MODULE – 2

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First Law of Thermodynamics - I
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Contents
2.1 Zeroeth law of thermodynamics
2.2 Joule’s experiment
2.3 Internal energy
2.4 Some definitions
2.4.1 System
2.4.2 Surroundings
2.4.3 Boundary
2.4.4 Universe
2.4.5 Closed system
2.4.6 Open system
2.4.7 Isolated system
2.4.8 Extensive properties
2.4.9 Intensive properties
2.5 First law of thermodynamics
2.6 Thermodynamic state and state functions
2.7 Worked out examples
2.8 Exercise
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2.1. Zeroeth law of thermodynamics
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The zeroeth law of thermodynamics states that “If two bodies A and B are in thermal
equilibrium with a third body C, then the bodies A, B and C are said to be in thermal equilibrium
with each other. See fig.2.1. In this figure one can notice that the bodies A and B are not in
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direct contact with each other, but they are individually in thermal equilibrium with body C.
However, if the equilibrium has to exist, then all bodies do present in equilibrium with each
other.

Fig.2.1: Thermal equilibrium of three bodies

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2.2. Joule’s experiment

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Measured amount of water was placed in an insulated container and agitated the water
with a rotating stirrer as shown in fig.2.2. The amount of work done on the water by stirrer was
carefully measured and the temperature changes of the water were accurately noted. It was
found that definite amount of work was required per unit mass of water for every degree of
temperature rise caused by stirring. The original temperature of the liquid was restored by
contact with a cooler object. Thus Joule was able to show conclusively that a quantitative
relationship exists between work and heat, and therefore heat is also a form of energy.

Fig.2.2. Joules experiment

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2.3. Internal energy
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In Joule’s experiment, energy was added to the fluid as work and later removed from the
fluid as heat. A question arises here is that where was the energy between the addition as work
and removal as heat. It is thought that this energy remained in fluid in another form as internal
energy. The internal energy of a substance does not include any energy that it may possess as a
result of its position or movement as a whole. Rather it is the energy of the molecules making up
the substance. From a microscopic point of view we can consider all materials as consisting of a
large number of particles such as molecules, atoms, electrons etc. These particles are in
continuous motion and therefore possess energy in several forms. The molecule as a whole
moves through space and possesses kinetic energy. This is called as the translational motion and
kinetic energy by this motion is given by mv2/2, where m is the mass and v is the velocity of the
molecule. The diatomic and polyatomic molecules rotate about the center of the mass and
possess energy due to rotational motion. This rotational energy is given by Iω2/2 where I is the
moment of inertia about the center of the mass and ω is the angular velocity. Atoms of the
molecule vibrate back and forth about their common center of mass. Because of this motion, the
molecule has vibrational energy. The electrons continuously move around the nucleus and some
kinetic energy is associated with this motion. The amount of this energy depends upon the orbit.
The electron spins and possesses some spin energy. The electrons and nucleus are held together
through columbic interactions and some potential energy is associated with these interactions.
Again molecules are held together by molecular binding forces and certain amount of potential
energy is associated with these intermolecular forces. Fig.2.3 illustrates these energies.

Fig.2.3: Different energies constituting internal energy (a) Translational kinetic energy (b)
Rotational kinetic energy (c) Vibrational energy (d) Nuclear binding energy (e) Electron energy
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 However, it is impossible to determine the total internal energy of a substance. However,
in thermodynamic analysis only changes in internal energy are required.

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2.4. Some definitions
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To develop the concepts of thermodynamic analysis it is necessary to understand the
following ideas that are helpful in the treatment of the subject.

2.4.1. System:- A thermodynamic system or simply a system refers to the definite quantity of
matter enclosed by a boundary on which the attention is focused. In other words, the
body or assemblage on which we focused our attention is called as system.

2.4.2. Surroundings:- All matter other than the system is called as surroundings.

2.4.3. Boundary:- The plane that separates the system from surroundings is known as
boundary. The boundary may be real or imaginary.

2.4.4. Universe:- The combination of system and surroundings is called as universe.

2.4.5. Closed system:- If transfer of matter does not occur between the system and
surroundings, such system is said to be a closed system. Therefore its mass is constant.

2.4.6. Open system:- If transfer of matter and energy occur between the system and
surroundings, such system is called as open system.

2.4.7. Isolated system:- If transfer of matter and energy does not occur between the system and
surroundings, such system is called as isolated system.

