THE COPPERBELT UNIVERSITY

SCHOOL OF MATHEMATICS AND NATURAL SCIENCES

DEPARTMENT OF PHYSICS
PHP 271
PROPERTIES OF MATTER AND THERMODYNAMICS

THERMODYNAMICS: LAWS OF THERMODYNAMICS

APPLICATIONS OF FIRST LAW OF THERMODYNAMICS

1. Specific Heat of a Gas (V and T independent)
In our previous lecture we did mention that the internal energy of a system is a single
valued function of the state variables, namely, pressure, volume, temperature etc. If
we take a gas as our system, we able to define its state completely just by knowing
any two of the variables P, V, T. Suppose we take temperature and volume as the
independent variables, what we get is

𝑈 = 𝑓(𝑉, 𝑇) (1)

Now, if we differentiate equation (1), we get

𝑑𝑈 = (𝜕𝑈⁄𝜕𝑇)𝑉 𝑑𝑇 + (𝜕𝑈⁄𝜕𝑉) 𝑇 𝑑𝑉 (2)

Let us suppose that an amount of heat δQ is supplied to our thermodynamic system

like an ideal gas and we also assume that as the heat is supplied, its volume increases
by dV at constant pressure P, then when we apply first law of thermodynamics

𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊

Where

1|Applications of First Law of Thermodynamics

 𝛿𝑊 = 𝑃. 𝑑𝑉

Rewriting first law of thermodynamics gives

𝛿𝑄 = 𝑑𝑈 + 𝑃. 𝑑𝑉

But equation (2) gives us an expression dU and by substitution in above equation we

get

𝛿𝑄 = (𝜕𝑈⁄𝜕𝑇)𝑉 𝑑𝑇 + (𝜕𝑈⁄𝜕𝑉) 𝑇 𝑑𝑉 + 𝑃. 𝑑𝑉 (3)

Now, let us divide each side by dT

𝜕𝑄⁄𝑑𝑇 = (𝜕𝑈⁄𝜕𝑇)𝑉 + (𝜕𝑈⁄𝜕𝑉) 𝑇 𝑑𝑉⁄𝑑𝑇 + 𝑃. 𝑑𝑉⁄𝑑𝑇

Taking out dV/dT on the left hand side will give us

(𝜕𝑄⁄𝑑𝑇)𝑉 = (𝜕𝑈⁄𝜕𝑇)𝑉 + [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ] 𝑑𝑉⁄𝑑𝑇 (4)

If the gas is heated at constant volume, specific heat capacity is given by

𝐶𝑉 = (𝛿𝑄⁄𝜕𝑇)𝑉

And 𝑑𝑉⁄𝑑𝑇 = 0

Applying the two expressions above to equation (4), we get

(𝜕𝑄⁄𝑑𝑇)𝑉 = (𝜕𝑈⁄𝜕𝑇)𝑉 = 𝐶𝑉 (5)

Then if we heat gas at constant pressure, the specific heat capacity is given by

𝐶𝑃 = (𝛿𝑄⁄𝜕𝑇)𝑃

Applying it to equation (4) gives us

2|Applications of First Law of Thermodynamics

 𝐶𝑃 = (𝜕𝑈⁄𝜕𝑇)𝑉 + [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ] (𝜕𝑉⁄𝜕𝑇)𝑃

Then replacing for CV we get

𝐶𝑃 = 𝐶𝑉 + [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ] (𝜕𝑉⁄𝜕𝑇)𝑃

Then we take specific capacities to the left side we get

𝐶𝑃 − 𝐶𝑉 = [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ] (𝜕𝑉⁄𝜕𝑇)𝑃 (6)

In an event that we have no work being done and no transfer of heat, we have

𝛿𝑄 = 0 = 𝑑𝑈 + 0

This implies that dU = 0, and we can write,

(𝜕𝑈⁄𝜕𝑉) 𝑇 = 0

From the ideal gas equation, which is

𝑃𝑉 = 𝑅𝑇

Which is also written as

𝑃(𝜕𝑉 ⁄𝜕𝑇)𝑃 = 𝑅 (7)

We can rearrange equation (6) and make some substitutions based on the above
expressions to get a new expression.

