TKM-307

Termodinamika Teknik Kimia I

5 - The Second Law: Entropy

 Process Direction

• No apparatus can operate in such a way that its only effec

t (in system & surroundings) is to convert heat absorbed by
a system completely into work done by the system
• It is impossible by a cyclic process to convert the heat abs
orbed by a system completely into work done by the syste
m.

• No process is possible which consist solely in the transfer

of heat from one temperature level to a higher one.

Partial conversion of heat into work is the basis for nearly all
commercial production of power.
 Heat Engine

Heat engines produce work from heat in a cyclic process

Essential to all heat-engine cycles are:

1. Absorption of heat into the system at a high temperature
2. Rejection of heat to surroundings at a lower temperature
3. Production of work
 Heat Engine

W  Q in  Q out  Q H  Q C

nett work output

Thermal efficiency: 
heat absorbed

W Q H  QC QC
   1
QH QH QH

For  to be unity (100%), QC must be zero. No engine has ever

been built for which this is true; some heat is always rejected.
 Carnot’s Theorem & Carnot Engine

Carnot engine operates between two heat reservoirs in such

a way that all heat absorbed is absorbed at the constant tem
perature of the hot reservoir and all heat rejected at the co
nstant temperature of the cold reservoir.

Any reversible engine operating between 2 heat reservoirs is

a Carnot engine; an engine operating on a different cycle mu
st necessarily transfer heat across finite temperature differen
ce and therefore cannot be reversible.

For two given heat reservoir, no engine can have a thermal

efficiency higher than that of a Carnot engine.
 Carnot Cycle with an Ideal Gas as Working Fluid

Step1: a - b
Reversible adiabatic compression until the te
mperature rise from TC to TH

Step 2: b – c
Reversible isothermal expansion to arbitrary p
oint c with heat absorption of QH
Work
Step 3: c – d
Reversible adiabatic expansion until the temp
erature decrease TC.

Step 4: d – a
Reversible isothermal compression to the initial state with heat rejection of QC
 Carnot’s Equation
Vc Vd
QH  RTH ln and QC  RTH ln
Vb Va
Vc
TH ln
QH Vb

QC Vc
TC ln
Vb
TH CV dT V TH CV dT V

TC R T
 ln a
Vb
and 
TC R T
 ln d
Vc

Va V
ln  ln d W QH  QC QC
Vb Vc    1
QH TH QH QH QH
or 
QC TC
Vc V TC
ln  ln d   1
Vb Va TH
 Example 5.1
A central power plant, rated at 800 000 kW, generates
steam at 585 K and discard 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?
 QH TH Q H QC
Entropy

Our analysis showed that Q or  0
T
C C TH TC

The equation suggests the existence of a property whose changes are given
by the quantities Q/T

When the isotermal steps are infinitesimal, the heat quantities become dQ:
or H  dQC  0
dQ dQ rev
TH TC  T
0

Thus the quantities dQrev/T sum to zero for the arbitrary cycle, exhibiting the
characteristic of a property. We call this property as entropy, S.

dQ rev
dS  dQ rev  T dS
T

There exists a property called entropy S, which is an intrinsic property of a

system, functionally related to the measurable coordinates which
characterize the system
 Characteristic of Entropy

• Entropy owes its existence to the second law, from which it ar

ises in much the same way as internal energy does from the f
irst law.

• The change in entropy of any system undergoing a finite reve

rsible process is dQ rev
S  
T
• When a system undergoes an irreversible process between t
wo states, the entropy change of the system is evaluated to a
n arbitrary chosen reversible process that accomplishes the s
ame change of state as the actual process. The integration is
not carried out for the irreversible path.
 Characteristic of Entropy

• Since entropy is a state function, the entropy changes of the i

rreversible and reversible processes are identical.

• The entropy change of a system caused by the transfer of he

at can always be calculated by dQ/T whether the heat transf
er is accomplished reversibly or irreversibly.

