Hukum Kedua

Termodinamika Termodinamika
Kerja & Panas
Kerja dapat diubah hampir seluruhnya menjadi
panas, energi potensial, energi kinetik atau
energi listrik. Efisiensi bisa mencapai 100%
dengan menghilangkan friksi.
Panas tidak dapat seluruhnya diubah menjadi Panas tidak dapat seluruhnya diubah menjadi
kerja, energi potensial, energi kinetik atau energi
listrik. Efisiensi tidak bisa lebih dari 40%.
Panas mengalir dari suhu tinggi ke suhu rendah,
tidak pernah sebaliknya.
Gerakan dengan friksi Gerakan dengan friksi
Reaksi kimia spontan Reaksi kimia spontan
Beberapa Proses Tak Dapat Balik
...... ...... pencampuran pencampuran
Transfer panas Transfer panas
TT
11
> T > T
22
Q
Ekspansi Ekspansi
P
1
> P
2
Statements of The Second Law
No apparatus can operate in such a way that its
only effect is to convert heat absorbed by a
system completely into work done by the system.
(Kelvin-Plank)
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 consists solely into
the transfer of heat from one temperature level
to a higher one. (Clausius)
Hukum I dan Hukum II
Hukum I :
- Energi dapat berubah dari suatu bentuk
energi menjadi bentuk energi lainnya
- Tidak bisa menjelaskan arah
perubahannya dan sifat perubahannya perubahannya dan sifat perubahannya
(spontan/tidak spontan)
Hukum II :
- Menjelaskan arah perubahan energi dan
sifat perubahannya, spontan/tidak spontan
Mesin Kalor
adalah suatu alat
atau mesin yang
menghasilkan
kerja dari panas
(kalor) dalam
suatu proses
siklis.
Essential to all heat-engine cycles are
absorption of heat into the system at a high
temperature, rejection of heat to the
surroundings at a lower temperature, and
production of work.
In operation, the working fluid of a heat
engine absorbs heat |Q
H
| from a hot
reservoir, produces a net amount of work
|W|, discard heat |Q
C
| to a cold reservoir,
and returns to its initial state.
Basic Thermodynamic Cycle of
Heat Engine
HEAT SOURCE
Q
in
Working
Substance
HEAT SINK
Pump
Engine W
Q
out
Substance
The first law:
C H
Q Q W =
The thermal efficiency of the engine:
C C H
Q
Q
Q
Q Q
Q
W
=

= 1
H H H
Q Q Q
If a thermal efficiency of 100% is not
possible for heat engines, what determines
the upper limits?
Refrigerator and Air Conditioner
High-temperature
SOURCE
Refrigerator
Q
H
Low-temperature
SINK
Refrigerator
W
Q
C
C net H
Q W Q + =
Carnots Theorem
No engine operating between two reservoirs
can be more efficient than a Carnot engine can be more efficient than a Carnot engine
operating those same two reservoirs
Hot reservoir at T
H
Eng E
|W|
Refrigerator
C
=
refrigerator
H
Q'
H
Q
H H
Q Q '
Hot reservoir at T
H
Cold reservoir at T
C
Cold reservoir at T
C
W Q
H
'
W Q
H

