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Unit 9: First Law of Thermodynamics

Learning Outcomes

Students should be able to:

(a) define and use the concepts of specific heat capacity and specific latent heat.

(b) show an understanding that internal energy is determined by the state of the system and
that it can be expressed as the sum of a random distribution of kinetic and potential
energies associated with the molecules of a system.

(c) relate a rise in temperature of a body to an increase in its internal energy.

(d) recall and use the first law of thermodynamics expressed in terms of the increase in
internal energy, the heat supplied to the system and the work done on the system.

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1 Specific Heat Capacity LO (a)

When two different substances receive the same amount of energy they are not likely to undergo
the same temperature change. The two substances are said to have different heat capacities.

Heat capacity of a body is defined as the quantity of heat absorbed or liberated by the body
per unit temperature change.

That is, Q
C
Δθ

where C is the heat capacity of the body, Q is the amount of heat and  is the change in
temperature. The S.I. unit for heat capacity is J K-1.

For the same material, heat capacity varies with the mass of the body. A more useful quantity
is the specific heat capacity which is the heat capacity per unit mass.

Specific heat capacity of a material is defined as the quantity of heat absorbed or liberated
per unit mass of the material per unit temperature change.

That is,
Q
c
mΔθ

where c is the specific heat capacity of the material, m is the mass of the material and  is the
change in temperature. The S.I. unit of specific heat capacity is J kg-1 K-1.

Thus heat capacity = mass x specific heat capacity i.e. C = m c

Example 1
An electric kettle contains 500 g of water at 15 oC. The heating element of the kettle is rated at
2.2 kW and the specific heat capacity of water is 4.2 × 103 J kg-1 K-1.

(a) What is the heat capacity of the water in the kettle?

(b) What is the minimum time it takes to raise the temperature of the water to 100 oC.

Solution:

(a) heat capacity C = m c

= 0.500 × 4.2 × 103
= 2.1 × 103 J K-1

(b) Assume no heat loss to surroundings, the time t is the minimum time
heat supplied by the heating element = C 
 P tmin = C 

2.2 × 103 × tmin = 2.1 × 103 × (100 – 15)

tmin = 81 s

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Example 2
Water at 26.0 oC passes through a tube and is heated by a heating coil. The power supplied to
the heating coil is 30.0 W. When water flows at a rate of 100 g min-1, the temperature of the
water leaving the end of the tube at steady state is 30.0 oC.

out in

Another liquid at 26.0 oC is then passed through the same tube and to get the same change in
temperature, the power is changed to 15.6 W and the rate of liquid flowing to 120 g min-1.
Calculate the specific heat capacity of the liquid if the specific heat capacity of water is assumed
to be 4200 J kg-1 K-1.

Solution:
By conservation of energy,

power supplied = rate of heat gained + rate of heat loss

by heater by water/liquid to the surroundings

m
P = c + h where h is rate of heat loss to the surroundings.
t

0 .100
For water: 30.0 = (4200) (30.0 - 26.0) + h ---------[1]
60

0.120
For liquid: 15.6 = c (30.0 - 26.0) + h ---------[2]
60

Solving [1] and [2], c = 1.7 × 103 J kg-1 K-1

Question: Why is h the same in both cases?

From Newton’s Law of Cooling, the rate of heat lost from a body to the surroundings is
proportional to its excess temperature over the surroundings.

By keeping the inlet and outlet temperatures of the tube constant in both cases, the excess
temperature of the apparatus over the surroundings remain unchanged. Hence h is the same
in both cases.

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2 Specific Latent Heat LO (a)

When heat is supplied at a constant rate to a substance, it undergoes a change of phase from
solid to liquid to finally to gas or vapour as shown in the figure.

boiling point

melting point

During the change in phase at melting point (solidliquid) and at boiling point
(liquidgas/vapour), the thermal energy added does not cause the temperature to rise. The
energy required to achieve the change of phase is called latent heat; the word latent meaning
“hidden”.

