Chem131 Chapter3

CHAPTER 3
The Second Law of Thermodynamics
SECOND LAW OF THERMODYNAMICS

Experimental observation: All spontaneous processes are irreversible Not all irreversible processes are spontaneous

vacuum plug
yes

vacuum
no

Experimental observation: All spontaneous processes are irreversible Not all irreversible processes are spontaneous water/ice at 0 C
water freezing at -10 C

Experimental observation: All spontaneous processes are irreversible Not all irreversible processes are spontaneous water/ice at 0 C
ice melting at +10 C

Some spontaneous processes have U and H > 0 (e.g., melting of ice at 10 C) Some spontaneous processes have U and H < 0 (e.g., freezing of water at -10 C)

Some spontaneous processes have U and H > 0 (e.g., melting of ice at 10 C) Some spontaneous processes have U and H < 0 (e.g., freezing of water at -10 C)
Issue: First law treats heat (q) and work (w) on an equal footing In reality they are not interchangeable: there are restrictions on how much q can be converted to w

Equivalent statements: (1) Kelvin: heat cannot, by a cyclic process, be taken from a reservoir and converted into work without simultaneously delivering heat from a higher to a lower temperature reservoir.
Hot reservoir, TH
qH
It is not possible to build a cyclic machine that converts heat into work with 100% efficiency! -w
Heat engine

Equivalent statements: (1) Kelvin: heat cannot, by a cyclic process, be taken from a reservoir and converted into work without simultaneously delivering heat from a higher to a lower temperature reservoir. (2) Clausius: In a cyclic process, heat cannot flow from a lower to a higher temperature reservoir without the expenditure of work on the system. Generalization: all natural processes are irreversible.
10

Equivalent statements: (1) Kelvin: heat cannot, by a cyclic process, be taken from a reservoir and converted into work without simultaneously delivering heat from a higher to a lower temperature reservoir. (2) Clausius: In a cyclic process, heat cannot flow from a lower to a higher temperature reservoir without the expenditure of work on the system. Generalization: all natural processes are irreversible. (3) It is impossible to achieve perpetual motion of the second kind, that is, to construct a machine that will convert heat into work isothermally. (4) No heat engine operating between two temperatures can be more efficient than a reversible heat engine operating between the same two temperatures.
Energy of universe is constant, but increasingly unavailable for useful work
11
HEAT ENGINES
A heat engine is a device that operates cyclically to convert heat to useful work.
(1) A substance (normally a gas) is in a container closed by a piston Work (2) The substance is heated and expands, causing a piston to move (work).
Heating
12
HEAT ENGINES
(1) A substance (normally a gas) is in a container closed by a piston (2) The substance is heated and expands, causing a piston to move (work). (3) The substance is then cooled down to the original temperature and the piston returns to its original position.
Cooling
13
HEAT ENGINES
(1) A substance (normally a gas) is in a container closed by a piston (2) The substance is heated and expands, causing a piston to move (work). (3) The substance is then cooled down to the original temperature and the piston returns to its original position. (4) The cycle starts again.
Heating
14
HEAT ENGINES
(1) A substance (normally a gas) is in a container closed by a piston (2) The substance is heated and expands, causing a piston to move (work). (3) The substance is then cooled down to the original temperature and the piston returns to its original position. (4) The cycle starts again.
Cooling
15
HEAT ENGINES
Hot reservoir, TH
qH
The engine: (1) Absorbs some amount of heat qH from a hot reservoir (a hot body such as a boiler) (2) Converts part of it to work (-w) done on the surroundings by, e.g., pushing a piston (3) The difference qH - (-w) = -qC is released back to the surroundings (a cold body such as a condenser ) as heat.
-w Heat engine
qC Important: The reservoirs are large so that their temperature is not affected
16
Cold reservoir, TC
HEAT ENGINES
For a cyclic process
U = 0
Efficiency:
work output per cycle w = = energy input per cycle qH
But...
U = 0 = q + w = q H + q C + w
qH + qC qC = =1+ qH qH
w = qH + qC
17
HEAT ENGINES
Carnots principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures TH and TC
Imagine:
super > rev
18
HEAT ENGINES
Imagine:
super > rev
Hot reservoir, TH Reversible heat engine qH -w
rev
w = qH
qC Cold reservoir, TC
19
HEAT ENGINES
Imagine:
super > rev
Hot reservoir, TH Reversible heat engine qH -w -W QH Super heat engine
rev
w = qH
super
qC Cold reservoir, TC QC
W = QH
20
HEAT ENGINES
Carnots principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures TH and TC Imagine: QH = 1.3 qH 10 cycles of the super engine = 13 cycles of the reversible engine
Hot reservoir, TH Reversible heat engine qH -w -W QH Super heat engine
rev
w = qH
super
qC Cold reservoir, TC QC
W = QH
21
HEAT ENGINES
Hot reservoir, TH Reversible heat pump qH w -W QH Super heat engine
QC
22
HEAT ENGINES
Hot reservoir, TH Reversible heat pump qH QH W qC Cold reservoir, TC

