The 2nd Law of

Thermodynamics
Termodinamika Teknik Kimia
(TKK61016 / 2 sks)

brone.ub.ac.id Universitas Brawijaya - Building Up Noble Future

 Outline
01 Capaian Pembelajaran
Materi Pembelajaran

02 The 2nd Law of Thermodynamics

Statement of Second Law, Heat engines and Heat pumps

03 Entropy and Efficiency

Entropy from the Microscopic Viewpoint, Entropy Balance
for Open Systems, Entropy Changes for the Ideal Gas State

04 Calculation of Ideal and Loss Work

Calculation of ideal work, calculation of loss work

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 Outcome & Contents
Calculating and analyzing the • Statements of the second law
efficiency of engines and heat
pumps based on The 2nd Law of • Entropy and Efficiency
Thermodynamics • Heat engine
• Heat pump
• Thermodynamic temperature scale
The Zeroth Law of Thermodynamics

“If two systems are separately in thermal equilibrium with a third

system, they are in thermal equilibrium with each other.”

The First Law of Thermodynamics

“Energy can neither be created nor destroyed. It can only be changed from one form to
another.”
Total Energy is Conserved
 The First Law of Thermodynamics
Q = ∆Ē + W
Heat absorbed
Work done
by the system
Change in the system’s by the system
internal energy

For Infinitesimal, Quasi-Static Processes

đQ = dĒ + đW
Total Energy is Conserved
“Energy can neither be created nor destroyed. It can
only be changed from one form to another.”
The Second Law of Thermodynamics
“The entropy of an isolated system increases in any irreversible process
and is unaltered in any reversible process.”
• This is sometimes called
The Principle of Increasing Entropy DS  0
Change in entropy
of the system
• This gives the Preferred (natural) Direction of Energy Transfer
• This determines whether a process can occur or not.
• can be used to classify Thermodynamic Processes into 3 Types
1. Natural Processes (or Irreversible Processes, or Spontaneous Processes)
2. Impossible Processes
3. Reversible Processes
Various Statements of the Second Law
1. “No series of processes is possible whose sole result is the
absorption of heat from a thermal reservoir and the
complete conversion of this energy to work.” That is
There are no perfect engines!
2. “It is impossible to extract an amount of heat QH from a hot
reservoir and use it all to do work W. Some amount of heat
QC must be exhausted to a cold reservoir.”

The Kelvin-Planck
statement of the
Second Law.
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 la: It is impossible by a cyclic process to convert the 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
Heat engine
absorption of heat at a high temperature
Heat-engine cycles into the system
production of work
High Temp
Hot Reservoir rejection of heat to
the surroundings at a lower temperature
QH
For  to be unity (100% therma
Work
W l efficiency)
I QC I must be zero.

QC
No engine has ever been built
for which this is true
Cold Reservoir
Low temp
Absolute value signs are used to make the equations Some heat is always rejected to
Fig. 1. Heat engine independent of the sign conventions for Q and W. the cold reservoir
 Heat Engines

W Q H − QC Q
W = QH − QC → = = = 1− C
QH QH QH
 = Efisiensi mesin kalor
 MESIN-MESIN PENDINGI
N

QC QC − W QC
W = Q H − QC → COP = = = −1
W W W
COP = Coefficient Of Performance mesin pendingin
Heat engine
Example
A central power plant, rated at 800,000 kW, operates using steam at 585 K and discards heat
to a river at 295 K. If the thermal efficiency of the plant is 70% of the maximum possible
value, how much heat is discarded to the river at rated power?
The Second Law Applied to Refrigerators

Efficiency
= (QC/W) = [(QC)/(QH - QC)]
The 2nd Law of Thermodynamics
Thermodynamic
can be used to classify

Processes into
3 Types:
1. Natural Processes
(or Irreversible Processes,

or Spontaneous Processes)

2. Impossible Processes
3. Reversible Processes (courtesy F. Remer)
Example 2
Sebuah turbin pada suatu steam power plant mengambil uap air dari
boiler pada temperatur 520oC and membuangnya ke condenser pada
temperatur 100oC. Tentukan efisiensi maksimumnya.

Jawab :
Efisiensi maksimum = efisiensi Carnot

TC 373
 = 1− = 1− = 0.53 = 53%
TH 793
 The Third Law of Thermodynamics

“It is impossible to reach a temperat

ure of absolute zero.”

