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# Chapter 2: Heat, Work, Internal Energy, Enthalpy, and the

## First Law of Thermodynamics

Problem numbers in italics indicate that the solution is included in the
Students Solutions Manual.
!estions on Concepts
2"#\$ Electrical current is passed through a resistor immersed in a liquid in an adiabatic
container. The temperature of the liquid is varied by 1C. The system consists solely of
the liquid. Does heat or wor flow across the boundary between the system and
#lthough wor is done on the resistor\$ this wor is done in the surroundings. %eat
flows across the boundary between the surroundings and the system because of
the temperature difference between them.
2"2\$ E&plain how a mass of water in the surroundings can be used to determine q for a
process. Calculate q if the temperature of 1.''(g water bath in the surroundings
increases by 1.)*C. #ssume that the surroundings are at a constant pressure.
+f heat flows across the boundary between the system and the surroundings\$ it will
lead to a temperature change in the surroundings given by
P
q
T
C

. ,or the
case of interest\$
1 1 -
1''' g ..1/ " g 0 1.)* 0 *.). 1' ".
surroundings P
q q mC T

2"%\$ E&plain the relationship between the terms exact differential and state function.
+n order for a function f1x,y2 to be a state function\$ it must be possible to write the
total differential df in the form
.
y
x
f f
df dx dy
x y
_ _
+

,
,
+f the form df as
written e&ists\$ it is an e&act differential.
2"&\$ 3hy is it incorrect to spea of the heat or wor associated with a system!
%eat and wor are transients that e&ist only in the transition between equilibrium
states. Therefore\$ a state at equilibrium is not associated with values of heat or
wor.
2"'\$ Two ideal gas systems undergo reversible e&pansion starting from the same P and
V. #t the end of the e&pansion\$ the two systems have the same volume. The pressure in
)(1
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
the system that has undergone adiabatic e&pansion is lower than in the system that has
undergone isothermal e&pansion. E&plain this result without using equations.
+n the system undergoing adiabatic e&pansion\$ all the wor done must come
through the lowering of U\$ and therefore of the temperature. 6y contrast\$ some
of the wor done in the isothermal e&pansion can come at the e&pense of the heat
that has flowed across the boundary between the system and surroundings.
2"(\$ # cup of water at )78 0 1the system2 is placed in a microwave oven and the oven
is turned on for 1 minute during which it begins to boil. 3hich of q\$ w\$ and U are
positive\$ negative\$ or 9ero!
The heat q is positive because heat flows across the system(surrounding boundary
into the system. The wor w is negative because the vapori9ing water does wor
on the surroundings. U is positive because the temperature increases and some
of the liquid is vapori9ed.
2")\$ 3hat is wrong with the following statement!: Because te well!insulated ouse
stored a lot of eat, te tem"erature didn#t fall muc wen te furnace failed. ;ewrite the
sentence to convey the same information in a correct way.
%eat can<t be stored because it e&ists only as a transient. # possible rephrasing
follows. 6ecause the house was well insulated\$ the walls were nearly adiabatic.
Therefore\$ the temperature of the house did not fall as rapidly when in contact
with the surroundings at a lower temperature as would have been the case if the
walls were diathermal.
2"*\$ 3hat is wrong with the following statement!: Burns caused \$y steam at %&&'C
can \$e more se(ere tan tose caused \$y water at %&&'C \$ecause steam contains more
eat tan water. ;ewrite the sentence to convey the same information in a correct way.
%eat is not a substance that can be stored. 3hen steam is in contact with your
sin\$ it condenses to the liquid phase. +n doing so\$ energy is released that is
absorbed by the sin. %ot water does not release as much energy in the same
situation\$ because no phase change occurs.
2"+\$ Describe how reversible and irreversible e&pansions differ by discussing the
degree to which equilibrium is maintained between the system and the surroundings.
+n a reversible e&pansion\$ the system and surroundings are always in equilibrium
with one another. +n an irreversible e&pansion\$ they are not in equilibrium with
one another.
)()
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
2"#,\$ # chemical reaction occurs in a constant volume enclosure separated from the
surroundings by diathermal walls. Can you say whether the temperature of the
surroundings increases\$ decreases\$ or remains the same in this process! E&plain.
=o. The temperature will increase if the reaction is e&othermic\$ decrease if the
reaction is endothermic\$ and not change if no energy is evolved in the reaction.
-ro.lems
P2.1\$ -.'' moles of an ideal gas at )7.'C e&pands isothermally from an initial volume
of )'.' dm
-
to a final volume of >'.' dm
-
. Calculate w for this process a2 for e&pansion
against a constant e&ternal pressure of 1.'' ? 1'
*
Pa and b2 for a reversible e&pansion.
a2 ( )
* - - -
1.''?1' Pa? >'.'()'.' ?1' m ..''?1' "
external
w P V

