Course No.

Phy- 1203(B), Heat & Thermodynamics, Physics Discipline, KU

Chapter - 5
The First Law of Thermodynamics

Md. Shohel Parvez

Assistant Professor
Physics Discipline, Khulna University, Khulna
 What do you mean by Thermodynamics?

• Deals with transformation /relationship between heat and other forms

of energy (mechanical, electrical or chemical energy).

 Laws of Thermodynamics.

o Zeroth law

• Introduces the concept of temperature and thermodynamic

equilibrium.

o First Law

• Represents relationship between heat and mechanical work.

o Second Law

• Depicts the manner in which these energy changes take place.

o Third Law

• States the properties of systems in equilibrium at absolute zero

temperature.

 What do you mean by Thermodynamic System?

o A definite quantity of matter (solid, liquid or gas) bounded by some

surface. (Homogeneous and heterogeneous system.)

 What are the Classes of System ?

o Open, closed and isolated.

 Zeroth Law of Thermodynamics
• The zeroth law of thermodynamics state that if two bodies A and B are
each separately in thermal equilibrium with a third body C, then A and
B are also in thermal equilibrium with each other.

• In another way if we consider two systems A and B insulated from

each other But in good thermal contract with C then A and B will
attain thermal equilibrium.
 First Law of Thermodynamics
If a certain amount of heat Q is supplied to a system which does external
work W in passing from state 1 to state 2, the amount of heat is equal to
sum of the increase in the internal energy of the system and the external
work done by the system. Mathematically,
Q= (U2-U1) + W
For a very small change in the state of the system, the law is expressed in
the differential form as
δQ= dU + δW
Where δQ, δW are not perfect differentials but dU is a perfect
differential because U is a function of the state of the system.
The amount of heat Q or δQ is positive if heat is supplied to the system
and negative if heat is removed from it. Similarly, the work W or δW is
positive when external work is done by the system in expansion and
negative if work in done on it in compression.

Significance of 1st law Limitations of 1st law

It is applicable to any process by Since it is based on the principle of

which a system undergoes a conservation of energy of a system but
physical or chemical change it does not specify the condition under
which a system can use its heat energy
It introduces the concept of internal
to produce a supply of mechanical
energy.
work.
It provides method for determining It also does not say how much of
the change in internal energy the heat energy can be converted
into work.
 Internal energy
The energy content of a system is called its internal energy. It is the
sum of following forms of energy of the system.
 Kinetic energy (KE) due to translational rotational and vibrational
motion of the molecules, all of which depend only on temperature.
 Potential energy (PE) due to intermolecular forces, which depends on
the separation between the molecules.
 The energy of electrons (𝑒 − ) and nuclei.
In practice, it is not possible to measure the total internal energy of a
system in any state. Only change in its value can be measured.
If the state of the system is changed from an initial state 1 to a final state
2, by supplying heat Q to the system and if W is the work done by the
system during the change, then increase in the internal energy of the
system is,
U2 - U1 = Q - W
Where U1 is the internal energy in state 1 and U2 the state 2.

Specific Heat: Heat capacity per unit mass is known as specific heat or
the quantity of heat required to raise the temperature of unit mass of the
material through 1 degree also the ratio of the heat supplied to rise in
temperature per unit mass.
𝑄 𝑑𝑄 If unit mole is used insted
C= = of unit mass n is used
𝑚.Δ𝑇 𝑑𝑇
insted of m
Where C is the specific heat, Q is the amount of heat ΔT is the change in
temperature.
This is valid for solid and liquid but in case of gas specific heat vary
from 0 to ∞. For example if a gas is compressed, it’s temperature rises,
without supplying any heat to it. So

0
𝐶= =0
𝑚. Δ𝑇
On the contrary, if the gas is allowed to expand freely; without any rise
in temperature (ΔT=0) then,

𝑄
𝐶= =∞
𝑚. 0
Hence, specific heat of a gas is defined by considering any one of the
two (either volume or pressure) is constant. Thus a gas has two specific
heats
 Cp the specific heat at constant pressure
 Cv the specific heat at constant volume.