23
Super heat engine
QC
HEAT ENGINES
Carnots principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures TH and TC after 10 cycles of the super engine:
qH = QH
but
super > rev
|W | > |w|
Hot reservoir, TH Reversible heat pump qH QH W qC Cold reservoir, TC
24
Super heat engine
QC
HEAT ENGINES
Carnots principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures TH and TC after 10 cycles of the super engine:
qH = QH
but
super > rev
|W | > |w|
Hot reservoir, TH Reversible heat pump qH QH W qC net work Cold reservoir, TC
25
Super heat engine
QC
HEAT ENGINES
Carnots principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures TH and TC net work come from some energy input U = 0 = q + w = q H + qC must +w but (in 10 cycles of the super-engine): qH = QH Hot reservoir, TH Reversible heat pump qH QH W qC net work Cold reservoir, TC
26
Super heat engine
QC
HEAT ENGINES
Carnots principle: No heat engine can be more efficient than a reversible heat engine when both engines work between the same pair of temperatures TH and TC net work come from some energy input U = 0 = q + w = q H + qC must +w the energy input must come from the cold reservoir... Hot reservoir, TH Reversible heat pump qH QH W qC net work Cold reservoir, TC
27
Super heat engine
QC
HEAT ENGINES
net work come from some energy input U = 0 = q + w = q H + qC must +w the energy input must come from the cold reservoir... NOT POSSIBLE BECAUSE VIOLATES THE KELVIN STATEMENT Heat cannot, by a cyclic process, be taken from a reservoir and converted into work without simultaneously delivering heat from a higher to a lower temperature reservoir.
Hot reservoir, TH Reversible heat pump qH QH W qC net work Cold reservoir, TC

28
Super heat engine
QC
HEAT ENGINES
net work come from some energy input U = 0 = q + w = q H + qC must +w the energy input must come from the cold reservoir... NOT POSSIBLE BECAUSE VIOLATES THE KELVIN STATEMENT Heat cannot, by a cyclic process, be taken from a reservoir and converted into work without simultaneously delivering heat from a higher to a lower temperature reservoir.
super > rev
(any engine) (reversible engine)
29
HEAT ENGINES
Two reversible heat engines
wA A = qA,H
B A
Hot reservoir, TH Reversible heat pump qA,H
wB B = qB,H
qB,H
A
qA,C Cold reservoir, TC
B
qB,C
Reversible heat engine
30
HEAT ENGINES
wA A = qA,H
A B
Hot reservoir, TH Reversible heat pump qA,H
wB B = qB,H
qB,H
B
A
qB,C
Reversible heat engine
31
HEAT ENGINES
wA A = qA,H
wB B = qB,H
A = B
All reversible engines operating between two given temperatures must have the same efficiency Hot reservoir, TH Reversible heat pump qA,H qB,H Reversible heat engine
B
A
qB,C
32
HEAT ENGINES
(any engine) (reversible engine)
irrev rev
33
HEAT ENGINES
All reversible engines operating between two given temperatures must have the same efficiency
rev = f (TH , TC )
34
CARNOT CYCLE
P P1 1 isotherm, TH I 2 Hot reservoir, TH qH
P2
qC Cold reservoir, TC V1 V2 V
1) Reversible, isothermal expansion
UI = 0
V2 qI = wI = RTH ln >0 V1
heat adsorbed by the system from the reservoir = work done by the system
35
CARNOT CYCLE
P P1 1 qH 2 Hot reservoir, TH
P2 4 III
isotherm, TC V1 V4 V2 V3 V
3) Reversible, isothermal compression
UIII = 0
qIII = wIII
V4 = RTC ln <0 V3
heat is released by the system = work is done on the system

