MODULE 3 - THE SECOND and THIRD LAW OF

THERMODYNAMICS
The entropy change of any system and its surrounding, considered together, resulting from any
real process is positive, approaching zero when the process approaches reversibility.

STATEMENTS OF THE SECOND LAW

 Statement 1: No apparatus can operate in such a way that its only effect (in system and
surroundings) is to convert heat absorbed by a system completely into work done by the system.
 Statement 2: No process is possible which consists solely in the transfer of heat from one
temperature level to a higher one.

Statement 1 says that not all of the heat of a certain system can be transformed or converted
completely into work because no apparatus is 100% efficient. Also, some of the heat may be
converted to other types of energy. This statement requires in addition no change in the system, a
requirement that is not met owing to the change in pressure.

Statement 1 may be expressed in an alternative way,

 Statement 1a: It is impossible by a cyclic process to convert the heat absorbed by a system
completely into work done by the system.

Cyclic requires that the system be restored periodically to its original state. In case of an ideal gas, an
increase in volume may be followed by steps that restore the original state, thus producing complete
cycle. This becomes a cyclic process if the process will be repeated.

The Kelvin-Planck statement: It is impossible to construct a device that will operate in a cycle and
produce no effect other than the raising of a weight and the exchange of heat with a single
reservoir.

The Clausius statement: It is impossible to construct a device that operates in a cycle and
produces no effect other than the transfer of heat from a cooler body to a hotter body.

HEAT ENGINES
Heat engines are devices or machines that produce work from heat in a cyclic process. All heat
engines absorb heat into the system at a high temperature, reject heat to the surroundings at a lower
temperature, and produce work. In operation, the fluid of an engine absorbs heat |QH| from a hot
reservoir, produces a net amount of work |W|, discards heat |QC| to a cold reservoir, and returns to its
initial state. The first law will then be:

|W|= |QH| - |QC|

The thermal efficiency of the engine is defined as: ƞ=net work output/heat absorbed.

|W| |QH| − |QC| |QC|

η= = =1−
|QH| |QH| |QH|

Carnot engine, a very special type of engine, operates in a completely reversible manner. The
characteristics of this ideal engine were first described by N.L.S. Carnot in 1824. The four steps involved
with the Carnot cycle are:
  Step 1: A system at an initial temperature of a cold reservoir at TC undergoes a reversible
adiabatic process that causes its temperature to rise to that of a hot reservoir at TH.
 Step 2: The system maintains contact with the hot reservoir at TH, and undergoes a reversible
isothermal process during which heat |QH| is absorbed from the hot reservoir.
 Step 3: The system undergoes a reversible adiabatic process in the opposite direction of step 1
that brings its temperature back to that of the cold reservoir at TC.
 Step 4: The system maintains contact with the reservoir at TC, and undergoes a reversible
isothermal process in the opposite direction of step 2 that returns to its initial state with
rejection of heat |QC| to the cold reservoir.

Any reversible engine operating between two heat reservoirs is a Carnot engine; an engine operating
on a different cycle must transfer heat across finite temperature differences and therefore cannot be
reversible.

CARNOT’S THEOREM
For two given heat reservoirs no engine can have a thermal efficiency higher than that of a Carnot
engine.

Here is the proof. Let us assume that ηE>ηC.

ηE>ηC
|W| |W|
>
|Q'H| |QH|

1 1
>
|Q'H| |QH|

|QH| - |Q’H| > 0

Heat is transferred from the cooler to the hotter reservoir without doing work on the surrounding. This
is a violation of the Clausius statement so Carnot’s theorem is proved.

The thermal efficiency of a Carnot engine depends only on the temperature levels and not upon the
working substance of the engine.

THERMODYNAMIC TEMPERATURE SCALES

θH |QH| Consider two Carnot engines, one operating between a hot
reservoir at temperature θH and a cold reservoir at
|QC|
temperature θC, and a second operating between the
θC |W|
|QC| reservoir θC and a still colder reservoir θF. Carnot’s theorem
|QF|
indicates that the thermal efficiency of the first engine is a
θF function of θH and θC:

QC
η=1− = ø(θH,θC)
|QH
 |QH| 1
= = (θH,θC)
|QC| 1 − ø(θH − θC)

For the second and third engine,

|QC| |QH|
= θC,θF = (θH,θF)
|QF| |QF|

|QH| (θH,θF)
=
|QC| (θC,θF)

|QH| ψ(θH)
=
|QC| ψ(θC)

|QH| ψ(TH)
=
|QC| ψ(TC)

IDEAL-GAS TEMPERATURE SCALE; CARNOT’S EQUATIONS

1. Reversible isothermal expansion from A to B at Th

2. Reversible adiabatic expansion from B to C. In the

course of this expansion, the temperature falls from Th
to Tc.

