Chapter 13

The Laws of Thermodynamics

 Introduction
■ The laws of thermodynamics define • The first law of thermodynamics:
physical quantities such as; • When energy passes, as work,
■ Temperature, as heat, or with matter, into or out of
a system, the system's internal
■ Energy, and energy changes in accord with the
■ Entropy. law of conservation of energy.
■ The laws describe the relationships • The second law of
between these quantities. thermodynamics:
■ Thermodynamics has traditionally • In a natural thermodynamic process,
recognized three fundamental laws, the sum of the entropies of the
interacting thermodynamic
simply named by an ordinal systems increases.
identification, the first law, the • The third law of
second law, and the third law. thermodynamics:
■ The zeroth law was established • The entropy of a system approaches
after the first three laws. a constant value as the temperature
approaches absolute zero. With the
• The zeroth law of exception of non-crystalline solids
thermodynamics defines thermal (glasses) the entropy of a system at
equilibrium and forms a basis for the absolute zero is typically close to
definition of temperature: zero.
• If two systems are each in thermal
equilibrium with a third system, they are
in thermal equilibrium with each other.
Work in Thermodynamic Processes –
Assumptions
• Dealing with a gas.
• Assumed to be in thermodynamic equilibrium;
• Every part of the gas is at the same temperature,
• Every part of the gas is at the same pressure.
• Ideal gas law applies.
 Work in a Gas Cylinder
• An isolated system in thermal equilibrium can
describe its macroscopic state with the
variables P, V, and T.
• For such a system, we describe its microscopic
state of internal energy with the variable U.
• Let us assume our system consists of gas
confined to a cylinder with insulated walls and
a movable frictionless piston of area A, as
shown on Right.
• The cylinder rests on a heat reservoir whose
temperature T is controlled by a knob.
• At equilibrium, the upward force on the piston
due to the pressure of the confined gas is equal
to the weight of the load on the top of the
piston.
 Work in a Gas Cylinder I
• Consider that we start at an initial state i, where the system is described
to have pressure 𝑃𝑖 , volume 𝑉𝑖 , and temperature 𝑇𝑖 .
• A change the system to a final state f, described to have pressure 𝑃𝑓 ,
volume 𝑉𝑓 , and temperature 𝑇𝑓 .
• The process of changing the system from the initial state to the final state
is a thermodynamic process.
• During such a process, work is done by the system to raise the piston
(positive work) or lower it (negative work).
• In addition, heat may be transferred into the system from the thermal
reservoir (positive heat) or vice versa.
• We assume that the state of the gas changes slowly enough to allow the
system to remain essentially in a thermodynamic equilibrium at all times.
• Reducing the load on the piston in such a way that the piston will move
upward through a differential displacement 𝑑 𝑠 with almost constant
upward force 𝐹.
• The differential work dW done by the gas during the displacement is:
𝑑𝑊 = 𝐹 ∙ 𝑑 𝑠 = 𝐹𝑑𝑠 = 𝑃𝐴𝑑𝑠 = 𝑃𝑑𝑉
Work in a Gas Cylinder II
 Work in a Gas Cylinder III
• If the gas expands, then dV is
positive and the work done by the
gas is positive,
• If the gas is compressed, dV is
negative, indicating that the work
done by the gas is negative.
• When we remove an appreciable
amount of load from the piston,
the volume of the gas changes
from 𝑉𝑖 to 𝑉𝑓 , and the total work
done by the gas is:
𝑉𝑓
𝑊= 𝑑𝑊 = 𝑃𝑑𝑉
