Gopalganj Science & Technology University

AN ASSIGNMENT ON

Course Code: MAT581

Course Title: Thermodynamics And Statistical Mechanics

Submitted By Submitted To
Name: Animesh Paul Name: Dr. Muhammad Minarul Islam
Student ID: 18MAT001 Associate Professor
Year: M.sc Department of Mathematics,
Semester: 2nd GSTU
Session: 2018-2019
Department of Mathematics,
GSTU

Submission Date: 10-05-2025

Chapter -1
***What is Work? Derive the equation of work. Or 𝒅𝒘 = 𝒑𝒅𝒗 ,Or 𝒘 =
∫ 𝒑𝒅𝒗
Solution: Work: the term ‘Work’ refers to an interchange of energy between a
system and its surrounds. Now a days we consider mechanical work, while the
work can always be expressed as ∫ 𝐹𝑐𝑜𝑠𝜃𝑑𝑠,in most cases of partical interest, the
work associated with a change in volume.
Let us consider a system of arbitrary shape as in figure, acted upon by an internal
hydrostatic pressure 𝑝𝑒,and the original boundary shown by full lines, is displaced
outward against the external pressure to a new position shown by dotted lines. If
the external force 𝑑𝐹exerted against a portion of the surface of area 𝑑𝐴 is
𝑑𝐹 =
𝑝𝑒𝑑𝐴…………………………………………………………………………(i)
And this position moves out a distance 𝑑𝑠 the work done against the external force
is,
𝑑𝑊 = 𝑑𝐹. 𝑑𝑠 = 𝑝𝑒𝑑𝐴𝑑𝑠
∴ 𝑑𝑊 = 𝑝𝑒𝐴𝑑𝑠
[Interchanging over the surface s, where A is the total surface of s]
But, 𝐴𝑑𝑠 is the increase in volume of the system dv, so the external work done
𝑑𝑊 = 𝑝𝑒𝑑𝑣 …………………………………………………………….……(ii)
If the process is reversible then by the definition the boundary walls are enential
in equilibrium at all instants and the external pressure is equal the internal
pressure p then we can get the above equation.
𝑑′𝑊 =
𝑝𝑑𝑣………………………………………………………………….……(iii)
If we divided through by the mass m or the number of moles n of system then the
work done per unit mass as per mole,𝑑′𝑤 and the right-hand side becomes
𝑝𝑑𝑣,the product of the pressure and the change in specific volume 𝑑′𝑊 = 𝑝𝑑𝑣
𝑣𝑏

𝑖. 𝑒. 𝑤 = ∫ 𝑝𝑑𝑣
𝑣𝑎

Which is the required work equation.

In an isobaric process the pressure is constant and the work is

𝑣𝑎)………………………………………………………………….(iv)
In an isothermal process the temperature is constant and the work is
 For an ideal gas 𝑝𝑣 = 𝑅𝑇]
………………………………………………………………………...…….(v)

***Establish the chain relation,

Solution: Suppose, three Variable 𝑥, 𝑦, 𝑧 connected by a functional relation is
𝐹(𝑥, 𝑦, 𝑧) = 0. Any two of the variables can be considered independent .so we get
as,
𝑥 = 𝑓1(𝑦, 𝑧) =
𝑥(𝑦, 𝑧)……………………………………………………………………..(i)
𝑦 = 𝑓2(𝑧, 𝑥) =
𝑦(𝑧, 𝑥)…………………………………………………….………………(ii)
𝑧 = 𝑓3(𝑥, 𝑦) =
𝑧(𝑥, 𝑦)………………………………………………………...…………….(iii)
Now we solve for ‘x’ and for ‘y’ from (i)&(ii) then

[By partial differentiation]

Eliminate ‘dy’ between the above two equations and collect the coefficients of dx
and dz , then

Or,

………………………………………….(iv)
But the change 𝑑𝑥 and 𝑑𝑧 are independent i.e. we can assigne any value to 𝑑𝑥
and any other value to 𝑑𝑧. Suppose let, 𝑑𝑧 = 0 & 𝑑𝑥 ≠ 0 ,then from (iv) we get

Or,
 …………………………………………………………………….(v)
Similarly, we can 𝑥𝑡 𝑑𝑥 = 0 & 𝑑𝑧 ≠ 0 then

. [using the relation (v)]

.
Which is called the chain relation.

