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Problem 1

1 2 Q 1 Q 2 T 10 T 20 W T f Let 
1
2
Q
1 Q
2
T 10
T 20
W
T
f
Let
 final equilibrium temperature of both bodies

Note that for constant mass and volume

dU NC dT

v

so

 U 1  Q 1  W 1  N 1 C 1 

U1 Q1 W1 N1C1 Tf T10

 U 1  Q 1  W 1  N 1 C 1  T

and

U2 Q2 W2 N2C2 Tf T20

Connect body 1 to body 2

via a Carnot engine

For the composite system, bodies 1 and 2 and the (cyclic) engine,

Since

N

1

N

  U Q  W W  U  1  N 2
 
U
Q
W
W

U

1
 N
2

U

2

C

1

 U eng  C  C 2

U
eng
 C
 C
2

W NC2Tf T10 T20

 C  C 2 W  NC  2T f  T 10  T

W

Maximum attainable work requires that all processes be reversible, so

S

dS

univ

S S S S

1

2

eng

T 1

dU

T P

dV

dS

T f

T

10

1 2 eng  T 1 dU  T P dV dS    T

dN

dU

 T 1 dU  T P dV dS    T f T 10

surr

0

T

1

T

S

2

dT

T

T

f

T

20

const. V, N

S

1

NCln

NC

NCln

S S 0

1

2

ln

T

f

T

10

ln

T T

f

20

T   T T  

f

10 20
10
20

0

This temperature is the minimum attainable equilibrium temperature. Any further

decrease in T f would result in

S

0 (which is impossible).

univ

Clearly, this is not the maximum attainable temperature since we can take some of or all of the produced work and return it to either body.

Note that

min

T

f

W max

will yield

NC

  

2

T

10

W

T

20

max

1

2

.

T

10

T

20

  

Any higher value of T f , yields smaller magnitude of W. Any lower value of T f , while increasing W, violates the 2 nd Law.

Now, consider a process in which there is no net change in the environment. Work is no longer produced, and there is no heat interaction with the environment. This is equivalent to isolating the two bodies and letting heat flowbetween them irreversibly.

Now

letting “ heat flow ” between them irreversibly. Now  U  U  Q 

U U Q W 0

1

2

NCTf T10 NCTf T20 0

T

f

1

2

T

10

In this case,

  

S

S

1

Now

T

T

T

T

10

T

2

10

4T T 0

20

10

20

20 2

2T T

10

20

20

2

S 0

2

10

T

so

S

2

and

irrev

T

f

f rev

T

T

20

NC ln

for all

2

T

f

T

10

T

20

T

10

, T

20

NC ln

T

10

T

20

2

4T T

10

20

(as expected for irreversible process)

(Note that

Hence, we have verified via the 2 nd Law the known mathematical result that the arithmetic mean is greater than the geometric mean.)

irrev

T

f

is the arithmetic mean and

rev is the geometric mean of T 10 and T 20 .

T

f

irrev

T

f

1

2

T

10

T

20

is the maximum attainable temperature. Any increase in

irrev

T

f

,

although it would yield a further increase in S , would fail to satisfy the 1 st Law.

C  8 J /g K T  373K T  273K 10 20 
C  8 J /g K
T
 373K
T
 273K
10
20
1
min
o
max
T
T
T
319K
46 C
T
T
T
f
10
20
 
f
10
20
 
2
W max
1
W max
 C 
 
2
T
T
2 
T
T

62.3 J/g
10
20
10
20
N
 
 
N
 

323K

o

50 C

 

Alternative method: To obtain the maximum possible work output let the heat engine operating between the two bodies be a (reversible) Carnot engine, whose upper and lower temperatures are the instantaneous temperatures of the two bodies (thereby ensuring reversible heat transfer between the engine and the two objects). Now, for the Carnot engine

T Q

H

H

T Q

C

C

 

0

T Q

1

1

T Q

2

2

Q

1

 

Q

H

Q

2

 

Q

C

But,

dU Q NCdT

1

1

1

and

dU

2

Q NCdT

2

2

(constant volume, mass)

So,

NCdT

1

T

1

NCdT

2

T

2

ln

T f

T 10

ln

T

f

T

20

0

T f dT T f  0  1   or T 1 T
T
f
dT
T
f
 0
1
 
or
T
1
T 10
T 20
T  T T 
f
10
20

Now for each infinitesimal Carnot cycle,

dT

2

T

2

0

(same result as before)



 W

T

1

T

2

Q

H

T

1

T

1

T

2

W

 