• When a process is irreversible on account of finite differences

in other driving forces, such as pressure, the entropy change
s is not caused solely by heat transfer, and for its calculations
one must devise a reversible means of accomplishing the sa
me change of state.
 Calculation of Entropy

For one mole of fluid undergoing a mechanically reversible pr

ocess in a closed system, using the first law, the defining e
quation for enthalpy one find:
dQ rev dH V dP
dS   
T T T
For an ideal gas: ig
S
T
C p dT P
  ln   (5.18)
R T0 R T  P0 
Although derived for a mechanically reversible process, this e
quation is a general equation for the calculation of entropy
changes, since it relates properties only and independent o
f process causing the change of state.
 Example 5.3

Methane gas at 550 K & 5 bar undergoes a reversibl

e adiabatic expansion to 1 bar. Assuming methane
to be an ideal gas at these conditions, determine it
s final temperature.
 Mathematical Statement of The Second Law

Stotal  0
This mathematical statement of the second law affirms
that every process proceeds in such a direction that
the total entropy change associated with it is positiv
e.
The limiting value of zero being attained only by a reve
rsible process.
No process is possible for which the total entropy decr
eases.
Return to a cyclic heat engine, it takes in heat |QH| from a heat
reservoir at TH, and discards heat |QC| to another heat reservoir
at TC. The total entropy change of the process is therefore the
sum of the entropy changes of heat reservoir:

 | QH | | QC |
Stotal  
TH TC

The work given by Eq. (5.1) is |W|=|QH| - |QC|. Elimination of |QC|

between these two equations and solution for |W| gives:

 TC 
| W | TC S total  | QH | 1  
 TH 
 Example 5.4

A 40-kg steel casting (Cp = 0.5 kJ/(kg.K) at a temper

ature of 450oC is quenched in 150 kg of oil (Cp =
2.5 kJ/(kg.K) at 25oC. If there are no heat losses,
what is the change of entropy of:
a. The casting
b. The oil
c. Both considered together
Entropy Balance for Open Systems

t
d (mS ) cv dS surr
 ( Sm) fs    SG  0
dt dt
t
dS surr Qj
 
dt j T . j
 Example 5.5

In a steady-state flow process, 1 mol s-1 of air at 600

K (326.85oC) and 1 atm is continuously mixed with 2
mol s-1 of air at 450 K (176.85oC) and 1 atm. The pro
duct stream is at 400 K (126.85oC) and 1 atm. Deter
mine the rate of heat transfer and the rate of entropy
generation for the process. Assume that air is an ide
al gas with CP= (7/2)R, that the surroundings are at
300 K (26.85oC), and that kinetic and potential-energ
y changes are negligible.
 Problem 5.6

An inventor claims to have devised a process which takes in

only saturated steam at 100oC (373.15K) and which by a com
plicated series of steps makes heat continuously available at
a temperature level of 200oC (473.15K), wwhere 2000 kJ of e
nergy as heat is liberated for every kilogram of steam taken in
to the process. Show whether or not this is possible. To give t
his process the most favorable conditions, assume cooling w
ater available in unlimited quantity at a temperature of 0oC (2
73.15K).
 Calculation of Ideal Work
In a steady-state flow process requiring work, there is an a
bsolute minimum amount of work required to accomplish co
mpletely reversible process.

In a process producing work, there is an absolute maximu

m work attained which is accomplished by completely rever
sible process.

For such a process, the entropy generation is zero, but writt

en for the uniform surrounding temperature Tσ
Wideal  H  T S
Ws(rev), is the work of a completely reversible process,
and given as Wideal
 Thermodynamic Efficiency

In a work produced process, Wideal is negative, Wideal is the

maximum work obtainable from a given change in the
properties
Wactual (Ws) < Wideal Ws
t 
Wideal

In a work required process, Wideal is positive, Wideal is the

minimum work required to bring a given change in the
properties
Wideal
Wactual (Ws) > Wideal t 
Ws
 Problem 5.7

A rigid vessel of 0.05 m3 volume contains an ideal ga

s, Cv = 5/2 R, at 500 K and 1 bar.
a. If heat in the amount of 12000 J is transferred to t
he gas, determine its entropy change
b. If the vessel is fitted with a stirrer that is rotated b
y a shaft so that work on the amount of 12000 J i
s done on the gas, what is the entropy change of
the gas if the process is adiabatic? What is DStota
l?
 Problem 5.12

