BAB 5

THE SECOND LAW OF

THERMODYNAOMICS
Thermodinamika Teknik Kimia I (B)
Dr. Siti Machmudah
machmudah@chem-eng.its.ac.id

www.its.ac.id www.chem-eng. its.ac.id INSTITUT TEKNOLOGI SEPULUH NOPEMBER, Surabaya - Indonesia

 From eq. : - simple additive terms
U=W+Q
- heat and work have a same unit of a joule

In fact : both has a difference kind and behavior

Conversion efficiency of 100%

Work is readily transformed into other forms : by elimination of:
-potential energy by elevation of a weight - Friction
-kinetic energy by acceleration of a mass - Dissipative process that
-electrical energy by operation of a generator transforms work into heat

Joule’s experiments → work is readily transformed completely into heat

Conversion of heat completely into :

- work or mechanical energy failed
- electrical energy

Regardless of improvements to the devices employed,

conversion efficiencies do not exceed about 40%.
STATEMENTS OF THE SECOND LAW
No apparatus can operate in such a way that its only effect (in system and
Statement 1: surroundings) is to convert heat absorbed by a system completely into work
done by the system

Statement 1a: 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

Cyclic process & efficiency

Power 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.
 absorption of heat at a high temperature
into the system
Heat-engine cycles production of work
rejection of heat to at a lower temperature
the surroundings

High Temp
Hot Reservoir (5.1)

QH

Work
W

QC

Cold Reservoir (5.2)

Low temp

Fig. 1. Heat engine

Absolute value signs are used to make the equations independent of the sign conventions for Q and W.

For  to be unity (100% thermal efficiency) No engine has ever been

I QC I must be zero. built for which this is true

Some heat is always rejected to the cold reservoir

CARNOT ENGINE
Heat engine operating in completely reversible manner
Any reversible engine operating between two heat reservoirs

Four step that make up a Carnot Cycle:

1. A system at the temperature of a cold reservoir Tc undergoes a reversible

adiabatic process that causes its temperature to rise to that of a hot reservoir at
TH.
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.
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.
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 it to its initial
state with rejection of heat |Qc| to the cold reservoir.
Carnot cycle
Consisting 4 reversible steps:

6
CARNOT’S THEOREM

For two given heat reservoirs no engine can have a thermal efficiency higher than
that of a Carnot engine
TH
For refrigerator combination, the net heat extracted
Hot Reservoir
from the cold reservoir is:
Q' H QH

W
E C Carnot engine operating among heat reservoirs at the
same two temperatures have same thermal efficiency.
Q'H − | W | QH − |W | Thus a corollary to Carnot’s theorem state:
The thermal efficiency of a Carnot engine depends only
Cold Reservoir on the temperature levels and not upon the working
TC
substance of the engine.

Fig. 2. Engine E operating

a Carnot refrigerator C
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. 3. 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 Qc I.
dV U = H = 0
dQ = CV dT + RT
V V P
dV (5.3) Q = RT ln 2 = − RT ln 2
dW = − RT V1 P1
V
Q = −W (5.4)
Figure 3: PV diagram showing
Carnot cycle for an ideal gas.

From (5.5) and (5.6), Carnot’s equation:

QH TH
(5.5) = (5.7)
(5.3) QC TC
W T
= = 1− C
QH TH (5.8)

TC natural (universe) = 300 K

For practical TH = 600 K then :
TC 300
 = 1− = 1− = 0.5
TH 600
Vc V
ln = ln d (5.6)
rough limit of a Carnot engine; actual heat
engines are irreversible, and their thermal
Vb Va efficiencies rarely exceed 0.35.
QH TH QH QC QH − QC QH QC
= or = without absolute = or + =0 (5.9)
QC TC TH TC value signs TH TC TH TC

This equation is applicable to the reversible Carnot cycle, also applies to other reversible cycles.

(A)
(B)
Fig. 4 Represents an arbitrary reversible cycle traversed by an arbitrary fluid.