On the Kelvin Temperature Scale,

T=0K
is often referred to as
“Absolute Zero”
 Still Another Statement of the
2nd Law of Thermodynamics

“In any spontaneous process, there is

always an increase in the entropy of the
universe.”
The Total Entropy S of the Universe
has the property that, for any
process, ∆S ≥ 0.
Order to disorder

Entropy is a measure of the disorder of a system.

This gives us yet another statement of the second law:

Natural processes tend to move toward a state of

greater disorder

Example:
If you put milk and sugar in your coffee and stir it, you wind up with
coffee that is uniformly milky and sweet. No amount of stirring will
get the milk and sugar to come back out of solution.
Thermodynamic Process

Valve
Vacuu Closed Gas
m
 Ideal-Gas Temperature Scale; Carnot's Equations
The cycle traversed by an ideal gas serving as the working fluid in a
Carnot engine is shown by a diagram in Fig. 2. It consists of four
reversible steps:
a~ b Adiabatic compression until the temperature rises from Tc to TH.
b~ c Isothermal expansion to arbitrary point c with absorption of heat I
QH I.
c~ d Adiabatic expansion until the temperature decreases to Tc.
d~ a Isothermal compression to the initial state with rejection of heat I
Power
Q c I.
plant the cycle

1. Liquid water at ambient temperature is pumped into a boiler at

high pressure.
2. Heat from a fuel (heat of combustion of a fossil fuel or heat from
a nuclear reaction) is transferred in the boiler to the water,
converting it to high temperature steam at the boiler pressure.
3. Energy is transferred as shaft work from the steam to the
surroundings by a device such as a turbine, in which the steam
expands to reduced pressure and temperature.
4. Exhaust steam from the turbine is condensed by transfer of heat
to the surroundings, producing liquid water for return to the
boiler, thus completing the cycle.
Heat Engines
In this analysis the ideal-gas-state working fluid is regarded
as the system. For the isothermal steps b → c and d → a,
Eq. (3.20) yields
For isothermal
DU = DH = 0
V2 P
dQ = CV dT + RT
dV Q = RT ln = − RT ln 2
V V1 P1
dV (5.3) Q = −W (5.4)
dW = − RT
V

(5.5)
Figure 2: PV diagram showing
Carnot cycle for an ideal gas.

From (5.5) and (5.6)

QH TH
= (5.7)
QC TC
W T
= = 1− C
QH TH (5.8)
TC natural (universe) = 300 K
If TH = 600 K then :
Vc V TC 300
ln = ln d (5.6)  = 1− = 1− = 0 .5
Vb Va TH 600
rough limit of a Carnot engine; actual heat en
gines are irreversible, and their thermal efficie
ncies rarely exceed 0.35.
Proses Isothermal
DU = DH = 0
Proses Adiabatis
V Kapasitas Cpanas
P dan C konstan
Tak ada perpindahan panas a
Q = RT ln 2 = − RT ln 2 ntara sistem dan lingkungan
P V

V1 P1
V2 P dT R dV
W = − RT ln = RT ln 2 =− karena CP dan CV
V1 P1 T CV V
konstan
Q = −W R / CV
T2  V1 
= 
T1  V2 
Proses Isobaris
DU =  CV dT dan DH =  CP dT R / CP C P / CV
T2  P2  P V 
=  dan 2 =  2 
Q =  CP dT dan W = − R(T2 − T1 ) T1  P1  P1  V1 
Q = DH

TV  −1 = konstant
Proses Isokoris TP(1− ) /  = konstant dan  =
CP

DU = C dT dan DH = C dT
V  P
PV  = konstant
CV
Q =  C dT
V dan W = 0
Untuk reversible adiabatis
Q = DU
 Kerja pada proses Adiabatis
dW = dU = CV dT
W = DU = CV DT (3.31)
C p CV + R R
 = = = 1+
CV CV CV
 −1
CV =
R
R DT
W = CV DT =
 −1
Karena RT1 = P1V1 dan RT2 = P2V2 maka :
RT2 − RT1 P2V2 − P1V1
W= = (3.32)
 −1  −1
Persamaan (3.31) dan (3.32) berlaku utk adiabatis, reversible atau tidak
Untuk proses reversible
(  −1) / 
P1V1  P2   RT  P ( −1) /  
W=   − 1 = 1
 2  − 1 (3.33)
 − 1  P1    − 1  1 
P 