Mayer’s Relation
Relation between Cv, Cp and R is called Mayer’s relation.

The internal energy of a system is a single valued function of the

state variables viz. pressure, volume, temperature etc. In the case of gas
any two of the variables P, V, T are sufficient to define completely its
state.
Let V and T are independent variables,
𝑈 = 𝑓(𝑉, 𝑇) … … … … … … … … . (i)
Differentiating equation (i)
𝜕𝑈 𝜕𝑈
dU=( )𝑉 dT + ( )𝑇 dV …… (ii)
𝜕𝑇 𝜕𝑉

If an amount of heat δQ is supplied to a thermodynamical system, say an

ideal gas and if the volume increases by dV at a constant pressure P then
according to the first law of thermodynamics
δQ = dU + δW
Here δW = P. dV
So δQ = dU + P. dV
Substituting the value of dU from equation (ii),
δ𝑈 𝜕𝑈
δQ = ( )𝑉 𝑑𝑇 + ( )𝑇 𝑑𝑉 + 𝑃𝑑𝑉 ….....(iii)
δ𝑇 𝜕𝑉

Dividing both sides by dT

δ𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉 𝑃𝑑𝑉
= ( )𝑉 + ( ) 𝑇 +
𝑑𝑇 𝜕𝑇 𝜕𝑉 𝑑𝑇 𝑑𝑇
δ𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉
Or ( ) = ( )𝑉 + ⦋𝑃 + )𝑇 …………..(iv)
𝑑𝑇 𝜕𝑇 𝜕𝑉 𝑑𝑇

δ𝑄 𝑑𝑉
If the gas is heated at constant volume, then ( )𝑉 = 𝐶𝑉 and =0
𝜕𝑇 𝑑𝑇

δ𝑄 𝜕𝑈
So ( )𝑉 = ( )𝑉 = 𝐶𝑣
𝑑𝑇 𝜕𝑇

δ𝑄
when the gas is heated at constant pressure, ( )𝑝 = 𝐶𝑃
𝑑𝑇
Now from equation (iv) we get,
𝜕𝑈 𝜕𝑈 𝜕𝑉
𝐶𝑃 = ( )𝑉 + ⦋𝑃 + ) ( )𝑃
𝜕𝑇 𝜕𝑉 𝑇 𝜕𝑇

𝜕𝑈 𝜕𝑉
𝐶𝑃 = 𝐶𝑉 + ⦋𝑃 + ) ( )𝑃
𝜕𝑉 𝑇 𝜕𝑇

𝜕𝑈 𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = ⦋𝑃 + ) ( )𝑃
𝜕𝑉 𝑇 𝜕𝑇

From Joule’s experiment, for an ideal gas on opening the stopcock, no

work was done and no heat transfer took place. So δQ = 0 = dU+0.
therefore dU = 0. Even though the volume changed, while the
temperature is constant, there is no change in internal energy. So ,
𝜕𝑈
( ) =0
𝜕𝑉 𝑇
From the ideal gas equation, PV=RT
𝜕𝑉
or, P ( )𝑝 =𝑅
𝜕𝑇

𝜕𝑉
𝐶𝑃 − 𝐶𝑉 = 𝑃 ( )𝑃 =R
𝜕𝑇

𝐶𝑃 − 𝐶𝑉 = R
This formula is known as Mayer’s relation.

Isothermal Process and Adiabatic Process:

An isothermal process is a change of a system, in which the temperature
remains constant: ΔT = 0
In thermodynamics, an adiabatic process is one that occurs without
transfer of heat or matter between a thermodynamic system and its
surroundings. In an adiabatic process, energy is transferred to its
surroundings only as work. The adiabatic process provides a rigorous
conceptual basis for the theory used to expound the first law of
thermodynamics, and as such it is a key concept in thermodynamics.
Adiabatic equation of a perfect gas
Consider 1 gram of working substance (ideal gas) perfectly insulated
from the surroundings. Let the external work done by the gas be 𝛿𝑊.
Applying the first law of thermodynamics
𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊
𝐵𝑢𝑡 𝛿𝑄 = 0
𝑎𝑛𝑑 𝛿𝑊 = 𝑃. 𝑑𝑉
Where P is the pressure of the gas and dV is the change in volume.