2.4.8. Extensive properties:- Properties that depend on the quantity of material in the system
are known as extensive properties. Eg: Total volume Vt, total internal energy Ut etc.

2.4.9. Intensive properties:- Properties that are independent of quantity of material in the
system are known as intensive properties. Eg: Temperature, pressure, density, specific
volume, molar volume, specific internal energy, molar internal energy etc.

Let V = volume per unit quantity, i.e., specific volume if expressed per unit mass of
material, or molar volume if expressed as unit mole of material. Then

Vt = mV or Vt = nV where m is the mass of the system and n represents the moles of

the system. Similarly we can say Ut = mU or Ut = nU.

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2.5. First law of thermodynamics for a closed system
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The first law of thermodynamics is stated as follows: “although energy assumes many
forms, the total quantity of energy is constant, and when energy disappears in one form, it
appears simultaneously in other forms”.

∴ ∆ (Energy of Universe) = 0

⟹ ∆ (Energy of system) + ∆(Energy of surroundings) = 0

The interaction between the system and surroundings occur by means of exchange of
energy in the form of heat and work.

∴ ∆(Energy of surroundings) = Q W
The total energy possessed by the system consists of types. At macroscopic level (i.e.,
the matter as a whole) possesses energy by virtue of position (known as potential energy) and by
virtue of motion (known as kinetic energy). These two forms of energy are known as external
forms of energy. It was also come to know from section 2.2 that internal energy also exists.
Therefore, the interaction between system and surroundings may cause the system to have a
change in these forms of energy viz., internal energy, kinetic energy and potential energy.

∴ ∆(Energy of the system) = ∆Ut + ∆ +∆

Hence, ∆Ut + ∆ +∆ = Q W …(2.1)

Sign convention:- Heat flow into the system is taken as positive, and heat flow out of the system
is taken as negative. Similarly, work done on the system is positive and the work done by the
system is negative. See fig.2.4.

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Fig.2.4. sign convention

Therefore, ∆Ut + ∆ +∆ = Q+W …(2.2)

Closed systems often undergo processes that cause no change in external potential or
kinetic energy, but only changes in internal energy. In such cases

∆Ut = Q + W …(2.3)
Eqn.(2.3) applies to processes involving finite changes in the system. For differential changes
dUt = dQ + dW …(2.4)
Equations (2.3) and (2.4) can be alternatively written as
Δ(nU) = n ΔU = Q + W …(2.5)
d(nU) = n dU = dQ + dW …(2.6)
By taking n = 1 mole, equations (2.5) and (2.6) become
ΔU = Q + W …(2.7)
dU = Q + W …(2.8)
Note: The basis for Q and W i.e., whether the heat and work are considered in extensive form as total quantities or
in intensive form evaluated per unit mass or mole can be decided by looking at the units for internal energy U.

Here, equation (2.6) gives a relation wherein internal energy is related to measurable
quantities. However, this relation, representing the first law of thermodynamics for a closed
system, allows us to compute the changes in internal energy. It will not facilitate us to obtain the
absolute value of internal energy. But, in thermodynamics we do not need the absolute value of
internal energy and we are concerned with the changes in internal energy only. Hence, the above
relations are useful for us. Further, it is to be understood that there is no definition for internal
energy. One has to realize that this is a primitive property in thermodynamics. This property has
been introduced by first law of thermodynamics.

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2.6. The thermodynamic state and state functions
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There are two types of quantities in thermodynamics, those which depend upon path and
those which do not. T, P and specific volume do not depend upon path. Fixing of any two of
these quantities automatically fixes all other such properties of a homogeneous pure substance
and therefore determines the condition or state of the homogeneous pure substance. Such
quantities are known as point functions or state functions. When two of them are fixed it is said
that the thermodynamic state of the substance is fixed.
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 The values of state functions can always be represented as points on a graph, hence they
are called as point functions. The differential of a state function is an infinitesimal change in the
property. The integration of such differential results in a finite difference between two values of
the property. An important mathematical property of such a differential is that, any correct
expression for it in terms of the state variables must be exact.

Work and heat, on the other hand, are not state properties, and they are dependent on the
path followed. They cannot be represented by points on a graph, but are represented as areas.
The differentials of heat and work are not referred to as changes, but are regarded as
infinitesimal quantities of heat and work. When integrated, these give not a finite change, but a
finite quantity.

Mathematically dQ and dW cannot be represented by expressions which are exact,

because these are not state functions or state variables. State functions represent an
instantaneous property of a system and always has a value. Work and heat appear only when
changes are caused in a system by a process which requires time.