***Establish the chain relation,

Solution: If we consider pressure(p), volume(v) and temperature(T) are
connected y the function F is 𝐹(𝑝, 𝑣, 𝑇) =
0………………………………………………………………………………..(i)
Where, 𝐹(𝑝, 𝑣, 𝑇) = 0 is called the equation of state.
Now, any two of the variables (𝑝, 𝑣, 𝑇) can be considered independent then
𝑝 = 𝑓1(𝑣, 𝑇) =
𝑝(𝑣, 𝑇)…………………………………………………………...………. (ii)
𝑣 = 𝑓2(𝑇, 𝑝) =
𝑣(𝑇, 𝑝)…………………………………………………………………………(iii
𝑇 = 𝑓3(𝑝, 𝑣) =
𝑇(𝑝, 𝑣)…………………………………………………………………. (iv)
Now we solve for ‘p’ and for ‘v’ from (ii)&(iii) then

.
Eliminate ‘𝑑𝑣’ from this above two equations, then we get

Or, .
 ……………………………..………….(v)
Here, the change of pressure (𝑑𝑝) and the change of temperature are
independent.so we an assign any value to 𝑑𝑝 & 𝑑𝑇 first, putting 𝑑𝑝 = 0 𝑎𝑛𝑑 𝑑𝑇
≠ 0, the equation (iv) becomes

using (vi)

***Define the coefficient of cubical expansion and the compressibility factor.

And find the cubical expansion and the compressibility factor for ideal gas,
Vander Waals gas and Clausius gas.
Define the coefficient of cubical expansion:
The definition of the coefficient of cubical expansion given in elementary text is

………………………………………………………. (i)
Where 𝑉2 and 𝑉1 are the volume at the temperature 𝑇2and 𝑇1
Here 𝛽̅ is the mean of fractional increase in volume, per degree rise in temperature
the true coefficient of volume expression 𝛽̅, at any temperature T is the limiting
value of the expression above when the increase in temperature and the
corresponding a volume change become infinitesimal.

……………………………………………
………..(ii)
If the temperature kept constant, then 𝛽̅ is

………………………………. ……………. (iii)

Again, in term of specific volume

……………………………………….. ……………….(vi)
Therefore, the rate of change of volume with respect to the change of temperature
(where pressure is constant) is called cubic expression.
Compressibility:
the mean compressibility of a metal, K is Defined by the equation
………………………………………………… ………..(i)
Where 𝑉1 and 𝑉2 are the volume at pressure 𝑃1 and 𝑃2 the true compressibility K
is the limiting value of the expression above when the change in pressure and
volume Infinitesimal.

……………………………………. .. ………..(ii)
If the temperature is constant the corresponding value of k is called the isothermal
compressibility, which is the partial of B with respect to fee at constant
temperature

……………. (iii)

………………………………………… …………………(vi)

If the temperature is v constant ,the corresponding value of k is called the

isothermal corresponding becomes the partial of V with the respect to P at
constant temperature ,

K= 1
2nd part:
For The ideal gas: We know the equation of ideal gas is
PV=RT ( 1)

i.e V=

But, the cubical expensions , β=

i.e (A)

Again, . Then the compressible

k= -
i.e k=1 (B)
𝑝

For a vander weals gas: The Vander weals gas equation is

i.e P= , Here

Again ,
𝑣−

Or, ,

Or,

‫؞‬K=
For clausius gas: The equation of the Clausius gas is p(v-b)=RT

‫؞‬
𝑅

Now ,

Or,

Finaly,

Or,

Or, K=
Problem: Verify the chain reaction for an ideal and vander waals gas.

Solution: We know that the chain relation is =−1

For an ideal gas: The gas equation is PV=RT

Then, p= , V= ,

Now , ,

So,

(verified)

For a Vander Waals gas: The gas equation is =RT

Then, P=
Now,

Again

So,

=−1 (verifyed)

For Clausius gas: The gas equation is 𝑃(𝑉 − 𝑏) = 𝑅𝑇 (𝑖𝑖)

Now
 ,

Then

=−1 (verified)

Chapter 5
Thermodynamics and Statistical
The first law of thermodynamics: The first law of thermodynamics is the
statement of the principal of conservation of energy. In very general term it asserts
the net flow of energy across the boundary of a system is equal to the change in
energy of the system. For this purpose of thermodynamics it is sufficient to
consider only two types of energy flow across a boundary. One of this consist of
work Done on or by the system another is a flow of heat either by conduction or
radiation here we can represent the first law of thermodynamics in mathematical
form as

𝑈2 − 𝑈1 = 𝑄 − 𝑊 − − − − − − − − − − − − − − − (𝑖)
Where,
U1=the energy of the system at start of a process
U2=the energy of the system at end of a process
W=the network done by the system
Q=the net hit theory into the system.
Again, for an infinitesimal process, the first law of thermodynamics becomes,

𝑑𝑈 = 𝑑′𝑄 − 𝑑′𝑊 − − − − − −(𝑖𝑖)

When both side of the above equation are divided by the mass at the number of
moles of a system, we get ,

𝑑𝑢 = 𝑑′𝑞 − 𝑑′𝑤 − − − − − − − −(𝑖𝑖𝑖)

Some important topic: The true heat capacity equation...