H H
Q Q '
If engine E has the greater efficiency,
( ) Q Q W Q W Q ' ' =
H H
H H
Q' Q and
Q Q'
W
> >
W
For the engine/refrigerator combination, the
net heat extracted from the cold reservoir is :
( )
H H H H
Q Q W Q W Q ' ' =
The net heat delivered to the hot reservoir is
also
H H
Q Q '
Since this is in violation of statement of the second
law, the original premise that engine E has a greater
efficiency then the Carnot engine is false. Carnot
theorem is proved.
Thus, a corollary to Carnots theorem state:
The thermal efficiency of a Carnot engine
depends only on the temperature levels and depends only on the temperature levels and
not upon the working substance of the
engine
A heat engine operating in a completely
reversible manner is called a Carnot
engine (N.L.S. Carnot, 1824):
Step 1: A system at the temperature of a
cold reservoir T
C
undergoes a reversible
adiabatic process that causes its
temperature to rise to that of a hot reservoir temperature to rise to that of a hot reservoir
at T
H
.
Step 2: The system maintains contact with
the hot reservoir at T
H
, and undergoes a
reversible isothermal process during which
heat |Q
H
| 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 T
C
.
Step 4: The system maintains contacts with the Step 4: The system maintains contacts with the
reservoir at T
C
, and undergoes a reversible
isothermal process in the opposite direction of
step 2 that returns to its initial state with
rejection of heat |Q
C
| to the cold reservoir.
The cycle traversed by an ideal gas serving as the working fluid in a Carnot engine
is shown by a PV diagram.
T
H
T
C
b
c
P
|Q
H
|
a b adiabatic compression
b c isothermal expansion
c d adiabatic expansion
d a isothermal compression
For the isothermal steps b c and d a
b
c
H H
V
V
RT Q ln =
and
a
d
C C
V
V
RT Q ln =
T
C
a
d
V
|Q
C
|
b
V
a
V
For adiabatic processes a b and c d
b
a
T
T
V
V
V
T
dT
R
C H
C
ln =

and
c
d
T
T
V
V
V
T
dT
R
C H
C
ln =

C
H
a d
b c
C
H
C
H
T
T
V V
V V
T
T
Q
Q
= =
) / ln(
) / ln(
H
C
H
C
H
T
T
Q
Q
Q
W
= = = 1 1
5 . 0
600
300
1 = =
Rough practical limits for of a Carnot engine; actual heat engines are irreversible
and rarely exceed 0.35.
A central power plant, rated at 800,000 kW, generates steam at 585K 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?
4957 . 0
585
295
1
max
= =
347 . 0 4957 . 0 7 . 0 = =
H
C
H
C
H
T
T
Q
Q
Q
W
= = = 1 1
347 . 0 = kW W 800000 =
kW Q
C
1505500 =
Entropy
A Carnot engine:
C
C
H
H
T
Q
T
Q
=
0 = +
C
C
H
H
T
Q
T
Q
0 = +
C H
dQ dQ
0 = +
C
C
H
H
T
dQ
T
dQ
0 =

T
dQ
rev
T
dQ
dS
rev
t
=

=
T
dQ
S
rev
t
There exists a property called entropy S, which
is an intrinsic property of a system, functionally
related to the measurable coordinates which

=
T
dQ
S
rev
t
related to the measurable coordinates which
characterize the system.
If a process is reversible and adiabatic,
dQ
rev
= 0, dS
t
= 0. The entropy of a system
is constant during a reversible adiabatic
process and the process is isentropic.
When a system undergoes an irreversible When a system undergoes an irreversible
process between two equilibrium states,
the entropy change of the system S
t
is
evaluated by an arbitrarily chosen
reversible process. Since entropy is a state
function, the entropy changes of the
irreversible and reversible processes are
identical.
Entropy changes of an ideal gas
For one mole of fluid undergoing a mechanically
reversible process in a closed system:
PdV dQ dU
rev
=
VdP PdV dU dH + + =
VdP dH dQ = VdP dH dQ
rev
=
dT C dH
ig
P
= P RT V / =
P
dP
R
T
dT
C
T
dQ
dS
ig
P
rev
= =
0
ln
0
P
P
T
dT
R
C
R
S
T
T
ig
P
=

For an ideal gas with constant heat capacities undergoing a reversible

adiabatic process:
0
ln
0
P
P
T
dT
R
C
R
S
T
T
ig
P
=

0 = S
1
2
1
2
ln ln 0
P
P
T
T
R
C
ig
P
=
ig
P
C R
P
P
T
T
/
1
2
1
2
|
|

\
|
=
R C C
ig
V
ig
P
+ =
ig
V
ig
P
C
C
=
/ ) 1 (
1
2
1
2

|
|

\
|
=
P
P
T
T
Penyelesaian Integral pada Entropi
( )
2
0
2
2
0 0
1
2
1
ln
0
T
T
D
CT BT A
T
dT
R
C
T
T
ig
p
=