𝑃. 𝑑𝑉
∴ 0 = 𝑑𝑈 + … … … … . . (𝑖)
𝐽
Where J is mechanical equivalent of heat.
 As the external work is done by the gas at the cost of its internal
energy, there is fall in temperature by 𝑑𝑇.
𝑑𝑈 = 1 × 𝐶𝑣 × 𝑑𝑇 (∴ 𝑚 = 1)

𝑃. 𝑑𝑉
𝐶𝑣 . 𝑑𝑇 + =0 … … … … … (𝑖𝑖)
𝐽
For an ideal gas of 1 gram, we have
𝑃𝑉 = 𝑅𝑇 … … … … … (𝑖𝑖𝑖)
Where R is ordinary gas constant.
Differentiating,
𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑅𝑑𝑇
Substituting the value of dT in equation (ii) ,
𝑃𝑑𝑉+𝑉𝑑𝑃 𝑃𝑑𝑉
𝐶𝑣 + =0
𝑅 𝐽
 𝑃𝑑𝑉
𝐶𝑣 𝑃𝑑𝑉 + 𝑉𝑑𝑃 + 𝑅 =0
𝐽

𝑅
𝐵𝑢𝑡, = 𝐶𝑝 − 𝐶𝑣
𝐽
∴ 𝐶𝑣 𝑃𝑑𝑉 + 𝐶𝑣 𝑉𝑑𝑃 + 𝐶𝑝 𝑃𝑑𝑉 − 𝐶𝑣 𝑃𝑑𝑉 = 0
𝐶𝑝 𝑃𝑑𝑉 + 𝐶𝑣 𝑉𝑑𝑃 = 0
Dividing by 𝐶𝑣 𝑃𝑉,

𝐶𝑝 𝑑𝑉 𝑑𝑃
+ =0
𝐶𝑣 𝑉 𝑃

𝐶𝑝
𝐵𝑢𝑡 = 𝛾
𝐶𝑣
 𝑑𝑃 𝑑𝑉
∴ + 𝛾 =0
𝑃 𝑉
Integrating,
log 𝑃 + 𝛾 log 𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
log 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 … … … (𝑖𝑣)
This is the equation connecting pressure and volume during an
adiabatic process and is known as Poisson’s law.
Now taking
𝑃𝑉 = 𝑅𝑇

𝑅𝑇
𝑃=
𝑉
Putting this value in equation (iv)

𝑅𝑇 𝛾
𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉

But r is constant
𝑅𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 … … … . . (𝑣)
𝑅𝑇
Also 𝑉=
𝑃

𝑅𝑇 𝛾
𝑃 [ ] = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃

𝑅𝛾 𝑇 𝛾
𝛾−1
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃
 𝑃𝛾−1
𝛾
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇
𝑇𝑃(1−𝛾)/𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
This is the required equation.
Work done during an isothermal process
When a gas is allowed to expand isothermally, work is done by it. Let
the initial and final volumes be 𝑉1 and 𝑉2 respectively.
A
Fig. represents the indicator
diagram. The shaded area represents
𝑑𝑉
the work done for changing the B