The specific heat capacity c of a substance as the ratio of the true heat capacity of
a system composed of that substance to the mass of the system.

The heat capacity in a process in which a system in subjected to a constant

external hydrostatic pressure is called the heat capacity at constant pressure which
is denoted by CP.
If a system is kept at constant volume while heat is supplied to it, the
corresponding heat capacity is called the hit capacity at constant volume and
represented by CP.

i.e

The energy equation: The energy equation of a system in the relation expressing
the internal energy u in the term of state variable. The equation cannot be drive
automatically from the equation of a state of the system, but experimental
measurement of heat capacity must be made in addition to collecting P-V-T data.

If the internal energy is u ,then

Problem:

If T and V independent, then prove that (a) ( 𝑑𝑢) =Cv

dvT .

Solution: Let us consider, the specific internal energy of a system to be express in

terms of T and V. Then u= u(T, V).

du= vdt

Tdv……………………………………….(i)

If we consider only systems for which d'w = Pdv, then the first Law of
Thermodynamics is..
du = d’q- d'w

or, d’q= du + d’w= vdt + Tdv+Pdv

or, d’q= vdt + (p + )dv…………………………(ii)

This equation is perfectly general, applying to any substance where and to any
reversible process. ( no need to write)

For aproaces at constant value dv = 0 and CV

Or, d’q = dTV.CV
 Or, CV.dTV vdT + (p +
Or, CV.dTV .

v [Hence (a) is proved]

Now, from the equation (2) we get, d’q = CVdT + (p + )dv

If a process of constant pressure, then Cp=CPdTP

Or, CPdTP= CVdT+ (p + )dv

Or, CP = Cv+ + (p + p

Or, Cp-Cv = (p + p

Or, Cp- ].vβ

Problem:
If T & P independent then prove that,

βv (b) (

© dq´T dpT

Solution:
Let us consider, the specific internal energy u of a system to be expressed
interm of T & P independent Variables, U=u(T,P)

Or, du = (𝜕𝑢 )p dT + (𝜕𝑣)T dp

𝜕𝑝 𝜕𝑝

Now, from the equation of first law of thermodynamics becomes,

du = d´q - d´w = d´q – pdv d´q = du+ pdv

d´q = [( ] dT + [( ] …..……………… (1)

here at the constant pressure, dp=0 & cp p d´q

= cp. dTp
cp = p ……………………….…………..(2)

= cp – p.v. p

βv
Hence (a) is proved.
Again, The general expression for cp in the equation (2) , can be write,

𝑑´q = cp dTp ]dp……………..…………..(3)

In a constant volume process, we get that,

cv d q
dT v

Or,d qv cvdTv

cvdTv cpdTv u

Or, p T p pv T dpv [using equation 3]

Or, cv cp up T p pv T Tp v [dividing both

side by TV ]

Or, cv cp up T p pv T pv T Tv p

Or, p T pv v pv
T v kv1 cv cp
u 1
u k

So, p T pvk cp cv
Hence (b) is proved.
Now, if the temperature is constant, then dT 0. So,
we get from equation (1)

u v
d qT p T p p T dpT
K

d qT cv cp dpT

So,
Hence (c) is proved.

Now,we know , d qs 0 then from the equation (1) we get,

u v
cpdTs p T p p T dps 0

Or,cp Tp s up T p pv T

Or, p s

1 1 cp cv K cp cv cp T

K
 T K cp cv

So, p s cp

Hence (d) is proved. from the first law of

thermodynamics we get,

𝑑𝑢 = 𝑑′𝑞 − 𝑑′𝑤, ⇒ 𝑑′𝑞 = 𝑑𝑢 + 𝑑′𝑤, ⇒ 𝑑′𝑞 = 𝑑𝑢 + 𝑝𝑑𝑣.