Soal No. 1
Pada gambar di bawah ini ditunjukkan siklus proses-proses yang
terjadi pada mesin diesel (gasoline internal combustion engine).

a). Tentukan tekanan dan temperatur pada setiap keadaan (titik)

dalam p1, V1 dan perbandingan panas jenis .
b). Hitung efisiensi dari mesin diesel ini

Jawab :

a). p1V1
p1V1 = nRT1 → T1 =
nR
p1V1
Titik 1 : p1 , V1 ,
nR
1 → 2 : Proses isokhorik
p1V1
= nR = konstan
T1
p1V1 p2V2 p2V2
= → T2 = T1
T1 T2 p1V1
p2 = 3 p1 V2 = V1
p1V1
T2 = 3T1 = 3
nR

p1V1
Titik 2 : 3p1 , V1 , 3
nR
1 → 2 : Proses adiabatik

p 2 V2 p 3V3 p 3V3
= → T3 = T2
T2 T3 p 2 V2

p 3  V2 
p 2 V2 = p 3V3 → =  
p 2  V3 

 V2 
V3 = 4V2 → p 3 = p 2  
 4V2 
p 3 = 3(0.25)  p1

 V2  V3 3p1V1 12(0.25)  p1V1
T3 =   
T2 = (0.25) (4) =
 V3  V2 nR nR
pV
Titik 3 : 3(0.25)  p1 , 4V1 , 12(0.25)  1 1
nR
3 → 4 : Proses isokhorik

p 3V3 p 4 V4 p 4 V4
= → T4 = T3
T3 T4 p 3 V3
p4
V4 = V3 → T4 = T3
p3
4 → 1 : Proses adiabatik

V 
p 4 V4 = p1V1 → p 4 = p1  1 
 V4 
V4 = 4V1 → p 4 = (0.25)  p1
 (0.25)  p1 12(0.25)  p1V1  p1V1
p 3 = 3(0.25) p1 → T4 = = 4(0.25)
3(0.25)  p1 nR nR

  p1V1
Titik 4 : (0.25) p1 , 4V1 , 4(0.25)
nR
b).
Q 41 = Q 23 = 0
Q12 = nC V (T2 − T1 ) Q34 = nC V (T4 − T3 )
p1V1
Titik 1 : p1 , V1 ,
nR
pV
Titik 2 : 3p1 , V1 , 3 1 1
nR
p1V1
Titik 3 : 3(0.25)  p1 , 4V1 , 12(0.25) 
nR
pV
Titik 4 : (0.25)  p1 , 4V1 , 4(0.25)  1 1
nR
p1V1 p1V1 pV
Q12 = nC V (T2 − T1 ) = nC V [3 − ] = 2C V 1 1
nR nR R
pV pV pV
Q34 = nCV (T4 − T3 ) = nC V [4(0.25)  1 1 − 12(0.25)  1 1 ] = −8(0.25)  C V 1 1
nR nR R
 1
W12 = W34 = 0 W23 = (p 3V3 − p 2 V2 )
1− 
1
W41 = (p1V1 − p 4 V4 )
1− 
p1V1 p1V1
Titik 1 : p1 , V1 , Titik 2 : 3p1 , V1 , 3
nR nR
p1V1
Titik 3 : 3(0.25)  p1 , 4V1 , 12(0.25) 
nR
pV
Titik 4 : (0.25)  p1 , 4V1 , 3(0.25)  1 1
nR
1 1 pV
W23 = (p 3V3 − p 2 V2 ) = [3(0.25)  p1 4V1 − 3p 1 V1 ] = 1 1 [12(0.25)  − 3]
1−  1−  1− 
1 1 pV
W41 = (p1V1 − p 4 V4 ) = [p1V1 − (0.25)  p 1 4V1 ] = 1 1 [1 − 4(0.25)  ]
1−  1−  1− 
pV
Wtotal = W12 + W23 + W34 + W41 = 1 1 [2 − 8(0.25)  ]
 −1
 p1V1 p1V1 pV
Q12 = nC V (T2 − T1 ) = nC V [3 − ] = 2C V 1 1
nR nR R
pV pV pV
Q34 = nCV (T4 − T3 ) = nC V [4(0.25)  1 1 − 12(0.25)  1 1 ] = −8(0.25)  C V 1 1
nR nR R
p1V1
Wtotal = W12 + W23 + W34 + W41 = [2 − 8(0.25)  ]
 −1
p1V1 pV
Q12 = Q H = 2CV Q34 = QC = −8(0.25)  CV 1 1
R R
p1V1
[2 − 8(0.25)  ]
W  −1 1 R
= = = [2 − 8(0.25)  ]
QH pV
2C V 1 1  − 1 CV
R
[2 − 8(0.25)  ] C p − C V [2 − 8(0.25)  ]
= = (  − 1) = [2 − 8(0.25)  ]
 −1 CV  −1