Q

1

T

1

T

2

T

1

 

Q

1



Q

1

T

2

T

1

 

Q

1



Q

2

(also follows from 1 st Law for engine)

W NC(dT dT )

1

2

Thus,

W NC2Tf T10 T20

(same result as before)

Problem 4.5

To maximize the produced work, the air in each cylinder should be brought to the conditions of the environment (i.e., the final state should be described by T atm , P atm ). To accomplish this, consider the following two step process:

Step 1: contact cylinder with Carnot engine to decrease initial temperature, T i , to final temperature of the atmosphere, T a , at constant volume

T i P i Q H1
T i
P i
Q
H1

W 1

Q C1 T a Let signs of Q H1 , Q C1 be defined for
Q C1
T a
Let signs of Q H1 , Q C1
be defined for Carnot engine

For cylinder:

of Q H1 , Q C1 be defined for Carnot engine For cylinder: dU  Q

dU QW

(constant volume)

dU NC dT

v

(constant volume, mass)

U NCv Tf Ti Q

but T f = T a

(constant C v )

Q QH1 QH1 NCv NCv Ti Ta Ta Ti

To obtain maximum value of W 1 , entire process must be reversible

S

cylinder

S

surr

cylinder: const V, N

S dS
S
dS

so

or

S

cyl

NC

v

lnT / T

a

i

NC ln

v

T T

a

i

Q T

C1

a

0

Q

C1

NC T lnT /T

v

a

a

i

Carnot

N

S

C v

T

dT

univ

S

0



surr

1 st Law for Carnot engine:

W

1

Q

H1

Q

C1

NC

NC

v

v

T

i

T

i

NC T

v

a



T

a

T

a

T i

T a

NC T

v

a

NC T

v

a

ln T

a

/ T

i

ln T / T

i

a

1

ln

T

i

T

a

 

Q

C1

T

a

  



Note that

 

ln

  

W T

1 T

NC T

v

a

i

a

1

T

i

T

a

 

 

W 1 0

(work produced by engine) for both

T

i

T

a

1

and

T

i

T

a

1

.

Alternative method: For the Carnot engine

But as

W Q Q

1

H1

Q

H1

Q

C1

T

T

a

0

C1

where T is the instantaneous temperature of the air in the cylinder, we have that

 W

1

 Q

H1 T

T

a

T

For the cylinder,

Thus,

W

1

NC

v

dU NC dT Q

v

   T

   T

T

T

a

  

dT

H1

(constant volume, mass)

With the temperature of the air starting from T i and ending at T a , we find that

W T

v

T

a

i

1 NC

NC T ln

v

a

T a

T

i

NC T

v

a

ln

     

T

i

T

a

1

T

i

T

a

  

which is the same result obtained previously.

Step 2:

Connect cylinder, now at T a , to an isothermal turbine

Note that after 1 st step, pressure of the cylinder has changed.

Step 1:

so let

PV NRT

i

i

P V

f

NRT

a

P

2i

P

f

P

i

  

T a  

T

i

P

f

P

i

  

T a

T i  

By connecting the cylinder with the turbine, change P 2i to P a. (In general, we may have P 2i greater than or less than P a . So air will flow out of or into cylinder until the pressures are equal).

T a P 2i W 2  P P 2i a First assume
T
a
P
2i
W
2
 P
P 2i
a
First assume

P a

T a

Eq. (4-77) and (4-78) in (TM)

W

2



n

out

in

VdP

V

RT

a

P

Note that work is always

produced

or

W

2

0

if

P

a

P

2i

P

2i

P

a

tank and turbine are isothermal

unit mass n is expanded at T a to P a

W

2



n

P a RT

P

t

a

P

t

dP

t

P

t

is instantaneous pressure inside cylinder

but

W n dN nRT ln P / P

2

a

tank

a

t

P V N

t

t

tank

RT

a

so

dN

tank

  V ln P a dP W 2 t t P t P a

V
ln
P
a dP
W 2
t
t
P
t
P a
P
t
V
ln
dP
W 2
 
t
t
P
a
P 2i
pressure at
beginning
of Step2
P
a
 P
V
P ln P
P ln P
W 2
t
t
t
t
t
a
P 2i
 
V
P ln P
P
P ln P
P
t
a
a
a
a
a
2i
V
P
ln
P 
a 
P
P
 
t
2i
2i
a
P
2i

ln P

2i

V

t

RT

a

dP

t

P

2i

P

2i

ln P

a

const V

const T

t

a

but

P

2i

P

i

 