3. Reversible isothermal compression from C to D at Tc.

4. Reversible adiabatic compression from D to A. The

temperature rises from Tc to Th.

For isothermal steps a→b and c→d,

Vb Vc
QH = RTHln QC = RTCln
Va Vd
Vb
|QH| THln( )
= Va
|QC| Vc
TCln ( )
Vd

For an adiabatic process with dQ=0,

CV dT dV
− =
R T V
For step b→c and d→a,
TH TH
CV dT Vb CV dT Va
= ln = ln
TC R T Vc TC R T Vd

Vb Va Vb Vc
ln = ln or ln = ln
Vc Vd Va Vd
|QH| TH
=
|QC| TC

|W| TC
η= =1−
|QH| TH

Example 1
A central power plant, rated at 800,000 kW, generates steam at 585K and discards heat to a river at 295K.
If the thermal efficiency of the plant is 70% of the maximum value, how much heat is discarded to the
river at rated power?

Given:

|W|= 800,000 kW TH=585 K TC=295 K

Required: |QC|

SOLUTION:

TC
ηmax = 1 −
TH
295
ηmax = 1 − = 0.4957
585

η=(0.7)(0.4957)=0.3470

1−η 1 − 0.347
QC = W = 800,000 = 1,505,500 kW
η 0.347

Final Answer: 1,505,500 kW

‸
TRY THIS: A Carnot engine receives 250 of heat from a heat-source reservoir at 523 ℃ and rejects
heat to a heat-sink reservoir at 50 ℃. What is the power developed and the heat rejected?
PROBLEM 1: The following heat engines produce power of 95,000 kW. Determine in each case the rates
at which heat is absorbed from the hot reservoir and discarded to the cold reservoir.
(a) A Carnot engine operates between heat reservoir at 750 K and 300 K.
(b) A practical engine operates between the same heat reservoirs but with a thermal efficiency ƞ =
0.35.

ENTROPY
There exists a property called entropy, which for systems at internal equilibrium is an intrinsic
property of the system, functionally related to the measurable coordinates that characterize the system.
For reversible processes, changes in this property may be calculated by the equation

dQ rev
dS =
T

where S is the entropy of the system and T is the absolute temperature of the system.

ENTROPY CHANGES OF AN IDEAL GAS

dU = dQrev - PdV

from the definition of enthalpy, H=U+PV,

dH = dU + PdV + VdP

dH = dQrev – PdV + PdV + VdP

dQrev = dH – VdP

For an ideal gas, dH=CPigdT and V=RT/P. With these substitutions and division by T,

dQrev dT dP
= Cpig −R
T T P

From the formula dS=dQrev/T, this becomes:

dT dP dS Cpig dT
dS = Cpig −R or = − dlnP
T P R R T
T
∆S Cpig dT P
= − ln
R To R T Po
Example 2
Methane gas at 550K and 5 bar undergoes a reversible adiabatic expansion to 1 bar. Assuming methane
to be an ideal gas at these conditions, find its final temperature.

SOLUTION:

For this process, ∆S = 0.

∆S Cpig s T2 P2
= ln − ln
R R T1 P1

0 Cpig s T2 P2
= ln − ln
R R T1 P1

Cpig s T2 P2
ln = ln
R T1 P1

Cpig s T2 P2 1
ln = ln = ln =− 1.䀀094
R T1 P1 5

Rearranging this equation for iterative solution,

T2 − 1.䀀094
ln =
T1 Cpig s
R

− 1.90䀀4
T2 = T1exp
Cpig s
R

T2=411.34K

MATHEMATICAL STATEMENT OF THE SECOND LAW

t 0

This states that the total entropy of every process is positive. No process is possible for which the
total entropy decreases.

For a Carnot Engine:

A carnot engine operates in cycles, therefore it does not undergo net changes in its properties.
The entropy change of a reservoir at TH (higher temperature):
−
= (Equation 1.)

The entropy change of a reservoir at TC (lower temperature):

−
= (Equation 2.)

Adding equations 1 and 2 will give:

−Q −Q TH−TC
∆Stotal = ∆StH + ∆StC = TH
+ Tc
= Q TH TC
 For the process of irreversible heat transfer, t is always positive since TH > TC . The
process becomes reversible as it approaches zero.