 = 1.4 →  = 2 − 8(0.25)1.4 = 0.85

Contoh Soal No. 2
Pada gambar di bawah ini ditunjukkan siklus mesin kalor yang
disebut mesin kalor Carnot. Mesin ini bekerja pada dua
temperatur TH dan TC. Nyatakan efisiensinya dalam TH dan TC
Jawab :
a → b : Isotermis
Vb
Wab = nRTH ln
Va
Vb
DU = 0 → Q H = nRTH ln
Va
c → d : Isotermis
Vd
Wcd = nRTC ln
Vc
Vd
DU = 0 → Q C = nRTC ln
Vc
 b → c : Adiabatis
p b Vb = p c Vc
nRTH
p b Vb = nRTH → pb =
Vb
nRTC
p c Vc = nRTC → pc =
Vc
nRTH  nRTC 
Vb = Vc
Vb Vc
 −1  −1 TH Vc −1
TH V b = TC V c → =  −1
TC Vb
d → a : Adiabatis

p d Vd = p a Va
nRTC
p d Vd = nRTC → pd =
Vd
nRTH
p a Va = nRTH → pa =
Va
nRTC  nRTH 
Vd = Va
Vd Va
 −1  −1 TH Vd −1
TC V d = TH V a → =  −1
TC Va
TH Vc −1 TH Vd −1 Vc −1 Vd −1
= = → =
TC Vb −1 TC Va −1 Vb −1 Va −1
Vc Vd Vb Vc
= → =
Vb Va Va Vd

Vb Vd
Q H = nRTH ln Q C = nRTC ln
Va Vc

Vd
nRTC ln
QC Vc TC
 = 1− = 1− = 1− Efisiensi mesin Carnot
QH V TH
nRTH ln b
Va
39
Entropy and the Clausius Inequality

The second law of thermodynamics leads to the definition of a new property called Entropy, a qu
antitative measure of microscopic disorder for a system. Entropy is a measure of energy that is n
o longer available to perform useful work within the current environment. To obtain the working d
efinition of entropy and, thus, the second law, let's derive the Clausius inequality.
dQrev dQrev
dQH dQC dQ DS t =  =
 Trev = 0
(5.11)
+ = 0 and (5.10) ACB T ADB T
TH TC

dQrev
The quantitiesT sum to zero for the arbitrary cycle
Entropy Change of Ideal Gas
dU = dQrev + dW and H = U + PV ; dW = PdV (5.12)
dH = dU + PdV + VdP and dH = dQrev − PdV + PdV + VdP
dQrev = dH − VdP and from dH = CP dT and V = RT / P (5.13)

DS C P dT
ig
dQrev dT dP
= C igP −R = − d ln P
T T P R R T
DS
T ig
C dT P
= P − ln (5.14)
R To R T Po
Entropy
• The second law of
thermodynamics leads to the
definition of a new property
called Entropy, a quantitative
measure of microscopic disorder
for a system.
• Entropy is a measure of energy
that is no longer available to
perform useful work within the
current environment. in

DS
T ig
C dT P
Entropy Change of Ideal Gas = P − ln
R To R T Po
Entropy Change of Ideal Gas
T
C igP dT   2 D   + 1  where :  =
T
T R T = A ln  + +
 o  o
BT  CT + 
2 2   ( − 1) To
o    To  2 
T

 dT / T
ig
C P
Mean heat capacity specific
C Pig = To
ln(T / To )
for entropy calculation S