(
(

\
|
+
|
|

\
|
+ + + =

0
T
T
=
D) C, B, A, T, ICPS(T0,
0
=

T
T
ig
p
T
dT
R
C
Dengan Matcad:
|
|

\
|
=

0
ln
0
T
T
T
dT
C
C
T
T
ig
P
S
ig
P
Kapasitas panas rata-rata untuk perhitungan
entropi
0
ln
0
T
T
C
T
dT
C
S
ig
P
T
T
ig
p
=

0
2
0
2
2
0 0
ln
1
2
1

T
T
T
D
CT BT A
R
C
S
ig
P
=
|

\
|

(
(

\
|
+
|
|

\
|
+ + + =

D) C, B, A, T, MCPS(T0, =
R
C
S
ig
P
Dengan Matcad:
0
ln
0
P
P
T
dT
R
C
R
S
T
T
ig
P
=

0
ln
T
T
C
T
dT
C
S
ig
P
T
ig
p
=

0 0
ln ln
P
P
T
T
R
C
R
S
S
ig
P
=

0
0
T T
S
T

Contoh perhitungan dengan

matcad matcad
The 2nd law mathematical statement
Let a quantity of heat |Q| be transferred from the hotter (T
H
)
to the cooler (T
C
) reservoir. The entropy changes of the two
reservoirs are:
t
H
T
Q
S
| |
=
t
C
T
Q
S
| |
=
For the process of irreversible heat transfer, S
total
is always
positive, approaching zero as the process becomes reversible.
H
T
C
T
|
|

\
|

= + =
C H
C H
t
H
t
H total
T T
T T
Q S S S | |
0
total
S
A 40 kg steel casting (C
P
= 0.5 kJ/kgK) at a temperature of 450C is quenched in
150 kg of oil (C
P
= 2.5 kJ/kgK) at 25C. If there are no heat losses, what is the
change in entropy of (a) the casting, (b) the oil, and (c) both considered together?
0 ) 25 )( 5 . 2 )( 150 ( ) 450 )( 5 . 0 )( 40 ( = + T T
C T
o
25 . 46 =
No heat losses:
K
kJ
T
T
mC
T
dT C
m
T
dQ
S
P
P
t
33 . 16 ln
1
2
= = = =

(a) the casting
K
kJ
T
T
mC
T
dT C
m
T
dQ
S
P
P
t
13 . 26 ln
2
= = = =

(b) the oil
K T T T
P
1

(b) the oil
(c) total entropy change
K
kJ
S S S
t
oil
t
cast total
80 . 9 = + =
Net rate of change
in entropy of
flowing streams
Time rate of
change entropy in
control volume
Time rate of
change entropy
in surroundings
Total rate
of entropy
generation
Entropy balance for open systems
0
) (
) ( = + +
G
t
surr cv
fs
S
dt
dS
dt
mS d
m S
&
&
0
) (
) (
,
= +
G
j
j
j
cv
fs
S
T
Q
dt
mS d
m S
&
&
&

In a steady-state flow process, 1 mol/s of air at 600 K and 1 atm is continuously

mixed with 2 mol/s of air at 450K and 1 atm. The product stream is at 400K and 1
atm. Determine the rate of heat transfer and the rate of entropy generation for the
process. Assume that air is an ideal gas with C
P
= (7/2)R, that the surroundings are
at 300K, and that kinetic- and potential-energy changes are negligible.
K T
s
mol
n
A
A
600
1
=
= &
C.V.
K T
s
mol
n
400
3
=
= &
T
Q
S S n S S n
T
Q
S n S n S n S
B B A A
B B A A G
) ( ) ( + =
=