T

a

T

i

 

Now, let us assume that

P

2i

P

a

W

2



n

out

in

VdP

P

t

P

a

RT

a

P

t

dP

t

(air flows into cylinder)

W nRT ln P / P W V ln P / P dP

2

but now

2

t

a

t

t

 

n

a

a

dN

t

tank

V

t

RT

a

W 2

V

t

P

a

ln

P 2i

a   

P

t

dP

P t

V

t

P

2i

ln

P

a

P

2i

dP

t

P

2i

P

a

  

which is the same as before

W

2

P

2i

V

t

ln

P

a

P

2i

 

1

P

a

P

2i



 

Note that

W

2

0

(work produced by turbine) for both

Letting



W

2

P

2i

PV

i

t

 

P

i

 

T a

 

T

i



 

T P

a

ln

a

T

i

T PT

i

i

a

 

1

P T

a

i

PT

i

a

 

 

P a

P

2i

Therefore, total work is

W W

1

2

, so

W

max

t

NC T

v

a

ln

T

i

T

a

   

1

T

i

T

a

  

PV

i

t

but N from Step 1 is given by

N

PV RT

i

t

i

 

T

a

T

i

  

ln

P T

a

i

PT

i

a

   

1

P T

a

i

PT

i

a

and P

2i

  

P

a

so

e.g.

V

t

W

max

t

1

m

3

PV

i

t

T

i

400K

  

T

a

T

i

   

C

v

R

R

  
   

ln

T

i

T

a

T

  T

1

i

a

C

v

20.7 J / mol K

5

P 8x10 N / m

i

2

ln

P T

a

i

PT

i

a

 

1

P T

a

i

PT

i

a

T

a

300 K

5

P a 10 N / m

2

price $0.32

T 4 P T 1 4 1 i  a i   T 3
T
4
P T
1
4
1
i
a
i
T
3
PT
8
3
6
a
i
a
W 
max
6.43x10 J 
5
thus
t
W
max
6 J
kJ
 
t
2.01x10
2010
or unit cost

price

$

$

0.56 kW-h/$

 

 

This corresponds to 1.8 $/kW-h, which is rather expensive, given that residential electricity rates average around 25 cents/kW-h.

Let us redo the problem by treating the process in “one-step” by choosing the tank+turbine as the system, in which there is a single net heat interaction and a single net work interaction. (Since the max, or min, work is a state function, the final result should not depend upon the path that was taken.)

result should not depend upon the path that was taken.) in or out Q W W
result should not depend upon the path that was taken.) in or out Q W W
result should not depend upon the path that was taken.) in or out Q W W
result should not depend upon the path that was taken.) in or out Q W W
result should not depend upon the path that was taken.) in or out Q W W

in or out

should not depend upon the path that was taken.) in or out Q W W Q
Q W W Q Q
Q W
W
Q
Q

Now, the system (tank+turbine) is an open system, so

dU

sys



Q



W

H dN

a

sys

If air flows into the system, the enthalpy of the stream is that of the surroundings, H a . If air is discharged to the surroundings, it must be discharged at the same temperature and pressure of the surroundings, so that H out = H a , to maximize the produced work (i.e., the air in the cylinder should be brought to the conditions of the environment).

Since H a is constant, the 1 st Law becomes

U

sys

Q

W

H

a

N

sys

Now consider the entropy balance, with reversible operation (i.e., zero entropy generation),

So

 Q   S *    S dN sys T a sys
Q
 
S
*
 S dN
sys
T
a
sys
a

dS

S

sys

Q

T

S

a

N

sys

Thus,

a

outlet or inlet stream has S= S a

 

Q

T

a

S

sys

T S

a

a

N

sys

Substituting the above into the 1 st Law yields

W 



U

U

sys

sys

N

f

sys

 

H

 

T

a

a

U

f

sys

N

sys

S

H

sys

a

 

T

a

N

T S

a

a

S

sys

sys

H

a

S

a

S

f

sys

T S

a

 

a

N

sys

N

i

sys



T

a

 

U

i

sys

H

a

T

a

S

a

S

i

sys

Now,

Also,

U

U

f

sys

i

sys

Therefore,

  H H

a

a

 RT C T C T

v

i

a

P

a

W



sys f

N

RT

a

sys i

N

 

and

S

a

S

sys

f 0

(same conditions)

sys

a

C

P

C T

P

a

ln

ln

T

a

T

i

T

a

T

i

R

ln

RT

a

P

a

P

i

ln

and

C T

v

i

S

a

S

i

C T

P

P

a

P

i

 

 

which upon further substitution and rearrangement yields the same expression as before

W

PV

i

t

  

T

a

T

i

   

C

v

R

  

ln

T

i

T

a

     

  1

T

i

T

a

ln

P T

a

i

PT

i

a

  

1

P T

a

i

PT

i

a

 

 

We can redo the problem in another manner as well. Instead of allowing flow across a turbine, we can imagine that the gas in the tank is connected to an expander/compressor in which the gas, treated as a closed system, is allowed to expand or contract until its final pressure and temperature are equal to that of the surroundings.

