TKM-307

Termodinamika Teknik Kimia I

4 - The Second Law: Entropy

 Process Direction

No apparatus can operate in such a way that its only

effect (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
absorbed by a system completely into work done by the
system.

No process is possible which consist solely in the transfer

of heat from one temperature level to a higher one.

Partial conversion of heat to 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
Conversion of heat to work always accompanied by
heat release to surroundings
 Heat Engine

W Qin Qout QH QC

nett work output

Thermal efficiency:
heat absorbed

W QH QC QC
1
QH QH QH

For to be unity, QC must be zero. No engine has ever been built

for which this is true; some heat is always rejected.
 Carnots Theorem & Carnot Engine

Carnot engine operates

between two heat
reservoirs
in such a way that all heat
absorbed is absorbed at
the constant temperature
of the hot reservoir
and all heat rejected at the
constant temperature of
the cold reservoir

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

efficiency higher than that of a Carnot engine.
 Carnot Cycle

Step1: A system at TC undergoes a reversible

adiabatic process that causes its
temperature rise to TH
Step 2: The system maintains contact with
the hot reservoir 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
reversible isothermal process in the opposite direction of the step 2 that returns
it to its initial state with heat rejection of QC to the cold reservoir
 Carnot Engine - Reversibility

Any reversible engine operating between 2 heat

reservoirs is a Carnot engine.

An engine operating on a different cycle must

necessarily transfer heat across finite temperature
difference and therefore cannot be reversible.
 Carnot Cycle with an Ideal Gas as Working Fluid

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

Step 2: b c
Reversible isothermal expansion to arbitrary
point c with heat absorption of QH

Step 3: c d
Reversible adiabatic expansion until the
temperature decrease TC.

Step 4: d a
Reversible isothermal compression to the initial state with heat rejection of QC
 Entropy
Q H TH Q H QC
Our analysis showed that or 0
Q C TC 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:
dQ H dQ C dQ rev
0 or 0
TH TC T

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 dQrev 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

arises in much the same way as internal energy does from
the first law.

The change in entropy of any system undergoing a finite

reversible process is dQ rev
S
T
When a system undergoes an irreversible process between
two states, the entropy change of the system is evaluated to
an arbitrary chosen reversible process that accomplishes the
same 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

irreversible and reversible processes are identical.

The entropy change of a system caused by the transfer of

heat can always be calculated by dQ/T whether the heat
transfer is accomplished reversibly or irreversibly.

When a process is irreversible on account of finite differences

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

For one mole of fluid undergoing a mechanically reversible

process in a closed system, using the first law, the defining
equation for enthalpy one find:
dQ rev dH V dP
dS
T T T

For an ideal gas: S T ig

C p dT P
ln
R T0 R T P0

Although derived for a mechanically reversible process, this

equation is a general equation for the calculation of
entropy changes, since it relates properties only and
independent of process causing the change of state.
 Example

Calculate S for each step of the cycle shown

below. Assume ideal gas with constant Cp.
 Problem 5.6

A quantity of an ideal gas, Cp = 7/2 R at 20oC & 1

bar and having a volume of 70 m3 is heated at
constant pressure to 25oC by the transfer of heat
from a heat reservoir at 40oC. Calculate the heat
transfer to the gas, the entropy change of the heat
reservoir, the entropy change of the gas, and
Stotal.
 Problem 5.7

A rigid vessel of 0.05 m3 volume contains an ideal

gas, Cv = 5/2 R, at 500 K and 1 bar.
a. If heat in the amount of 12000 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 on the amount of 12000 J
is done on the gas, what is the entropy change of
the gas if the process is adiabatic? What is
Stotal?
 Example 5.3

Methane gas at 550 K & 5 bar undergoes a

reversible adiabatic expansion to 1 bar. Assuming
methane to be an ideal gas at these conditions,
determine its final temperature.
 Heat Engine

W Qin Qout QH QC

nett work output

Thermal efficiency:
heat absorbed

W QH QC QC
1
QH QH QH

For to be unity, QC must be zero. No engine has ever been built

for which this is true; some heat is always rejected.
 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
positive.
The limiting value of zero being attained only by a
reversible process.
No process is possible for which the total entropy
decreases.
 Thermodynamic Efficiency

In a process producing work, there is an absolute maximum

work attainable which is accomplished by completely
reversible process. For irreversible process,
Wactual produced < Wideal
Ws t Wideal

In a process requiring work, there is an absolute minimum

amount of work required which is accomplished by
completely reversible process. For irreversible process,
Wractual required > Wideal
Wideal
Ws
t
 Problem 5.12

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

following 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

efficiency if T1 = 500 K, T2 = 800 K, T3 = 2000 K, and T4 =
1000 K
 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
pressure to 300 K
b. From 300 K & 2 bar, the gas is compressed isothermally
to 4 bar
c. The gas returns to its initial state along a path for which
the product PT is constant.

