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Second Law of Thermodynamics t t −QC QC T H −T C

∆ Stotal =∆ S H + ∆ S C = + =QC
T H TC THTC
Topics:
I. Entropy and Entropy Balances
II. Ideal Heat Engines or Refrigerators
III. Entropy Balance of Flow Processes
ღ Application of 2nd Law to Heat Engines
 Heat Engines – produces useful work that
employ the flow of heat as their energy
The Second Law of Thermodynamics
source; device of a machine that produces
 Entropy, S – systems at internal
work from heat in a cyclic process
equilibrium is an intrinsic property,
 Heat reservoirs – bodies imagined capable
functionally related to the measurable
of absorbing or rejecting unlimited
state variables that characterize the
quantities of heat without temperature
system
change
d Qrev
d St= |W |=|Q H|−|QC|
T
 Thermal Efficiency – ratio of network
 dSt of any system and its surroundings,
output to heat absorbed
and resulting from any real process, is
positive, approaching zero when the |W |
ƞ=
process approaches reversibility. |QH|−|QC|
¿ Q H ∨¿= ¿ ¿
Mathematically, ¿ Q H ∨¿=1−¿ Q C ∨ ¿¿
∆ Stotal ≥ 0 ¿ Q H ∨¿ ¿
∆ S system + ∆ S surroundings ≥0
impossible to construct an
ღ Two individual statements of 2nd Law engine that, operating in a
 Kelvin-Planck: impossible to construct a cycle, produces no effect (in
device which operates on a cycle and system and surroundings)
produces no other effect than the transfer other than the extraction of
of heat from a single body in order to heat from a reservoir and the
produce work. performance of an equivalent
amount of work.
 Clausius: impossible to construct a device
which operates on a cycle and produces no
ღ Heat Engines and Heat Pumps
other effect than the transfer of heat from
a cooler body to a hotter body.  Carnot Engine – heat engine operating in a
completely reversible manner; NLS Carnot
ღ Application of 2nd Law to Simple Heat 1824
Transfer  Carnot’s Theorem:
 No process is possible which consist solely 1. For two given heat reservoirs no engine
of the transfer of heat from one can have thermal efficiency higher than
temperature level to a higher one. that of a Carnot Engine.
2. The thermal efficiency of a Carnot
 T is constant,
Engine depends only on the
Q
∆ S= temperature levels and not upon the
T
working substance of the engine
 A quantity of heat Q is transferred to or
Schematic Diagrams:
from a reservoir at temperature T.
 Carnot engine
 TH > T C
 Carnot heat pump or refrigerator
 If QH = -QC
QH −Qc
∆ StH = =
TH TH
t QC
∆ SC =
TC
 - Rely sa temp

 Carnot Heat Pump

 a -> b ; adiabatic compression with temp
– carnot cycle traversed in opposite
rising from TC to TH
direction
 b -> c ; isothermal expansion to arbitrary
– usual measure of quality of heat pump
point c with absorption of heat QH
is the coefficient of performance (COP)
 c -> d ; adiabatic expansion with temp
QC
ω= decreasing to TC
W
 d -> a ; isothermal compression to the initial
TC
ω carnot = (refrigeration) state with rejection of heat QH
T H −T C

 Carnot Heat Cycle

o Step 1: A system at an initial
temperature of a cold reservoir at
TC undergoes a reversible adiabatic
process that causes its temperature
to rise to that of a hot reservoir at
TH.
o Step 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.
o 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.
o Step 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.

PV diagram showing a Carnot cycle for a working

fluid in the ideal-gas state.
 Solution:

N = W/ QH
W = QH – QC

ncarnot = 1 – QC/QH = 1 – 295/585 = 0.4957

N = W/ W+QC
0.70(0.4957) = 800 000/800 000 + QC
|QC| = 1505541.946 kW
QC = -1505541.946 kW = 1505.54 MW

Carnot’s Engine Efficiency

 Efficiency of a Carnot engine approach unity
only when TH approaches infinity or TC
approaches zero.
 All heat engines operate at η less than
unity.
 Two reversible device working at the same
temperature limits will have the same η For a -> b (adiabatic compression)

T2/T1 = (P2/P1)^k-1/k
940/300 = (8.4/P1)^1.4-1/1.4
P1 = 0.1543 MPa

V1

PV=nRT
V1 = nRT1/P1
V1 = 0.05kg x x1000 x 1/28.9647 x 2.314 x
Given: 300 / 0.1543 x 10^6
W = 800 000 kW V1 = 0.0279 m^3
TH = 585 K
TC = 295 K V2
n = 0.70 ncarnot
PV=nRT
Required: QC V2 = nRT2/P2
 V2 = 0.05kg x x1000 x 1/28.9647 x 2.314 x
940 / 8.4x 10^6
V2 = 1.6061 x 10 ^-3 m^3

For b -> c (isothermal expansion)

QH = nRTlnV3/V2
QH = nRTlnP2/P3
4.2x10^3 j = (0.05 x 1000 x 1/28.9647)
(8.314)(940) ln(8.4/P3)
P3 = 6.1528 MPa

V3

V3 = 2.1927 x 10 ^-3 (using Boyle’s)

For c -> d (adiabatic expansion)

P4

T4/T3 = (P4/P3)^k-1/k
300/940= (P4/6.1528)^1.4-1/1.4
P4 = 0.1130 MPa

V4
PV=nRT
V4 = nRT4/P4
V4 = 0.05kg x x1000 x 1/28.9647 x 2.314 x
300 / 0.1130 x 10^6
V4 = 0.0381 m^3

Overall Cycle

N = 1 – TC/TH = 1- 300/940
n = 0.6809 = 68.09%
n = W/QH

0.6809 = W/4.2
W = 2.8598 J = 2.86 kJ

QC
W = QH – QC
2.86 = 4.2 – QC
QC = 1.34
QC = -1.34 kJ Given:
Methane
Entropy T1 = 550 K
P1 = 5 bar
P2 = 1 bar

Using Perry’s: (page 2-179)

C1 = 0.33298 x 10^5
C2 = 0.79933 x 10^5
C3 =2.0896 x 10^3
C4 = 0.41602 x 10^5
C5 = 991.96

dS/R =(Cp)s/R ln T/To – ln P/Po

0 = (Cp)s/R ln T/To – ln P/Po
ln P/Po = (Cp)s/R ln T/To
(8.314) ln 1/5 = (Cp)s ln T/550
-13.3809 = (Cp)s ln T/550

(Cp)s

Cp = C1 + C2 (C3/T/sinh(C3/T))^2 +
C4(C5/T/cosh(C5/T))^2
Cp = 49549.8286 j/kmol
Cp = 49.5498 J/mol

-13.3809 = (Cp)s ln T/550

-13.3809 = (49.5498) ln T/550
T = 419.8379 K

I. Sensible Heat Effects

ღ Temperature Dependence of the Heat
Capacity