The latent energy of fusion supplied during melting is to break down the lattice structure, i.e. to
break the intermolecular bonds of the solid.

The latent heat of vaporization supplied during boiling is to increase the intermolecular
separation of the molecules and to do work as the gas expands against atmospheric pressure.

In both melting and boiling,

- the potential energies of the molecules are generally increased as the molecules are
separated further apart.

- the total kinetic energies of the molecules are unchanged since temperature remains
constant.

Latent heat is defined as the quantity of heat absorbed or liberated by a substance in order to
change the substance from one phase to another phase without a temperature change.

The S.I. unit for latent heat is joule, J.

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Specific latent heat of fusion of a substance is defined as the quantity of heat energy required
to convert per unit mass of solid to liquid without a change in temperature.

Q
Lf 
m

where Lf is the specific latent heat of fusion and m is the mass of the substance.
The S.I. unit for specific latent heat of fusion is J kg-1.

Specific latent heat of vaporisation of a substance is defined as the quantity of heat energy
required to convert per unit mass of liquid to vapour without a change in temperature.

Q
Lv 
m

where Lv is the specific latent heat of vaporisation and m is the mass of the material.
The S.I. unit for specific latent heat of vaporisation is J kg-1.

Note : Both evaporation and boiling represent a change of phase from liquid to vapour. However
evaporation can take place at any temperature, whereas boiling takes place at a fixed
temperature(boiling point). Furthermore evaporation takes place at the surface of the liquid,
wheras boiling occurs in the body of the liquid.

The average kinetic energy of the molecules in the substance does not change during melting
or boiling because the temperature of the substance remains unchanged during each process.

Example 3

Why is Lv higher than Lf for the same substance?

e.g. for ethanol, Lv = 8.54 × 105 J kg-1 and Lf = 1.04 × 105 J kg-1

The increase in intermolecular separation is much greater during vaporisation than during
melting.

As such, the work done against the intermolecular forces is much larger. In addition, a small
amount of work is done to overcome the atmospheric pressure as the vapour expands.

Therefore the specific latent heat of vaporisation is higher than specific latent heat of fusion.

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3 Internal Energy LO (b), (c)

We have seen from the previous topic that molecules of a gas possess kinetic energies due to
their random motion. Not all molecules have the same kinetic energy because they are moving
with different speeds, but the sum of all the kinetic energies will be a constant at that particular
temperature.

For a real gas, because the molecules exert intermolecular forces on each other, there will be
a certain potential energy due to the forces between the molecules and their positions relative
to each other. Thus for a real gas, the internal energy is given by the sum of the potential
energies and the kinetic energies of all the molecules.

Fig. 3 The molecules of a gas

have both kinetic and
potential energies.

The internal energy U, of a system, is the sum of a random distribution of kinetic and potential
energies associated with the molecules of a system.

U  K.E. microscopic   P.E. microscopic

Microscopic kinetic energy

 The microscopic KE arises from the continuous random motion of the particles.

 For monatomic gases, the microscopic KE refers to translational motion of atoms.

 For diatomic and polyatomic gases, the kinetic energies include other forms such as
rotational and vibrational kinetic energies of the molecules.

The temperature T of a gas is a measure of the mean kinetic energy of particles in

the gas.

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Microscopic potential energy

 The microscopic PE arises from the intermolecular forces and they depend on the type of
bond between the particles and the intermolecular separation.

 Potential energy is the highest when the particles are separated far apart, and the potential
energy drops as the particles are nearer. This is similar to gravitational potential energy: the
potential energy is high when the object is high above the ground and low when the object
is subjected to the gravitational attractive force and moves nearer to the ground.

Ideal Gas

For an ideal gas, there are no intermolecular forces. Therefore, the potential energy of the
molecules is zero. The internal energy of an ideal gas is simply equal to the total kinetic energy
of the molecules.

3 3 3
internal energy of an ideal gas U = NkT = nRT = pV
2 2 2

Note:
 U is proportional to the product NT or nT or pV.