The general equation for work of a heat engine for TC and TH is:
Tc
W = − Tc∆Stotal + QH 1 −
TH

Wmax= 0

For an irreversible adiabatic process in a closed system shown in the figure below,

U= 0
A
− W = Qrev= B dQrev

Example 3
‸
A 40-kg steel casting ( = 0.5 t
) at a temperature of 450 ℃ is quenched in 150 kg of oil ( = 2.5
‸
t
) at 25 ℃. If there are no heat losses, what is the change in entropy of (a) the casting, (b) the oil, and
(c) both considered together?

SOLUTION:

The final temperature t of the oil and the steel casting is found by an energy balance. Because the change
in energy of the oil and steel together must be zero,

mCP∆T steel + mCP ∆T oil =0

kJ kJ
(40 kg)( 0.5 kg K
)(t - 450℃) + (150 kg)( 2.5 kg K
) (t - 25℃) = 0

Solving for t= 4䀀.52 ℃

(a) Change in the entropy of the casting:

Cp dT 2
∆ =m T
= m ln
1

kJ 273.15+4䀀.52 kJ
= (40 kg) (0.5 kg K
) ln 273.15+450 = -1䀀.33 K

(b) Change in entropy of the oil:

‸ 273.15+4䀀.52 ‸
∆ = (150 kg) (2.5 t
) ln273.15+25
= 2䀀.13
(c) Total entropy change:
‸ ‸ ‸
t = -1䀀.33 + 2䀀.13 = 9.80

(The total entropy change is positive, the entropy of the casting has decreased)

PROBLEM 2: A rigid vessel of 0.0䀀 m3 volume contains an ideal gas, Cv= (5/2) R, at 500 K and 1 bar.
(a) If heat in the amount of 15,000 J is transferred to the gas, determine its entropy change.
(b) If the vessel is fitted with a stirrer that is rotated by a shaft so that work in the amount of 15,000 J
is done on the gas, what is the entropy change of the gas if the process is adiabatic? What is ∆ t ?
What is the irreversible feature of the process?

PROBLEM 3: A Carnot engine operates between temperature levels of 䀀00 K and 300 K. It drives a Carnot
refrigerator, which provides cooling at 250 K and discards heat at 300 K. Determine a numerical value
for the ratio of heat extracted by the refrigerator ( “cooling load” ) to the heat delivered to the engine
(“heating load”)

PROBLEM 4: A refrigeration system cools a brine from 25℃ to -15℃ at the rate 20 kg/s. Heat is
discarded to the atmosphere at a temperature of 30℃. What is the power requirement if the
thermodynamic efficiency of the system is 0.27? The specific heat of the brine is 3.5 kJ kg-1℃-1.
ENTROPY BALANCE FOR OPEN SYSTEMS
Entropy is not conserved. From the previous discussion, it is stated the in every process, the
entropy change is positive, and approaches zero towards a reversible process.

In a reversible process the total entropy is equal to zero, and for an irreversible process it is equal
to a positive quantity.

The statement of balance, expressed as rates, is therefore:

Net rate of Time rate of Time rate of

change of Total rate
change in change of
+ entropy + = of entropy
entropy of entropy in
in control generation
flowing streams surroundings
volume
General rate form of the entropy balance:

+ + = 0

Where;

= rate of entropy generation

= net rate of gain in entropy of the following streams

= t t t t t香

= = t t t t香 t t t
,

Where;

Qj = heat transfer with respect to a particular part of the control surface

Tσ, j = temperature in the surroundings

The equation then becomes:

+ + = 0
,

For a steady-state flow process, is zero, thus, the equation becomes:

- = 0
,

But since the mass flow rate ( ) is the same for both streams, the equation becomes:

∆S - = 0
,

Example 4
t t
In a steady-state flow process, 1 of air at 䀀00 K and 1 atm is continuously mixed with 2 of air at
450 K and 1 atm. The product stream is at 400 k and 1 atm. A schematic representation of the process is
shown in the figure below. Determine the rate of heat transfer and the rate of entropy generation for the
 7
process. Assume that air is an ideal gas with 香 = 2 , that the surroundings are at 300 K. and that
kinetic- and potential –energy changes are negligible.

