to sinks T2z‐‐‐‐‐‐‐‐‐‐T2q etc.
Now let the sources be supplied with their quantities of heat by
a series of reversible heat pumps receiving quantities of heat
Q0a , Q0b ‐‐‐‐‐‐‐‐‐‐ Q0n from a single reservoir T0.