THE SECOND LAW

OF
THERMODYNAMICS
Notes Set 4
ENUNCIATED SECOND LAW OF THERMODYNAMICS

The second law of thermodynamics assert that processes

occur in a certain direction and that the energy has quality
as well as quantity.
The 1st law of thermodynamics places no restriction on the
direction of a process, and satisfying the 1st law does not
guarantee that the process will occur. Thus, we need
second law to identify whether a process can occur or not.
Illustration

The energy stored in a hot container (higher temperature) has

higher quality (ability to transfer heat) in comparison with the
energy contained (at lower temperature) in the surrounding.
GENERAL STATEMENT OF 2ND LAW OF
THERMODYNAMICS

Second law of thermodynamics generalize our experience with

spontaneous (Natural) process and can be stated as followed;-

1. KELVIN-PLANCK STATEMENT.
It is impossible to construct a device which operates on a cycle
and produce no other effect than the transfer of heat from a
single body to produce work.
This means that it is impossible to construct an engine whose
sole purpose is to convert the heat from a high temperature
source/reservoir into an equal amount of work.
2. CLAUSIUS STATEMENT
It is impossible to construct a device which operates on a cycle and
whose sole result is the transfer of heat from low temperature to
high temperature.
This mean heat transfer can only occur spontaneously in the
direction of temperature decrease unless external work is done on
the system.
3. Heat can not by itself pass from a cold to a hot body.
4. All spontaneous processes are irreversible and are accompanied
by a degradation of energy.
5. Every system when left to itself, will on average,
change towards a system of maximum probability.

APPLICATION OF 2ND LAW OF THERMODYNAMICS

Thermal engineering. Second law of thermodynamics is
applied in Designing of;-
 Heat engine,
Refrigeration system and
 Heat pump.
HEAT ENGINE

• Is a device which converts heat energy to work

(mechanical).
Heat engine has three main components i.e. the
reservoir, the sink and the working substance.
Heat engine uses heat from out reservoir to
perform work (W), rejected some heat
ILLUSTRATION
Illustration

HEAT Qh Qc
WORKING SINK AT
RESEVOIR AT
SUBSTANCE LOW
HIGH
TEMPERATUR
TEMPERATURE
E

WORK,W
Heat engine
EFFICIENCY OF HEAT ENGINE

• Is the ratio of the work output (w) to the heat

input (supplied), Qh.
Example
1. A heat engine absorbs 4500J of heat energy from a hot reservoir
and discards 2500J into the environment.
(a) How much work is performed by this heat engine.
(b) Calculate the thermal efficiency of this engine
Given, Qh = 4500J
Qc = 2500J
W = Qh-Qc= 2000J

(b) Thermal efficiency = ×100%

Thermal efficiency = ×100%
= 44.44%
NB. The efficiency of heat engine cannot be 100%
since some heat rejected.
2. A steam engine performs 6000J of work while
discarding 14000J into a cold reservoir per cycle.
(a). How much heat energy is absorbed by the hot
reservoir per cycle.
(b). Calculate the thermal efficiency of the steam engine.

(c). What is the power rating of this engine in

watts and hp if it takes 0.25 seconds to complete
a cycle.
(d). How much mechanical work is performed by
this engine in 1hour.
Soln.
Work output, w = 6000J, Heat rejected, Qc =
14000J
(a) Heat supplied, Qh = work output (W) + heat
rejected (Qc)
Qh = 6000J + 14000J = 20,000J per
cycle
(b) Thermal efficiency = ×100%
= ×100%
= 30%
(c) Power =
Work output, W = 6000J, Time, t = 0.25s
Power, P = = 24,000 W per cycle

NB. 1 hp = 746 Watts

24,000watts = = 32.17hp
(d) power, P = 24,000W,
Time, t = 1hrs = 60mins × 60 sec = 3600s
Work output, W = power × time = 86400000J
Factors that affect the efficiency of a heat engine

1) Temperature of the reservoir: the higher the temperature of the reservoir, the higher the efficiency of the
engine and the vice versa is true.

2)Temperature of the surrounding /atmosphere/sink: the lower the temperature of the atmosphere, the
more efficient is the heat engine. For example in countries with colder atmospheres, the efficiency of the
engine is higher than in hotter countries.