What is the thermal efficiency of the cycle?

 Example 5.4

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

temperature 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
 Problem 5.11

A piston/cylinder device contains 5 mol of an ideal

gas, Cp = 5/2 R, at 20oC & 1 bar. The gas is
compressed reversibly and adiabatically to 10 bar,
where the piston is locked in position. The cylinder
is then brought into thermal contact with a heat
reservoir at 20oC, and heat transfer continues until
the gas also reaches this temperature. Determine
the entropy changes of the gas, the reservoir, and
Stotal
 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
requires 35% more work than a reversible
adiabatic compression from the same initial state
to the same final pressure. What is the entropy
change of the gas?
 Classical Lost Work & Process
Analysis
The ideal work is the maximum amount of work
which can be done by the process by operating
reversibly within the system and by transferring
heat between the system and the surroundings
reversibly.
Wlost Wideal Wactual
The lost work:
Wlost T Ss Q

For processes containing several units, lost-work

calculations 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

exhausts at 0.1 MPa. The turbine delivers 85% of
the shaft work of a reversible-adiabatic turbine
although it is neither reversible nor adiabatic. Heat
losses to the surroundings at 20oC are 9 kJ/kg
steam.
Determine temperature, entropy change of the
steam 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 the lost work in the process and the
thermodynamic efficiency of the process.
 Example 4.9

Assume that 100 kg of methane gas/h is

adiabatically 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. Determine 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

oC diekpansi satu tahap dalam sebuah turbin
sehingga tekanannya menjadi 1,5 bar pada
kondisi jenuhnya. Turbin bekerja secara
adiabatik dengan efisiensi 85%. Perkirakan
(dalam sistem satuan SI):
Kualitas uap keluar turbin
Kebutuhan uap air agar dihasilkan daya sebesar 50
MWatt
Kerja ideal, kerja musnah dan perubahan entropi
total, jika temperatur lingkungan 25 oC
 Problem 5.8

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

heat exchanger from 20oC to 100oC by another
stream of the same ideal gas which enters at
180oC. The flow rates of the two streams are the
same, and heat losses from the exchanger are
negligible.
a. Calculate the molar entropy changes of the two
gas streams for both parallel and counter-current
flow in the exchanger
b. What is Stotal in each case?
 Carnot Cycle

Suatu mesin Carnot menyerap panas sebesar 400

kJ dari sumber panas pada 525 oC dan melepas
panas 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-

ireversibel pada 130 oC dari 3 bar menjadi 6.5 bar
dalam sebuah alat silinder berpiston. Kerja yang
dibutuhkan untuk kompresi ini 30% lebih besar
dari kerja untuk proses reversibelnya. Selama
kompresi, sejumlah panas dibuang ke lingkungan
yang memiliki temperatur konstan sebesar 25 oC.
Hitung perubahan entropi dari gas, penerima
panas dan total!
 2nd law
Uap jenuh dengan tekanan 5 bar dan temperatur 151,87
oC berada dalam silinder yang volumnya 0,750 m3.
Silinder tersebut dilengkapi dengan piston yang dapat
bergerak bebas. Uap air tersebut kemudian dikompresi
secara reversibel sampai diperoleh uap air yang
memiliki tekanan 12 bar dan temperatur 187,99 oC.
Selama proses kompresi berlangsung, terjadi
pembuangan panas ke lingkungan sejumlah 2000 kJ.
Temperatur lingkungan 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

temperatur -168 oC dan tekanan 1 Mpa. Gas nitrogen
tersebut kemudian dikompresi secara adiabatik dalam
sebuah kompresor sehingga temperatur dan tekanannya
masing-masing menjadi 63 oC dan 6 MPa. Dari
deskripsi proses tersebut:
Dengan mengasumsikan gas nitrogen sebagai gas ideal,
perkirakan daya yang dibutuhkan (dalam kWatt),
efisiensi mekanik (dalam %) dan perubahan entropi gas
nitrogen pada proses kompresi tersebut! Ambil = 1,4.
Dengan menggunakan diagram P-H gas nitrogen terlampir,
jawablah kembali pertanyaan soal a!
 7

Karbon tetrakhlorida cair sebanyak 5 kg mengalami perubahan secara

reversibel pada tekanan konstan sebesar 1 bar dalam sistem tertutup.
Akibat perlakuan tersebut, temperatur fluida mengalami perubahan
dari 0 oC menjadi 56 oC. Sifat-sifat dari CCl4 cair pada 1 bar dan 0 oC
diasumsikan 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
berlangsung (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
kesimpulan yang dapat diambil!
Ambil nilai temperatur lingkungan sama dengan hasil perhitungan soal
b!