CHAPTER TWO

2.0 : THE FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics is popularly called the law of conservation of energy.
This law is stated as follows:

Energy can be neither created nor destroyed. If it disappears in one form it

must reappear in some other equivalent form.

This statement also implies that the energy of the universe is constant. If there is an
increase in the energy of the system, there must be a decrease in the energy of the
surroundings and vice versa.

2.1 : Statement of the first law of thermodynamics

Consider an example of a balloon with some air in it placed under sunshine to receive a
quantity of heat q. Since the balloon is our system it contains total energy U, once it receives
quantity of heat q its internal energy changes or increases due to the increase in kinetic energy
of the gaseous molecules. The molecules start moving at a high speed colliding with each
other and the walls of the balloon exerting pressure on the balloon making it to expand and its
volume increases.

Mathematical formulation of the law of conservation of energy is called the first law of
thermodynamics. In terms of energy, heat and work the first law of thermodynamics is
written as:

∆U = q ± w

Here: ∆U = Change in the internal energy of the system

∆U = U (final) – U (initial) if U (final) > U (initial) then ΔU is a

positive and vice versa. Since ΔU has both size and direction then it is
regarded as a vector quantity

q = Heat absorbed by the system

+w = Work done on the system (it includes all possible types of work)

Delta (∆) is not used before q and w

Reason. q and w depend on path and there is no initial and final heat or work of the system.
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The concept of heat or work comes into picture only during the change. If there is no
change, there is no heat or work. But the system has energy.

Change in internal energy and heat exchanged in an isochoric process

The change in internal energy is equal to the heat exchanged between the systems and
surrounding at constant volume. Let us prove it.
The first law of thermodynamics states that ∆U = q ±w where ∆U is the change of internal
energy, q is the heat exchanged between the system and surroundings and w is the work done
against an opposing force.
The mechanical work at constant pressure due to volume change is given by

w = –P ×∆V

Where ∆V is the volume change and P is the constant pressure. For such a case the first law of
thermodynamics can be written as:

∆U = q + w = q – P×∆V

In an isochoric process volume is constant and ∆V = 0, therefore, the product P×∆V is also
zero. Thus, for an isochoric process the first law of thermodynamics can be written as

∆U = q at constant volume

Or ∆U = qv

Here subscript 'V' in qv indicates that volume (V) is constant. The relation ∆U = qv is a link
between the chemical energy (∆U) and thermal energy (q).

Need of a new thermodynamic property- the enthalpy

In the laboratory usually the experiments are performed at constant atmospheric pressure and
the volume is allowed to change. So the measured value of ∆U cannot account for the actual
heat exchanged between the system and surroundings at constant pressure. Hence, there is a
need of new function that can account for the total heat content. That is, we need a function
that must reflect as to how much heat is absorbed or liberated in the process at constant
pressure. This new property is called heat content or enthalpy.

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Definition of enthalpy (H)

It is the quantity of heat a body

contains. The enthalpy (H) is defined

by

H = U + PV where U is the internal energy, P is the pressure and V

is the volume

Sign conventions of ∆JI

When heat is absorbed by the system at constant pressure its enthalpy is increased so the
value of ∆H is positive. When ∆H is positive, the process is said to be endothermic.
When heat is liberated by the system at constant pressure its enthalpy is decreased so the
value of ∆H is negative. When ∆H is negative, the process is said to be exothermic.

Relation between ∆H and q

The enthalpy is defined by

H = U + PV

For a change in the states of the system

∆H =∆ (U + PV)

= ∆U + (P× ∆V+ V× ∆P) (i)

First law of thermodynamics states that

∆U = q + w = q – P× ∆V

(ii)
i) From equations (i) and (ii), we get

∆H = (q – P×∆ V) + (P× ∆V+ V× ∆P)

= q + V×∆P

When pressure is constant, ∆P = 0, and thus V × ∆P = 0, therefore

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 ∆H = q at constant pressure

Or, ∆H = qp

Here subscript 'P' in qp is used to state that pressure is constant in the process.

2.2 : Heat capacity

The quantity of heat needed to cause unit rise in the temperature of a substance is called its
heat capacity. It is denoted by symbol C and defined by.
q
C = ∆T

Units of heat capacity. Heat (q) is expressed in joules (J) and temperature in kelvin (K).
Therefore, heat capacity is expressed in the units of joules per kelvin (J K–1). Heat capacity is
an extensive property because the heat needed to raise the temperature of the system depends
on its size.

2.2.1 : Molar heat capacity. It is defined as the quantity of heat needed to cause unit rise

in the temperature of one mole of a substance. Molar heat capacity is denoted by Cm.