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2.7. Worked out examples
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E.2.1. An insulated and non-conducting container filled with 9.072 kg of water at 20oC is fitted
with stirrer. The stirrer is made to turn by lowering a weight having a mass of 22.68 kg.
the local acceleration of gravity is 9.81 m/s2. The weight slowly falls a distance of 9.14
m while turning the stirrer. Assuming that all the work done by gravity on the weight is
transferred to the water determine:

(a) The amount of work done on the water in J.

(b) The internal energy change of the water in J.
(c) The final temperature of the water in oC.
(d) The amount of heat which must be removed from the water to return it to its initial
temperature.
(e) The total energy change of the universe because of (i) the process of lowering the
weight (ii) the process of cooling the water back to its initial temperature, and (iii)
both of these process taken together.

Solution:-

(a) The amount of work done on the water is equivalent to decrease in the potential
energy of the mass.

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 W = mgh = 22.68 X 9.81 X 9.14 = 2033 J
(b) ∆U = Q + W = 0 + 2033 = 2033 J (here Q = 0, because no heat is added)
(c) Mass of water, mw = 9.072 kg; Cp of water = 4.184 kJ/kg.oC;
Initial temperature of water, T1 = 20oC; Final temperature of water = T2 (say).
mcp∆T = 2033 ⟹ ∆T = 2033/(9.072X4184) = 0.054oC
∴ T2 = 20.054oC
(d) The amount of heat that must be removed is 2033 J
(e) (i) Change in internal energy of water due to lowering of weight, ∆U = 2033 J
Change in P.E of the mass due to lowering of weight, ∆Ep = -2033 J
Total energy change of the universe because of lowering the weight =
∆ (Energy)system + ∆ (Energy)Surr = ∆U + ∆Ep = 2033 – 2033 = 0
(ii) With reference to Surroundings QSurr = 2033 J; For the system ∆U = -2033 J
∴Total energy change of the universe because of cooling process =
∆ (Energy)system + ∆ (Energy)Surr = ∆U + QSurr = -2033+2033 = 0
(iii) If these processes were done together, then the total energy change of the
universe is zero.

E.2.2. Rework example E.2.1 taking into account that the container changes in temperature
along the water and has a heat capacity equivalent to 2.268 kg of water. Work the
problem in two ways: (I) by taking water and the container as the system (II) by taking
water alone as the system
Solution:-

Way-I

In this problem the system is water and the container together. Take the mass of the
system as 9.072 + 2.268 = 11.34 kg.

(a) The amount of work done on the system (water + container) is equivalent to decrease
in the potential energy of the mass.
W = mgh = 22.68 X 9.81 X 9.14 = 2033 J
The work done caused an increase in the internal energy of the system (water +
container). Because Q = 0
∆U = Q + W = 0 + 2033 = 2033 J
∆T = 2033/(11.34X4184) = 0.043oC
The amount of work done on water = 2033X9.072/11.34 = 1626 J
(b) The work done caused an increase in the internal energy of the system (water +
container). Because Q = 0
∆U = Q + W = 0 + 1626 = 1626 J
(c) Mass of system = 11.34 kg; Cp of system = 4.184 kJ/kg.oC;
Initial temperature of system, T1 = 20oC; Final temperature of system = T2 (say).
mcp∆T = 2033 ⟹ ∆T = 2033/(11.34X4184) = 0.043oC
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 ∴ T2 = 20.043oC
The final temperature of water = 20.043oC
(d) The amount of heat that must be removed is 1626 J
(e) (i) Total energy change of the universe because of lowering the weight =
∆ (Energy)system + ∆ (Energy)Surr = ∆U + ∆Ep = 2033 – 2033 = 0
(ii) With reference to Surroundings QSurr = 2033 J; For the system ∆U = -2033 J
∴Total energy change of the universe because of cooling process =
∆ (Energy)system + ∆ (Energy)Surr = ∆U + QSurr = -2033+2033 = 0
(iii) If these processes were done together, then the total energy change of the
universe is zero.