SOLUTION:

Q = ṅH − ṅA HA − ṅB HB = ṅA H − HA + ṅB H − HB

= ṅA CP T − TA + ṅB CP T − TB = CP ṅA T − TA + ṅB T − TB
7 J
= 2
8. 314 1 400 − 䀀00 + 2 400 − 450 = − 8, 729. 7 s

Q T T Q
G = ṅA SA − ṅB SB − = Cp ṅB ln + ṅB ln −
Tσ TA TB Tσ
7 400 400 8,729.7 J
= 2
8. 314 1 ln 䀀00 + 2 ln 450 + 300
= 10.44䀀 Ks

Example 5
An inventor claims to have devised a process which takes in only saturated steam at 100 ℃ and
which by a complicated series of steps makes heat continuously available at a temperature level of 200 ℃,
where 2,000 kJ of energy as heat is liberated for every kilogram of steam taken into the process. Show
whether or not this process is possible. To give this process the most favourable conditions, assume
cooling water available in unlimited quantity at a temperature of 0 ℃

SOLUTION:
 ∆H = Q + WS

Q = Q' + Qσ =− 2000 + Qσ

∆H = 0.0 − 2䀀7䀀 =− 2000 + Qσ

Qσ =− 䀀7䀀.0 kJ
kJ
∆S = 0.0 − 7.3554 =− 7.3554
K
2000 kJ
∆St = = 4.227
200 + 273.15 K
䀀7䀀.0 kJ
∆St = = 2.4748
0 + 273.15 K
kJ
∆Stotal =− 7.3554 + 4.227 + 2.4748 = − 0.䀀53䀀
K
 The process describe is impossible.

PROBLEM 5: A Hilsch vortex tube operates with no moving mechanical parts, and splits a gas stream into
two streams: one warmer and the other cooler than the entering stream. One such tube is reported to
operate with air entering at 5 bar and 20℃, and air streams leaving at 27℃ and -22℃, both at 1 atm. The
mass flowrate of warm air leaving is 䀀 times that of the cool air. Are these results possible? Assume air to
be an ideal gas at the conditions given.
CALCULATION OF IDEAL WORK
In a steady state process requiring work, a minimum amount must be expended to bring about a
specific change of state in the flowing fluid. In a process producing work however, requires a maximum
amount to achieve the desired change of state in the flowing fluid. In either case, the limiting value
obtains when the specific change of state is accomplished completely reversibly.

The entropy generation for a completely reversible process is zero. The heat exchange of the system and
the surrounding must occur at the temperature of the surroundings, Tσ

- =0 or Q= ∆( )

The energy balance for a steady state process is :

1 2
∆ + 2
+ tt = +

Substituting Q in this equation;

1 2
∆ + 2
+ tt = ∆( ) + (rev)

= ( )
1 2
= ∆ + 2
+ tt − ∆( )

For most applications for chemical processes:

= ∆ − ∆( )

For a single stream flowing through the system, the equation becomes:

= ∆ − ∆

Division by puts this equation on a unit-mass basis:

= ∆ − ∆

A completely reversible process is hypothetical, devised solely to find the ideal work associated with a
given change of state. Its only connection with an actual process is that it brings about the same change
of state as the actual process, allowing comparison of the actual work of a process with the work of a
hypothetical reversible process.

If = t = t

ƞ ( t 香 t ) =

If = 香t = t

ƞ ( t ) =
Example 䀀
What is the maximum work that can be obtained in a steady state flow process from 1 mol nitrogen
(assumed an ideal gas) at 800 K and 50 bar? Take the temperature and pressure of the surroundings as
300 K and 1.0133 bar.

SOLUTION:
T
ig J
∆H = CP dT = 8.314 × ICPH 800,300;3.280,0.593E − 3,0.0,0.040E + 5 =− 150䀀0
T0 mol
T2
ig dT P2 1.0133 J
∆S = CP − Rln =− 150䀀0 − 8.314 ln − = 3.042
T1 T P1 50 mol

ࢊ ࢋ =∆ − ∆ =− 쳌䁦 䁦 − 䁦䁦 .䁦૙ =− 쳌 ૞

Example 7
Rework Example 䀀, make use of the equation for ideal work. Use the following equations.