 For a fixed amount of an ideal gas, U  T.

3
When temperature changes by T, the change in internal energy, U  nRT .
2

Evaporation

Evaporation is the process by which a liquid becomes vapour at any temperature. For a given
external pressure, the evaporation rate increases with temperature, reaching a maximum at
boiling point.

possible for molecule to escape if it has

air sufficient kinetic energy

liquid molecule

attractive force due to other molecules

Due to the continual motion and collisions between the molecules in a liquid, their speeds
change continually. Consider a molecule reaching the surface from within the liquid. If it has a
kinetic energy large enough to do work against the attractive forces of the other molecules in
the liquid and against the atmospheric pressure, then it is able to escape from the liquid to
become a molecule of a vapour.

During evaporation, since molecules having larger kinetic energies escape, the average kinetic
energy of the remaining molecules in the liquid decreases. Therefore the temperature drops
and the liquid cools.

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4 Thermodynamics LO(d)

There are two obvious ways in which we can increase the internal energy of a gas: we can heat
it, or we can do work on it.

Q: Thermal energy or Heat Q is a transfer of energy due to a difference of temperature between

two bodies. For example, heat can be added by using another hot body such as a electrical
heater or a hot bath.

W: Work W is a transfer of energy by mechanical means, such as compressing the gas. For
example, work can be done on a gas by a movable piston or using a bicycle pump.

Thermodynamics is the name given to the study of processes in which energy is transferred as
heat and as work to a system.

4.1 First Law of Thermodynamics

We all know that energy is conserved. All the energy we put into a gas by heating it and by
doing work on it must end up with an increase in the internal energy of the gas. This is stated in
the First Law of Thermodynamics.

The first law of thermodynamics states that the increase in internal energy of a system is equal
to the sum of heat supplied to the system and the work done on the system.

Mathematically, it can be stated as

U = increase in internal energy = Ufinal – Uinitial

U = Q + W Q = heat/thermal energy supplied to the system
W = work done on the system

The sign conventions are:

U is +ve if U increases, U is -ve if U decreases
Q is +ve if heat is supplied to system, Q is -ve if heat is removed from system
W is +ve if work is done on the system, W is -ve if work is done by the system
We can also replace W with Won to remind ourselves that this term in the equation is the work
done on the system, i.e.

U = Q + Won

since the W in the equation is positive when work is done on the system.

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The internal energy of a system depends only on the state of the system.
The state of the system is defined by its pressure p, volume V and temperature T. It does
not depend on the process or path through which the system is brought from its initial
to its final state.

For example, if we regard all the gas in a cylinder to be the system, then the first law states that
its internal energy only depends on factors such as the amount of gas in the cylinder, the
pressure of the gas in the cylinder and its temperature. Another cylinder fills with same amount
of gas under the same conditions, that is, in the same state, will have the same internal energy.

The P-V is a graph of pressure versus volume to illustrate the different processes a fixed mass
of ideal gas can undergo. Each point A, B, and C on the graph represents the state of the gas
described by its pressure p, volume V and temperature T.

Checkpoint:

The following p-V diagram(see diagram below) of a gas G is shown below. One mole of gas
G was initially at state A. Gas G undergoes process X to reach state C. The internal energy of
the gas G at state C is found to be UC.

If one mole of the same gas, gas G, was initially at state B and undergoes process Y to reach
state C, what will be the internal energy of the gas G at state C?

Answer: UC
The internal energy of a system depends only on the state of the system.
At state C, gas has the same P, V and T, therefore the same internal energy.

For change in Internal Energy:

If the system is an ideal gas, If the system is not an ideal gas or

p, V and T are not given, then use
Internal energy of ideal gas, U = EK
since EP of ideal gas is 0. U = Q + Won
U = EK = 3/2 nRT = 3/2 pV

Change in internal energy,

∆U = 3/2 nR (Tf – Ti ) or ∆U = 3/2 (PfVf –PiVi)

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The increase in internal energy of a system is equal to the sum of heat supplied
to the system and the work done on the system.