𝑉𝑖
• During the change in volume of
the gas, the pressure and
temperature of the gas may also
change.
• To evaluate the integral in the last
equation, we need to know how
the pressure varies with volume.
• The total work done during the
expansion or compression of the
gas depends on the specific path
taken from the initial state i to the
final state f.
Work in a Gas Cylinder IV
 PV Diagrams
• Path a—The gas expands from 𝑉𝑖
to 𝑉𝑓 while the pressure
decreases from 𝑃𝑖 to 𝑃𝑓 .
• The work done by the gas along this
path is positive and represented by
the coloured area under the curve
between i and f.
• Path b—The gas first expands
from 𝑉𝑖 to 𝑉𝑓 at constant pressure
𝑃𝑖 , and then its pressure is
reduced to 𝑃𝑓 at constant volume
𝑉𝑓 .
• The work done along this path is 𝑃𝑖
(𝑉𝑓 − 𝑉𝑖 ).
 PV Diagrams I
• Path c—The pressure of the gas is
first reduced from 𝑃𝑖 to 𝑃𝑓 by
cooling at a constant volume 𝑉𝑖 ,
and then allowing the gas to
expand from 𝑉𝑖 to 𝑉𝑓 at constant
pressure 𝑃𝑓 .
• The work done along this path is
𝑃𝑓 (𝑉𝑓 − 𝑉𝑖 ).
• Path d—The gas is compressed
from 𝑉𝑖 to 𝑉𝑓 while the pressure
increases from 𝑃𝑖 to 𝑃𝑓 .
• The work done along this path is the
negative of the coloured area under
the curve.
 PV Diagrams II
• Path e—The net work done by the • The heat energy transfer Q
system during a closed cycle is the depends on the thermodynamic
sum of the positive work done
process (or the path) chosen
during the expansion and the
negative work done during the between the initial and final
compression. states of a system.
• The net work done by the gas is
positive and is represented by the
enclosed area between the two
curves.
• The net work done by a system W
depends on the thermodynamic
process (or the path) chosen
between its initial and final
states.
 PV Diagrams III
■ The work done depends on the particular path;
■ Same initial and final states, but different amounts of work are done,
■ Note work on gas is negative in 1st and 3rd example.
 First Law of Thermodynamics
■ The law is based on the energy ■ Energy transfers occur due to:
conservation law; ■ By doing work;
■ The law of conservation of energy ■ Requires a macroscopic
displacement of an object
states that the total energy of through the application of a
an isolated system is constant. force.
■ It relates changes in internal ■ By heat;
energy to energy transfers due to ■ Occurs through the random
molecular collisions.
heat and work.
■ Applicable to all types of ■ Both result in a change in
processes. the internal energy, ∆𝑈 of
the system;
■ Provides a connection
■ Neglecting macroscopic
between microscopic and potential energy.
macroscopic worlds.
 First Law of Thermodynamics I
• If a system undergoes a change
from an initial state to a final state,
then;
∆𝑈 = 𝑈𝑓– 𝑈𝑖 = 𝑄 + 𝑊
∆𝑈 = 𝑄 + 𝑊
• Q is the energy transferred to
the system by heat,
• W is the work done on the system,
• ∆𝑈 is the change in internal
energy.
• The quantity Q−W is the same for all
thermodynamic processes.
• It depends only on the initial and
final states of the system and is
path-independent.
• This law states that a change in
internal energy in a system can
occur as a result of energy transfer
by heat or by work, or by both.
• The first law can also be presented
as;
∆𝑈 = 𝑄 − 𝑊
• The reason is that work is defined in
these treatments as the work done
by the gas rather than on the gas, as
in the earlier treatment.
• The internal energy U of a system
increases if energy is added via heat
Q and decreases if energy is lost via
work W done by the system.
 Internal energy of an Ideal gas

