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Lecture Note 2: The Basic Laws of Thermodynamics 2-1

PHYS 121: PHYSICS 2 2nd Sem SY 2021-2022

Lecture Note 2: The Basic Laws of Thermodynamics

Instructor: Ruelson Solidum Course: BS ECE 1A & BS ECE 1B

Note: Online Distance Learning, USTP/CSM/Department of Physics

Reference: University Physics by Young & Freedman
Learning Outcomes: The students completed this course should:

1. UNDERSTAND THE THERMODYNAMIC SYSTEM

2. LEARN IMPORTANCE ON THE FIRST LAW OF THERMODYNAMICS.
3. UNDERSTAND DEEPER THE SECOND LAW OF THERMODYNAMICS

The first law of thermodynamics is a version of the law of conservation of energy adapted for thermodynamic
systems. It tells us that the change in internal energy of a thermodynamic system is equal to the heat added
to the system and the work done by the system.
The second law of thermodynamics on the other hand constrains the first law by which processes allowed
by the first law actually occur. For instance, it tells us that energy never flows by heat spontaneously from
a cold object to a hot object. Understanding of both laws helps us analyze combustion engines and the
principle that limits their efficiency

2.1 The Thermodynamic Processes

Thermodynamic processes are processes that involve changes in the state of thermodynamic systems. A
thermodynamic system can interact with its surroundings or environment in at least two ways, one of which
is heat transfer and the other one is through work done into or out the system

2.2 Heat and Work

A thermodynamic system may exchange energy with its surroundings by means of heat Q, work W or both.
In this lecture note, we will be using sign conventions:.

1. (Q > 0). When the heat flows into the system, with a corresponding input of energy into the
system.
2. (Q < 0). When the heat flows out of the system.
3. (W > 0). When work is done by the system against its surroundings, which corresponds to energy
leaving the system.
4. (W < 0). When work is done on the system by the surroundings, which presents an amount of
energy entering the system. Figure 2.1 Illustrates the sign conventions.
2-2 Lecture Note 2: The Basic Laws of Thermodynamics

Figure 2.1: Sign conventions for exchange of energy on a system with its surroundings.

2.3 Work Done During Volume Change

We can express the work done by the system in infinitesimal volume change in a finite volume from V1 to
V2 as

Z V2
W = pdV (2.1)
V1

We can represent this relationship as a graph of p as a function of V in a pV -diagram. Figure 2.2 shows a
simple example. Work is positive when the system expands as in from Va to Vb in the pV -diagram of Figure

Figure 2.2: The work done equals the area under the curve on a pV -diagram. 1) undergoing an expansion
with varying pressure, 2) undergoing a compression with carying pressure and 3) expansion with constant
pressure

2.2. If instead a compression happens, say from Vb to Va , its volume decreases, the system is compressed
and it gives a negative area. It does a negative work on its surroundings.
For an ideal gas that undergoes an isothermal (constant-temperature) expansion at temperature T , its volume
changes from V1 to V2 . The done by the gas is equal to

p1
W = nRT ln (2.2)
p2

We will leave this to you as an exercise to derive the expression.

Lecture Note 2: The Basic Laws of Thermodynamics 2-3

2.4 Internal Energy

Internal energy of a system,U , can be tentatively defined as the sum of the total kinetic energies of all its
constituent particles plus the sum of the total potential energies of interaction among particles. This is in
consideration that matter is made up of atoms and molecules, which in turn are made up of particles having
kinetic and potential energies.
For systems undergoing changes in state, the internal energy may change from an initial value U1 to a final
value U2 . This change in internal energy can be described as

∆U = U2 − U1 (2.3)

2.5 The First Law of Thermodynamics

As stated in the opening sentences of this chapter, the first law of thermodynamics is a generalization of the
principle of conservation of energy to include energy transfer through heat as well as mechanical work.
Say for example we add a quantity of heat Q to as system which does no work (W = 0), its internal
energy then increase by Q which tells us that ∆U = Q. If a system does work W by expanding against
its surroundings and no heat is added during the process, energy leaves the system and the internal energy
decreases: W is positive, Q = 0, and ∆U = −W . When both heat transfer and work occur, the total change
in internal energy is
∆U = U2 − U1 = Q − W (2.4)
which we can rewrite in the form
Q = ∆U + W (2.5)