U = Q + W

Example 4

Using the first law of thermodynamics, if 2500 J of heat is added to a system, and 1800 J of
work is done on the system, what is the change in internal energy of the system?

Solution:
The heat added to the system Q = +2500 J
The work done on the system Won = +1800 J
So from 1st law of thermodynamics, U = Q + Won
= 2500 + 1800 = 4300 J

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4.2 Work done by volume change W

Consider a system, consisting of a fixed mass of gas, enclosed in a cylinder by a frictionless

movable piston of cross-sectional area A.

p, V A
gas F

dx movable piston

The gas is allowed to expand such that it pushes the piston to the right through a distance dx
which is so small that the pressure p remains practically constant during the expansion.

Force exerted by the gas on the piston during expansion F = pressure x area = pA
Work done by the gas, dWby = F dx
= pA dx
= p dV where dV = A dx

In general, if the volume of the gas changes from Vi to Vf , the total work done by the gas is

Vf

W by =  p dV = area under p-V graph

Vi

For example in the diagram, when a gas expands from A to B under constant pressure,

work done = area

under p-V graph

Work done by gas = area under p-V graph

= p (VB – VA)

During the expansion from AB, work done by gas is +ve since VB is larger than VA.
Note that Won and Wby are equal value but opposite signs.
i.e. Won = – Wby,
so work done on the gas Won is –ve during expansion from AB.
In general:
When a gas expands, work is done by the gas, so Wby is +ve and Won is –ve.
When a gas is compressed, work is done on the gas, so Wby is –ve and Won is +ve.

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Example 5
In the following p-V diagrams, calculate the work done on the gas from state A to B.
(a)

Solution:
Work done = area under p-V graph
= 6.0 x 105 x (6.0-2.0)x10-3
= 2400 J

Since the gas is expanding from A B,

work is done by the gas, so
work done on the gas Won = -2400 J

(b)

Solution:
Work done = area under p-V graph
= ½ (2.0+4.0)x105 x(6.0-2.0)x10-3
= 1200 J

Since the gas is compressed from BA, work

is done on the gas, so
work done on the gas Won = +1200 J

4.3 p-V diagram

A p-V diagram(see diagram below) is a graph of pressure versus volume to illustrate the
different processes a fixed mass of ideal gas can undergo. Each point A, B, and C on the graph
represents the state of the gas described by its pressure p, volume V and temperature T.

The temperature T of each state can be calculated using the ideal gas equation pV = nRT where
p and V can be read from the graph and n is the amount of gas in moles.

Since internal energy is determined by the state of the system, the internal energies at A,
B and C are different if their temperatures T (or the product PV ) are different.

A cycle is a process during which a gas

undergoes several changes but finally
returns to its original state. In the figure
shown, process ABCA is a cycle.

When a gas is brought round a complete

cycle, there is no net change in internal
energy.
U = 0.

The net work done W = area enclosed by the

cycle ABCA

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4.4 Simple Thermodynamic Processes

We shall discuss four simple thermodynamic processes that an ideal gas can undergo and
apply the first law of thermodynamics to each process.

1. Isochoric (Isovolumetric) Process (constant volume process)

In isovolumetric or isochoric process,
volume is kept constant, V = 0
Work done W = 0
Apply 1st law: U = Q + Won
=Q+0
=Q
any heat Q added or extracted from system will
result in U. Since U changes, temperature T also
changes.

2. Isobaric Process (constant pressure process)

In isobaric process, pressure is kept constant.
Work done = area under p-V graph
= PV = P(VB – VA)
Won is –ve during expansion from AB.
Won is +ve during compression from BA.

Apply 1st law : U = Q + Won, all terms are non-

zero.

