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first draft 9/23/04, second Sept Oct 2005 minor changes 2006, used spell check, expanded example
Kelvin-Planck: It is impossible to construct a device that will operate in a cycle and produce no effect other than the raising of a weight and the exchange of heat with a single reservoir. Clausius: It is impossible to construct a device that operates in a cycle and produces no other effect than the transfer of heat from a cooler body to a hotter body. Woud: used to: 1) predict the direction of processes
2) establish the conditions of final equilibrium
3) determine best possible theoretical performance of a process
if it is impossible to have a heat engine with 100% efficiency, how high can it go?? define ideal process, termed reversible process: a process that, once having taken place, can be reversed without changing either the system or surroundings examples irreversible; piston expanding against stop
reversible; piston expanding by removing and replacing weights; excerpt from VW&S page 166 good
description of reversible and irreversible processes
Let us illustrate the significance of this definition for a gas contained in a cylinder that is fitted with a piston. Consider first Fig. 6.8, in which a gas (which we define as the system) at high pressure is restrained by a piston that is secured by a pin. When the pin is removed, the piston is raised and forced abruptly against the stops. Some work is done by the system, since the piston has been raised a certain amount. Suppose we wish to restore the system to its initial state. One way of doing this would be to exert a force on the piston, thus compressing the gas until the pin could again be inserted in the piston. Since the pressure on the face of the piston is greater on the return stroke than on the initial stroke, the work done on the gas in this reverse process is greater than the work done by the gas in the initial process. An amount of heat must be transferred from the gas during the reverse stroke in order that the system have the same internal energy it had originally. Thus the system is restored to its initial state, but the surroundings have changed by virtue of the fact that work was required to force the piston down and heat was transferred to the surroundings. Thus the initial process is an irreversible one because it could not be reversed without leaving a change in the surroundings. In Fig. 6.9 let the gas in the cylinder comprise the system and let the piston be loaded with a number of weights. Let the weights be slid off horizontally one at a time, allowing the gas to expand and do work in raising the weights that remain on the piston. As. the size of the weights is made smaller and their number is increased, we approach a process that can be reversed, for at each level of the piston during the reverse process there will be a small weight that is exactly at the level of the platform and thus can be placed on the platform without requiring work. In the limit, therefore, as the weights become very small, the reverse process can be accomplished in such a manner that both the system and surroundings are in exactly the same state they were initially. Such a process is a reversible process. 9/25/2006
Carnot cycle example steam power plant - working substance steam boiler - heat transferred from high T (constant) reservoir to steam - steam T only infinitesimally lower than reservoir => reversible isothermal heat transfer process. (phase change fluid - vapor is such a process turbine - reversible adiabatic (no heat transfer) T decreases from T H to TL condenser - heat rejected from working fluid to T L reservoir (infinitesimal T) some steam condensed pump - temperature raised to T H adiabaticly can reverse and act as refrigerator
Carnot cycle four basic processes: 1. reversible isothermal process in which heat is transferred to or from the T H reservoir 2. reversible adiabatic process in which the temperature of the working fluid decreases from T H to TL 3. reversible isothermal process in which heat is transferred to or from the T L reservoir 4. reversible adiabatic process in which the temperature of the working fluid increases from T L to TH Carnot cycle most efficient, and only function of temperature
thermal =
=1
QH QL
( ) TH = f( TL) TL
f TH
thermal = 1
TL
TH
most efficient
initial values
0.2680 = 1
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TH := Find T , T ( H L)
TL
TH 373.134 = TL
273.134
VW&S has 273.15 changed to 273.16 to correspond to triple point of water 0.01 deg_C
Entropy
inequality of Clausius ... for fig 7.1 1 dQ = QH QL > 0
1 T
dQ 0
1 T
dQ =
=0
if ..
1 dQ
1 T
dQ = 0
1 dQ 0
and ...
1 T
dQ = 0
1 dQ = QH QL_irrev > 0
and ...
1 T
dQ =
QH TH
QL_irrev TL
<0
if heat engine becomes more irreversible such that W => 0.. as ... 1 dQ = 0 1 T dQ < 0 => all irreversible engines 1 dQ 0 1 T dQ < 0
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90% quality, 15 kPa 1 - saturated liquid, 0.7 MPa Pump 4 10% quality, 15kPa Condenser
dQ = T 1
dQboiler + T 1
1 1 1 dQboiler + 1 dQcondenser
dQcondenser = Tcondenser
T Tboiler 1 mass := 1kg h fg := 2066.3 kJ kg kJ kg h fg := 2373.1 kJ kg MPa := 10 Pa T1 := 164.97
6
kJ := 10 J
kPa := 10 Pa
boiler ...