This is the mathematical statement of the first law of thermodynamics. The interpretation is that,
when heat Q is added to a system, some of the added energy remains within the system while
some leaves the system as the system does work against its surroundings.
Q and W are not the same in general for different paths. However, from experiments it was found that for
different materials ∆U is path independent. The change in internal energy of a system during any
thermodynamic process depends only on the initial and final states, not on the path leading
from one to the other.
Exercise.A series of thermodynamic processes is shown in Figure 2.3. As shown, heat of 200J is added to
the system in the process ab while 400J of heat is added in process bd.Find

1. the change in internal energy in the process ab.

2. the change in internal energy in the process abd;
3. the total heat added in the process acd.

Solution. (a) The system does work since volume is constant in the process ab:

Wab = 0 =⇒ ∆Uab = Qab = 200J

(b)The expansion with pressure p remains constant while the volume changes from V1 to V2 happens at
process bd, from Eq. (2.1),
Wbd = p(V2 − V1 ) = 120J
2-4 Lecture Note 2: The Basic Laws of Thermodynamics

Figure 2.3: pV -diagram of the process

The total work done for the process abd and the total heat is

Wabd = Wab + Wbd = 0 + 1200J = 1200J

Qabd = Qab + Qbd = 200J + 400J = 600J

The internal change in energy for the process abd can then be solved using Eq. (2.4)

∆Uabd = Qabd − Wabd = 600J − 120J = 480J

(c) Because ∆U is independent of the path from a to d, the change in internal energy for path acd is the
same as for the path abd:
∆Uacd = ∆Uabd = 480J

For infinitesimal changes in state, the first law of thermodynamics can be written in differential form:

dU = dQ − dW (2.6)

in which a small amount of heat dQ is added to the system, the system does a small amount of work dW
and its internal energy changes by an amount dU .

2.6 Types of Thermodynamic Processes

2.6.1 Adiabatic process

A process with no heat transfer into or out of a system, that is, Q = 0. This no transfer of heat flow can be
done either by thermally insulating the system or carrying out the process so quickly so that there will be
no time for heat flow of appreciable amount to happen. From our first law of thermodynamics, we have an
adiabatic process that is
∆U = U2 − U1 = −W
Lecture Note 2: The Basic Laws of Thermodynamics 2-5

Figure 2.4: pV -diagram for the four different processes for a constant amount of an ideal gas.

When a system expands adiabatically, W is positive (the system does work on its surroundings), so ∆U is
negative and the internal energy decreases. When a system is compressed adiabatically, W is negative (work
is done on the system by its surroundings) and U increases. The work can be calculated from a pV diagram,
in which for an ideal gas undergoing adiabatic processes, we can show that

pV γ = const
where the adiabatic index of gas is given by
γ = Cp /CV
For an ideal gas,
∆U = nCV (T1 − T2 )
Since Q = 0 and W = −∆U , the work done by an ideal gas during an adiabatic process is,
W = nCV (T2 − T1 )

Which may also also be written in terms of pV = nRT

CV 1
W = (p1 V1 − p2 V2 ) = (p1 V1 − p2 V2 )
R γ−1

2.6.2 Isochoric process

Isochoric process sometimes also called isovolumetric process is a constant-volume process. Since the volume
of the system is constant, it does no work on the surroundings thus we have W = 0 and from the first law
of thermodynamics, we have
∆U = U2 − U1 = Q
The energy transfer by heat in a constant volume process is given by
Q = nCV ∆T
2-6 Lecture Note 2: The Basic Laws of Thermodynamics

2.6.3 Isobaric process

Isobaric process is a constant pressure process as the gas expands or is compressed. None of the quantities
∆U , Q, and W is zero in this process. From Equation 2.1, we can calculate W where we have

W = p(V2 − V1 )