3. Isothermal Process (constant temperature process)

In isothermal process,
temperature is kept constant, T = 0.
hence no change in internal energy, i.e. U = 0

Work done W = area under p-V graph

Apply 1st law: U = Q + Won
0 = Q + Won
 Q = -Won = Wby
During isothermal expansion from AB, any heat Q
added is converted to work done by the gas.
During isothermal compression from BA, heat Q
extracted from system equals work done is on gas.
4. Adiabatic Process (Q = 0)
In adiabatic process, the system is very well-insulated
or lagged, so that no heat can enter or leave the
system, i.e.
Q=0

Apply 1st law; U = 0 + Won = Won

In adiabatic expansion, Won is –ve, so U is –ve,

 temperature decreases, gas cools

In adiabatic compression, Won is +ve, so U is +ve,

 temperature increases, gas is hotter.

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Example 6

A series of thermodynamic processes is shown in the p-V diagram below. In process AB, 150
J of heat is added to the system and in process BC, 600 J of heat is added.
Calculate
(a) the internal energy change in the process AB,
(b) the internal energy change in process BC,
(c) the internal energy change in process CA,
(d) the total heat added in cyclic process ABCA.
p/104 Pa

B C
8.0

3.0
A

2.0 5.0 V/10-3 m3

(a) Process AB: isochoric
V = 0  Won = 0
Solution: UAB = Q + Won = 150 + 0 = 150 J

(b) Process BC:isobaric

4 -3
Work done on gas W = -pV = -8.0 × 10 x (5.0 – 2.0) × 10 = -240 J
U BC = Q + Won
= 600 +(– 240)
= 360 J

(c) In a cyclic process, net change in internal energy U ABCA = 0

So U AB + U BC + U CA = 0
150 + 360 + U CA = 0
 U CA = - 510 J

(d) Work done on gas from C to A = area under line CA

= ½ (3.0+8.0) x 104 x (5.0-2.0) x 10-3
= 165 J
Net work done on gas from ABCA, Wnet = WBC + WCA
= (-240) +165
= -75 J
= area enclosed by triangle ABCA
Apply the 1st law to the cyclic process,
UABCA = Qnet + Wnet
0 = Qnet + (-75)
Qnet = +75 J

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Example 7
A cylinder fitted with a frictionless piston contains an initial volume of 5.0  10-4 m3 of an ideal
gas at a pressure of 1.0  105 Pa and a temperature of 300 K. The gas is (i) heated at constant
pressure to 450 K, then (ii) cooled at constant volume to the original temperature of 300 K. The
heat extracted from the gas during stage (ii) is 38 J.

(a) Illustrate these changes on a p-V diagram.

(b) Calculate the work done by the gas in pushing back the piston in process (i).
(c) Calculate the heat gain in process (i).

Solution:

(a) p/105 Pa

(i) b
1.0 a
(ii)
450 K
c
300 K
V/10-4 m3
5.0 7.5

In stage (i), p is constant. So V  T.

Va Ta 5.0  10 4 300
  
Vb Tb Vb 450
-4 3
Vb = 7.5 × 10 m

5 -4 -4
(b) Work done by gas, Wab = p (Vf – Vi) = 1.0 × 10 (7.5 × 10 – 5.0 × 10 ) = 25 J

(c) T in stage (i) = – T in stage (ii)

Since, for an ideal gas, U  T,

U in stage (i) = – U in stage (ii)

Qab + Wab = − ( Qbc + Wbc )
Qab + (-25) = − ( − 38 + 0 )
Qab = 63 J

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Appendix
Determination of specific heat capacity of a solid
The specific heat capacity of a metal can be determined using a cylindrical block of the metal
as shown in the Figure.
The mass m of the metal block is measured
using a balance.

An electrical heater and a thermometer are

inserted into holes in the metal block. The
initial temperature i is recorded.

The circuit is closed and the values of current

I and p.d. V are noted. At time t, measured
using a stopwatch, the final temperature f is
recorded.

Assuming no energy loss to the surroundings,

mc(f - i) = VIt
where c the specific heat capacity can be
determined.

Question: If there is energy loss H to the surroundings due to poor lagging, what modification(s)
should be made to the equation mc(f - i) = VIt ?