Units of molar heat capacity. Heat capacity is expressed as J K–1 and the amount is expressed
as mol. Therefore, molar heat capacity is expressed as J K–1 mol–1 (pronounced as joule per
Kelvin per mol). It should never be written as J/K/mol.
Molar heat capacity is an intensive property, because it is a ratio of two extensive properties.

2.2.2 : Specific heat capacity. It is defined as the quantity of heat needed to cause unit rise in

the temperature of unit mass of a substance. Specific heat capacity is denoted by small c or
small s. It is expressed in the units of J K–1 g–1

2.2.3 : Heat capacity at constant volume and at constant

pressure

From the first law of thermodynamics we know that the heat exchanged between the system
and surroundings depends on the experimental conditions, For example,

(i) Heat exchanged at constant volume = qV = ∆U

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 (ii) Heat exchanged at constant pressure = qP = ∆H

Therefore, depending on the experimental conditions the following two types of heat capacities
are defined.

(1) Heat capacity at constant volume

CV = q v = ∆U
∆T ∆T

For small temperature change the heat capacity at constant volume is expressed as

CV = ⎛⎜ ∂U ⎞⎟
⎝ ∂T ⎠V
C
Molar heat capacity at constant volume = CV,m = V

CV = n× CV,m

(2) Heat capacity at constant pressure

CP = q P = ∆H
∆T ∆

For small temperature change the heat capacity at constant pressure is expressed as

CP = ⎜⎛ ∂H ⎞⎟
⎝ ∂T ⎠P

Molar heat capacity at constant pressure = CP,m CP

=n

CP = n× CP, m

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2.3 : Relation between CP and CV
(i) Ratio of heat capacities

(a) For monotomic gas such as He: CP, m /CV, m = 1.67

(b) For diatomic gas such as H2: CP, m /CV, m = 1.40

(c) For triatomic gas such as CO2: CP, m /CV, m = 1.33

Cp and Cv are related by the equation that Cp-Cv =R

From the first law of thermodynamics
H=U+PV…………………………… (i)
Given that PV=nRT for one mole of (n=1) then PV= RT
H =U+RT
Taking differentials on both sides, we get
dH=dU+RdT………………………(ii)
From dU = dQ+PdV at constant volume, PdV=0
Then du=dQ
𝑑𝑄𝑣
From Cv= then dQv = CvdT
𝑑𝑇
du=CvdT (At constant volume)……………….(iii)
At constant pressure
dH = dQ =CpdT
ie dH =CpdT……………………(iv)
Substituting for dU and dH from equation (iii) and (iv) to equation (ii)
CpdT=CvdT+RdT
CpdT= (Cv+R) dT
Cp =Cv+R
Cp-Cv=R

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 2.4 : Concept of work in thermodynamics

Work is a result of action against an opposing force. It is equal to the force multiplied by
displacement
w = –F× ∆x

Where ∆x is the path length over which action is taken and F is the force against which work
has to be done.

If F = 0, then w = 0. That is, if there is no opposing force, then the motion itself cannot
produce any work.

If ∆ x = 0, then w = 0. That is, if there is no motion, even the strongest opposing force
cannot generate any work.

Mechanical work involving gas

In a system when gases are involved, the mechanical work is equal to pressure (P)
multiplied by change of volume (∆V).

w = –F×∆x
F
= ×A×∆x
A

= –P×∆v

Here P = F = Force per unit area = pressure

A

and ∆V = A ×∆x = Area × displacement = change of volume

Significance of minus sign in the expression w = – P×∆V

As per IUPAC recommendations the symbol w has to be used for work done on the system.

During compression work is done on the system thus volume decreases and ∆V is
negative. Therefore, work done on the system is positive as is clear from the relation w = –P
×∆V
During expansion volume increases and ∆V is positive so the work done on the system is negative
as is clear from the relation w = –P × ∆V. But in this case work done by the system is positive

during expansion as given by –w = P × ∆V.

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Illustration of work and sign of its value
w = + 200 kJ implies that 200 kJ work is done on the system. This will
(i) increase the energy of the system. Since the work done on the system is
positive, it represents compression.

w = –250 kJ implies that - 250 kJ work is done on the system. Thatis, in the
(ii) process the energy of the system would decrease. A decreasein energy suggests
that the work is done by the system. Thus w = - 240kJ stands for - w = 240 kJ =
work done by the system and the given valuecorresponds to a process of
expansion.
Expressions for work under different conditions

It has been stated that work is a path dependent quantity. It has different values if
the
change is brought under different experimental conditions. For example, for the
changes
between the same initial state and same final state of a system

(i) Work done under isothermal condition is different from the work
done under adiabatic condition.

(ii) Work done under isothermal reversible condition is different from the
work done under isothermal irreversible condition.