Now, the 1 st Law for a closed system requires that

U Q W

But now

W W

net

W

atm

where

recovered by the process. Note that

produced. (We do not simply allow the gas to freely expand against or be contracted by the atmosphere. The pressure difference between the system and the atmosphere can be exploited to generate work.)

W

atm

is the work done on the atmosphere and

W W W

net

atm

W

net

0

is the net work that can be , which is the net work

For reversible operation,

 

S

S



S

surr

Q

surr

T

a

0

0

 

S

Q

T

a

0

so

Q T S

a

Thus,

W

U

NC

 

v

Now,

Q

T

a

  

T

i

U

T

a

NT

a

S

 

C

p

ln

W atm

 

P

a

V

atm

P

a

V

 

NP

a

T

a

T

i

R

ln ln

P

a

P

i

 

 

RT

a

P

a

RT

i

P

i

  

NR

  

T

a

T

i

P

a

P

i

  

So, with

W W W

net

atm

, we find that

W

net

NRT

a

NRT

a



C

v

R

C

v

R

1

1

T

i

T

a

T

i

T

a

C

p

R

ln

T

a

T

i

ln

P

a

P

i

 

1

PT

a

i

PT

i

a

ln

T

i

T

a

ln

PT

a

i

PT

i

a

 

1

PT

a

i

PT

i

a




With

NR PV /

i

i

T , we recover the same expression as before, with

i

V V

i

t

.

Note that the closed system, which can either be compressed or expanded, always yields

W 0

net

. But why?

When expanded, some of the work done by the gas must be lost in pushing back the

atmosphere, that is

magnitude is smaller than the magnitude of W). When the gas is compressed, so that

W atm

takes away from what is produced by the gas (though its

W 0 , we now have that

W

atm

0

, in which

W

atm

W

. We recover the excess work

(over W) done by the atmosphere, which arises due to the reversible operation of the process. This difference in the two works again leads to a net production of work for the process.

Note that in the open system analysis,

incoming or outgoing stream, which includes the work required for the outgoing stream to push back the surroundings or the work required for the incoming stream to push itself into the system.

W atm

is accounted for by the H a term for the

The idea of removing the work done by the atmosphere to yield the net work that can be recovered by the expansion/compression is a subtle concept. We can proceed in even

another way that avoids the need to explicitly determine

the system (which is again closed) and the atmosphere as our combined system (which is also a closed system). All heat interactions are therefore internal, i.e., between the system and atmosphere only. While the total volume is fixed, there is still work being delivered to some external agent, so the combined system is not isolated (although adiabatic). So,

W net

. For example, let us treat

U U U

sys

atm

For example, let us treat  U  U  U sys atm  Q 

Q W

Note that

U

atm

Q

atm

and

But with

U

Q

sys

sys

Q

sys

Q

atm

W

atm

W

sys

(acts as both a pressure and thermal reservoir)

we see that

W

sys

W

atm

W

(where W is equal to

by the atmosphere, which cannot be recovered, is automatically accounted for)

W

net

in the previous analysis; in this approach, the work done on or

Now,

U

W atm

atm

Q

atm

W

atm

P V P V

a

atm

a

sys

For reversible operation,

S S

sys

atm

0

Finally,

with

S

atm

Q atm

T

a

W U U

sys

then

atm

U

Q

T S

a

T S

a

sys

sys

atm

atm

T S P V

a

sys

a

sys

which leads to same expression as before

Whether we apply an open system, or closed system analysis, the net effect of each process is the same, where air is taken from some initial state to a final state with the same conditions as the surroundings. Hence, it is encouraging (though of course expected if all had been done correctly) that both analyses yield the same result.