Determination of specific heat capacity of a liquid

A reliable method for a liquid is based on continuous flow. The apparatus is as shown.

out in

The liquid flows over the heater at a constant rate. When the inlet temperature in and the outlet
temperature out are steady, the voltmeter reading V1 and ammeter reading I1 are recorded. The
mass of liquid M1 collected in time t is noted. Initially

Thermal energy supplied = thermal energy gained by liquid + energy losses to surroundings
V1 I1 t = M1 c (out - in) + H
where c is the specific heat capacity and H is the thermal energy lost to the surroundings.

For the second set of readings, the temperatures are unaltered and therefore energy lost to the
surroundings H is unchanged.
V2 I2 t = M2 c (out - in) + H
Subtracting the two equations give
V2 I2 t - V1 I1 t = (M2 - M1) c (out - in)
Hence thermal energy losses have been eliminated and c can be determined.

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Supplementary Notes
What is the Second Law of Thermodynamics?

The First Law of Thermodynamics states that energy cannot be created or destroyed; the
total quantity of energy in the universe stays the same. The Second Law of Thermodynamics is
about the quality of energy. It states that as energy is transferred or transformed, more and
more of it is wasted. The Second Law also states that there is a natural tendency of any isolated
system to degenerate into a more disordered state.

Saibal Mitra, a professor of physics at Missouri State University, finds the Second Law to be the
most interesting of the four laws of thermodynamics. “There are a number of ways to state the
Second Law," he said. "At a very microscopic level, it simply says that if you have a system that
is isolated, any natural process in that system progresses in the direction of increasing disorder,
or entropy, of the system.”

All processes result in an increase in entropy. For example, crystals can form from a salt solution
as the water is evaporated. Crystals are more orderly than salt molecules in solution; however,
vaporized water is much more disorderly than liquid water. The process taken as a whole results
in a net increase in disorder.

In practice, however, all exchanges of energy are subject to inefficiencies, such as friction and
radiative heat loss, which increase the entropy of the system being observed. Therefore,
because there is no such thing as a perfectly reversible process, if someone asks what is the
direction of time, we can answer with confidence that time always flows in the direction of
increasing entropy.

The Second Law indicates that thermodynamic processes, i.e., processes that involve the
transfer or conversion of heat energy, are irreversible because they all result in an increase in
entropy. Perhaps one of the most consequential implications of the Second Law, according to
Mitra, is that it gives us the thermodynamic arrow of time.

Source: http://www.livescience.com/50941-second-law-thermodynamics.html

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Unit 09 Thermodynamics Tutorial Questions

(Solutions are given for Questions 2, 5, 6 and 10.)

Specific Heat Capacity and Specific Latent Heat

1 An ice cube of mass 25.0 g and temperature 0.0 oC is dropped into a glass of water of
mass 300 g and initial temperature 20.0 oC. What is the final temperature of the mixture?
Given specific heat capacity of water = 4200 Jkg-1 K-1;
specific latent heat of fusion of ice = 334000 Jkg-1. [12.3 oC]

Solution:
Latent heat gained by + heat gained by = Heat lost by water
ice to melt to water to reach final temp from 20 oC to final temp

0.025 x 334000 + 0.0250x4200(Tf – 0.0) = 0.300x 4200x(20.0 - Tf)

Tf = 12.3 oC

2* (N14/I/18) Equal masses of three liquids X, Y and Z are heated from room temperature.

Energy is supplied by heating at the same rate to each liquid. The graph shows how the
temperature of each liquid varies with time after heating starts.

Which liquid X, Y or Z has the largest specific heat capacity?

dθ
Solution: Since Power supplied P = mc
dt
1 dθ
For the same mass m and same power P supplied, c  where is the gradient
dθ dt
dt
dθ
From graph, Y has the least gradient , so its c is the largest.
dt

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3 (N10/III/1) A student carries out an experiment to determine the specific latent heat of
vaporisation of water. Water is boiled in a beaker by means of an electric heater. The
power P supplied to the heater is measured. When the water is boiling at a constant rate,
the mass m of water evaporated in 5.0 minutes is determined. Data for the power P and
the mass m for two different values of P are shown in the table.