•Adjacent adiabatic curves (in A) Represent a Carnot cycle &

Each pair of : Eq. (5.9) applies.
•Isothermal connecting curves

Each Carnot cycle has its own pair of isotherms TH and TC and associated heat quantities QH and QC

dQH dQC dQrev dQrev dQrev dQrev (5.11)

+ = 0 and  T = =  = ACB T ADB T
=
t t
0 (5.10) dS ; S
TH TC T
dQ
The quantities rev sum to zero for the arbitrary cycle
T
Summary of Entropy
 ENTROPY CHANGES OF AN IDEAL GAS
dU = dQrev − PdV and H = U + PV (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)

S C P dT
ig
dQrev dT dP
= C igP −R = − d ln P
T T P R R T
S
T ig
C dT P
= P − ln (5.14)
R To R T Po
T
C igP dT   2 D   + 1  T
T R T = A ln  +  BTo +  CTo +  2To2  2 ( − 1)
 (5.15) where :  =
To
o  
T

C
ig
Mean heat capacity specific for P dT / T
(5.16)
entropy calculation C Pig = To
S ln (T / To )
C Pig   D   + 1   − 1 
S
= A +  BTo +  CTo2 + 2 2    (5.17)
R    To  2  ln  

S C Pig T P
= S
ln − ln (5.18)
R R To Po
Example 1 Methane gas at 550 K and 5 bar undergoes a reversible adiabatic expansion to 1 bar.
Assuming methane to be an ideal gas at these conditions, determine its final temperature.
MATHEMATICAL STATEMENT OF THE SECOND LAW

Consider two heat reservoirs, one at temperature TH and

a second at the lower temperature Tc. Let a quantity of
heat |Q| be transferred from the hotter to the cooler
reservoir. The entropy changes of the reservoirs at TH and
at Tc are:

Fig. 5. Cycle containing an irreversible

adiabatic process A to B

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.
Entropy (S)

dQrev Entropy adalah fungsi keadaan

dS  (state function), tidak tergantung
T
pada lintasan
Perubahan entropy dari kondisi A ke B:

S = S B − S A
Untuk lintasan reversibel dari A ke B:
B
dQrev
S = 
A
T

14
Entropy & Reversibilitas
TH  High temp. reservoir:
dQ 1
Q S H =  =  dQ
TH TH
−Q
TC S H = Tanda (-): panas
TH meninggalkan reservoir

 Low temp. reservoir:

dQ 1
SC =  =  dQ
TC TC
Q
SC = Tanda (+): panas menuju
TC reservoir
15
Entropy & Reversibilitas
 Total perubahan entropy
Stotal = S H + SC  TH − TC 
− QH QC Stotal = Q  
Stotal = +  TH TC 
TH TC
Jika TH>TC ➔ S = positive (+)
Jika TH →TC ➔ S → 0 Proses mencapai kesetimbangan
(reversibel)

 Untuk berbagai proses  Untuk proses reversibel

Stotal  0 HK II Stotal = 0

16
 •
Q
u2 u2

Control volume

P u1
V,U,H •
Ws

Entropy balance can be written as an energy balance

for processes in which fluid enters, exits, or flows
through a control volume

The important difference:

Entropy is not conserved
 (5.19)

(5.20)
•
S G is the rate of entropy generation
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

(5.21)
 For a steady-state flow process the mass and entropy of the fluid in the control volume are constant.

d(mS)CV/dt is zero, so that :

(5.22)

If in addition there is but one entrance and one exit, with m the same for both stream:

(5.23)
Example 2
Example 3 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.
H = Q + W
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 through given change of state of the fluid flowing through
the control volume. In either case 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 2 • • •
[( H + u + zg ) m] fs = Q + Ws
2
If the potential and kinetic energy can be omitted:
Rework the example 3, 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.

For the steam :

3
CALCULATION OF LOST WORK : Work that is wasted as the result of irreversibilities in a process
“The greater the irreversibility of a process, the greater the rate of entropy production
and the greater the amount of energy that becomes unavailable for work.“
The two basic types of steady-flow heat exchanger are characterized by their flow
patterns: cocurrent (a) and countercurrent (b). 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. Consider the two cases, for each of which the
following specifications apply:
TH, = 400 K TH, = 350 K TC, = 300 K nH = 1 mol s-1
The minimum temperature difference between the flowing streams is 10 K. Assume
that both streams are ideal gases with Cp = (7/2)R. Find the lost work for both cases.
Take T = 300 K.
 1 2 • • •
[( H + u + zg ) m] fs = Q + Ws
2
From the thermodynamic point the rate of countercurrent case is much more efficient.
 “Absolute entropy is zero for all perfect crystalline substances at
absolute zero temperature.”
→ Measurements of heat capacities at very low temperatures
If entropy is zero at T = 0 K:
dQrev
dS t =  (5.13)
T
(5.40)
Kerjakan soal pada buku Smith van Ness
• Problem:
• 5.2, 5.4, 5.10, 5.17
• 5.19, 5.21, 5.25, 5.33
- SELAMAT BELAJAR -