Thermodynamics

Shivansh Jaiswal
December 29, 2022

1 Introduction
Thermodynamics we learn is mostly concerned about ideal gases and their be-
havior and hence the equation P V = nRT will be of great importance in our
study of the subject, and we shall make extensive use of it. Note that most
of the times when we speak of doing work, we are doing it on the piston or
something like that.

2 Kinetic Theory of Gases

Consider a single molecule in a gas container, of cubic dimensions with side L.
If the molecule has a velocity ⃗v , then the time taken to cover distance L in x
direction is
2L
t1 =
vx
Average force is thus given by
∆me vx
Fav = = me vx2
t1
Now since on an average this will be same for all the three directions, taking
average the average force due to 1 molecule is
1
Fav = mv̄ 2 = kT
3
From here we obtain r
3kT
⃗vrms =
me
Note that we can write force as equal to pressure times volume because that
is pretty much what force is. We can also thus write pressure in terms of density
as,
1
P = ρv̄ 2
3
With this our discussion of KTG ends.

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3 Equipartion Theorem
The theorem states that for every degree of freedom, i.e for every axis around
which the object can move freely about, the energy associated with it is 12 kT
where k is the boltzmann constant. Note that Translational KE is 12 mv 2 , Ro-
tational KE is 21 Iω 2 , similarly PE of vibration is 12 kx2 . This helps form an
analogy, but is not correct. Note that in each case there is a quadratic degree
of dependence of some variable. The derivation comes from something like nor-
malization of the boltzman factor but we will not concern ourselves with it, but
the proof is still given at the end, addition to which is that we said E = αx2
because we know there’s a quadratic degree of dependence, and also the people
who derived it most likely assumed E = α2 x2 to be the dependence, but found
that the constant is useless, so modern proofs just assume α instead.
Hence the total internal energy of a system is given by
1
U= N f kT
2
where f = degree of freedom, N = number of molecules.

4 First Law of Thermodynamics

This law essentially re-states the conversation of energy, and the equation of the
first law is:

∆U = Q + W

Sometimes also stated as, but always note the sign convetion. Negative means
done by the system, positive means done on the system. Easily remembered by
W = −p∆V
∆U + W = Q
Where Q and W are Heat and Work respectively. Note that both of those
are energy in transit and are path functions, not state functions. Heat requires
there to be a difference of temperature whereas work doesn’t require any differ-
ence of temperature

For example, a resistor getting heated due to battery is a example of work,

but the resistor attaining thermal equilibrium when battery is turned off, is an
example of heat.

5 Heat Capacities
If a quantity of heat ∆Q raises the temperature of body through ∆T then heat
capacity is given by:
∆Q
C= J/K
∆T

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 We are here assuming all of these to be the specific heat capacities and not
the over all heat capacities.
Using the first law of thermodynamics
dU dW
C= −
dT dT
Defining Cv to be at constant volume and Cp to be at constant pressure and
replacing dW with −pdV so that dV nR
dT = P , we get

Cp = Cv + R

Earlier we said U = 21 N f RT , considering rate of change of U wrt T , we find

dU N Rf
Cv = =
dT 2
Using similar (same) reasoning

dU dW N (f + 2)R
Cp = + =
dT dT 2

6 General Work
There are 4 types of process we can encounter

• Isochoric Constant Volume

• Isotherms Constant temperature
• Isobaric Constant pressure
• Adiabatic No flow of heat b/w surrounding and system

Isochoric Since ∆V = 0 and −p∆V = W we have W = 0

Isotherms Temperature is same hence volume changes as heat flows on to
the system. Hence the work done by the gas on the piston or something is,
Z Vf Z Vf
dV Vf Pi
W = P dV = nRT = nRT ln = nRT ln
Vi Vi V V i P f

Adiabatic Expansion Note that U = f2 pV hence

f f 1
W = −∆U = − (p2 V2 − p1 V1 ) = (p1 V1 − p2 V2 ) = (p1 V1 − p2 V2 )
2 2 1−γ

Alternate Derivation is from using P V γ = c so that P = cV −γ hence

 −γ+1 Vf
V p1 V1 − p2 V2 Cv (p1 V1 − p2 V2 )
W = c ⇒W = ⇒W =
−γ + 1 Vi γ−1 R

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 Why is P V γ = k in adiabatic expansion?
Consider the total derivative of U = f2 pV and using the first law,

f f f f
dU = dpV + pdV ⇒ pdV + dpV + pdV = 0
2 2 2 2
Integrating and taking exponential on both sides,
f +2
PV f =c
f +2 Cp
Hence we obtain f = γ as the constant γ. Note that γ is also Cv as we
Cp
defined them earlier. Essentially there is no significance of appearing here.
Cv
Also CRv = γ−1
1
as you can show by just plugging in values.
There are actually a ton of ways to derive all the things I’ve written, and
whatever i’ve written is pretty discontinuous and tries to combine all of them
into one. But the actual ways were:

• (1) Use the fact that ∆Q = 0 in the first law, integrate and all to obtain
Cv
T2 V2 R
T1
R
= 1 and then finally obtain P V γ = k, by replacing 1 +
V1 Cv = γ.
This is the most continuous and elementary way.

• (2) With the knowledge of degree of freedoms, the derivation is almost

same as (1) but here the forms are in freedom degrees instead.
• (3) Here, we use the fact that P V γ = k and use this fact to derive the
work done, value of γ is obtained only by proving that P V γ is constant.

All this may make it seem like this part is very important but it isn’t I just
discussed it so much because its kind of interesting...

Another important result is

T2 V1 γ−1
=
T1 V2
Which follows from the proof we discovered earlier. All this is very weird right
now...
Moreover, also note that the curve for P vs V graph of the adiabatic expansion
is steeper than that of isotherms case, but γ always stays between 1 and 3, so
even though graph of P vs V will be steeper, its not like dependence is at the
order of 100 or something.

The curves look something like this:

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 Which is which, is upto you to guess...

7 Second Law of Thermodynamics

The second law of thermodynamics is stated in many different ways and is es-
sentially any statement which helps us predict whether a process is possible or
not (or reversible or something). We will give 3 interpretations here instead of
the usual 2.

Kelvin-Plank Statement: This statement states that it’s not possible for
all the heat an engine takes to be converted to work. That is if, Q1 is taken
from a reservoir, W is work provided W ! = Q1 , and some heat must be left,
and transferred to another reservoir.

Clausius Statement: This statement states that it’s not possible for a en-
gine to solely transfer heat from a cold body to a hot body. Note that real
engines are possible because that engine takes some work too, like some work
is inputted to the engine, which overall gives it enough heat for it to flow to a
hot body. Its a cyclic and not spontaneous process.

Carnot’s Statement: This statement states that of all the possible engines,
Carnot’s engine is the most efficient one for a choice of reservoirs at tempera-
tures T1 and T2

All of these statements can definitely be proved using contradiction, but it

is understood that the reader is acquainted with the necessary knowledge. But
the proof of 3rd statement is as follows:

In reference to this figure assume that there’s a engine E which is more efficient

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than the Carnot engine and we want to prove it doesn’t exist, note that net heat
′ ′
extracted from reservoir at temp Tl is Ql − Ql and Th is Qh − Qh . If these 2
quantites are equal, then this engine won’t be possible by Clausius’s statement.
By first law,
′ ′ ′ ′
W = Qh − Ql = Qh − Ql ⇒ Qh − Qh = Ql − Ql
′
Now, Qh − Qh is positive so all the carnot engine is doing is dumping heat from
lower reservoir to upper one, without any work in between (like if you put the
system in a black box, that’s what it is doing). Hence it’s not possible and
Carnot’s engine is the most efficient one.

A schematic diagram of a carnot engine is as follows:

Two key results are

Qh Th
=
Ql Tl
VB VC
=
VA VD
The proof of these comes from one of the results we discussed earlier along with
realising the properties of isotherms and adiabats

8 Proof of Equipartion Theorem

Let the energy E of a particular system be given by

E = αx2 ,

where α is some positive constant and x is some variable (see Fig. 19.2). Let us
also assume that x could in principle take any value with equal probability. The
probability P (x) of the system having a particular energy αx2 is proportional
2
to the Boltzmann factor e−βαx (see eqn 4.13), so that after normalizing, we

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have 2
e−βαx
P (x) = R ∞ ,
−∞
e−βαx2 dx
and the mean energy is
R∞ 2
∞ αx2 e−βαx dx
Z
−∞ 1 1
⟨E⟩ = EP (x)dx = R∞ = = kB T.
−∞ −∞
e−βαx2 dx 2β 2