Step 1, reversible, adiabatic expansion from initial state to 1.0133 bar,

+ =∆ → =∆ = ' −
Step 1 1

Step 2, cooling to the final temperature

− 2
Step 2 t = → t = − '
= 2 − ' − ∆

Total = + t =∆ − ∆

SOLUTION:

∆ = 0.0 − 2䀀7䀀 =− 2䀀7䀀

‸
∆ = 0.0 − 7.3554 =− 7.3554

=∆ − ∆

=− 2䀀7䀀 − 273.15 − 7.3554

‸
=− 䀀䀀䀀.9
t

=
−
䁦䁦 + ૞ . 쳌
= . = 쳌૞૞.૞
䁦䁦 − 䁦
LOST WORK
- Work that is wasted due to the irreversibilities
- Difference between the actual work process and the ideal work of the process
Wlost = Ws − Wideal
The rate form is,
lost = s − ideal
For the actual work, this is given by;
1 2
s = ∆ H+ u + zg −Q
2 fs
For the ideal work, this is given by;
lost = Tσ∆(S )fs − Q
Division by m, will give
Wlost = Tσ∆S − Q
The total rate of entropy generation as a process is
Q Q
ṠG = ∆(S )fs − Tσ
, division by m will give ṠG = ∆S − Tσ

Multiplication by T ,
TσṠG = Tσ∆(S )fs − Q
lost = TσṠG
The second law of thermodynamics requires:
ṠG 0 and SG 0
lost 0 and lost 0

Example 8
The two basic types of steady-flow heat exchanger are characterized by their flow patterns:
concurrent and countercurrent. The two types are indicated in the figure below. In concurrent flow, heat
is transferred from a hot stream, flowing from left to right, to a cold stream flowing in the same direction,
as indicated by arrows. In countercurrent flowing in the opposite direction.
Consider the two cases, for each of which the following specifications apply:

TH1 = 400K TH2 = 350K TC1 = 300K ṅH = 1 mol S

The minimum temperature difference between the flowing streams is 10K. Assume that both streams are
ideal gases with = 7 2 . Find the lost work for both cases. Take = 300 K.

ṅH ∆H H + ṅC ∆H C =0

ṅH CP TH2 − TH1 + ṅC CP TC2 − TC1 = 0

Sṅ fs = ṅH s H + ṅC S C

TH ṅ TC2
∆ Sṅ fs = ṅH CP ln T 2 + ṅC ln T
H1 H C1

Iost = Tσ∆ Sṅ fs

Case I, Concurrent flow

ṅC 400 − 350
= = 1.25
ṅH 340 − 300
7 350 340 J
∆ Sṅ fs = 1 8.314 ln + 1.25ln 300 = 0.䀀䀀7 K s
2 400

J
iost = Tσ ∆ Sṅ fs = 300 × 0.䀀䀀7 = 200.1
s

Case II, Countercurrent flow

ṅ 400 − 350
= = 0.555䀀
ṅ 390 − 300
7 350 390 J
∆ Sṅ fs = 1 2
8.314 ln 400 + 0.555䀀ln 300 = 0.35䀀 Ks

⺁ = ∆ ṅ = 䁦䁦 䁦. 쳌 = 䁦 .૞

 From thermodynamic point of view, the countercurrent case is much more efficient

THE THIRD LAW OF THERMODYNAMICS

The third law of thermodynamics states that the absolute entropy is zero for all perfect
crystalline substances at absolute zero temperature. Absolute zero temperature means a thermodynamic
system has the lowest energy. It corresponds to −273.15 °C on the Celsius temperature scale and to
−459.䀀7 °F on the Fahrenheit temperature scale.The calometric date of the absolute entropy of a gas at
temperature T based on calorimetric data is:

Tf ( Cp )s ∆Hf Tv (Cp )t ∆Hv T (Cp) s

S= 0 dT + + Tf
dT + + Tv T
dT
T Tf T Tv

Where Tf is the fusion temperature and Tv = is the vaporization temperature.

PROBLEM 䀀: A flue gas is cooled from 1,100 to 150℃, and the heat is used to generate saturated steam at
100℃ in a boiler. The flue gas has a heat capacity given by:

Cp T
= 3.83 + 0.00051
R K

Water enters the boiler at 100℃, and is vaporized at this temperature; its latent heat of vaporization is
2,25䀀.9 kJ/kg.

a. With reference to a surroundings temperature of 25℃, what is the lost work of this process in kJ/mol
of flue gas?
b. With reference to a surroundings temperature of 25℃, what is the maximum work in kJ/mol of flue
gas that can be accomplished by the saturated steam at 100℃ if it condenses only, and does not subcool?
c. How does the answer to Part b compare with the maximum work theoretically obtainable from the
flue gas itself as it is cooled from 1,100 to 150℃?

Prepared by:
Engr. Reggie A. Dueňas
Instructor I