P/W m/g
140 14.1
95 8.2

(a) Suggest why, in order to obtain a reliable result for the specific latent heat, the mass
m is determined for two different values of P.

(b) Calculate the value for the specific latent heat L of vaporisation. [2.29 × 106 J kg-1]

Solution:
: (a) need 2 equations to eliminate the rate of heat loss h to the surrounding in the
calculations, thus obtaining a more accurate value for L.
m
(b) By conservation of energy, P  Lh
t
140 = 14.1 × 10-3/(5.0 × 60) × L + h ----(1)
95 = 8.2 × 10-3/(5.0 × 60) × L + h -----(2)
Solving L = 2.29 × 106 J kg-1

4 The graph refers to an experiment in which an initially solid specimen of nitrogen absorbs
heat at a constant rate. Nitrogen melts at 63 K and the specific heat capacity of solid
nitrogen is 1.6 × 103 J kg-1 K-1.
T/K

73

63

53 time/s
0 160 400 600

Assume no heat losses.

(a) Calculate the specific latent heat of fusion of nitrogen.
(b) Calculate the specific heat capacity of liquid nitrogen.
[2.4 × 104 J kg-1, 2.0 × 103 J kg-1K-1]
Solution:
(a) Let P be the rate of heat absorbed
P×t = m cs 
P × (160 – 0) = m (1.6 × 103) (63 - 53) (1)
P × t‘ = m Lf
P × (400 – 160) = m Lf (2)
160 / 240 = (1.6 × 104) / Lf (1)/(2)
Lf = 2.4 × 104 J kg-1

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(b) P×t = m cl 
P × (600 – 400) = m cl (73 - 63) (3)
160 / 200 = 1.6 × 103 / cl (1)/(3)
cl = 2.0 × 103 J kg-1 K-1

5* Explain why the latent heat of vaporisation is greater than latent heat of fusion for the
same substance. (e.g. for ethanol, Lv = 8.54 × 105 J kg-1 and Lf = 1.04 × 105 J kg-1)

Solution:
The energy required to completely separate the molecules from liquid state to vapour state
is much greater than the energy required to break the lattice structure/rigid bonds of solid
to become liquid. Furthermore energy must be provided to push back the atmosphere as
the liquid turns into vapour since the volume of vapour is much greater than the volume of
the liquid.
Therefore the specific latent heat of vaporisation is greater than specific latent heat of
fusion.

Internal Energy
6 (a) What do you understand by the internal energy of a system?
(b) State the physical quantities which affect the internal energy of any system.
(N96/III/5 part)

Ans: (a) Internal energy of a system is the sum of the kinetic energy of all the molecules
due to their random motion and the potential energy of all the molecules due to
their positions relative to each other and the forces between them.

(b) k.e. depends on Thermodynamic temperature T(or product PV), amount of

substance n,
p.e. depends on intermolecular forces and separation of molecules.

7 A substance changes from solid to liquid at its normal melting temperature. What change
if any, occurs in the average kinetic energy and the average potential energy of its
molecules?

average kinetic energy average potential energy

A constant constant
B increases constant
C increases decreases
D constant increases

Ans: D. average k.e. remains constant since temperature remains constant at melting point.
Average p.e. increases because lattice structure/bonds broken

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First Law of Thermodynamics

8 (N09/I/21) A fixed mass of ideal gas at high pressure is contained in a balloon. The balloon
suddenly bursts, causing the gas to expand and cool. In this situation, which row describes
the values of U, Q and W where U = Q + W, according to the first law of
thermodynamics?