Rearranging the first law equation, we obtain

Q = ∆U + p∆V

Since the change in internal energy for an ideal gas is just ∆U = nCV ∆T , the ideal gas law is p∆V = nR∆T
and Q = nCp ∆T we can substitute these quantities to the equation above and obtain an expression for the
molar heat capacities of an ideal gas
Cp = CV + R (2.7)
We now define γ = Cp ?CV as the ratio of heat capacities.For ideal monoatomic gas,we have γ = 5/3 = 1.67
and for ideal diatomic gas, we have γ = 7/5 = 1.40

2.6.4 Isothermal process

Isothermal process is a process of constant temperature. For this process to proceed, any heat flow into or
out of the system must occur slowly enough that equilibrium is maintained. None of the quantities ∆U , Q,
and W is zero for this process. The work for an isothermal process is given by Equation 2.2.

Isochoric Isobaric Isothermal Adiabatic

Qin nCV ∆T nCp ∆T nCV ∆T + nRT ln(V2 /V1 ) 0
Wout 0 p∆V nRT ln(V2 /V1 ) nCV (T2 − T1 )
∆U = Qin + Wout nCV ∆T nCV ∆T nCV ∆T nCV (T2 − T1 )

Table 2.1: First law and thermodynamic processes for ideal gas

Problem. Figure 2.5 shows a pV -diagram for 0.0040mole of ideal H2 gas. The temperature of the gas does
not change during the segment bc.

1. What volume does this gas occupy at point c?

2. Find the temperature of the gas at points a, b, and c.

3. How much heat went into or out of the gas during segments ab, ca and bc?

4. Find the change in internal energy of this hydrogen during segments ab, bc, and ca

Solution. Segments ab is isochoric, bc is isothermal, and ca is isobaric. For bc, = 0, ∆U = 0, and

Q = W = nRT ln(Vc /Vb ). For an ideal H2 (diatomic), CV = 5/2R and Cp = 7/2R. ∆U = nCV ∆T for any
process of an ideal gas.
(a) Tb = Tc . For states b and c, pV = nRT =constant so pb Vb = pc Vc
   
pb 2.50atm
Vc = Vb = (0.35L) = 3.50L
pc 0.25atm
Lecture Note 2: The Basic Laws of Thermodynamics 2-7

Figure 2.5: pV -diagram of the processes

(b)The temperature at point a is

pa Va
Ta = = 266K
nR
In same volume case Va = Vb so for states a and b, using pV = nRT so

Ta Tb
=
pa pb

In point b and c they have same isotherm so that Tb = Tc

Tc = Tb = Ta (pb /pa ) = 2660K

(c) USing the previous results. For process ab we can get the heat Q flowing through the system:

Q = nCp ∆T = n(5/2R)∆T

which gives us the result of

Q = +199J
The positive result means heat goes into the gas. Q > 0
For process ca
Q = nCp ∆T = n(7/2R)∆T
which gives us the result of
Q = −279J
The negative result means heat goes out of the gas. Q < 0
For process bc
Q = W = nRT ln(Vc /Vb ) = +204J
Heat goes into the gas.
(d) For Process ab
∆U = nCV ∆T = n(5/2R)∆T = +199J
2-8 Lecture Note 2: The Basic Laws of Thermodynamics

The internal energy increases. For process bc since ∆T = 0 so the change in internal energy is also zero i.e.
∆U = 0,imply that the internal energy remains the same.
For process ca: the internal energy

∆U = nCV ∆T = n(5/2R)∆T = −199J

Thus, in this process the internal energy decreased.

2.7 Heat Engines

A heat engine is any device that transforms heat partly into work. It takes in energy by heat and partially
converts it to other forms, such as electrical and mechanical energy. Usually, this energy by heat it takes in
called the working substance is any matter that can undergo inflow and outflow of heat. Say for example
we have a mixture of air and fuel for internal combustion engines.
Heat engines undergoing a cyclic process are the easiest to analyze. Consider for instance the heat engine
diagram shown in Figure 2.6 where the engine carries some working substance during which (1) energy is
transferred by heat from a source at a higher temperature, (2) work is then done by the engine and (3) the
energy is expelled from the engine to a source at lower temperature. When a system is carried through a
cyclic process, its initial and final internal energies are equal. From our first law of thermodynamics, we have