Way-II

(a) The amount of work done on water = 1626 J

(b) The internal energy change of water = 1626 J
(c) The final temperature of water = 20.043oC
(d) The amount of heat that must be removed is 1626 J
(e) (i) Total energy change of the universe because of lowering the weight =
∆ (Energy)system + ∆ (Energy)Surr = (∆U)water +(∆U)Container + ∆Ep =
1626 + 407 - 2033 = 0
(ii) With reference to Surroundings QSurr = 2033 J;
∴Total energy change of the universe because of cooling process =
∆ (Energy)system + ∆ (Energy)Surr = (∆U)water +(∆U)Container + ∆Ep
= - 1626 – 407 +2033 = 0
(iii) If these processes were done together, then the total energy change of the
universe is zero.

E.2.3. Heat in the amount of 7.5 kJ is added to a closed system while its internal energy
decreases by 12 kJ. (a) How much energy is transferred as work? (b) For a process
causing the same change of state but for which the work is zero, how much heat is
transferred?
Solution:- (a) Q = +7.5 kJ (+ve, heat added to the system)

Δ 12

Δ ⇒ ∆

12 7.5 19.5 kJ

(b) Δ 12
W=0

Δ ⇒ 12

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E.2.4. (a) How much difference in elevation will result in a change in potential energy
equivalent to 2326 J/kg of the substance considered?
(b) A fluid has a velocity of 30.48 m/s when entering a piece of apparatus. With what
velocity must the fluid leave the apparatus so that the difference in entering and
leaving kinetic energies is equivalent to 2326 J/kg of the fluid?
(c) What conclusions are indicated by these examples?

Solution:- (a) ∆ . ∆ 1

∴∆ 237.1
.

(b) ∆ . ∆

1 30.48 ⁄

2326 30.48

⟹ 74.7 ⁄

(c) To bring the required change the change in elevation required is much more
compared to the change in velocity.
E.2.5. Calculate the work done by 1 mol of a gas during reversible isothermal expansion from
an initial volume V1 to a final volume V2 when the equation of state is P(V-b) = RT
where b and R are positive constants. If the gas were ideal would the same process
produce more or less work?

Solution:- For the gas obeying

We can write

| . 2.5 1

For the ideal gas

. 2.5 2

Now

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 ∴ 1 1

∴ 02 15

In equations (2.5-1) and (2.5-2) the minus sign indicates that the work is done by the system on
the surroundings. Therefore, work done by the given gas is more than ideal gas.

Proof:

Since is b is positive

E.2.6. Steam is admitted to the cylinder of a steam engine at a constant pressure of 20.4
atm. The bore of the cylinder is 20.32 cm, and the stroke of the piston is 30.48 cm. How
much work is done per stroke?

Solution:- P = 20.4 atm = 20.4 X 101325 = 2067030 Pa

Dia of cylinder, d = 20.32 cm = 0.2032 m

Length of the cylinder, l = 30.48 cm = 0.3048 m

Volume of cylinder = 0.2032 0.3048 0.04

∴ 0.04 0

Work done per stroke

= - 2067030 (0 – 0.04)

= 82681 J = 82.68 kJ

E.2.7. If 4.536 kg of water is evaporated at atmospheric pressure until a volume of 8.17 m3 is

occupied, how much work is done?
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Solution:- Let density of water = 1000 kg/m3

Mass of water = 4.536 kg

.
∴ Volume of water, 4.536 10

Assume that it is equipped with a non-leaking frictionless piston in a cylinder,

Then 8.17 1 101325

∴ Work done = 101325 8.17 4.536 10

=827365 J = 827.4 kJ
E.2.8. One mole of a gas undergoes a reversible non-flow change from state 1 to state 2. If the
process is represented by a straight line on a PV diagram, show that
W = ½ (P1+P2)(V2-V1).
Solution:- For 1 mol of gas

2 ∆12

The ‘-‘ sign indicates that work is done by the system on the surroundings.
E.2.9. An electric motor under steady load draws 9.7 amperes at 110 volts, delivering 0.93 kW
of mechanical energy. What is the rate of heat transfer from the motor, in kW?
Solution:- Total energy supplied to the motor = 9.7 X 110
= 1067 W
= 1.067 kW
Energy delivered as mechanical energy = 0.93 kW

∴ Energy dissipated as heat = 1.067 – 0.93

= 0.137 kW

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E.2.10. An egg, initially at rest, is dropped onto a concrete surface and breaks. With the egg
treated as the system, answer the following:

(a) What is the sign of W?

(b) What is the sign of ∆Ep ?
(c) What is ∆Ek ?
(d) What is ∆Ut ?
(e) What is the sign of Q ?

In modeling this process, assume the passage of sufficient time for the broken egg to
return to its initial temperature. What is the origin of the heat transfer of part (e)?