𝐶𝑃 − 𝐶𝑉 = 𝑃 (𝜕𝑉⁄𝜕𝑇)𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 (𝜕𝑉⁄𝜕𝑇)𝑃

But we know that

(𝜕𝑈⁄𝜕𝑉) 𝑇 = 0

And replacing for it in the equation above equation we get

𝐶𝑃 − 𝐶𝑉 = 𝑃 (𝜕𝑉⁄𝜕𝑇)𝑃 = 𝑅

3|Applications of First Law of Thermodynamics

Therefore, we have

𝐶𝑃 − 𝐶𝑉 = 𝑅 (8)

Equation (8) is known as Mayer’s relation.

Now, let us revisit equation (3)

𝛿𝑄 = (𝜕𝑈⁄𝜕𝑇)𝑉 𝑑𝑇 + (𝜕𝑈⁄𝜕𝑉) 𝑇 𝑑𝑉 + 𝑃. 𝑑𝑉

We can rewrite it by factoring out dV to get

𝛿𝑄 = (𝜕𝑈⁄𝜕𝑇)𝑉 𝑑𝑇 + [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ]𝑑𝑉 (9)

If the process is at constant temperature it means that dT = 0, and replacing it in

equation (9) we get

(𝛿𝑄) 𝑇 = 𝑃(𝑑𝑉) 𝑇 + (𝜕𝑈⁄𝜕𝑉) 𝑇 (𝑑𝑉) 𝑇 (10)

This equation is a representation of the amount of heat energy supplied to a system

in an isothermal reversible process and is equal to the sum of the work done by the
system and increase in its internal energy.

Reversible Adiabatic Process

We know that for an adiabatic process, there is no transfer of heat and we can write

𝛿𝑄 = 0

Now, substituting this into equation (9) we get

0 = (𝜕𝑈⁄𝜕𝑇)𝑉 𝑑𝑇 + [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ]𝑑𝑉

And we also replace for specific heat at constant volume, we get

0 = 𝐶𝑉 𝑑𝑇 + [𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ]𝑑𝑉

Which we can rewrite as

4|Applications of First Law of Thermodynamics

 𝐶𝑉 𝑑𝑇 = −[𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ]𝑑𝑉

We can divide the above equation by 𝑑𝑉 to get

𝐶𝑉 (𝜕𝑇⁄𝜕𝑉) = −[𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ] (11)

Now, the isobaric coefficient of expansion is given by

1
𝛼= (𝜕𝑉 ⁄𝜕𝑇)𝑃
𝑉

Multiplying each side of the above equation by V we get

𝛼𝑉 = (𝜕𝑉 ⁄𝜕𝑇)𝑃

We can substitute for αV in our earlier equation just above equation (8)

𝐶𝑃 − 𝐶𝑉 = 𝑃 (𝜕𝑉⁄𝜕𝑇)𝑃

And we get

𝐶𝑝 − 𝐶𝑉
=𝑃
𝛼𝑉

Now, recall that if the volume changes while the temperature is constant, there is
no change in the internal energy

(𝜕𝑈⁄𝜕𝑉) 𝑇 = 0

Or

(𝜕𝑈⁄𝜕𝑉 )𝑇 = 0 = 𝑃 − 𝑃

Or

𝐶𝑝 − 𝐶𝑉
(𝜕𝑈⁄𝜕𝑉 )𝑇 = ( )−𝑃 (12)
𝛼𝑉

Rearranging equation (12)

5|Applications of First Law of Thermodynamics

We get

𝐶𝑝 − 𝐶𝑉
( ) − 𝑃 = (𝜕𝑈⁄𝜕𝑉 )𝑇
𝛼𝑉

𝐶𝑝 − 𝐶𝑉
−( ) = −[𝑃 + (𝜕𝑈⁄𝜕𝑉) 𝑇 ] (13)
𝛼𝑉

Look at equations (11) and (13), we can make up a relation as given below

𝐶𝑝 − 𝐶𝑉
𝐶𝑉 (𝜕𝑇⁄𝜕𝑉 ) = − ( )
𝛼𝑉

Dividing each side by CV, we get

𝐶𝑝 − 𝐶𝑉
(𝜕𝑇⁄𝜕𝑉 ) = − ( ) (14)
𝛼𝑉𝐶𝑉

Equation (14) applies to an adiabatic reversible process.

2. Isochoric process (Constant Volume)

An isochoric process is a process in which there is no change the volume. As we
know the external work at constant volume is zero (δW=0). So from first law of
thermodynamics, the heat absorbed is given by

𝛿𝑄 = 𝑑𝑈

This shows us that at constant volume, the internal energy is equal to the heat
absorbed because external work on the system is zero.