36
CARNOT CYCLE
P P1 1 qH 2 adiabat 4 II 3 qC Cold reservoir, TC V1 V4 V2 V3 V Hot reservoir, TH
P2
2) Reversible adiabatic expansion
qII = 0
wII < 0
UII = +wII = CV (TC TH )

work done by the system
37
CARNOT CYCLE
P P1 1 qH 2 adiabat IV 4 3 qC Cold reservoir, TC V1 V4 V2 V3 V Hot reservoir, TH
P2
4) Reversible adiabatic compression
qIV = 0
wIV > 0
UIV = +wIV = CV (TH TC )

work done on the system
38
CARNOT CYCLE
P P1 1 isotherm, TH I adiabat IV 4 III II 2 adiabat 3 qC Cold reservoir, TC V3 V Hot reservoir, TH qH
P2
isotherm, TC V1 V4 V2
U around the cycle is zero
39
CARNOT CYCLE
P2
w = (wI + wII + wIII + wIV ) = RTH ln
The net work is done by the gas on the surroundings
V2 V1
+ RTC ln
V4 V3
40
CARNOT CYCLE
P2

adiabatic process for a perfect gas
V2 V1
T2 = T1
V1 V2
R/CV
TH V2
R/CV
= TC V3
R/CV
+ RTC ln
V4 V3
TH V1
R/CV
= TC V4
R/CV
41
CARNOT CYCLE
P P1 1 isotherm, TH I adiabat IV 4 III II 2 adiabat 3
TH V2
R/CV
= TC V3
R/CV
TH V1
R/CV
= TC V4
R/CV
P2
V2 V3 = V1 V4

V2 V1
+ RTC ln
V4 V3
w = RTH ln
V2 V1
+ RTC ln
V2 V1
42
CARNOT CYCLE
TH V2
R/CV
= TC V3
R/CV
TH V1
R/CV
= TC V4
R/CV
P2
V2 V3 = V1 V4

V2 V1
+ RTC ln
V4 V3
w = R(TH TC ) ln
V2 V1
43
CARNOT CYCLE

We know:
P2
w = R(TH TC ) ln
q = qI
V2 V1
w R(TH TC ) ln(V2 /V1 ) = = qI RTH ln(V2 /V1 )
TH TC = TH
44
CARNOT CYCLE

We know:
P2
w = R(TH TC ) ln
q = qI
V2 V1
w R(TH TC ) ln(V2 /V1 ) = = qI RTH ln(V2 /V1 )
TH TC = <1 TH
45
CARNOT CYCLE
P P1 1 isotherm, TH I adiabat IV 4 III II 2 adiabat 3 We know:
Ucycle = 0
P2
qcycle = wcycle
qcycle = qI + qIII
V
isotherm, TC V1 V4 V2 V3
TH TC w qI + qIII = = = TH qI qI
qI + qIII TH TC = qI TH
46
CARNOT CYCLE
P P1 1 isotherm, TH I adiabat IV 4 III II 2 adiabat 3 We know:
Ucycle = 0
P2
qcycle = wcycle
qcycle = qI + qIII
V
isotherm, TC V1 V4 V2 V3
TH TC w qI + qIII = = = TH qI qI
qI + qIII TH TC = qI TH
qIII qI + =0 TC TH
47
CARNOT CYCLE
P2
Carnots cycle
qIII qI + =0 TC TH
48
ENTROPY
49
ENTROPY
Sum of Carnot cycles
cycle
qrev =0 T
In the limit of an infinite number of Carnots cycles
qrev =0 T
qrev = state function T