(1)

But, at constant volume we get then

Now, the general expression for 𝑐𝑣 in equation (2) can be inserted. in equation

At a constant pressure process we get,

(Hence (b) is proved)

No, At constant temperature we get, 𝑑𝑇 = 0, then the equation (1) becomes,

(Hence (c) is proved)

But, in adiabatic process we have, 𝑑′𝑞𝑠 = 0, then from (1) we get:

(Hence (d) in Proved)

Problem: The internal energy of a certain gas may be represented by the empirical
equation 𝑢 = 𝑎𝑇 − 𝑏𝑝, where 𝑎 and 𝑏 are constants, the coefficient of thermal
expression and compressibility are respectively and .find the capacity at
constant 𝑐𝑉 in terms of 𝑎, 𝑏, 𝑝 and 𝑇

Solution: Given that, the internal energy equation of a certain gas,

𝑢 = 𝑎𝑇 − 𝑏𝑝
(1)
Now, we know,
 Here, and given that thermal enpention

Again we know that,

∴ 𝑐𝑣 = 𝑎 − 𝑏𝑝/𝑇 which is the required equation. 𝑐𝑣 interms of 𝑎, 𝑏, 𝑃

and 𝑇.
Problem: compute the work done in a reversible adiabatic experision of a vander waals
gas by direct evolution of ∫ 𝑝𝑑𝑣 and compare with 𝜔 = 𝐶𝑣(𝑇1 − 𝑇2) − 𝑎(1/𝑣1 −
1/𝑣2). & similarly find for ideal gas & clausius gas
solution:
We know the vander waals gas equation is,
(𝑝 + 𝑎/v²)(𝑣 − 𝑏) = 𝑅𝑇
(1)
(where 𝑎, 𝑏 are constant.)
Now Consider a reversible adiabatic expension for 𝑣ander waals gas is,

(𝑃 + 𝑎/𝑣²)(𝑣 − 𝑏)ᵞ = constant = 𝑐 (say ) (2)

So, the work done in adiabatic expenssion of a vander waals gas is,
𝑣2 𝑣2 −𝛾𝑑𝑣 [∵ from euation (2)𝑤𝑒 𝑔𝑒𝑡
 𝜔 = ∫𝑣1 (𝑝 + 𝑎/𝑣²)𝑑𝑣 = ∫𝑣1 𝑐(𝑣 − 𝑏)

𝑣2 −𝛾𝑑𝑣 = 1/1 − 𝛾 ⋅ [𝑐(𝑣 − 𝑏)1−𝛾]𝑣𝑣12

⇒ 𝜔 = 𝑐 ∫𝑣1 (𝑣 − 𝑏)

where c the constant in equation (2).

But to state that means that

constant = 𝑐.
Hence when inserting the upper limit in (3) ,

we get, 𝑐 = (𝑝2 + 𝑎/𝑣22)(𝑣1 − 𝑏)𝛾, While at

the lower limit we let,

𝑐 = (𝑃1 + 𝑞𝑉1)(𝑣1 − 𝑏)3

Then,

(4)
The work can also be found by realizing that since no heat flow into or out of a
system. In an adiabatic process the work is done while at the expense of the
internal energy of the system, Hence

𝑢2 − 𝑢1 = −𝜔 i. e 𝜔 = 𝑢1 − 𝑢2. (5)
But,
Now, we know,

2𝑑𝑣 [ Integrating both

⇒ ∫ 𝑑𝑢 = ∫ 𝐶𝑉 𝑑𝑡 + ∫ 𝑎/𝑣 sides

[⸪ considering limit]

– T1) + a (

i.e. (u1 – u2) = ꞷ = 𝑐𝑣 (T2 – T1) )

(6)
Here, the equation (iv) & (vi) both are the equations of work done of a Vander
Waals gas.
Similarly, if we consider an ideal gas then the work done,

ꞷ=

⸫ꞷ=
For an ideal gas, PV = RT and
If the process is adiabatic then, P𝑉𝛾=constant = c
i.e. P =c

When inserting the upper limit in (A)

We let, c = P , while at the lower limit

We let, c = P ,then

ꞷ = 1 . (P2V2 - P1V1) . . . . . . . . . .
The work also can be found by realizing that since no heat flow into or out of a
system in an adiabatic process the work is done wholly at the expense of the
internal energy of the system. Hence, u2 – u1 = - ꞷ, and for an ideal gas, ꞷ = u1
– u2 .

But, we know,

=> du = 𝑐𝑣 𝑑𝑇
=> (u2 – u1) = 𝑐𝑣 (T2 – T1)
∴ ꞷ = 𝑐𝑣 (T2 – T1)
Where, 𝑐𝑣 is constant.
Again, u2 = (u1 - 𝑐𝑣T1) + 𝑐𝑣T2 is called the energy equation of an ideal gas .

For Clausius gas:

We know the Clausius gas equation is, P (V-b) = R ...........
(C)
Now the work done in adiabatic expansion is,

But, P(𝑉 − 𝑏)𝛾 = constant = c (say). So, ꞷ= .

from the first law of thermodynamics we get,

𝑑𝑢 = 𝑑′𝑞 − 𝑑′𝑤, ⇒ 𝑑′𝑞 = 𝑑𝑢 + 𝑑′𝑤, ⇒ 𝑑′𝑞 = 𝑑𝑢 + 𝑝𝑑𝑣.