p 1 := 0.7MPa q 1_2 := h fg
deg_C q = h
q 1_2 = 2066.3 kJ kg
h f := 225.94
T3 := 53.97
x 4 := 0.1
h 4 := h f + x 4 h fg
q 3_4 := h 4 h 3
q 3_4 = 1898.48
kJ kg
T_deg_C + 273.15 = T_deg_K int_dQ_over_T := q 1_2 T1 + 273.15 + q 3_4 T3 + 273.15 int_dQ_over_T = 1.087 kJ kg
deg_K
is < 0
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entropy
plot data
2.5
1.5
0.5 0.5
1.5
2.5
1 T
dQ = 0
reversible ...
A -B
dQ = 0 = T 1
dQA + TA 1
1 TB
dQB
A-C
dQ = 0 = T 1
dQA + TA 1
1 TC
dQC
dQB = TB 1
1 TC
dQC
1 T
dQ is independent of
Qrev
T
reversible ... entropy is an extensive property and entropy per unit mass is = S dQrev. = S2 S1
(7.2), W (2.13)
1 T
(7.3)
9/25/2006
example Carnot
Carnot cycle four basic processes: 1. reversible isothermal process in which heat is transferred to or from the T H reservoir 2. reversible adiabatic process in which the temperature of the working fluid decreases from T H to TL 3. reversible isothermal process in which heat is transferred to or from the T L reservoir 4. reversible adiabatic process in which the temperature of the working fluid increases from T L to TH
plot data
1 to 2
2
i := 1 .. 2 Q1_2 dQrev. = S2 S1 = TH T 1
2 to 3 - adiabatic i := 2 .. 3 3 to 4
4 3
1 T
dQrev. = 0 = S3 S2
S3 = S2
2 S
Q3_4 dQrev. = S2 S1 = TL T 1
i := 3 .. 4
4 to 1 - adiabatic
S
1 T
dQrev. = 0 = S1 S4
S1 = S4
i := 4 .. 5
4 T
i := 1 .. 5
S T
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Q = dE + W Q = dU + W
(5.4)
W = F d = p Ads = p dV T ds = du + p v T ds = dh v dp
dH = dU + p dV + V dp QED (7.6)
(7.7)
applicable to BOTH reversible and irreversible processes as they are relationships between state variables
reversible cycle from 1 to 2 to 1 (not labeled) A - B and ... irreversible cycle from 1 to 2 to 1 (not labeled) A - C
2.5
1.5
0.5 0.5
1.5
2.5
A - B reversible ... dQ = 0 = T 1
2
dQA + TA 1
1 TB
dQB
A - C irreversible dQ = T 1
2
dQA + TA 1
1 TC
dQC < 0
inequality of Clausius
dQA + TA 1
2 1 dQB T dQA + TB 1 A
1 TC
dQC > 0
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dQB TB 1
1 TC
dQC > 0
dQB > TB 1
1 TC
dQC
is a property and although calculated for reversible process, is identical between states for irreversible. substitute into inequality above ...
1 1 dSC > 2
1 TC
Q T
S2 S1
equality holds when reversible and when dQ irreversible, the change of T entropy will be greater 1 than the reversible
2
(W 2.14)
dSsystem
dSsurr =
since heat is transferred FROM surroundings, To > T therefore ... dSnet Q thus ... 1
0 T0
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S1 = St + s mi = entropy_of_system_at_time_t i
S2 = St_t + s me = entropy_of_system_at_time_t_plus_t e
S2 S1 = St_t St + s me s mi e i
(7.44)
etc .....
(m_dotese) (m_dotisi)
n n c_v
Q_dot c_v T
(7.49)
= when reversible
d Sc_v = 0 dt
(7.50)
(m_dotese) (m_dotisi)
n n c_v 9/25/2006
(
m_dotese)
(
m_dotisi)
n t n c_v
Q_dot c_v T
(7.54)
= when reversible
d (m s) dt = m2 s2 m1 s1 c_v dt
0
in control volume
(
m_dotese)
dt = (
mese)
n n
(m_dotisi)
dt = (
misi)
n t n
m2 s2 m1 s1 +
(
mese)
(
)
n n
(7.55)
= when reversible
since the temperature over the control volume is uniform at any instant of time
t Q_dot Q_dot c_v 1 c_v dt = dt Q_dot c_v dt = T T T c_v c_v 0 t t
in first integral T can be a function of space (location in c. v.) U(niform) S(tate) => T only dependent on time
(
mese)
(
)
n n
Q_dot c_v dt mi si T
0
(7.56)
= when reversible
10