Why the efficiency of a heat engine cannot be 1

It is impossible to convert the entire heat input to work out output. A portion of the heat has to be rejected
to the sink.
 THE CARNOT ENGINE CYCLE
• Carnot cycle is an ideal heat engine cycle that
uses an ideal gas. it composed of four reversible
processes;-
Reversible isothermal expansion
Reversible adiabatic expansion
Reversible isothermal compression
Reversible adiabatic compression
ILLUSTRATION OF THE CARNOT ENGINE
P-V GRAPH FOR THE CARNOT CYCLE
 During process 1 - 2 (reversible isothermal expansion), heat is transferred to the gas from the high temperature
reservoir . The gas expands ( V1 to V2) and pressure decrease (P1 to P2) at a constant temperature.

Along 2-3 (reversible adiabatic expansion), The

temperature of the system decreases (T1 to T2),
pressure decrease (P2 to P3) and volume slightly
increase (V2 to V3).
Along 3-4(reversible isothermal compression), The
system rejects heat Q2 to a lower temperature
reservoir at a constant temperature T2, The
volume of the gas decrease (V3 to V4) and
• Along 4-1 (reversible adiabatic compression),work is done on the gas
as a result of compression. Volume of the gas decrease (V4 to V1) and
temperature rises (T2 to T1) then the next cycle begins.
 EFFICIENCY OF A CARNOT ENGINE

Efficiency of any heat engine, e= =

e=1-
NB. The efficiency of a Carnot engine is
dependent on the temperature difference
between the reservoir and the sink.
 THERMODYNAMIC
TEMPERATURE SCALE
Also known as the kelvin scale, it defines temperature in terms of
the thermal energy of a system.
It’s a fundamental concept in thermodynamics and used to
measure absolute temperatures.
The thermodynamic temperature T of a reservoir is directly
proportional to the amount of heat at each reservoir.
It only depends on the reservoir (what characterizes the reservoir).
=k
=-k; The negative sign indicates < 0.
Therefore = - ( only the function of reservoir tempt.)

where Th and Tc are expressed on the

thermodynamic scale
Example.
1. 7500J of heat energy is absorbed by a heat
engine from a hot reservoir at 600K and 6000J
is released into the cold reservoir at 300K.
(a). How much work is performed by this heat
engine.
(b). Calculate the efficiency of this heat engine.
Soln.
(a). Qh=7500J, Th=600K, Qc=6000J & Tc=300K
Work output, W= Qh-Qc
W=(7500-6000)J
W=1500J
(b). Efficiency=1-= 1-= 0.2=20
• 2. A heat engine releases heat into the cold
reservoir at 500k with a Carnot efficiency of
25%. what exhaust temperature will increase the
Carnot efficiency to 60%.
Tc=500K, =25%=0.25
From, =1-
0.25=1-, Th=666.67K
0.6=1-
Tc=266.67K
 ENTROPY
• Entropy is the measure of disorderness or randomness of the system.
NB: Entropy is a spontaneous process.
Is a state function
And is denoted by S and measured in
• Entropy is affected by temperature. Increase in temperature increases entropy as particles gain
energy and move further apart.
Entropy change Ds =Q/T
Where Q is heat added to the system(J)
T is temperature

• Consider gas molecules in two closed containers A and B

Gas molecules in container B are more free to move due to large available space thus more disordered
and more entropy.
Entropy can also be refer to as the measure of
the amount of unavailability of energy or
degradation of energy.
 Consider sugar dissolved in water. The chemical
bonds among sugar molecules breakdown, sugar
molecules spread out in water as the result, The
entropy of the system increases due to
disorderness of sugar molecules.
Qn. Can we uterlize energy released during chemical
breakdown ? NO

The energy just increased the disorderness of the

system. It is called unavailable energy which increase the
entropy of the system.
NB. The entropy of the system increases by addition of
heat through any mechanism or from any source.
When an amount of energy is added to a system by
some reversible process, the change in entropy of the
system is defined
1. What is the entropy change when 100J of heat
is added to a system at 300K

2. Calculate the entropy of a system with 10 possible

microstates at 400K But Boltzmann's constant =( )
3. A system undergoes a process where 200J of heat
is added at 500K. What is the entropy change
4. What is change in entropy when 1 kmole of an ideal gas at 335K
and 10 bar is expanded irreversibly to 300K and 1 bar? Cp=29.3
kJ/kmol K
𝞓 = (constant T)
dS = (non constant T)

For an isolated system of two objects, the transfer of

energy from object at to the object at increases the
entropy.

Heat begins to flow from body at higher temperature

to body at lower temperature until thermal
equilibrium is attained where the new temperature
Change in entropy, 𝞓S = 𝞓-𝞓=
Where TIHF= intermediate temperature between
high and final temperature.

