A note on Thermodynamics

1
1.1

Required Mathematics
Perfect & Imperfect differential

Consider the integral

Z

10

x2 + 4dx

(1)

. The adjacent plot (See fig. 1.1) gives the plot of the function x2 + 4. The area under
the graph gives the integral of the function.

The result of the integral is performed in the way :

10

Z
0

Figure 1: fig. 1.1

x3
x + 4dx =
+ 4x
3


10
=
0

Now Consider another integral,

Z 10
xy(x) + 4 dx

1120
3

(2)

To perform the integral one will require the function y(x)

explicitly. The integral cant be performed unless the
form of y(x) is given. Now consider the case that the integral has to be performed over
the curve given by y = x2 . The integral gives,
Z 10
Z 10
x y(x) + 4 dx =
x3 + 4 dx
0
0
 4
10
x
=
+ 4x
4
0
= 2540
(3)

But when the same integral Eq.2 is evaluated for the curve given by y(x) = x then the
integral gives,
Z 10
Z 10
x y(x) + 4 dx =
x2 + 4 dx
0
0
 3
10
x
=
+ 4x
3
0
1120
(4)
=
3
Thus clearly the integral of the type given by Eq.1 is complete in the sense we do not
need any more information to evaluate the integral. Also the integral gives zero when
evaluated over a cycle.
On the other hand, the integral of the type given by Eq.2 is incomplete in the sense that
to evaluate this we need to know the path over which the integral has to be performed.
The value of the integral depends on the path and, not necessarily the closed path
integral gives zero. Any integral that is complete will be denoted by dx or dy etc. &
or dy
etc.
the other type of integral that is path dependent will now on be denoted by dx

1.2

Partial differentiation

Functions in real life are all functions of many variables. Such a function of many variables, for example f(x,y,z,. . . ) can be differentiated with respect to any one of the variable.
Consider the derivative of the function with respect to x. Such a derivative is defined by,
f (x + x, y, z, . . .) f (x, y, z, . . .)
f
= lim
x x0
x
Example: Find out the partial derivative of the potential
"
#
1
q
q
p
(x, y, z) =
p
40
x2 + y 2 + (z d)2
x2 + y 2 + (z + d)2

(5)

about z at z = 0 plane. Also find the electric fields x component.

Solution: Taking partial derivative of (x, y, z) about z, we get,
"
#

1
q(d + z)
q(z d))
=

3
z
40 (x2 + y 2 + (z + d)2 ) 23
(x2 + y 2 + (z d)2 ) 2
Hence the partial derivative at z = 0 will be given by,


dq
=

z z=0 2(x2 + y 2 + d2 ) 23
The electric field at a point in xdirection will be given by,
"
#

qx
1
1
=

3
x
40 (x2 + y 2 + (z + d)2 ) 23
(x2 + y 2 + (z d)2 ) 2
2

(6)

(7)

(8)

First Law of Thermodynamics

This law is, another form of conservation of energy. This law is important because this
law first establishes the fact that mechanical and thermal energies are same & it describes
the thermal energy of the system.
Mathematical form:
= dU + dW

dQ

(9)

is the heat given to the system, dU is the change in internal energy due to
Where dQ
is the workdone by the system. By system we mean anything,
the heat given & dW
for example, a cylinder containing gas or a cup of tea etc.
Consider a gas contained in a cylinder that has a frictionless piston attached with
it. If the cylinder exerts a pressure p that increases the volume of the gas by
amount dV then the workdone by the gas becomes,
= pdV
dW

(10)

& the first law of thermodynamics becomes,

= dU + pdV
dQ

(11)

In general, thermodynamic work done by a system is expressed by a intrinsic

parameter x and differential of the associated extrinsic parameter dX by,
= xdX
dW

(12)

A system with many such pair of intrinsic and extrinsic pair does the work which
is given by,
X
=
dW
xi dXi
(13)
i