3. Isobaric Process
This is the process in which a system undergoes a change at constant pressure. Let
Q be the heat absorbed by such a system and let the volume increase from initial
volume V1 to final volume V2. So from the first law we get

𝑄 = (𝑈2 − 𝑈1 ) + 𝑊

6|Applications of First Law of Thermodynamics

Which can also be expressed as

𝑄 = (𝑈2 − 𝑈1 ) + 𝑃(𝑉2 − 𝑉1 )

𝑄 = (𝑈2 − 𝑃𝑉2 ) − (𝑈1 − 𝑃𝑉1 )

𝑄 = 𝐻2 − 𝐻1 (15)

Here 𝐻 = 𝑈 + 𝑃𝑉

What we notice from equation (15) is that the heat absorbed by a system at constant
pressure is equal to increase in a quantity H which is known as the enthalpy. The
enthalpy is a function of thermodynamic variables. Enthalpy is also known as the
heat function at constant pressure.

4. Adiabatic Process
This is a process in which a system undergoes from an initial state to a final state in
such a way that there is no heat leaves or enters the system.

In an adiabatic process

𝑄=0

So, from first law of thermodynamics

𝑈2 − 𝑈1 = −𝑊

For an ideal gas

𝑈2 − 𝑈1 = 𝐶𝑉 𝑑 𝑇

Therefore

𝑊 = −𝐶𝑉 𝑑 𝑇

7|Applications of First Law of Thermodynamics

W is the work done by the system. So, when a system does work adiabatically the
internal energy decreases. If the system is compressed adiabatically then work
done is negative. So, in compression

𝑈2 − 𝑈1 = −(−𝑊) = 𝑊

So in adiabatic compression, the internal energy increases. Such processes occur

suddenly or very quickly.

Adiabatic Equation of a Perfect Gas

Let us consider a 1 gram of the working substance (idea gas) perfectly insulated from
the surroundings. Then let the external work done by the gas be δW.

From first law of thermodynamics, we have

𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊

But for an adiabatic system change in heat δQ is zero and we know that 𝛿𝑊 = 𝑃. 𝑑𝑉
where P is the pressure of the gas and dV is the change in volume.

Replacing all these in first law of thermodynamics we get

𝑃. 𝑑𝑉
0 = 𝑑𝑈 + (𝑖)
𝐽

Where J is a mechanical equivalent of heat.

As the external work is done by the gas at the cost of its internal energy, there is a
reduction in temperature by dT.

Now internal energy can be given as

𝑑𝑈 = 𝑚𝐶𝑉 𝑑𝑇

𝑑𝑈 = 1 𝑥 𝐶𝑉 𝑑𝑇

8|Applications of First Law of Thermodynamics

Replacing in equation (i), we get

𝑃. 𝑑𝑉
𝐶𝑉 𝑑𝑇 + =0 (𝑖𝑖)
𝐽

For an ideal gas of 1 gram, we have

𝑃𝑉 = 𝑟𝑇 (𝑖𝑖𝑖)

Where r is an ordinary gas constant

If we differentiate equation (iii) we get

𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑟𝑑𝑇

Substituting the value of dT in equation (ii), we shall get

𝑃𝑑𝑉 + 𝑉𝑑𝑃 𝑃𝑑𝑉

𝐶𝑉 [ ]+ =0
𝑟 𝐽

Then dividing through by r, we get

𝑃𝑑𝑉
𝐶𝑉 [𝑃𝑑𝑉 + 𝑉𝑑𝑃] + 𝑟 =0
𝐽

Now, we can set r/J as

𝑟
= 𝐶𝑃 − 𝐶𝑉
𝐽

And replacing for it in the above equation, we get

𝐶𝑉 𝑃𝑑𝑉 + 𝐶𝑉 𝑉𝑑𝑃 + 𝐶𝑃 𝑃𝑑𝑉 − 𝐶𝑉 𝑃𝑑𝑉 = 0

𝐶𝑉 𝑉𝑑𝑃 + 𝐶𝑃 𝑃𝑑𝑉 = 0

Dividing through by 𝐶𝑉 𝑃𝑉,

9|Applications of First Law of Thermodynamics

 𝐶𝑉 𝑑𝑉 𝑑𝑃
. + =0
𝐶𝑃 𝑉 𝑃

But we can set Cp/Cv as

𝐶𝑃
=𝛾
𝐶𝑉

Therefore

𝑑𝑃 𝑑𝑉
+𝛾 =0
𝑃 𝑉

Integrating,

log 𝑃 + 𝛾𝑙𝑜𝑔𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝑙𝑜𝑔𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑖𝑣)

Equation (iv) above connecting pressure and volume in an adiabatic process is

known as Poisson’s law.