TILF= intermediate tempt. Between low and final

tempt.
𝞓s=Q()
Total entropy change in isolated system is always
+ve.
is the mean of two temperature.
1. Calculate the entropy of evaporation of dry saturated steam at 500kPa.
Data: From the steam tables, latent heat of vaporization DHv=2106 kJ/kg, Saturation temperature
of steam=425K.
2. Calculate the entropy change for the following gas phase reaction occurring at 1 bar and 298K.
CO(g) + 1/2O2(g) CO2(g) ΔH=2.8318x10^5J/mol
The absolute entropies of CC, O2 and Co2 are respectively 198kJ/mol, 205.2kJ/mol, 213.8kJ/mol.
Can you calculate the entropy change as the ratio of the reaction to the temperature of the
reaction? Why?

3. 1kg of super heated steam at 1.5MPa and 523K (H=292.35kJ/kg, S=6.71kJ/kg/K) is contained in
a piston cylinder assembly. The unit is kept at ambient conditions of 300K and the steam
condenses to saturated liquid(H=845kJ/kg, S=2.32kJ/kg/K) at constant pressure. Calculate the
change in entropy.

At constant pressure, ΔH=Q supplied

Heat given out by steam during condensation=-ΔH=2923.5-845=2078.5kJ/kg
ΔS of surrounding is
SECOND LAW OF THERMODYNAMICS

The entropy of the isolated system never decreases. It

either remains constant (reversible process) or
increases (irreversible process).
The total entropy of any system and that of the
surrounding always increases.
NB: The entropy of a system can decrease only when it
interacts with some other system whose entropy
increases in the process.
CALCULATION OF ENTROPY CHANGE.
Calculation of entropy change can be done in;-

1. Phase change
2. Process involving ideal gas
3. Adiabatic mixing process
4. Isothermal mixing of ideal gas
5. Chemical reaction
PHASE CHANGE.
The entropy change in phase change like fusion, evaporation
and sublimation can be evaluated by the value of latent heat of

i. solid to liquid (fusion, 𝞓)

phase change and the tempt. at which the phase is carried out.

ii. liquid to gas (vapourization, 𝞓)

iii. solid to gas (Sublimation, 𝞓)
For vaporization, The entropy change for
reversible process at constant tempt. Is given by
𝞓S=
Example.

Calculate the entropy of vaporization of dry

saturated steam at 500KPa and 425k. (latent heat

𝞓S===4.96KJ/KgK
of vaporization is 2106KJ/Kg).
PROCESS INVOLVING IDEAL GAS

Assume the value for specific heat are constant. From

the 1st law of thermodynamic for closed system,
dQ= dU + dw …………………………………(1)
When the process is reversible and the work
involved is only work of expansion, Dw=Pdv
Substituting in eqn. (1)
dQ = dU+PdV
For an ideal gas, dU=, P=
dQ= +RT (dividing thru by T)

= +RT(), Where =dS

Integrating
𝞓S = In+RIn……………………….(2)
Where suffixes 1 & 2 indicate the property of the
gas at state 1 and 2 respectively.
At constant volume, 𝞓S=In()…………….(3)
BUT =-R

Example.
Determine the entropy change when 2Kg of gas at 277K
is heated at constant volume to a temperature of 368K.
Take specific heat at a constant volume=1.42KJ/KgK.
𝞓S=mIn
= 2(1.42)In
= 0.806KJ/Kg
ADIABATIC MIXING PROCESS

• when two substance at different temperature T1 & T2 are mixed

together adiabatically at constant pressure, then both will attain an
intermediate temperature T.

The change in entropy of each substance and the whole system is calculated by,
∆=dQ/T= = ∆===In
Entropy change for whole system, ∆S = ∆+∆
∆S = In+In
CALCULATIONS ON ADIABATIC MIXING INVOLVING
ENTROPY
• 10 kg of water at 375k is mixed adiabatically with 30 kg of water at275k.what is the change
in entropy (assume specific heat capacity of water =4.2kJ/ kgk and it’s independent of
temperature)

From equation of heat balance.