Problem 4.10 (TM)

constant P 757 cm 3 /min 343.2 K T f 1514 cm 3 /min 283.2
constant P
757 cm 3 /min
343.2 K
T
f
1514 cm 3 /min
283.2 K
T
f
W

We can allow reversible heat transfer between the hot and cold streams via the use of a Carnot engine (or series of Carnot engines) to generate work. The maximum power that can be produced will be generated when the two streams are brought to the same final temperature.

So begin by first determining the maximum power output from the thermal contact (via the use of a Carnot engine) of the hot and cold streams. A steady-state 1 st Law balance and entropy balance, for complete reversible operation and with the Carnot engine included within the system, yield the following

0

0

Q  W   H    h in , W  
Q
W
H
h in
,
W
H
H
h in
,
h out
,
Q
S
*
S
T
h in
,

H

h out

,

n   H  H  n h c in , c out ,
n
H
H
n
h
c in
,
c out
,
c

n   H  H  2 n h c in , c out
n
H
H
2 n
h
c in
,
c out
,
h
n 
2
n
c
h

S

h out

,

  S  S  2 n c in , c out , h
S
S
2
n
c in
,
c out
,
h

n

h

So,

Sh,in Sh,out 2Sc,out Sc,in

For constant pressure and a constant isobaric heat capacity, along with

above implies that

or

C

P

T

f

ln

T

h in

,

T

f

2

C

P

T

h in

,

2

T

c in

,

1/3

ln

T

f

T

c in

,

301.9 K

  T S   

P

C P

T

, the

Now return to the first law balance, which for constant pressure and constant C P yields

n  H  H    H  H  2 n h
n
 H
H
H
H
2 n
h
h out
,
h in
,
c out
,
c in
,
h

W

  

n

h

C

P

T

f

n C

h

P

3

T

f

T

h in

,

T

h in

,

2

2 C

P

T

c in

,

T

f

0

T

c in

,

 

This power output can now be used to run a Carnot refrigerator that operates between the environment at 10 o C and the cold water stream entering component B. (While this power output can be directly dissipated into the cold water stream entering B, a higher rate of energy transfer into the cold stream will occur through the use of the Carnot engine.)

B work T
B
work
T
occur through the use of the Carnot engine.) B work T 283 K T out work
283 K T out work T
283 K
T out
work
T

With the Carnot engine again defined to be part of the system, as the diagram on the right indicates, the 1 st Law and entropy balance become

So,

Hence,

0

0

Q  W   H   ,in in Q S *  
Q
W
H
,in
in
Q
S
*
S
T
in

H

out

n h
n
h

S

out

reversible operation  S  T in   H out  n h S out 

 H  H  n  Q  W  Q  W out
H
H
n
Q
W
Q
W
out
in
h
,in

work produced by the 1 st Carnot engine

Hout Hin nh TSout Sin nh nhCp 3Tf Th,in 2Tc,in

n h C p  3 T f  T h , in  2 T

C

p

T

out

T

out

T

c in

,

T

c in

,

T

ln

T C

p

T

out

T

c in

,

ln

T

out

T

c in

,

 

T

h in

,

3

C

2

p

T

c in

,

T

f

3

T

h in

,

2

T

c in

,

T

h in

,

2

c in

,

T

1/3

 

T

out

332.2 K

The electrical heater now only needs to warm the incoming hot stream from 332.2 K to 343.2 K. A 1 st Law balance on the electrical heater indicates that the required power is

W heater

,

757 cm /min

H

H

3

in

n n C  T h h P h in ,
n
n C
T
h
h
P
h in
,

1 min/60 s

out

T

out

1 g/cm

3

1 mol/18 g



9.07



8.314 J/mol-K



11 K

581.4 W

We can improve the process in the following manner, requiring even less electrical energy than before. Note that after the hot and cold water streams are brought into thermal contact via a Carnot engine they achieve a final temperature of 301.9 K. The surroundings, however, are at a lower temperature of 283.2 K. We can therefore, through the use of another Carnot engine, lower the temperatures of these two exiting stream to be that of the environment, generating an even greater work output than before.

T f 283.2 K work T
T f
283.2 K
work
T

With the Carnot engine again being part of the system, an entropy balance (with reversible operation) indicates that

Q   3 n T  S  S   3 n T
Q 
3 n T
S
S
3
n T C
ln
T 
3
n T C
ln
T c in
,
h
out
in
h
P
h
P

T

f

T

f

A 1 st Law balance yields the following additional power output

0

Q  W  , extra
Q
W
, extra

H

in

 W  3 n  C  T  , extra h P c
W
 3
n
C
T
,
extra
h
P
c in
,


H

out

3

n h
n
h

T

f

T C

P