50
ENTROPY
Sum of Carnot cycles
cycle
qrev =0 T
In the limit of an infinite number of Carnots cycles
qrev =0 T
qrev dS = T
S =
state 2
state 1
qrev = S2 S1 T
51
ENTROPY
qrev dS = T
S =
state 2
state 1
qrev = S2 S1 T
qrev
is not an exact differential
is not a state function
qrev T
is an exact differential
is a state function
52
ENTROPY
Calculation of entropy change - Pure substance
qrev dS = T
dU = q + w q = dU + Pext dV qrev = dU + P dV
S (V, T )
53
ENTROPY
qrev dS = T
S (V, T )
dS =
S T
dT +
V
S V
dV
T
qrev = dU + P dV
dU P dS = + dV T T
54
ENTROPY
dS =
S T
dT +
V
S V
dV
T
dU P dS = + dV T T
dU =
U T
but...
dT +
V
U V
dV
T
1 dS = T
U T
1 dT + T
U V
P dV + dV T
55
ENTROPY
1 dS = T
U T
1 dT + T
U V
P dV + dV T
CV P 1 dS = dT + + T T T
U V
dV
56
ENTROPY
CV P 1 dS = dT + + T T T S T
U V
dV
dS = S T S V CV = T
dT +
V
S V
dV
T
P 1 = + T T
U V
dV
57
ENTROPY
S T
CV = T
S V
P 1 = + T T
U V
dV
for a state function
2 f (x, y ) 2 f (x, y ) = x y y x
S T
= T
S V
T V
58
ENTROPY
S T
CV = T
S V
P 1 = + T T
U V
dV
S T
= T
S V
T V
1 T
U T
= T
P 1 + T T
U V
T V
59
ENTROPY
1 T
U T
= T
P 1 + T T
U V
T V
1 U 1 P P 1 = 2 2 T V T T T T T
2
U V
1 + T
U T V
1 T
P 1 + T T
U V
1 = T
P T
V
60
ENTROPY
1 T
P 1 + T T
U V
1 = T
P T
S V
P 1 = + T T
U V
dV
S V
=
T
P T
61
HOW TO CALCULATE ENTROPY CHANGES

S for an isothermal expansion of a perfect gas from V1 to V2 at temperature T
dS =
S T
dT +
V
S V
dV dS =
T
S T
dT +
V
P T
dV
V
dS =
P T
dV
V
Perfect gas
P V = nRT
P T
nR = V
62

dS =
S T
dT +
V
S V
dV dS =
T
S T
dT +
V
P T
dV
V
P T
nR = V
S = n R
V2
V1
dV V
V2 S = n R ln V1
independent of the path
63

S for a process occurring at constant volume
dS =
S T
dT +
V
S V
dV dS =
T
S T
dT +
V
P T
dV
V
dS =
S T
dT
V
From last lecture...
S T
CV = T
dS =
S T
CV dT = dT T
64

S for a process occurring at constant volume
dS =
S T
dT +
V
S V
dV dS =
T
S T
dT +
V
T2
P T
dV
V
dS =
S T
CV dT = dT T
S =
T1
dT CV T
T2 S = CV ln T1
(assuming the CV is independent of T)
65
FEW OTHER DEFINITIONS & RELATIONS

qrev dS = T
But...
dU P dS = + dV T T
H = U + PV
dH = dU + P dV + V dP
dU = dH P dV V dP
dH V dP dH P dV V dP P dV dS = dS = + T T T T T T
66

qrev dS = T
But...
dU P dS = + dV T T
H = U + PV
dH = dU + P dV + V dP
dU = dH P dV V dP
dH V dP dS = T T
67

dH V dP dS = T T
But...
dH = CP =
H T H T
dT +
P
H P
dP
T
CP V 1 H dS = dT + + dP T T T P T
68