■ Earlier, the internal energy of an ideal monoatomic gas was

expressed as:
3
𝑈 = 𝑛𝑅𝑇
2

• The change in the internal energy, ∆𝑈, for such a gas is given by
3
∆𝑈 = 𝑛𝑅∆𝑇
2
■ The molar specific heat at constant volume for an ideal gas;
3
𝐶𝑣 = 𝑅
2
■ The change in internal energy can be expressed as
∆𝑈 = 𝑛𝐶𝑣 ∆𝑇
 Degree of freedom
• The size of the molar specific heat • Degree of freedom is different
depends on the structure of the ways a gas molecule can store
energy.
gas molecule and how many
• Each degree of freedom
different ways it can store energy. 1
contributes 𝑅 to the molar
2
• A monatomic gas such as helium specific heat.
can store energy as motion in • An atomic ideal gas can move in
three different directions. three directions, it has a molar
specific heat capacity;
• A gas such as hydrogen, on the 1 3
other hand, is diatomic in normal 𝐶𝑣 = 3 𝑅 = 𝑅
temperature ranges, and aside 2 2
from moving in three directions, it • A diatomic gas like molecular
oxygen, 𝑂2 , can also tumble in
can also tumble, rotating in two two 1 different directions adding
different directions. 2 × 𝑅 = 𝑅:
2
• A gas composed of molecules with 3 5
more ways to store energy will 𝐶𝑣 = 𝑅 + 𝑅 = 𝑅
2 2
have a larger molar specific heat.
 Some special cases of the first law of
thermodynamics
Isolated Systems Cyclic Processes
• Isolated system is one that is not • A cyclic process is one that starts and
interacting with its surroundings. ends at the same state.
• In this case, no energy transfer by • It is non isolated, therefore the
heat takes place, i.e. Q = 0, internal energy must again be zero, U
• The work done by the system is = 0.
zero, i.e. W = 0,
• Then, from the first law we have U
• Then, from the first law we have:
= 0. W=Q
• Thus, we conclude that the • On the PV curve, a cyclic process
internal energy of an isolated appears as a closed curve as shown in
system remains constant. path (e).
𝑈 = constant • For this clockwise cyclic path, the net
work done by the system (and Q)
equals the area enclosed by the path.
 Some special cases of the first law of
thermodynamics-Adiabatic process
• An adiabatic process is one that
occurs so rapidly or occurs in
thermally insulated systems during
which no transfer of heat energy
enters or leaves the system, i.e. Q=0.
∆𝑈 = 𝑊
• Heat cannot enter or leave the system
because of the insulation.
• The only way of transferring energy to
the system is by work.
• If a gas expands adiabatically such that
W is positive, then U is negative, and
hence the temperature of the gas
decreases.
• For an ideal gas undergoing an
adiabatic process, it can be shown
that
𝑃𝑉 𝛾 = const
𝐶𝑝
• Where 𝛾 = , called the adiabatic
𝐶𝑣
index.
• Adiabatic processes play an important
role in mechanical engineering;
• Expansion of a mixture of gasoline
vapour and air in a combustion engine,
• Leading to a temperature
increase/decrease.
• The free expansion process is an
adiabatic process, i.e. Q = 0, in which
no work is done on or by the system,
i.e. W = 0;
𝑄 = 𝑊 = 0 ⟹ ∆𝑈 = 0
• A free expansion differs from any other
thermodynamic process since it cannot
be performed slowly in a controlled way.
• The gas is not in thermal equilibrium and
its pressure is not the same everywhere.
Some special cases of the first law of
thermodynamics-Adiabatic process I
 Some special cases of the first law of
thermodynamics-Isobaric process

• An isobaric process is one that takes • The work done by the gas on
place at constant pressure. its environment must come at
• For the isobaric process; Q, W, and U are all the expense of the change in
non-zero. its internal energy, ∆𝑈.
• The isobaric process could be established by Q =∆U−W=∆U+P∆V
transferring heat energy Q to or from the
gas by any mechanism. • Using the ideal gas law, 𝑃∆𝑉 =
• This transfer causes the gas to expand or 𝑛𝑅∆𝑇 and the change the
contract depending on the sign of Q. 3
internal energy ∆𝑈 = 𝑛𝑅∆𝑇:
2
• In the PV diagram, the first process in 3 5
path (b) and the second process in path 𝑄 = 𝑛𝑅∆𝑇 + 𝑛𝑅∆𝑇 = 𝑛𝑅∆𝑇
2 2
(c) are examples of isobaric processes. The energy transfer can be also
• The work done by the gas as it expands expressed as;
or contracts in this isobaric process is 5
expressed as; 𝑄 = 𝑛𝑅∆𝑇 = 𝑛𝐶𝑝 ∆𝑇
2
𝑊𝑖𝑠𝑜𝑏𝑎𝑟𝑖𝑐 = 𝑃(𝑉𝑓 − 𝑉𝑖 )
 Some special cases of the first law of
thermodynamics-Isobaric process I

• The molar heat capacity at constant

pressure, 𝐶𝑝 .
• The sum of the molar heat capacity at
constant volume, 𝐶𝑣 , and the gas
constant R:
𝐶𝑝 = 𝐶𝑣 + 𝑅
 Some special cases of the first law of
thermodynamics - Isovolumetric process