And hence we get the general form of first law of thermodynamics,

X
= dU +
dQ
xi dXi

(14)

Note: The above equations Eq.9 & Eq.11 shows that the difference of two non-exact
differentials can be exact.
Perpetual Machine of first kind: A hypothetical machine that violates the first
law of thermodynamics is called perpetual machine of first kind. Validity of first
law of thermodynamics in global scale ensures that such a machine can never be
possible.
Question: A wheel is rotating in space where is no friction and hence one predicts,
under certain criterion (such as, it doesnt feel any gravitational force by any object
etc.) this will rotate upto the end of universe. Does his prediction violates first law of
thermodynamics?
3

Second Law of Thermodynamics

Second law of thermodynamics restricts us by stating that some processes are not possible
though the first law of thermodynamics is maintained.
One statement (given by Clausius): It is impossible to construct a device which,
operating in a cycle, will produce no other effect than transfer of heat from
a colder to a hotter body.
Not going into details, I am trying to enlighten the important outcomes of this law:
It gives complete definition of reversible process.
It gives another perfect differential (Just like internal energy in the case of first law
of thermodynamics) dS which is defined for reversible processes only as:
T dS = dU + pdV

(15)

For reversible processes, thus, we find that

dS =

dQ
T

(16)

dS >

dQ
T

(17)

dS

dQ
T

(18)

& for irreversible processes,

Thus for any processes in universe,

For any adiabatic process we will have, dS 0.

The function S is called Entropy. The above conditions give that the entropy
of a system always increases. This gives the unidirectionality of thermodynamic
processes. Any process for which entropy decreases is not possible.
Perpetual machine of second kind: Any machine that doesnt violate first law
of thermodynamics but violates second law, is called perpetual machine of second
kind. Such a machine will extract heat indefinitely (cyclic process) from a body
and convert all of it into work or it will take heat from a cold body and supply it
to a hot body without any external work. Second law of thermodynamics denies
the existence of such a machine.

Engines & Refrigerators

Engine: An engine is a device that does some work in expense of some other energy,
such as heat in our case. A thermodynamic engine consists of a system(cylinder+gaseous
substance), two or more heat sinks etc that works in quasistatic reversible process and
delivers some mechanical energy from heat. To understand this, let us take the famous
Carnots Engine.
4

Carnots Engine: Here we take a cylinder with

which a perfectly friction-less piston is attached.The
walls of the engine is thermally insulated except the
bottom which allows energy exchange but no matter
exchange. Within the cylinder, there is kept some
amount of ideal gas and it remains there always. The
system, along with two heat reservoir, one at temperature T1 & other at temperature T2 makes the Carnots
engine. Clearly this is an ideal engine.

Efficiency of an engine: If Q1 is the heat given

to the system from the reservoir and then the system works by an amount W then the efficiency of the Figure 2: Schematic diagram of a
engine is,
typical themodynamic engine
W
W ork output
=
(19)
=
Heat given
Q1
Now from first law of thermodynamics,
W = Q1 Q2
Thus the definition of efficiency of an engine can also be given by,
Q1 Q2
Q2
=
=1
Q1
Q1

(20)

(21)

From second law of thermodynamics, (it is another statement not excerpted before) the necessary condition for the engine to be reversible is that, the value of
Q2 is finite. Thus, < 1, i.e. No engine can give 100% performance.
Refrigerator: A refrigerator is a device that extracts
heat from a body and throws it out in expense of some
mechanical energy. A thermodynamic refrigerator is
made of the same components that makes a thermodynamic engine. The only difference is that, the system
here pulls out some energy and puts to the hot reservoir, and obviously, some work is done on the system
Efficiency of Refrigerator: The efficiency of a refrigerator operating between two temperature baths is
given by,
Q2
Q2
Heat extracted f rom cold reservoir
=
=
=
W ork input
W
Q1 Q2
(22)
where we have used Eq.20.
Figure 3: Schematic diagram
of a typical themodynamic refrigerator