(iii) Work done for free expansion is different from the work done under any
other condition

2.5 : Thermal equilibrium

The law of thermal equilibrium is called the zeroth law of thermodynamics. This law states
that
if two systems A and B are separately in thermal equilibrium with a third system C, then A and
B will also be in the thermal equilibrium with each other. That is,
If A = C ... thermal equilibrium between A and C
and B = C ... thermal equilibrium between B and C

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Then A = B ... thermal equilibrium between A and B
Zeroth law of thermodynamics forms the basis of measurement of temperature of a system
by a thermometer. When a thermometer is brought in contact with a system both attain
thermal equilibrium. Thus, the thermometer records a constant temperature of the system

2.6 Joule’s Law

Joule’s law states that the internal energy of an ideal gas is independent of its volume at a
constant temperature. Mathematically it is expressed as
⎛ ∂U ⎞
⎜ ⎟ =0 Joule’s law
∂V
⎝ ⎠T

This law also means that internal energy of a given amount of an ideal gas depends on its

temperature only. Thus at a constant temperature there is no change in the internal

energy of an ideal gas as the volume is changed.

2.6.1 : Experimental verification of Joule’s law

Joule performed an experiment to demonstrate the law that for a gas (∂U/∂V)T = 0.
The experimental setup is sown in Fig.2.1

Fig. 2.1 Joule’s experiment of expansion of

air from vessel A into an evacuated
vessel B

A glass bulb A was filled with air and connected through a stopcock to an evacuated bulb B.

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The assembly was placed in a water bath and its initial temperature was recorded. When the
stopcock was opened the gas expanded into the bulb B and thus occupied both the bulbs.
The final temperature of the water bath was recorded but no change in the temperature was
observed.

Calculation of work (w)

For a reversible isobaric process

Work done = w = – P× ∆V = – P (V2 –V1) when P is constant

In this process the work done on the system is negative thus the work is done by the system

For an isothermal reversible process

w = – nRT ln (V2/V1).

But for an ideal gas nRT =PV

Therefore, w(c) = – nRT ln (V2/V1) = – PV ln (V2/V1)

For isothermal reversible change of states of an ideal gas

(i) w = – 2.303 nRT log V2 = –2.303 nRT log P1
V P2
(ii) q = – w (iii) ∆U = 0 and (iv) ∆H = 01

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Calculation of w, q, ∆U and ∆H for adiabatic and reversible changes in the states of an
Ideal gas

Adiabatic change: q = 0

Reversible change: Change is slow and T, P, and V are changed

Ideal gas: PV = n RT

Calculation of q

The change is adiabatic, therefore, q = 0

Calculation of ∆U

In adiabatic process there is change of temperature and for a small change of

temperature (dT) the change of internal energy is given by

dU = Cv dT

For a finite change of temperature of a fixed amount of the gas from an initial value of T1 to a
final value of T2 the change of internal energy is obtained on integrating equation. Thus when
Cv is constant

U2 – U1 = Cv (T2 – T1)

Or, ∆U = Cv × ∆T= n Cv. m ×∆T

where, CV. m = molar heat capacity of the gas at constant volume and n is the amount of the
gas
Calculation of w

For a small change in volume (dV) of a gas the small quantity of mechanical work (dw) is
given by dw = – PdV

For an ideal gas PV = nRT and P = nRT/V. Thus

dw = – nRT dV
V

A direct calculation of work (w) is not possible because the integration of the above equations
is difficult as in an adiabatic reversible process each one of T, P and V will change.
Calculation of w from ∆U: For adiabatic process q = 0 and first law of thermodynamic gives
∆U = w. Thus

w = ∆U = Cv × ∆T = n Cv. m × ∆T

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Calculation of ∆H

∆H = H2 – H1

= (U2 + P2V2) – (U1 + P1V1 )

= (U2 – U1)+ (P2V2 – P1V1)

Since, U2 – U1=∆U = CV (T2 – T1)

(P2V2 – P1V1) = (n RT2 – n RT1)

Therefore,

∆H = CV (T2 – T1) + n R(T2 – T1)

= (CV + n R) (T2 – T1)

= CP (T2 – T1)

= n CP, m (T2 – T1)

Here, (CV + n R) = CP = n CP. m

Derivation of T–P–V relations for adiabatic and reversible process

Purpose of derivation: The relation w=∆U = CV (T2 – T1) is used to calculate the desired
quantities when T2 and T1 are known. When instead of T2 the values of P1, V1, T1 and P2 , V2 are
given, we need relations between T, P and V.
Derive the expressions reve rsi ble ad i abati c w ork under the following conditions

(A) When T1, V1 and V2 are given

(B) When T1, P1 and P2 are given

(C) When P1, V1 and P2, V2 are given

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