• An isovolumetric process (isochoric • In an isovolumetric process,

process) is one that takes place at the change in internal energy
constant volume. of a system equals the energy
• In the PV diagram, the second process transferred to the system by
in path (b) and the first process in path heat;
(c) are examples of isovolumetric 𝑄 = 𝑛𝐶𝑣 ∆𝑇
processes.
• In such a process, the value of the work
done by the gas is zero, i.e. W =0,
because the volume does not change.
• The application of the first law of
thermodynamics to an isovolumetric
process, we get:
∆𝑈 = 𝑄
 Some special cases of the first law of
thermodynamics- Isovolumetric process I
 Some special cases of the first law of
thermodynamics - Isothermal process
• An isothermal process is one that takes place at
constant temperature.
• During an isothermal process, the temperature of
a system doesn’t change.
• In an ideal gas the internal energy U depends only
on the temperature, so it follows that ∆𝑈 = 0
because 𝑇 = 0.
• The first law of thermodynamics gives;
𝑄 = −𝑊
• The gas is ideal and the process is quasi-static, we
can use the expression 𝑃𝑉 = 𝑛𝑅𝑇 for each point
on the path;
𝑉𝑓
𝑑𝑉 𝑉𝑓
𝑊 = 𝑛𝑅𝑇 = 𝑛𝑅𝑇 ln
𝑉 𝑉𝑖
𝑉𝑖
• If the gas expands, the work W equals the positive
of the
𝑉𝑓
shaded area under the PV curve due to
ln 𝑉 > 0.
𝑖
𝑉𝑓
• If the gas is compressed then ln 𝑉 < 0 and the
𝑖
work done is the negative of the area under the
PV curve.
Some special cases of the first law of
thermodynamics-Summary
 Heat engines and the second law
of thermodynamics
■ A heat engine takes in energy by heat and partially converts it
to other forms;
■ Partial because it rejects some heat,
■ Since heat flows from hot to cold, the intake is at higher temperature
than the reject.
■ In general, a heat engine carries some working substance
through a cyclic process during which;
■ Energy is transferred by heat from a source at a high temperature,
■ Work is done by the engine, and
■ Energy is expelled by the engine by heat to a source at lower
temperature.
 Heat engines and the second law
of thermodynamics I
• The engine absorbs energy 𝑄ℎ from the
hot reservoir, does work 𝑊𝑒𝑛𝑔 , then gives
up energy 𝑄𝑐 to the cold reservoir.
• negative work is done on the engine, so
that 𝑊 = −𝑊𝑒𝑛𝑔 .
• ∆𝑈 = 0, Because the working substance
goes through a cycle process.
• The first law of thermodynamics,
therefore becomes;
∆𝑈 = 0 = 𝑄 + 𝑊 → 𝑄𝑛𝑒𝑡 = −𝑊 = 𝑊𝑒𝑛𝑔
• The work 𝑊𝑒𝑛𝑔 done by a heat engine
equals the net energy absorbed by the
engine.
𝑊𝑒𝑛𝑔 = 𝑄ℎ − 𝑄𝑐
 Heat engines and the second law
of thermodynamics II
• The work done by the engine for a
cyclic process is the area enclosed by
the curve representing the process
on a PV diagram.
• The thermal efficiency e of a heat
engine is defined as the work done
by the engine, 𝑊𝑒𝑛𝑔 , divided by the
energy absorbed during one cycle.
𝑊𝑒𝑛𝑔 𝑄ℎ − 𝑄𝑐 𝑄𝑐
𝑒≡ = =1−
𝑄ℎ 𝑄ℎ 𝑄ℎ
• 𝑒 = 1 (100% efficiency) only if 𝑄𝑐 =
0, thus, no energy expelled to cold
reservoir.
 Heat engines and the second law
of thermodynamics II-Heat pumps and
refrigerators
• Heat engines can run in reverse;
• Energy is injected, that is, work done on (not by)
the engine,
• Energy is extracted from the cold reservoir,
• Energy is then transferred to the hot reservoir.
• This process means the heat engine is
running as a heat pump;
• A refrigerator and air conditioner is a common type
of heat pump,
• 𝑄𝑐 is extracted from the interior of the refrigerator
and delivered 𝑄ℎ as to the warmer air in the
kitchen,
• The coefficient of performance for a
refrigerator or an air conditioner is the
magnitude of the energy extracted from the
cold reservoir, 𝑄𝑐 , divided by the work W
performed by the device:
𝑄𝑐 𝑄𝑐
𝐶𝑂𝑃 = =
𝑊 𝑄ℎ −𝑄𝑐
 The second law of thermodynamics
■ It states that No heat engine
operating in a cycle can absorb
energy from a reservoir and use