Solution:-
Many answers are possible to this problem and the answer is dependent on what state you
choose as the final state.

(a) Let the egg initially possesses some potential energy by virtue of its elevation from
the concrete surface. If the egg were freely dropped, its potential energy converts into
kinetic energy and just before the egg touches the concrete surface, entire potential
energy is converted into kinetic energy. With this kinetic energy the egg strikes the
concrete surface. We can view this situation as the egg doing a work equivalent to its
kinetic energy on the concrete surface and in turn the concrete surface performs an
equivalent work on the egg by virtue of Newton’s third law. Because of this work
done by the concrete surface on the egg, the egg gets internal energy increased
equivalent to this work which is ultimately equivalent to the change in potential
energy. Therefore we can now say that net work done is zero. Hence, there is no
question of the sign of W.
(b) In thermodynamics, Δ means always (final - initial). Since final potential energy is
zero and initial potential energy is some finite value, therefore sign of ΔEp is
negative.
(c) If we consider that final state is just before touching the concrete surface, since ΔEp +
ΔEk = 0, ΔEk = - ΔEp.
(d) If we consider that the egg immediately after touching the concrete surface as final
state, then applying first law
ΔUt + ΔEp + ΔEk = Q + W

Here ΔEk = 0, Q = 0 and W = 0. Therefore ΔUt = - ΔEp.

(e) If we consider that after the egg breaking by absorbing internal energy, its
temperature increases. Therefore, heat flows from system to surroundings.
Therefore, the sign of Q is negative.

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E.2.11. A vessel of volume V contains n moles of gas at high pressure. Connected to the vessel
is a capillary tube and stopcock. When the stopcock is opened slightly, the gas leaks
slowly into a cylinder equipped with a non-leaking frictionless piston in which the
pressure remains constant at the atmospheric pressure P0.

(a) Show that, after as much gas as possible has leaked out, an amount of work
W = P0(nV0 – V) has been done, where V0 is the molar volume of the gas
atmospheric pressure and temperature.

(b) How much work would be done if the gas leaked directly into atmosphere?

Solution:-

(a)

Initial volume of gas in the cylinder 0

Final volume of gas in the cylinder
If the process were reversible

(b) 

Initial number of moles in the tank

Final number of moles in the tank
Let
In the surroundings, change of volume due to mol gas which has escaped
from the tank is given by
0
If the external pressure is , then work done by the gas

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2.8. Exercise
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P.2.1. A nonconducting container filled with 25 kg of water at 20oC (293.15 K) is fitted with a
stirrer, which is made to turn by gravity acting on a weight of mass 35kg. the weight falls
slowly through a distance of 5m in driving the stirrer. Assuming that all work done on the
weight is transferred to the water and that the local acceleration of gravity is 9.8 m/s2,
determine the

(a) Amount work done on the water

(b) Internal energy change of water
(c) Final temperature of the water, for which cp=4.18 kJ/(kg . oC )
(d) Amount of heat that must be removed from the water to return to its initial
temperature
(e) Total energy change of the universe because of (i) the process of lowering the weight,
(ii) the process of cooling the water to its initial temperature , and (iii) both processes
together

P.2.2. Rework problem P.2.1 for an insulated container that changes in temperature along with
the water and has a heat capacity equivalent to 5 kg of water. Work the problem with

(a) The water and container as the system

(b) The water alone as the system

P.2.3. Water flow over a waterfall 100 m in height. Take 1 kg of the water as the system, and
assume that it does not exchange energy with surroundings.

(a) What is the potential energy of the water at the top of the falls with respect to the
base of the falls?

(b) What is the kinetic energy of the water just before it strikes bottom?

(c) After the 1 kg of water enters the stream below the falls, what change has
occurred in its state?

P.2.4. A gas is confined in a cylinder by a piston. The initial pressure of the gas is 7 bar and the
volume is 0.1 m3. The piston is held in place by latches in the cylinder wall. The whole
apparatus is placed in a total vacuum. What is the energy change of the apparatus if the
restraining latches are removed so that the gas suddenly expands to double its initial
volume, the piston striking other latches at the end of the process?

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P.2.5. If the process described in P.2.4 is repeated, not in a vacuum but in air at atmospheric
pressure of 101.3 kPa, what is the energy change of the apparatus? Assume the rate of
heat exchange between the apparatus and the surrounding air is slow compared with the
rate at which the process occurs.

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