(1)

But, at constant volume we get then

 (𝐴)
Now, the general expression for 𝑐𝑣 in equation (2) can be inserted. in equation

At a constant pressure process we get,

(Hence (b) is proved)

No, At constant temperature we get, 𝑑𝑇 = 0, then the equation (1) becomes,

(Hence (c) is proved)

But, in adiabatic process we have, 𝑑′𝑞𝑠 = 0, then from (1) we get:
 (Hence (d) in Proved)
Problem: The internal energy of a certain gas may be represented by the empirical
equation 𝑢 = 𝑎𝑇 − 𝑏𝑝, where 𝑎 and 𝑏 are constants, the coefficient of thermal
expression and compressiblity are respectively and .find the capacity at
constant 𝑐𝑉 in terms of 𝑎, 𝑏, 𝑝 and 𝑇

Solution: Given that, the internal energy equation of a certain gas,

𝑢 = 𝑎𝑇 − 𝑏𝑝
(1)
Now, we know,

Here,

Again we know that,

∴ 𝑐𝑣 = 𝑎 − 𝑏𝑝/𝑇 which is the required equation. 𝑐𝑣 interms of 𝑎, 𝑏, 𝑃
and 𝑇.
Problem: compute the work done in a reversible adiabatic experision of a vander waals
gas by direct evolution of ∫ 𝑝𝑑𝑣 and compare with 𝜔 = 𝐶𝑣(𝑇1 − 𝑇2) − 𝑎(1/𝑣1 −
1/𝑣2). & similarly find for ideal gas & clausius gas
solution:
We know the vander waals gas equation is,

(𝑝 + 𝑎/v²)(𝑣 − 𝑏) = 𝑅𝑇
(1)
(where 𝑎, 𝑏 are constant.)
Now Consider a reversible adiabatic expension for 𝑣ander waals gas is,

(𝑃 + 𝑎/𝑣²)(𝑣 − 𝑏)ᵞ = constant = 𝑐 (say ) (2)

So, the work done in adiabatic expenssion of a vander waals gas is,
𝑣2 𝑣2 −𝛾𝑑𝑣

𝜔 = ∫𝑣1 (𝑝 + 𝑎/𝑣²)𝑑𝑣 = ∫𝑣1 𝑐(𝑣 − 𝑏)

𝑣12 −𝛾𝑑𝑣 = 1/1 − 𝛾 ⋅ [𝑐(𝑣 − 𝑏)1−𝛾]𝑣𝑣21 (3) ⇒ 𝜔 = 𝑐

∫𝑣 (𝑣 − 𝑏)

where c the constant in equation (2).

But to state that means that

(𝑝1 + 𝑎/𝑣1²)(𝑣1 − 𝑏)7 = (𝑝2 + 𝑎/𝑣22)(𝑣2 − 𝑏)7 = constant = 𝑐. Hence

when inserting the upper limit in (3) ,

we get, ,
While at the lower limit we let,
 𝑐 = (𝑃1 + 𝑞𝑉1)(𝑣1 − 𝑏)3

Then,

The work can also be found by realizing that since no heat flow into or out of a
system. In an adiabatic process the work is done while at the expense of the
internal energy of the system, Hence

𝑢2 − 𝑢1 = −𝜔 i. e 𝜔 = 𝑢1 − 𝑢2.
(5)

But,

Now, we know,

2𝑑𝑣 [ Integrating both

⇒ ∫ 𝑑𝑢 = ∫ 𝐶𝑉 𝑑𝑡 + ∫ 𝑎/𝑣 sides

[⸪ considering limit]

– T1) + a (

i.e. (u1 – u2) = ꞷ = 𝑐𝑣 (T2 – T1) )

(6)
Here, the equation (iv) & (vi) both are the equations of work done of a Vander
Waals gas.
Similarly, if we consider an ideal gas then the work done,

ꞷ=

⸫ꞷ=(
For an ideal gas, PV = RT and
If the process is adiabatic then, P𝑉𝛾=constant = c
i.e. P =c

When inserting the upper limit in (A)

We let, c = P , while at the lower limit

We let, c = P ,then
ꞷ = 1 . (P2V2 - P1V1) . . . . . . . . . . (B)
The work also can be found by realizing that since no heat flow into or out of
a system in an adiabatic process the work is done wholly at the expense of the
internal energy of the system. Hence, u2 – u1 = - ꞷ, and for an ideal gas, ꞷ =
u1 – u2 .