it entirely for the performance of
an equal amount of work;
𝑊𝑒𝑛𝑔
𝑒= <1
𝑄ℎ
■ 𝑄𝑐 ≠ 0 , some Qc must be
expelled to the environment.
■ Therefore e must always be less
than 100%.
 Reversible and Irreversible Processes
• No heat engine can be more • Although real processes are
efficient than one that can be always irreversible, some are
run backwards. almost reversible.
• If a real process occurs so
• In a reversible process, every
slowly that the system is
state along the path is an virtually always in equilibrium,
equilibrium state, so the system the process can be considered
can return to its initial conditions reversible.
by going along the same path in
the reverse direction.
• A process that doesn’t satisfy
this requirement is irreversible.
• Most natural processes are
irreversible—the reversible
process is an idealization.
 Reversible and Irreversible Processes-
The Carnot engine
• Carnot cycle delivers the maximum • The cycle consists of two adiabatic and two
isothermal processes, all reversible, shown
possible efficiency. on the next slide.
• First descried by Sadi Carnot a • For a Carnot engine, the following
French engineer in 1824. relationship between the thermal energy
transfers and the absolute temperatures
• Carnot’s theorem states that: can be derived:
• No real engine operating between 𝑄𝑐 𝑇𝑐
two energy reservoirs can be more =
𝑄ℎ 𝑇ℎ
efficient than a Carnot engine
operating between the same two • The efficiency of a Carnot engine can be
reservoirs. expressed as
𝑇𝑐
• In a Carnot cycle; 𝑒𝑐 = 1 −
𝑇ℎ
• An ideal gas is contained in a cylinder • All Carnot engines operating reversibly
with a movable piston at end, between the same two temperatures have
• The temperature of the gas varies the same efficiency.
between 𝑇𝑐 and 𝑇ℎ ,
• All real engines operate irreversibly, due to
• The cylinder walls and the piston are friction and the very short cycles, and are
thermally nonconducting. therefore less efficient than the Carnot
engine.
Reversible and Irreversible Processes-The
Carnot engine I
Reversible and Irreversible Processes-The
Carnot engine II
 Second Law of Thermodynamics-
Entropy
• The second law can also be stated in terms of a quantity called entropy (S).
• The Second Law of Thermodynamics states that the entropy of the Universe
increases in all natural processes.
• In short: Heat cannot spontaneously flow from a colder location to a hotter
location.
• The change in entropy of a system is equal to the energy flowing by heat
into (or out of) the system as the system changes from one state (A) to
another (B) by a reversible process, divided by the absolute temperature:
𝑄𝑟
∆𝑆 =
𝑇
• When energy is absorbed, Q is positive and entropy increases,
• When energy is expelled, Q is negative and entropy decreases.
• The limit on heat engine efficiency can be derived directly from entropy
only increasing.
 Third law of thermodynamics-Entropy and
Disorder
■ The third law of thermodynamics states:
■ As the temperature of a system approaches absolute zero, all
processes cease and the entropy of the system approaches a
minimum value.
■ This law of thermodynamics law of nature connecting entropy
with absolute zero of temperature.
■ This law provides an absolute reference point for the
determination of entropy.
■ Entropy can be described as a measure of a system’s disorder.
■ A disorderly arrangement is much more probable than an orderly one
if the laws of nature are allowed to act without interference.
■ Isolated systems tend toward greater disorder, and entropy is a measure
of that disorder..
𝑆 = 𝑘𝐵 ln 𝑊
• 𝑘𝐵 is the Boltzmann's constant and W is a number proportional to the
probability that the system has a particular configuration.
• It is impossible to reach the absolute zero of temperature by any finite
number of processes.