  2 D   + 1   − 1 
C ig
= A +  BTo +  CTo + 2 2   
 
P
  To  2  ln 
S

DS C Pig T P
= S
ln − ln
R R To Po
Entropy
Example
For the ideal gas state and constant heat capacities, Eq. (3.23b) for a reversible
adiabatic (and therefore isentropic) process can be written:

Show that this same equation results from the application of Eq. (5.10) with ΔSig = 0.
Entropy Balance for open system
Entropy balance can be written as an
energy balance for processes in which fluid
enters, exits, or flows through a control
volume

Sum of three
The important difference:
Entropy is not conserved

•
SG is the rate of entropy generation
Entropy Balance for open system

The first term: the net rate of gain in entropy of the flowing streams, i.e., the
difference between the total entropy transported out by exit streams and the total
entropy transported in by entrance streams.

The second term: the time rate of change of the total entropy of the fluid contained
within the control volume.

The third term: entropy changes in the surroundings, the result of heat transfer
between system and surroundings
Entropy Balance for open system
Example
An inventor claims to have devised a process which takes in only saturated steam at 100°C and which by
a complicated series of steps makes heat continuously available at a temperature level of 200°C. The
inventor claims further that, for every kilogram of steam taken into the process, 2,000 kJ of energy as
heat is liberated at the temperature level of 200°C. Show whether or not this process is possible. In
order to give the inventor the benefit of any doubt, assume cooling water available in unlimited quantity
at a temperature of 0°C.

• A continuous process takes in saturated steam, and heat is made

continuously at T' = 200°C.
• Cooling water is available at T = 0°C. Assume therefore that the
steam is condensed and cooled to 0°C. All the heat liberated in this
operation cannot be made available at temperature level T' = 200°C,
because this would violate statement 2 of the second law.
• We must suppose that some heat Q is transferred to the cooling
water at T = 0°C. The process must satisfy the first law.

DH = Q + W
Entropy Balance for open system
Entropy Balance for open system
Entropy Balance for open system
 Calculation of
Ideal work and
Loss Work

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Calculation of Ideal work
Steady-state flow process:
Requiring work: Producing work:
An absolute minimum amount An absolute maximum amount
which must be expended to accomplish the which may be accomplished as the result of a
desired change of state of the fluid flowing In either case given change of state of the fluid flowing
through the control volume. through the control volume.

The limiting value obtains :

1. The change is accomplished completely reversibly
2. For such a process, the entropy generation is zero

1 • • •
D[( H + u 2 + zg ) m] fs = Q+ Ws
2
Calculation of Ideal work
If the potential and kinetic energy can be ommitted:
Calculation of Ideal work
Example
Rework the previous example, by the use of ideal work principles

Procedure
Calculate the maximum possible work Wideal of 1 kg
of steam in a flow process from saturated steam at
100°C to liquid water at 0°C.

Whether this work is sufficient to operate a Carnot

refrigerator rejecting 2,000 kJ as heat at 200°C and
taking heat from the unlimited supply of cooling
water at 0°C.
Calculation of Ideal work
For the steam :
Calculation of loss work
Loss work is work that is wasted as the result of irreversibilities in a process
Calculation of loss work
Calculation of loss work
Example
The two basic types of steady-flow heat exchanger are characterized by their flow patterns:
Cocurrent and countercurrent. Temperature profiles for the two types are indicated in Fig.
5.6. In cocurrent 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 flow,
the cold stream, again flowing from left to right, receives heat from the hot stream flowing in
the opposite direction.
The lines relate the temperatures of the hot and cold streams, TH, and TC respectively, to QC
, the accumulated rate of heat addition to the cold stream as it progresses through the
exchanger from the left end to an arbitrary downstream location. The following
specifications apply to both cases:
Calculation of loss work
Calculation of loss work
1 2 • • •
D[( H + u + zg ) m] fs = Q+ Ws
2
Calculation of loss work
Calculation of loss work
 Tim Dosen

1 Dr. Mar`atul Fauziyah, S.T. 2 Dr. Eng. Ir. Christina W. K., S.T., M.T.
marafauziyah@ub.ac.id christinawahyu@ub.ac.id

instagram.com/marafauziya instagram.com/chisachizu

+62 856-4572-9792 +62 821-7840-7006

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Thank You
See you on the next meeting!

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