U2 − U1 = 0 = Q − W =⇒ Q = W

Figure 2.6: Schematic energy flow diagram for a heat engine

which tells us that the net heat flowing into the engine in a cyclic process equals the net work done by the
engine. As we can see from figure 2.6, QH and QC are the heat absorbed and rejected respectively by an
engine during a one cyclic process. The heat net Q = QH + QC = |QH | − |QC |. Thus, from the first law

W = Q = |QH | + |QC | (2.8)

The thermal efficiency e of a heat engine is defined as the ratio of the work done by the engine and the
energy absorbed during one cycle:

 
W QC  QC 
e= =1+ =1−
  (2.9)
QH QH QH 
Lecture Note 2: The Basic Laws of Thermodynamics 2-9

We can think of thermal efficiency of the engine as the ratio of the benefit to the cost incurred. From
equation 9.9, we can see that to have an engine of 100% efficiency or e = 1, QC should be zero, which
means that no energy must be expelled in the cold reservoir. However, a heat engine which uses all the
input energy into mechanical work is impossible. This is strongly supported and suggested by experimental
evidences. This leads us to one of the statements of the second law of thermodynamics, the engine statement
or Kelvin-Planck statement:

No heat engine operating in a cycle can absorb energy from a reservoir and use the energy
completely into mechanical work.

2.7.1 Refrigerators and Heat Pumps

Air conditioners and refrigerators are examples of heat engines that operates in reverse. For this engines,
energy is injected into the engine which is the work W in Figure 2.5, resulting in heat being extracted from
the cold reservoir and given off to the hot reservoir. The system now works as a heat pump. The heat pump
requires a net input of mechanical work unlike a heat engine has a net output of work. QC is positive while
W and QH are both negative for the energy flow diagram shown in Figure 2.7. From the first law for a cyclic

Figure 2.7: Schematic energy flow diagram for a heat engine.

process, we have
QH + QC − W = 0 =⇒ −QH = QC − W

Since both QH and W are negative,

|QH | = QC + |W | = |QC | + |W | (2.10)

From our equation, we can see that the best heat pump for a refrigerator or air conditioner is one that which
removes the greatest amount of energy from the cold reservoir in exchange for the least amount of work that
is |QC |/|W | should have a very large ratio. This ratio is called the coefficient of performance (COP ), which
we can denote with κ, is given by

|QC | |QC |
κ= = (2.11)
W |QH | − |QC |

Heat naturally flows spontaneously from hotter to colder bodies, never the reverse. Our refrigerator and air
conditioners does take heat from a colder to hotter bodies, however, this requires an input of mechanical
2-10 Lecture Note 2: The Basic Laws of Thermodynamics

energy. From this analysis, we can restate the second law of thermodynamics in an alternative statement
which we call the refrigerator statement or Clausius statement of the second law:

It is impossible for any process to have as its sole result the transfer of heat from a cooler to
a hotter body.

The conversion of work to heat and the heat flow from hot to cold across a finite temperature gradient are
irreversible processes. The engine and refrigerator statements of the second law state that these processes
can be only partially reversed. Processes that proceed spontaneously in one direction but not the other
are irreversible processes. Most thermodynamic processes that occur in nature are irreversible processes.
However, we can think of a class of idealized reversible processes that is always very close to being in
thermodynamic equilibrium.

Figure 2.8: : Four-stroke cycle used in gasoline/petrol engines (adapted from www.shutterstock.com)

2.8 Internal Combustion Engines

Internal-combustion engines are heat engines that generates power by burning of gasoline, oil, or other fuel
with air inside the engine, the hot gases produced are being used to drive a piston or do other work as they
expand. The combustion of fuel occurs with an oxidizer in a combustion chamber that is an integral part of
the working fluid flow circuit. Figure 2.8 shows a four-stroke engine which is an internal-combustion engine
in which the piston completes four separate strokes while turning the crankshaft. A stroke refers to the full
travel of the piston along the cylinder, in either direction. The figure also shows the operation of this type
of engine. First, a mixture of fuel and air flows into the cylinder through the intake valve while the piston
descends, which increases the volume of the cylinder from V (volume when the piston is all the way up) to a
maximum volume rV (volume when the piston is all the way down). The variable r is called the compression
ratio whose value ranges from 8 to 10 for our present-day automobiles. After the intake stroke (1), the intake
valve closes and the mixture is adiabatically compressed to a volume which is the compression stroke (2).
The mixture is then ignited by the. spark plug, and the heated gas mixture adiabatically expands back to
rV , pushing the piston and doing work. This is the combustion or power stroke (3). Lastly, the exhaust
valve opens, pushing the combusted products during the exhaust stroke, leaving the cylinder ready for the
next intake.
Lecture Note 2: The Basic Laws of Thermodynamics 2-11