&
& &
&
& & &
&
C.V.
K T
s
mol
n
B
B
450
2
=
= &
Q
&
s J T T C n T T C n H n H n H n Q
B P B A P A B B A A
/ 7 . 8729 ) ( ) ( = + = =
& & & & &
&
Ks
J
T
Q
T
T
C n
T
T
C n
B
P B
A
P A
446 . 10
300
7 . 8729
500
400
ln ) 2 (
600
400
ln ) 1 ( ) 314 . 8 )(
2
7
(
ln ln
=
+
(

+ =
+ =

&
& &
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 200C. The inventor claims further that, for every
kilogram of steam taken into the process, 2000 kJ of energy as heat is liberated at
the temperature level of 200C. Show whether or not this is possible. In order to
give the inventor the benefit of any doubt, assume cooling water available in
unlimited quantity at a temperature of 0C.
T = 200C
kJ Q 2000 =

Q Q Q Q + = +

= 2000
s
W Q H + =
kgK
kJ
S
kg
kJ
H
3554 . 7
2676
1
1
=
=
apparatus
kJ Q 2000 =

= 0C

Q
Saturated steam
at 100 C
Liquid water
at 0 C
0 . 0
0 . 0
2
2
=
=
S
H

Q H + = = 2000 2676 0 . 0
kJ Q 0 . 676 =

K
kJ
S 3554 . 7 3554 . 7 0 . 0 = =
K
kJ
S
t
227 . 4
15 . 273 200
2000
=
+
=
K
kJ
S
t
4748 . 2
15 . 273 0
0 . 676
=
+
=
K
kJ
S
total
6536 . 0 4748 . 2 227 . 4 3554 . 7 = + + =
Calculation of ideal work
In any steady-state flow process requiring work, there is an
absolute minimum amount which must be expended to
accomplish the desired change of state of the fluid flowing
through the control volume.
In a process producing work, there is an absolute
maximum amount which may be accomplished as the maximum amount which may be accomplished as the
result of a given change of state of the fluid flowing
through the control volume.
The limiting value obtains when the change of state
associated with the process is accomplished completely
reversibly.
For such a process, the entropy generation is zero :
0 ) ( =

T
Q
m S
fs
&
&
fs
m S T Q ) ( &
&
=

) ( ) (
2
1
2
rev W m S T m zg u H
s fs
fs
&
& & + =
(

\
|
+ +

fs
fs
ideal
m S T m zg u H W ) (
2
1
2
& &
&

(

\
|
+ + =

( )
fs fs ideal
m S T m H W ) ( & &
&
=

S T H W
ideal
=

s
ideal
t
W
W
required work
&
&
= ) (
ideal
s
t
W
W
produced work
&
&
= ) (
What is the maximum work that can be obtained in a steady-state flow process
from 1 mol of 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?
mol
J
E E ICPH dT C H
T
T
ig
P
15060 ) 5 040 . 0 , 0 . 0 , 3 593 . 0 , 280 . 3 ; 300 , 800 ( 314 . 8
0
= + = =

For an ideal gas, enthalpy is independent of pressure, and its change is given:
mol
J
P
P
R
T
dT
C S
T
T
ig
P
042 . 3
50
0133 . 1
ln 314 . 8 15060 ln
2
1
1
2
= = =

J
S T H W 15973 ) 042 . 3 )( 300 ( 15060 = = =
mol
S T H W
ideal
15973 ) 042 . 3 )( 300 ( 15060 = = =

Or, Step 1, reversible, adiabatic expansion from initial state to 1.0133 bar, T
Step 2, cooling to the final temperature
H W Q
S
= +
Step 1
) (
1
H H H W
S

= =
) (dQ
T
T T
dW
Carnot

=
Step 2
S T H H
T
dQ
T Q W
T
T
Carnot
= =

) ' (
2
'
2
S T H W W W
Carnot S ideal
= + =

Total
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 200C. The inventor claims further that, for every
kilogram of steam taken into the process, 2000 kJ of energy as heat is liberated at
the temperature level of 200C. Show whether or not this is possible. In order to
give the inventor the benefit of any doubt, assume cooling water available in
unlimited quantity at a temperature of 0C.
T = 200C
kJ Q 2000 =