An ideal gas, Cp = 7/2 R, undergoes a cycle consisting of the f

ollowing mechanically reversible steps:
a. An adiabatic compression from P1, V1, T1 to P2, V2, T2
b. An isobaric expansion from P2, V2, T2 to P3 = P2, V3, T3
c. An adiabatic expansion from P3, V3, T3 to P4, V4, T4
d. A constant-volume process from P4, V4, T4 to P1, V1 = V4, T1

Sketch this cycle on a PV diagram and determine its thermal e

fficiency if T1 = 500 K, T2 = 800 K, T3 = 2000 K, and T4 = 100
0K
 Problem 5.13

A reversible cycle executed by 1 mol of an ideal gas for which

Cp = 5/2 R consist of the following processes:
a. Starting at 600 K & 2 bar, the gas is cooled at constant pr
essure to 300 K
b. From 300 K & 2 bar, the gas is compressed isothermally t
o 4 bar
c. The gas returns to its initial state along a path for which th
e product PT is constant.

What is the thermal efficiency of the cycle?

 Problem 5.11

A piston/cylinder device contains 5 mol of an ideal g

as, Cp = 5/2 R, at 20oC & 1 bar. The gas is compre
ssed reversibly and adiabatically to 10 bar, where
the piston is locked in position. The cylinder is the
n brought into thermal contact with a heat reservoi
r at 20oC, and heat transfer continues until the gas
also reaches this temperature. Determine the entr
opy changes of the gas, the reservoir, and DStotal
 Irreversibility

One mole of an ideal gas, Cp = 7/2 R is compressed

adiabatically in a piston/cylinder device from 2 bar
& 25oC to 7 bar. The process is irreversible and re
quires 35% more work than a reversible adiabatic
compression from the same initial state to the sam
e final pressure. What is the entropy change of the
gas?
 Classical Lost Work & Process Analysis

The ideal work is the maximum amount of work whic

h can be done by the process by operating reversi
bly within the system and by transferring heat bet
ween the system and the surroundings reversibly.
The lost work: W  W  W
lost ideal actual

Wlost  T  Ss  Q
For processes containing several units, lost-work cal
culations can be made for each unit and summed
to determine the overall value.
 Example 4.7

Steam enters a turbine at 1.5 MPa & 500oC and exh

austs at 0.1 MPa. The turbine delivers 85% of the
shaft work of a reversible-adiabatic turbine althoug
h it is neither reversible nor adiabatic. Heat losses
to the surroundings at 20oC are 9 kJ/kg steam.
Determine temperature, entropy change of the stea
m leaving the turbine, & the lost work
 Example 4.8

Assume that 5000 kg/h of oil with a heat capacity of

3.2 kJ/kg.K is to be cooled from 220 to 40oC, using
a large quantity of water which can be assumed to
be at a constant temperature of 30oC. Determine t
he lost work in the process and the thermodynami
c efficiency of the process.
 Example 4.9

Assume that 100 kg of methane gas/h is adiabaticall

y compressed from 0.5 MPa & 300 K to 3.0 MPa &
500 K after which it is cooled isobarically to 300 K
by a large amount of water available at 290 K. Det
ermine the efficiency of the compressor.
If the surroundings are assumed to be at 290 K, do a
thermodynamic analysis of the process.
Assume ideal gas.
Cp = 35.58 J/mol.K
Cv = 27.27 J/mol.K
 8

Steam dengan tekanan 12 bar dan temperatur 200 o

C diekpansi satu tahap dalam sebuah turbin sehi
ngga tekanannya menjadi 1,5 bar pada kondisi j
enuhnya. Turbin bekerja secara adiabatik denga
n efisiensi 85%. Perkirakan (dalam sistem satua
n SI):
Kualitas uap keluar turbin
Kebutuhan uap air agar dihasilkan daya sebesar 50
MWatt
Kerja ideal, kerja musnah dan perubahan entropi tot
al, jika temperatur lingkungan 25 oC
 Problem 5.8