2.8.1 The Otto Cycle

An Otto cycle is an idealized thermodynamic cycle that is most commonly found in automobile engines. It
describes the functioning of a typical spark ignition piston engine. The working substance usually gasoline
is carried through the following processes:
At point a in Figure 2.9, the mixture of air and gasoline enters the cylinder

1. a −→ b.mixture is compressed to point b and is then ignited

2. b −→ c.heat QH is added to the system by burning the gasoline
3. c −→ d.adiabatic expansion (power stroke)

4. d −→ a.cooling of gas by the outside air and |QC | is rejected on the exhaust

Figure 2.9: The pV-diagram for the Otto Cycle. 1-Adiabatic compression, 2-Heating at constant volume,
3-Adiabatic expansion, 4-Cooling at constant volume.

Since and equivalent amount of gasoline and air enters again at point a, we may consider the process to be
cyclic. QH and QC which are added and rejected respectively happens at constant volume, thus, we have

QH = nCV (Tc − Tb )
and
QC = nCV (Ta − Td )

and for the two adiabatic process we have,

Ta (rV )γ−1 = Tb (rV )γ−1

and
Td (rV )γ−1 = Tc (rV )γ−1

Substituting these to Equation (2.7), the efficiency of this engine is equal to

1
e=1− (2.12)
rγ−1
which is the thermal efficiency in Otto Cycle. We will leave this to you as an exercise to be proven.
2-12 Lecture Note 2: The Basic Laws of Thermodynamics

With r = 8 and γ = 1.4 (air), e = 0.56 or 56 percent. We can increase the efficiency for this kind of engine
by increasing r however, this will also increase the temperature at the end of the adiabatic compression of
the air and fuel mixture which might result to an spontaneous explosion of the mixture during compression
instead of burning it in the ignition process. We call this pre-ignition which can cause a knocking sound
and damage the engine. Have you ever heard of the octane rating of gasoline? This is actually a measure
of a fuels antiknock qualities. The higher the octane number, the more compression the fuel can withstand
before detonating (igniting). Fuels with a higher octane rating are used in high performance gasoline engines
that require higher compression ratios.

2.8.2 The Diesel Cycle

This type of engine is similar in operation with the Otto Cycle. In it, fuel is ignited by heat generated during
the compression of air in the combustion chamber, into which fuel is then injected. This is in contrast to
igniting the fuel-air mixture with a spark plug as in the Otto cycle engine. A little before the beginning of
the power stroke, the injectors start to inject fuel directly into the cylinder, just fast enough to keep the
pressure approximately constant during the first part of the power stroke. The working substance is carried
through the following process:

Figure 2.10: The pV-diagram for the Diesel Cycle. 1-Adiabatic compression, 2-Fuel ignition, heating at
constant pressure, 3-Adiabatic expansion, 4-Cooling at constant volume.

1. a −→ b. at point a, air is compressed adiabatically to point b

2. b −→ c. constant pressure heating.
3. c −→ d. adiabatic expansion.
4. d −→ a. cooling at constant volume.