10(375-T)=30(T-275)

T=300K

Total entropy d S =ds1+ds2

Ds=1.59kJ/K
• A steel casting at temperature 725Kand weighing 35kg is quenched in 150kg oil at 275k.if
there are no heat losses determine the change in entropy. ( Cp of steel =0.888kJ/ kgK and
that of oil is 2.5 KJ/ kgK)
ISOTHERMAL MIXING OF IDEAL GASES

• Consider the mixing of two or more ideal gases at

temperature T and pressure P.
Let the mole fraction of each component in the mixture be
represented by . The entropy change for ideal gases is given
by,
∆S=-R, R=ideal gas constant=8.314
For example, if two ideal gases A and B are mixed
isothermally then the entropy change is,
∆S=-R(In+In
mixed, the resulting entropy change is given by ∆S=-R
Gibbs paradox. When two distinct ideal gases are

NB. The equation hold if the gases are different.

When the gases are the same, the change in
entropy on mixing should be zero.
CHEMICAL REACTION

• Entropy change in a chemical reaction is evaluated

through the use of absolute entropy of various
component taking part in the reaction.
∆S= -
Where, n and m are the coefficients of product and reactant in
the balanced equation.
Example 1
Determine the entropy change for the following spontaneous
reaction at 298K.
 2 (∆K, ∆=130.6J/mol K
∆=192.6J/mol K
• +3

∆S = ∆- ∆
= 2(192.6)-((191.5+3(130.6))
= -198.2J/mol K
Example 2
Determine the entropy change when 5.0g of propane react with
excess oxygen.
Equation: +4(l)

(∆S )=213.74J/molK, ∆S ,
∆S()=269.9J/mol K & ∆S ) =205.138J/mol K)
(Answer -374.73J/mol K)
 3RD LAW OF THERMODYNAMICS
 The absolute entropy is zero for a perfect crystalline substance at absolute
zero of temperatures.
 A perfect crystalline substance at the absolute zero of temperature would meet this requirement and should
have zero entropy. Using the experimental data on the heat capacity of perfect crystalline substances at very
low temperatures their entropy at 0 K was calculated and it was shown that they all have same entropy values
at this temperature. These observations lead to the postulate of the third law of thermodynamics: The
absolute entropy is zero for a perfect crystalline substance at absolute zero
NOTE: Third law of thermodynamics can be utilized to calculate the absolute entropy of
substances at a given temperature by assigning the value zero for entropy of the
crystalline form of the substance at absolute zero. This is done by measuring the heat
capacity at different temperatures and the latent heats of phase transition that the
substance must have undergone to arrive at the present state from the initial state of
absolute zero of temperature. For example, let the melting point of the substance be Tf
and the boiling point be Tb. The entropy at T, where T is above the boiling point may be
evaluated as;
EXAMPLES
1.It is known that the molar heat capacity of a substance at low
temperatures can be approximated by the relation CP = aT^3 , where a
is a constant. Determine the molar entropy of a metal at 10 K if the
molar heat capacity at this temperature is 0.45 J/mol K.
2. Calculate the absolute entropy of water vapour at 473 K and 101.3
kPa above273 K base temperature. Compare this with the value
reported in steam tables (S = 7.829 kJ/kg K). The average heat capacity
of water = 4.2 kJ/kg K and that of water vapour between 373 K and 473
K = 1.9 kJ/kg K. The latent heat of vaporisation at 373 K = 2257 kJ/kg.
APPLICATIONS OF LAWS OF
THERMODYNAMICS
• Flow processes
• Refrigeration
• Liquefaction process
• The steam power plant
• Internal combustion engines
• Gas-turbine power plant
FLOW PROCESSES
• The first and second laws can be used to develop some of the basic
equations used in fluid mechanics.
• For this to be possible, we assume that the fluid flow is unidirectional
and the fluid properties do not change in the direction perpendicular
to the direction of flow. This means that the properties at any point in
the flow system are average values applicable for the entire cross-
section.
CONTINUITY EQUATION
 For a control volume, the law of conservation of mass may be written as:
Rate of accumulation of mass + Net rate of mass out by = 0
within the control volume the flowing streams
Mathematically, it becomes:
+
ρ is the average fluid density
A is the fluid cross-sectional area
u is the average fluid velocity
For steady-state flow process, there is no accumulation of mass within the control volume and
the equation becomes:
ENERGY EQUATION
Total energy balance equation
= Q* - Ws
Mechanical energy balance equation

Z is the height above a reference plane

Q* is the rate at which heat is supplied to the fluid

Ws is shaft work
Example
Water flowing upward through a vertical pipe enters a reducer with a velocity of 1m/s. The
diameters at the entrance and exit of the reducer are 0.2m and 0.1m respectively. If the
pressure at the entrance to the section is 105kPa, what is the pressure at the exit given that
the entrance and exit are 5m apart?