U Q W

A negative negative positive

B negative zero negative
C positive zero negative
D positive negative positive

Ans: B. It is an adiabatic expansion because when balloon suddenly burst, no

time allowed for heat transfer, so Q = 0

9 An ideal gas expands isothermally, doing 250 J of work.

(a) What is the change in internal energy?
(b) How much thermal energy is absorbed in the process?
[0 J, 250 J]
Solution:
(a) Isothermal process  no change in T  U = 0 J
(b) U = Q + W
0 = Q + (-250)
 Q = 250 J

10* Use the first law of thermodynamics to explain the change, if any, in the internal energy
(a) of the water in an ice cube when the ice melts, at atmospheric pressure, to form a
liquid without any change of temperature,
(b) of the gas in a tyre when the tyre bursts so that the gas suddenly increases in
volume. Assume that the gas is ideal.

Solution:
(a) volume decreases from ice to water, so work done on the system. However this
small volume change so work done on system si negligible (W 0)
thermal) energy absorbed to break lattice structure of ice (Q is +ve)
so internal energy increases
(b) gas expands so work done by gas (against atmosphere) (W is -ve)
no time for thermal energy to enter or leave the gas (Q 0)
so internal energy decreases

11 (N16/I/19) A fixed mass of gas undergoes changes of pressure and volume as shown.

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When the gas is taken from state P to state Q by the stages PR and RQ, 3 J of work is
done by it and there is a thermal transfer of 8 J of energy into it.

When the same resultant change is achieved by stages PS and SQ, 1 J of work is done
by the gas. In this case, what is the thermal transfer of energy? [Q = +6 J]

Solution:. U is the same for PRQ and PSQ since their initial and final states are
the same.
U = Q1 + W1 = Q2 + W2
8 – 3 = Q2 -1
Q2 = +6 J, i.e. there is thermal transfer of 6 J into the gas.

12 A fixed mass of an ideal gas undergoes a cycle ABCA of changes, as shown in the
figure.

(a) During the change from A to B, the energy supplied to the gas by heating is 442 J.
Use the first law of thermodynamics to calculate the increase in internal energy of the
gas

(b) During the change from B to C, the energy extracted from the gas is 313 J. Calculate
the change in internal energy of the gas.

(c) Calculate the change in internal energy for the change from C to A.

(d) Calculate the net work done by the gas during the cycle ABCA.

[265 J, -313 J, +48 J, 71J]

Solution:
(a) Won = - p V isobaric process
= - 5.2 x105 (5.0 – 1.6) x10–4 = -177 J
U = Q + Won
= 442 +(– 177) = 265 J
 (b) U = Q + Won isochoric process
= -313 + 0 = -313 J
(c) For a cyclic process, net change in internal energy = 0
So UAB + UBC +UCA = 0
265 + (-313) +UCA = 0  UCA = +48 J
(d) net work done by gas = area enclosed by ABCA
= ½ (5.0 – 1.6) x 10–4x (5.2 – 1.0) x105
= 71 J

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13 (N14/III/3) A fixed mass of an ideal gas undergoes the cycle of changes XYZX as
shown.

At point X, the temperature of the gas is 290 K.

(a) Calculate the amount of gas.
(b) Determine, for this mass of gas, the magnitude of
(i) the work done during the change from X to Y,
(ii) the change in the internal energy during one complete cycle XYZX.
(c) Some energy changes during one cycle XYZX are shown in the table. Use your
answers to (b) to complete the table.

change work done heating supplied increase in

on gas/ J to gas/ J internal energy/ J
XY + 570
YZ + 540 0
ZX 0
[0.050 mol, 226 J]
Solution: Note that figure given is a V-p diagram, not a p-V diagram!
: (a) Apply pV = nRT at point X.
2.4 × 105 × 5.0 × 10-4 = n × 8.31 × 290  n = 0.050 mol
(b) (i) W = pV = 2.4 × 105 (14.4 – 5.0) 10-4 = 226 J
(ii) U = 0 J during one complete cycle
(c)
change work done heating supplied increase in
on gas/ J to gas/ J internal energy/ J
XY -226 + 570 +344
YZ + 540 0 +540
ZX 0 -884 -884

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