An ideal gas, Cp = 7/2 R, is heated in a steady-flow h

eat exchanger from 20oC to 100oC by another stre
am of the same ideal gas which enters at 180oC. T
he flow rates of the two streams are the same, an
d heat losses from the exchanger are negligible.
a. Calculate the molar entropy changes of the two g
as streams for both parallel and counter-current fl
ow in the exchanger
b. What is DStotal in each case?
 Carnot Cycle

Suatu mesin Carnot menyerap panas sebesar 400 k

J dari sumber panas pada 525 oC dan melepas p
anas ke penerima panas pada 50 oC. Perkirakan
kerja yang dihasilkan, perubahan entropy sumber
panas, penerima panas dan total!
 2nd law

Satu mol gas ideal dikompresi secara isotermal-irev

ersibel pada 130 oC dari 3 bar menjadi 6.5 bar dal
am sebuah alat silinder berpiston. Kerja yang dibu
tuhkan untuk kompresi ini 30% lebih besar dari ke
rja untuk proses reversibelnya. Selama kompresi,
sejumlah panas dibuang ke lingkungan yang mem
iliki temperatur konstan sebesar 25 oC. Hitung per
ubahan entropi dari gas, penerima panas dan total
!
 2nd law
Uap jenuh dengan tekanan 5 bar dan temperatur 151,87 o
C berada dalam silinder yang volumnya 0,750 m3. Sil
inder tersebut dilengkapi dengan piston yang dapat ber
gerak bebas. Uap air tersebut kemudian dikompresi se
cara reversibel sampai diperoleh uap air yang memiliki
tekanan 12 bar dan temperatur 187,99 oC. Selama pro
ses kompresi berlangsung, terjadi pembuangan panas
ke lingkungan sejumlah 2000 kJ. Temperatur lingkunga
n diketahui sebesar 27 oC. Perkirakanlah:
a. Prosentase uap air yang mengembun
b. Perubahan entalpi dan energi dalam (dalam kJ/kg)
Kerja yang dibutuhkan untuk kompresi tersebut (dalam kJ)
Perubahan entropy uap air, lingkungan dan total
 2nd law

Gas nitrogen dengan laju 2 ton/jam mula-mula memiliki temp

eratur -168 oC dan tekanan 1 Mpa. Gas nitrogen tersebu
t kemudian dikompresi secara adiabatik dalam sebuah k
ompresor sehingga temperatur dan tekanannya masing-
masing menjadi –63 oC dan 6 MPa. Dari deskripsi prose
s tersebut:
Dengan mengasumsikan gas nitrogen sebagai gas ideal, per
kirakan daya yang dibutuhkan (dalam kWatt), efisiensi m
ekanik (dalam %) dan perubahan entropi gas nitrogen pa
da proses kompresi tersebut! Ambil  = 1,4.
Dengan menggunakan diagram P-H gas nitrogen terlampir, ja
wablah kembali pertanyaan soal a!
 7

Karbon tetrakhlorida cair sebanyak 5 kg mengalami perubahan secara re

versibel pada tekanan konstan sebesar 1 bar dalam sistem tertutup. A
kibat perlakuan tersebut, temperatur fluida mengalami perubahan dari
0 oC menjadi 56 oC. Sifat-sifat dari CCl4 cair pada 1 bar dan 0 oC dia
sumsikan tidak dipengaruhi temperatur:  = 1,2 x 10-3 K-1, CP = 0,84
kJ kg-1 K-1, dan  = 1,590 kg/m3. Tentukanlah:
a. Perubahan entropi dari karbon tetrakhlorida cair
b. Temperatur lingkungan pada saat proses perubahan tersebut berl
angsung (dalam oC)
Jika proses berlangsung secara ireversibel, perkirakan efisiensi mekanik
alat apabila kerja yang mampu dihasilkan sebesar 11,67 kJ!
Berkaitan dengan soal c, hitunglah perubahan entropi total! Apa kesimpul
an yang dapat diambil!
Ambil nilai temperatur lingkungan sama dengan hasil perhitungan soal
b!
Conversion of heat to work always accompanied by
heat release to surroundings