But, we know,

=> du = 𝑐𝑣 𝑑𝑇
=> (u2 – u1) = 𝑐𝑣 (T2 – T1)
∴ ꞷ = 𝑐𝑣 (T2 – T1)
Where, 𝑐𝑣 is constant.
Again, u2 = (u1 - 𝑐𝑣T1) + 𝑐𝑣T2 is called the energy equation of an ideal gas .

For Clausius gas:

We know the Clausius gas equation is, P (V-b) = R ..........
. (C)
Now the work done in adiabatic expansion is,

But, P(𝑉 − 𝑏)𝛾 = constant = c (say). So, ꞷ= .

we sec that it pomible to absorb a positive quantity of heat aries

convert it wholly in to woke. But it in against the 2nd ie. con not
positive. ie. When the number of teserint of heat we know Σ → ∫
(integration) exchange only infinitesimal amour
become ……….. (1)
Then the integrals become n (1)
Again, if the proem in reversible, then for the reverse process

ie.

from (1) and (1) are get (Which proves the theorem)

Question: show that entropy of a process always increases. or Discum ab

'Entropy changes of a closed system During an irreversible proves".

Solution: comider a reversible cycle where the state is changed from

1 to 2 along the path a and 2 to 1 along the path b
.

For z a reversible^ cyclic proem,

∮ 𝑑𝑡 = 0 … … … (1)

Now consider on irreversible path 𝐶 from state at state 1. Applying clausius

inequility for the cycle of process 𝐴 and 𝐶. ie.
from the equation (1) and (2) we get.
Since the path 𝐵 is reversible and entropy in a property then

Which shows that the effect of irreversibility is always to increases the entropy
of a system.

Problem: show that, for an ideal gas the entropy 𝒔 = 𝒄𝒗𝐥𝐧 𝒑/𝒑𝟎 +
𝒄𝒑𝐯/𝒗𝟎 + 𝒔𝟎 and internal energy .
Solution: consider, one gram of a perfect or ideal gas at a presure p volume 𝑣
and temperature 𝑇. Let the quantity of heat given to the gas be 𝑆𝑄. From the
pst law of thermodynamics we get

For one gram gas 𝑑𝑢 = 𝐶𝑣𝑑𝑇 where volume in constant

for an ideal gas we know 𝑃𝑉 = 𝑅𝑇

∵ entropy, 𝑑𝑠 = 𝑑𝑄/𝑇
If temperature is changed from 𝑇0 to 𝑇 then volume tho changed from 𝑣0 to 𝑉
Then by integrating both vide of (1) is, .
⇒ (𝑆 − 𝑆0) = 𝑐𝑉In𝑇/𝑇0 + 𝑅In𝑉/𝑣0 (𝑖𝑖)
But we know that, 𝑐𝑝 − 𝑐𝑣 = 𝑅

∴ 𝑠 = 𝑐𝑉In(𝑃/𝑃0) + 𝑐𝑝ln 𝑉𝑣0 + 𝑠0 (shown)

Again, we have,
𝑢1(shown) problem: one kilogram of water is heated by an electric heating coil
from 20∘C to 80∘C. Compute the change in entropy of (a) the water (b) the
universe. (a) Here, given that

𝑇𝐴 = 20∘∘CC == ((2080++273273))kK==293353 KK..

𝑇𝐵 = 80
Here,

𝑐𝑝 = 4,18 × 103 Joule / kilogram der.

Now change in entropy in, 𝑚𝑐𝑝log( 𝑇𝐵/𝑇𝐴)

where, 𝑚= man of water.
𝑇𝐴 = in the internal temperature
𝑇𝐵 = in the final temperature
⇒ 𝑑𝑆 = 1 × 4.18 × 103log (353/293) = 778.715 Joule/kilogram deg. ( Answers)

Since ∫ 𝑑𝑄 = 𝑚𝑒𝑝 × change of wat

∴ 𝑑𝑠 = −710.48 Joul/kilogram degrees

(b)
Then the change in entropy of the universe = (778.715 −
710.48)Joule / kilogram
 = 67.9999 = 68 Joule /
kilogram (Answer)
Problem: 1 kgm of water at a temperature of 280∘K is mixed with. 2 kgm of
water at a temperature of 310∘K in a thermally insulated vended find the
change in entropy of the universe.