Taking 𝑃𝑉 = 𝑟𝑇

Or

𝑟𝑇
𝑃=
𝑉

Replacing for P in equation (iv) we get

𝑟𝑇
( ) . 𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉

𝑟𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

But ris a constant so we can write above expression as

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 𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑣)

We can also write equation (iii) as

𝑟𝑇
𝑉=
𝑃

We can substitute for V in equation (iii) to get

𝑃[𝑟𝑇⁄𝑃]𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Or

𝑟𝛾𝑇𝛾
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝛾−1

Or

𝑃𝛾−1
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑣𝑖)
𝑇𝛾

So we see that in an adiabatic process, we have three important relations:

i. 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
ii. 𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑃𝛾−1
iii. = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑇𝛾

5. Cyclic Process
The first law of thermodynamics for a cyclic process can be stated as

∮ 𝑑𝑄 = ∮ 𝑑𝑈 + ∮ 𝑑𝑊

For such a process, the system is restored to the initial state at the end of the cycle.

We note that internal energy is a state function so ∮ 𝑑𝑈 = 0

11 | A p p l i c a t i o n s o f F i r s t L a w o f T h e r m o d y n a m i c s
And the first law of thermodynamics can now be set as

∮ 𝑑𝑄 = ∮ 𝑑𝑊

Hence, total work obtained equals to net heat supplied. This tells us that no work is
achieved if no heat is supplied. We can also say that work can only be achieved when
there is a flow of energy.

So from our diagram above we can write:

𝑄 = 𝑎𝑟𝑒𝑎 𝑜𝑓 𝐴𝐶𝐵𝐷𝐴

6. Non-isolated system
The sum of systems together with surroundings constitute the universe. Transfer of
heat is able to flow between the system and its surroundings in an isolated system.
The internal energy raises by an amount dU in such a system when an amount of
heat δQ is supplied and external work δW is done. So from first law of
thermodynamics, we have

𝛿𝑄 = 𝑑𝑈 + 𝛿𝑊

𝑑𝑈 = 𝛿𝑄 − 𝛿𝑊

12 | A p p l i c a t i o n s o f F i r s t L a w o f T h e r m o d y n a m i c s
The change in heat δQ is positive because heat is supplied to the system. The external
work done δW is also positive because work is done by the system not on the system.

If we apply the first law of thermodynamics to the surroundings, which loses heat of
δQ and receives amount of work δW, we see that both amount of heat δQ and work
δW are negative for the surroundings.

Therefore, change in internal energy of surroundings

𝑑𝑈 ′ = −𝛿𝑄 − (−𝛿𝑊)

𝑑𝑈 ′ = 𝛿𝑊 − 𝛿𝑄

𝑁𝑒𝑡 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 = 𝑑𝑈 + 𝑑𝑈 ′

= (𝛿𝑄 − 𝛿𝑊) + (𝛿𝑊 − 𝛿𝑄) = 0

So, we see that net change in internal energy is always zero.

7. Isothermal Process
This is a system that is perfectly conducting to the surrounding without a temperature
change.

Let us consider a working substance at a certain pressure and temperature with a

volume that is represented by point A in the figure above.

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As the pressure is decreased, work is done by the working substance at the expense
of the internal energy which results in a fall of temperature. Since the system
conducts perfectly, the temperature will be constant as it absorbs heat from the
surrounding. In the figure we see that to move from A to B, the system absorbs heat
from the surrounding at constant temperature and in moving from B to A, the system
gives heat back to the surrounding at constant temperature. The line AB is known as
an isothermal curve or just an isothermal.

The equation for an isothermal process is

𝑃𝑉 = 𝑅𝑇 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡(𝑓𝑜𝑟 1 𝑔 𝑜𝑓 𝑔𝑎𝑠)

For n gram molecules of a gas,

𝑃𝑉 = 𝑛𝑅𝑇

But we know that for an ideal gas in an isothermal process the change in internal
energy is zero, that is,

(𝑈2 − 𝑈1 ) = 0

So, from the first law of thermodynamics, we shall have

Heat absorbed equals to work done, which is

𝑄=𝑊

Thus, in an isothermal process the heat supplied to an ideal gas is equal to the work
done by the gas.

For now, we end here, we shall look at indicator diagrams and Carnot’s Ideal Heat
Engine.

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