CP V 1 H dS = dT + + dP T T T P T dS = S T dT +
P
S P
dP
T
S (T, P )
69

CP V 1 H dS = dT + + dP T T T P T dS = S T dT +
P
S P
dP
T
S T S P
CP = T V 1 = + T T H P
70

dS = S T S P CP = T V 1 = + T T H P
not measurable
S T
dT +
P
S P
dP
T
S T
P T
= T
S P
T P
71

dS = S T S P CP = T V 1 = + T T H P
not measurable
S T
dT +
P
S P
dP
T
1 = V
P thermal expansion
V T
S P
V T
= V
72

dS =
S T
dT +
P
S P
dP
T
dS =
S P
dP =
V T
dP
P
Perfect gas
P V = nRT
V T
nR = P
73

dS =
S T
dT +
P
S P
dP
T
V T
nR = P
dP dS = n R P RT /V2 dP S = n R P RT /V1
V2 S = n R ln V1
independent of the path
74

S for a process occurring at constant pressure
dS =
S T
dT +
P
S P
dP
T
S T
dS =
P
CP = T
S T
CP dS = dT dT T
S =
T2
T1
T2 dT CP S = CP ln T T1
75

S for a perfect gas from (V1, T1, P1) to (V2, T2, P2) We can use either S(T,V) or S(T,P)
dS =
S T
dT +
V
CV dS = dT + T P T nR = V
S V
P T
dV
T
dV
V
CV nR dS = dT + dV T V
T2 V2 S = CV ln + nR ln T1 V1
76

S for an adiabatic reversible expansion of a gas
Pext P1, V1
S =?
T1 P2, V2 T2 V
qrev dS = T
q = qrev = 0
S = 0
77

S for an adiabatic irreversible expansion of a gas
Pext P1, V1
S =?
T1 P2, V2 T2 V
qrev dS = T
q = qirrev = 0
S = 0
S must be calculated over a reversible path that connects the initial and final states of the irreversible adiabatic expansion
78
THERMODYNAMIC TEMPERATURE SCALE

Up to now, ideal gas temperature scale depends on the substance We should not have to rely on any particular substance or eq. of state to define a temperature Carnots cycle (independent of the substance)
rev
qC =1+ = f (C , H ) qH
qC C = qH H
Choose a reference temperature (triple point of water)
|q | = tr |qtr |
tr = 273.16
|q | T = 273.16K |qtr |
79
REVERSIBILITY & IRREVERSIBILITY

Suniv = Ssys + Ssurr
Reversible processes
dSuniv = dSsys + dSsurr
qsys qsurr = + Tsys Tsurr qrev qrev = + Tsys Tsurr
system qrev
Tsys = Tsurr
surroundings
Suniv = 0
80

Irreversible adiabatic processes (closed system) P reversible isotherm, T 1 2 reversible adiabat 3 2 V
1 irreversible adiabat
81

Irreversible adiabatic processes (closed system) P 4 reversible isotherm, T 3 reversible adiabat
S12 + S23 + S34 + S41 = 0

reversible adiabats reversible adiabat
S23 = S41 = 0
1 irreversible adiabat 2 V
dU =
S12 = S34
q34 = T
( q + w) = q34 + w = 0
q34 > 0
w = q34
Not possible! it violates the 2nd law of thermodynamics (Kelvins statement)

82

S12 + S23 + S34 + S41 = 0

S23 = S41 = 0
dU =
S12 = S34
q34 = T
( q + w) = q34 + w = 0
S12 0
w = q34
83

S12 + S23 + S34 + S41 = 0

S23 = S41 = 0
dU =
S12 = S34
q34 = T
( q + w) = q34 + w = 0
S12 = 0
w = q34
S12 > 0
84