Solution: Given that,

𝑚1 = 1kgm, 𝑚2 = 2kgm.
𝑇1 = 280k, 𝑇2 = 310k.
(1)
Let, the final temperature be T K. Then we get,

𝑚1 × 𝑠 × (𝑇 − 𝑇1) = 𝑚2 × 𝑠 × (𝑇2 − 𝑇) [consider specific neat of water, 𝑠 = 1]

⇒1 × 1 × (𝑇 − 280) = 2 × 1 × (310− − 𝑇) ⇒ 𝑇 − 280 = 610 − 2𝑇
⇒3𝑇 = 890, ∴ 𝑇 = 296.667 K.
(ii) Change in entropy when the temperature of 1 kgm. of water ruses from

280 K to 296.667 K then,

𝑠1 − 𝑠]

Joule/kilogram
(iii) Change in entropy when the temperature of 2 kg water. Decreases from
310 K to 296.667 K, then

Δ𝑆2 = −2 × log (310/296.667) = −0.087.924 Joule /kg

(v). Champ in entropy when the temperature of (1 + 2)kgm = 3kgm of water

increases from

joule/k𝑔.
Adding (ii) and (iii). Then we get, Δ𝑆1 + Δ52 = −(0.0578 + 0.08794)

∴ So the change in entropy of universe = ΔS + (Δ𝑆1 + Δ52) = 0.02 × 736

Joule/kilogram

Problem: A mass 𝒎 of a liquid at a temperature 𝑻𝟏 is mixed with equal

mass of the same liquid at a temperature𝑻𝟐. The system in there insulated.
Show that the entropy change of the universe is

, and prove that this is necessary positive.

Solution: Consider the first temperature of the mixer is equal to T0 and T1>T2.
After mixing heat lost by the liquid of temperature T1 and heat gained by the
liquid at temperature T2 but they are equal. i.e.
Lost of heat=gained of heat

Now the change in entropy when the temperature change from T1 to T0 of m unit
liquid , then

Again the change of entropy when temperature change from T2 to T0 of m unit

liquid , then

Then the chamge of total universe entropy , ∆𝑠 = ∆𝑠1 + ∆𝑠2

2nd part

Again,

i.e.
(Proved)

Problem: Two identical bodies of constant heat capacity ,originally at engine

operating in infinitesimal reversible cycles. If the bodies remain at constant
temperatue and undergo no change of pressure. Show that (a) the final
temperature Tf is ,(b) The work obtain is Cp(T1+T2-2Tf) .

Solution: (a) Let, T1>T2 and hot body falls from T2 to Tf .

Then the lose of entropy is =

Again the change of entropy from T1 to Tf which is gain, then

Thus the total change = gain of entropy – lose of entropy

Since there is no change then m

𝑇𝑓 = √𝑇1𝑇2 (proved)
(b) Let,𝑄2 be the quantity of heat when the temperature change from 𝑇2 to 𝑇𝑓
then 𝑄2 = 𝐶𝑝(𝑇2 − 𝑇𝑓) and 𝑄1 be the quantity of heat when the change of
temperature is 𝑇1 to 𝑇𝑓 then 𝑄1 = 𝐶𝑝(𝑇𝑓 − 𝑇1). Now, the total work done W=
𝑄2 − 𝑄1

= 𝐶𝑝(𝑇2 − 𝑇𝑓) + 𝐶𝑝(𝑇𝑓 − 𝑇1)

=𝐶𝑝(𝑇1 + 𝑇2 − 2𝑇𝑓) (Proved).

Combined first and second laws

Q1. Some important note: The first law of thermodynamics i. 𝑑𝑄 = 𝑑𝑢 + 𝑑𝑤
(1). But 𝑑𝑤 = PdV = work.
∴ Interns of mole, then we get, 𝑑 𝑞 = 𝑑𝑢 + 𝑑 𝑤
′ ′

⇒ 𝑑𝑢 = 𝑑′𝑞 − 𝑑′𝜔 = 𝑑′𝑐𝑖 − 𝑃𝑑𝑣

we know, the second law of thermodynamics is. 𝑑′𝑞 = 𝑇𝑑.

Here, entropy, 𝑑𝑠 = 𝑑𝑞 ∴ 𝑑′𝑞 = 𝑇 ⋅ 𝑑𝑠. Now combining (II) and (iii) then we
get, which is called the fundamental equation
thermodynamics.

• Cubical Expansion,
𝑝

• Compressibility,

Basic relation: 1.
5. When T and V be independent then we have,

a) -p c)

d)
6. When T and V be independent then we have,
a) =pvk -𝑘⁄𝛽̅ (𝐶𝑝 − 𝐶𝑣)

c)
7. When P and V be independent then we have,

a) -p c)

d)

Chain relation between (P,V,T): 1. 1 2.