2676 2676 0 . 0 = = H
K
kJ
S 3554 . 7 3554 . 7 0 . 0 = =
kgK
kJ
S
kg
kJ
H
3554 . 7
2676
1
1
=
=
apparatus
kJ Q 2000 =

= 0C

Q
Saturated steam
at 100 C
Liquid water
at 0 C
0 . 0
0 . 0
2
2
=
=
S
H
K
mol
J
S T H W
ideal
9 . 666
) 3554 . 7 )( 15 . 273 ( 2676
=
=
=

kJ
T T
T
W Q
7 . 1577
0 200
15 . 273 200
9 . 666
| | | |
=

+
=

Lost work
Work that is wasted as the result of irreversibilities in
a process is called lost work:
ideal S lost
W W W
Q m zg u H W
S
&
&
&
=
(

\
|
+ + =
2
2
1
Q m zg u H W
fs
S
& =
(

\
+ + =
2
fs
fs
ideal
m S T m zg u H W ) (
2
1
2
& &
&

(

\
|
+ + =

Q m S T W
fs lost
&
&
&
= ) (

Surrounding temperature T

T
Q
m S S
fs G
&
&
&
= ) (
0 =
G lost
S T W
& &

0 =
G lost
S T W

The two basic types of steady-flow heat exchanger are characterized by their flow
patterns: cocurrent and countercurrent. Consider the two cases, for each of which
the following specifications apply:
The minimum temperature difference between the flowing streams is 10K. Assume
that both streams are ideal gases with C
P
= (7/2)R. Find the lost work for both
cases. Take T

= 300 K.
s
mol
n K T K T K T
H C H H
1 300 350 400
1 2 1
= = = = &
T
400 K
T
H
T
C
T
H
T
C
Cocurrent Counter current
350 K
300 K
Q m zg u H W
fs
S
&
&
&
=
(

\
|
+ + =
2
2
1
0 ) ( ) ( = +
C C H H
H n H n & &
0 ) ( ) (
1 2 1 2
= +
C C P C H H P H
T T C n T T C n & &
C C H H fs
S n S n n S ) ( ) ( ) ( + = & & &
Negligible pressure change
|
|

\
|
+ =
1
2
1
2
ln ln ) (
C
C
H
C
H
H
P H fs
T
T
n
n
T
T
C n n S
&
&
& &
Q n S T W
fs lost
&
&
&
= ) (

Case I, cocurrent:
J 340 350 7
| | | |
Case I, cocurrent:
25 . 1
300 340
350 400
=

=
H
C
n
n
&
&
Ks
J
n S
fs
667 . 0
300
340
ln 25 . 1
400
350
ln ) 314 . 8 (
2
7
) 1 ( ) ( =
|

\
|
+
|

\
|
= &
s
J
n S T W
fs lost
1 . 200 667 . 0 300 ) ( = = = &
&

Case II, countercurrent:

5556 . 0
300 390
350 400
=

=
H
C
n
n
&
&
Ks
J
n S
fs
356 . 0
300
390
ln 5556 . 0
400
350
ln ) 314 . 8 (
2
7
) 1 ( ) ( =
|

\
|
+
|

\
|
= &
s
J
n S T W
fs lost
7 . 106 356 . 0 300 ) ( = = = &
&

From thermodynamic point of view, the countercurrent case is much more efficient.
The third law of thermodynamics
The absolute entropy is zero for all perfect crystalline
substances at absolute zero temperature.
When the form is noncrystalline, e.g., amorphous or glassy,
calculations show that the entropy of the more random
form is greater than that of the crystalline form. form is greater than that of the crystalline form.
The absolute entropy of a gas at temperature T:

+

+ +

+ =
T
T
g P
v
v
T
T
l P
f
f
T
S P
v
v
f
f
dT
T
C
T
H
dT
T
C
T
H
dT
T
C
S
) (
) ( ) (
0