Irreversible adiabatic processes (closed system)
S > 0
Irreversible adiabatic processes (isolated system)
S > 0
The universe can be considered as an isolated system
Suniv = Ssys + Ssurr > 0

Suniv 0
irreversible process
85
MOLECULAR CONNECTION
T U molecular kinetic energy all energies [kinetic, potential (electronic, vibrational, rotational, nuclear, ...)]
dqrev dS = T
Higher S
more probable states
86
Higher S more probable states
A more uniform distribution much more probable than a very uneven one
=
probability ? probability ? probability ? probability ?
1/4
1/4
probability
1/4 1/2
1/4
87
=
probability probability probability
1/4
1/2
1/4
macroscopic states
A macroscopic state is associated with many microscopic states
88
=
probability probability probability
1/4
1/2
What is a microscopic state? Depends on the system
1/4
For an ideal gas If you know at an instant of time where every molecule is and what its velocity is you have the full microscopic state
89
Some macroscopic states have many more microscopic states consistent with it (e.g, same P, T, components)
Let p = probability of a thermodynamic state
number of microstates consistent with a given thermodynamic state p= total number of microstates
S = k ln p
k = Boltzmanns constant true for anything
entropy is associated with the microscopic states of highest probability

90
S = k ln p
S order / disorder
more disorder more probable more microstates
p2 S = k ln p1
difficult !!!
S =
qrev T
91
S = k ln p
order / disorder
92

Chem131 Chapter3

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Chem131 Chapter3

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CHAPTER 3

The Second Law of Thermodynamics

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

water freezing at -10 C

SECOND LAW OF THERMODYNAMICS

ice melting at +10 C

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

SECOND LAW OF THERMODYNAMICS

Energy of universe is constant, but increasingly unavailable for useful work

work output per cycle w = = energy input per cycle qH

super > rev

super > rev

Hot reservoir, TH Reversible heat engine qH -w

super > rev

Hot reservoir, TH Reversible heat engine qH -w -W QH Super heat engine

Hot reservoir, TH Reversible heat engine qH -w -W QH Super heat engine

Hot reservoir, TH Reversible heat pump qH w -W QH Super heat engine

Hot reservoir, TH Reversible heat pump qH QH W qC Cold reservoir, TC

Super heat engine

super > rev

Super heat engine

super > rev

Super heat engine

Super heat engine

Super heat engine

Hot reservoir, TH Reversible heat pump qH QH W qC net work Cold reservoir, TC

Super heat engine

super > rev

(any engine) (reversible engine)

Reversible heat engine

Reversible heat engine

(any engine) (reversible engine)

1) Reversible, isothermal expansion

3) Reversible, isothermal compression

heat is released by the system = work is done on the system

2) Reversible adiabatic expansion

UII = +wII = CV (TC TH )

4) Reversible adiabatic compression

UIV = +wIV = CV (TH TC )

U around the cycle is zero

w = (wI + wII + wIII + wIV ) = RTH ln

The net work is done by the gas on the surroundings

w = (wI + wII + wIII + wIV ) = RTH ln

The net work is done by the gas on the surroundings

w = (wI + wII + wIII + wIV ) = RTH ln

The net work is done by the gas on the surroundings

w = (wI + wII + wIII + wIV ) = RTH ln

The net work is done by the gas on the surroundings

work output per cycle w = = energy input per cycle qH

w R(TH TC ) ln(V2 /V1 ) = = qI RTH ln(V2 /V1 )

work output per cycle w = = energy input per cycle qH

w R(TH TC ) ln(V2 /V1 ) = = qI RTH ln(V2 /V1 )

In the limit of an infinite number of Carnots cycles

qrev = state function T

In the limit of an infinite number of Carnots cycles

is not an exact differential

is not a state function