In a diesel engine, air is compressed adiabatically with a compression ratio r typically between 15 and 20.
Also, because there is no fuel in the cylinder during most of the compression stroke, pre-ignition cannot
occur which improves the efficiency and ensures reliable ignition when the fuel is injected. The efficiency of
diesel cycle engine is given by:

αγ − 1
 
1
e=1− (2.13)
rγ−1 γ(α − 1)

where α is the cut-off ratio V3 /V1 which is the ratio between the end and start volume for combustion phase.
This ratio can also be expressed in terms of temperature
Lecture Note 2: The Basic Laws of Thermodynamics 2-13

T3 can be approximated to the flame temperature of the fuel used. T1 can be approximated to the inlet
air temperature. The additional complexity for the Diesel formula comes around since the heat addition
is at constant pressure and the heat rejection is at constant volume. For typical values of r and γ = 1.4,
the theoretical efficiency of the idealized diesel engine is about 0.65 to 0.70. While these may be appear to
be very efficient, diesel engines must be built to much tighter tolerance and fuel-injection system requires
careful maintenance
Since diesel engines do not compress the fuel, but rather compress only the air and then inject fuel into air
which was heated by compression, fuels with lower octane number (but higher in cetane) are ideal for diesel
engines.

2.9 The Carnot Engine

Engines working in Otto and diesel cycle although form a cycle are not reversible cycle as the working
medium changes after each cycle. The Carnot cycle, on the other hand, is a reversible cycle where a working
fluid undergoes a cycle of isothermal expansion, adiabatic expansion, isothermal compression and adiabatic
compression. This is a theoretical thermodynamic construct which provides an upper limit on the efficiency
that any classical thermodynamic engine can achieve consistent with the second law.
The conversion of work to heat is an irreversible process. As previously seen from the Otto cycle and diesel
cycle, the purpose of the heat engine is a partial reversal of this process, the conversion of heat to work giving
us only with great enough efficiency possible. For maximum heat engine efficiency then, we must avoid all
irreversible processes. The Carnot cycle gives us an idea that n ideal engine would involve only reversible
processes

Figure 2.11: The pV -diagram for a Carnot cycle for an ideal gas.

1. a −→ b.the gas expands isothermally at temperature TH absorbing heat QH

2. b −→ c.it expands adiabatically until its temperature drops to TC
3. c −→ d.it is compressed isothermally at TC , rejecting heat |QC |
4. d −→ a.it is compressed adiabatically back to initial state at temperature TH

For the isothermal processes, we have

Vb
QH = Wab = nRTH ln
Va
2-14 Lecture Note 2: The Basic Laws of Thermodynamics

and
Vd Vc
QC = Wcd = nRTC ln = −nRTC ln
Vc Vd

The ratio of the two quantities of heat is

QH ln(Vc /Vd
= −(TC /TH ) (2.14)
QC ln(Vb /Va )

For the adiabatic processes

TH Vbγ−1 = TC Vcγ−1
and
TH Vaγ−1 = TC Vdγ−1

simplified expression came out as

Vb Vc
=
Va Vd

and Equation 2.14 becomes,

QH TC
=− (2.15)
QC TH
The efficiency of the Carnot Engine from 2.9 is

TC TH − TC
ecarnot = 1 − = (2.16)
TH TH

This equation tells us that the efficiency of the Carnot engine depends only on the temperature of the two
heat reservoirs. The efficiency is large when the temperature difference is large, and is very small when the
temperatures are nearly equal. Now since the Carnot cycle is reversible in every step, we can reverse it to
make the engine into a Carnot refrigerator whose coefficient of performance κ is given by

TC
κ= (2.17)
TH − TC

Exercise.A Carnot engine is operated between two heat reservoirs at temperatures of 620 K and 325 K. (a)
If the engine receives 6.45 kJ of heat energy from the reservoir at 620 K in each cycle, how many joules per
cycle does it discard to the reservoir at 325 K? (b) How much mechanical work is performed by the engine
during each cycle? (c) What is the thermal efficiency of the engine?
Solution. (a) For a Carnot cycle, using Eq.2.15 the heat discarded to the cold reservoir is