Problem: Drive the following thermodynamics relation:

(𝑖𝑖)𝑇𝑑𝑠 = 𝑐𝑝𝑑𝑇 − 𝛽̅𝑣𝑇𝑑𝑝 (𝑖𝑖𝑖)𝑇𝑑𝑠 =

(𝑣𝑖)𝑐𝑝 −
Solution: Let us first consider the internal energy equation where T & v be
independent. i.e.
𝑢=
𝑢(𝑇, 𝑣) (𝑖)

i.e.

From the combined first and second law,

From (𝑖𝑖) we can also write,

(𝑖𝑣)
But equation (𝑖𝑖𝑖) and (𝑖𝑣) must be equal, then

Since 𝑑𝑇 and 𝑑𝑣 are independent, their coefficients in the two proceeding

equation must be equal, therefore

(𝑣𝑖)

& (𝑣𝑖𝑖)
Here, the second derivative of 𝑠 with respect to 𝑇 and 𝑣 is independent of the
order of differentiation i.e.

Again, -P

................................................................(X)

From (VIII) we get ,

But, when T&V be independent then we get,

From (XI) & (XII) we get, XIII)

(Hence VI is proved)

From (XIII) we get,

XIV)

Again we know that,

From (XIV) we get,

Hence ( VII) is proved

From (8) we get,

] (hence (5) proved)

Again for the three Tds equation: From(3)we
get,
T

dv [from(8)]

dv (hence(1) is proved)
For (2) Tds = cpdT −
βvTdp: if the entropy s be a funtion of p and T,i. e S = S(P,T) then

……………….(1)
But,from the maxwells equation we know,

Again we know that,

Now,multiplying both side of(1)by T.then we get,

For (3) dv: when,the entropy is a function of p&v I.e S =

But, from Maxwell's relation we know that,

and
Then (1) becomes,

since, in
adiabatic process,
 𝑑′𝑞s = 0 = 𝑇 ⋅ 𝑑𝑠

from previous two relation we get,

.
putting this value in (ii) then →

(proved)

Problem: Derive the thermodynamic relation

Solution:

(i) We know the Max well's relation is,

………………………………………….(i)

[partially differentiation w.r.t ]

 ……………………………………….(ii)

But, (𝜕𝑠⁄𝜕𝑇)𝑣 = 𝐶𝑣⁄𝑇

(proved)

(ii) From Maxwell relation we get,

………………………………….(i)
Now, partially differentiating (i) w.r. to 𝑇. then.

……………………………..(ii)
But. we know that,

………………………………(iii)
 (Hence complete the drive)

(iii) Consider, a internal energy is a function of 𝑃 & 𝑇. i.e P and 𝑇 are

independent Then,

𝑢 = 𝑢(P, 𝑇)
……..……………………………(i)

………………………….(ii)

………………(iii)
But,

Now, at the constant pressure, 𝑑𝑝 = 0 and (𝑑′𝑞/𝑑𝑇)𝑝 = 𝑐𝑝

Now, from (iv) we get,

…….…………….(vi)

At the content volume,

But we know, , putting this value in (𝑣𝑖𝑖) then.

For, .

We know the 𝑇 ⋅ 𝑑𝑆 relation b, . consider the system is

in adiabatic proces. then
Problem: Derive Maxwell’s four Thermodynamic relation

Solution: From the first law of thermodynamic , We know ,

𝑑𝑈 = 𝑑𝑄 − 𝑑𝑊 = 𝑑𝑄 − 𝑃𝑑𝑉 − − − − − − − (𝑖)
Again, from 2nd law of thermodynamic is
𝑑𝑄 = 𝑇𝑑𝑆 − − − − − − − (𝑖𝑖)
Now, Combining (i) & (ii) then we get,
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 − − − − − − − (𝑖𝑖𝑖)
Which is a equation of (U,T,S&V). Now consider (in the equation) S and V be
independent and the yare the function of (x,y)
Putting this value in (iii), then,

Similarly, U is a function of (x,y), i.e U=U(x,y) 𝜕𝑈 𝜕𝑈

(iv) & (v) are identical so.

Here , the co-efficient of dx & dy are equal, then

Since, dU is a perfect differential, then we use Euler’s condition,

Now, consider Temperature and Volume are independent , so

T=x and V=y, . Then

From (vii) we get ,

Henced (ii) is proved.

Again, consider Temperature and Pressure are independent , so

T=x and P=y, . Then

Putting this value in (vii) then we get ,

Henced (iii) is proved.

Also, we consider Entropy and Pressure are independent , then

S=x and P=y, . Then

Putting this value in (vii) then we get
,
𝑃

Henced (iv) is proved.

Finally, we consider Volume and Entropy are independent , then

V=x and S=y, . Then

Putting this value in (vii) then we get
,
𝑉

Henced (i) is proved.

Which are the Maxwell’s four Thermodynamic relations.