volume from 𝑉1 to 𝑉2 . a b
𝑉1 𝑉2
Now the work done

𝑉2
𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = 𝑃𝑑𝑉 = 𝐴𝑟𝑒𝑎 𝐴𝐵𝑏𝑎
𝑉1

Considering one gram molecule of the gas

𝑃𝑉 = 𝑅𝑇

𝑅𝑇
𝑃=
𝑉

𝑉2
𝑑𝑉
𝑊 = 𝑅𝑇
𝑉1 𝑉

𝑉2
𝑊 = 𝑅𝑇 × 2.303 log10
𝑉1
 Also 𝑃1 𝑉1 = 𝑃2 𝑉2

𝑉2 𝑃1
=
𝑉1 𝑃2

𝑃1 𝑃1
∴ 𝑊 = 𝑅𝑇 × 2.303 log10 = 𝑅𝑇𝑙𝑛
𝑃2 𝑃2
Here the internal energy of the system is zero (because the
temperature remains constant). So the heat absorbed by the system is
equal to the work done by it.
Work done during an adiabatic process
During an adiabatic process, the system is thermally insulated from
the surroundings. The gas expands from volume 𝑉1 to 𝑉2 as shown by
indicator diagram [fig before].
The work done by the gas for an increase in volume dV is 𝑃𝑑𝑉.
Work done when the gas expands from 𝑉1 to 𝑉2 is given by

𝑉2
𝑊= 𝑃 𝑑𝑉 = 𝐴𝑟𝑒𝑎 𝐴𝐵𝑏𝑎
𝑉1

We know, during an adiabatic process

𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝐾

𝐾
𝑃= 𝛾
𝑉

𝑣2
𝑑𝑉
𝑊=𝐾
𝑣1 𝑉𝛾
 𝐾 1 1
= 𝛾−1 − 𝛾−1
1−𝛾 𝑉 𝑉1
2
Since A and B lie on the same adiabatic,
𝛾 𝛾
𝑃1 𝑉1 = 𝑃2 𝑉2 = 𝐾

1 𝐾 𝐾
𝑊= 𝛾−1 − 𝛾−1
1−𝛾 𝑉 𝑉1
2

𝛾 𝛾
1 𝑃2 𝑉2 𝑃1 𝑉1
= 𝛾−1 − 𝛾−1
1−𝛾 𝑉 𝑉1
2

1
𝑊= 𝑃2 𝑉2 − 𝑃1 𝑉1 … … . (𝑣𝑖)
1−𝛾
 Taking 𝑇1 and 𝑇2 as the temperatures at points A and B respectively
and considering one gram molecule of the gas,
𝑃1 𝑉1 = 𝑅𝑇1
𝑃2 𝑉2 = 𝑅𝑇2
Substituting these values in equation (vi)

1
𝑊= 𝑅𝑇2 − 𝑅𝑇1
1−𝛾

𝑅
𝑊= 𝑇2 − 𝑇1
1−𝛾

𝑅
𝑊= [𝑇1 − 𝑇2 ]
𝛾−1
 Hence the work done in adiabatic process depends only upon the
initial and final temperatures 𝑇1 and 𝑇2 . Thus the work done along any
adiabatic between two isothermals is independent of the particular
adiabatic.
Relation between adiabatic and isothermal elasticities
During an isothermal process
𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Differentiating,
𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 0

𝑉. 𝑑𝑃
𝑃= … … … . . (𝑖)
−𝑑𝑉
From the definition of elasticity of a gas
 𝑑𝑃
𝐸𝑖𝑠𝑜 =
−𝑑𝑉
𝑉
𝑉𝑑𝑃
= … … … (𝑖𝑖)
−𝑑𝑉
From (i) and (ii)
𝐸𝑖𝑠𝑜 = 𝑃 … … … (𝑖𝑖𝑖)
Now during an adiabatic process
𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
Differentiating
𝑃𝛾𝑉 𝛾−1 𝑑𝑉 + 𝑉 𝛾 𝑑𝑃 = 0

𝑉𝑑𝑃
= 𝛾𝑃 … … … . . (𝑖𝑣)
−𝑑𝑉
 From the definition of elasticity of a gas

𝑑𝑃
𝐸𝑎𝑑𝑖 =
−𝑑𝑉
𝑉
𝑉. 𝑑𝑃
= … … … … (𝑣)
−𝑑𝑉
From (iv) and (v)
𝐸𝑎𝑑𝑖 = 𝛾𝑃 … … … . 𝑣𝑖
Comparing (iii) and (vi)
𝐸𝑎𝑑𝑖 = 𝛾𝐸𝑖𝑠𝑜
Thus, the adiabatic elasticity of a gas is γ times the isothermal
elasticity