QC = −QH (TC /TH ) = −3.38 × 103 J

(b) and the work W can be calculated by

|W | = |QH | − |QC | = 3.07 × 103 J

(c) the thermal efficiency of the engine is

e = W/QH = 0.476 = 47.6%

Lecture Note 2: The Basic Laws of Thermodynamics 2-15

2.10 Entropy

The second law of thermodynamics can be stated as a quantitative relation with the concept of entropy.
Several processes proceed naturally in the direction of increasing disorder and entropy provides a quantitative
measure for this. Consider again an infinitesimal expansion of an ideal gas. From the first law, we have,

nRT
dQ = dW = pdV = dV
V
or can be written as
dV dQ
=
V nRT

The fractional volume change dV /V is a measure of the increase on disorder and it is proportional to dQ/T .
We define the entropy S of the system during an infinitesimal reversible process at absolute temperature T
as
dQ
dS = (2.18)
T

The total entropy change ∆S for a reversible isothermal process is

Q
∆S = S2 − S1 =
T
For any reversible process, Z 2
dQ
∆S =
1 T
and the total entropy change during any reversible process is zero,
Z 2
dQ
=0
1 T

In Carnot cycle,
SH + ∆SC = 0
and
QH QC
+ =0 (2.19)
TH TC
For any irreversible process, the total entropy change is greater that zero, that is, ∆S0. When all systems
taking part in a process are included, the entropy either remains constant or increases. In other words, there
is no process wherein entropy decreases.

2.11 Third Law of Thermodynamics

The first and second laws of thermodynamics are well established. These two laws of thermodynamics
constitute a solid foundation of physical science as demonstrated in the previous sections and also by their
robustnes and longevity. On the other hand,the Third Law, which was first addressed by Nerst, is still been
subjected to controversies and disputes. This law is sometimes stated as follows:

The entropy of a system approaches a constant value as its temperature approaches the
absolute zero. The constant value is called the residual entropy of the system.
2-16 Lecture Note 2: The Basic Laws of Thermodynamics

A classical formulation by Nerst for the third law is:

It is impossible for any process, no matter how idealized, to reduce the entropy of a system
to its absolute-zero value in a finite number of operations.

One of the possible applications of the third law is that it might provide a useful tool to decide on the
eventual presence of states that are out of equilibrium. The other implications and applications of this law
however is beyond the scope of this lecture.

2.12 Exercises.
1. Six moles of an ideal gas are in a cylinder fitted at one end with a movable piston. The initial
temperatures of the gas is 27.0C and the pressure is constant. As part of a machine design project,
calculate the final temperature of the gas after it has done 24.0 × 013 J of work.

2. A gas in a cylinder expands from a volume of 0.110m3 to 0.320m3 . Heat flows into the gas just rapidly
enough to keep the pressure constant at 1.65 × 105 Pa during the expansion. The total heat added is
1.15 × 105 J. (a) Find the work done by the gas. (b) Find the change in internal energy of the gas.

3. A diesel engine performs 2200J of mechanical work and discards 4300J of heat each cycle. (a) How
much heat must be supplied to the engine in each cycle? (b) What is the thermal efficiency of the
engine?

4. (a) Calculate the theoretical efficiency for an Otto-cycle engine with γ = 1.40 and r = 9.50. (b) If this
engine takes in 10, 000J of heat from burning its fuel, how much heat does it discard to the outside
air?

5. A 4.50kg block of ice at 0.00C falls into the ocean and melts. The average temperature of the ocean is
3.50C, including all the deep water. By how much does the melting of this ice change the entropy of
the world? Does it make it larger or smaller?

6. A sample of ideal gas is expanded to twice its original volume of 1.00m3 in a quasi-static process for
which P = αV 2 , with α = 5.00atm/m6 as shown in Figure 2.12. How much work is done on the
expanding gas

Figure 2.12: Exercise No. 6

7. (a)Determine the work done on a fluid that expands from i to f (b)How much work is performed on
the fluid if it is compressed from f to i along the same path? as indicated in Figure 2.13
Lecture Note 2: The Basic Laws of Thermodynamics 2-17

Figure 2.13: Exercise no.7

8. A refrigerator has a coefficient of performance of 3.00. The ice tray compartment is at −20.0C and
the room temperature is 22.0C. The refrigerator can convert 33.0g of water at 22.0C to 30.0g of ice at
−20.0C each minute. What input power in watts is required?
9. A gasoline engine has a compression ratio of 6.00 and uses a gas for which γ = 1.40. What is the
efficiency if it is operated in an idealized Otto cycle?