b2
-
1 1 -
-
>'.' dm
ln -.''mol?8.-1. " mol 0 ?-'' 0?ln 8.))?1' "
)'.' dm
f
re(ersi\$le
i
V
w n)T
V

-2"2\$ -.'' moles of an ideal gas are compressed isothermally from >'.' to )'.' 5 using
a constant e&ternal pressure of *.'' atm. Calculate q\$ w\$ U\$ and *.
.
.
).'- 1' "@ ' and '
).'- 1' "
w U *
q

-2"%\$ # system consisting of *7.* g of liquid water at )/8 0 is heated using an
immersion heater at a constant pressure of 1.'' bar. +f a current of 1.*' # passes through
the 1'.'(ohm resistor for 1*' s\$ what is the final temperature of the water! The heat
capacity for water can be found in #ppendi& #.
( )
( )
)
\$ )
\$
\$
)
1 1
1
1 1
1
@
*7.*g
1.*'# ?1'.' ohm 1*' s A ?7*.)/1 " mol 0 ?)/8 0
18.') g mol
-1) 0
*7.* g
?7*.)/1 " mol 0
18.') gmol
P m i
P m f i f
P m
f
+ )t nC T
q + )t nC T T T
nC
T

P2.4\$ ,or 1 mol of an ideal gas\$ Pexternal , P B )'' ? 1'
-
Pa. The temperature is changed
from 1''C to )*.'C\$ and CV,m B -4)). Calculate q\$ w\$ U\$ and *.
( )
1 1
\$
-
8.-1. " mol 0 )/8 0 -7- 0 /-* "
)
V m
U nC T

)(-
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
( )
\$ \$
1 1
-
*
8.-1. " mol 0 )/8 0 -7- 0
)
1.*> 1' "
B
P m V m
P
* nC T n C ) T
q

+

-
/-* " 1.*> 1' " >). "
P
w U q +
-2"'\$ Consider the isothermal e&pansion of *.)* mol of an ideal gas at .*' 0 from an
initial pressure of 1*.' bar to a final pressure of -.*' bar. Describe the process that will
result in the greatest amount of wor being done by the system with
-.*'bar
external
P
and calculate w. Describe the process that will result in the least amount of wor being
done by the system with
-.*' bar
external
P
and calculate w. 3hat is the least amount of
wor done without restrictions on the e&ternal pressure!
The greatest amount of wor is done in a reversible e&pansion. The wor is given by
1 1
-
1*.' bar
ln ln *.)* mol?8.-1. " mol 0 ?.*' 0 ?ln
-.*' bar
)8.>?1' "
f
i
re(ersi\$le
i f
V
P
w n)T n)T
V P

The least amount of wor is done in a single stage e&pansion at constant pressure with the
e&ternal pressure equal to the final pressure. The wor is given by
( )
1 1 -
1 1
1 1
*.)* mol?8.-1. " mol 0 ?.*' 0?-.*' bar? 1*.1?1' "
-.*' bar 1*.' bar
external f i external
f i
w P V V n)TP
P P

_

,
_

,
The least amount of wor done without restrictions on the pressure is 9ero\$ which occurs
when Pexternal B '.
P2.6\$ Calculate * and U for the transformation of 1 mol of an ideal gas from )7.'C
and 1.'' atm to -)7C and 17.' atm if
1 1
\$
)'./ '.'.) in units of " 0 mol .
0
P m
T
C

+
)(.
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
\$
>''
-''
>''
)
-''
- -
.
1 mol )'./ '.'.)
0 0
)'./ >'' -'' " '.')1 "
0
>.)7 1' " *.>7 1' "
1.1/ 1' "
f
i
T
P m
T
* n C dT
T T
d
T

_
+

,
1

_
+
1

,
1
]
+

( )
. 1 1
-
1.1/ 1' " 8.-1. " 0 mol -'' 0
/..1 1' "
U * PV * n) T

-2")\$ Calculate w for the adiabatic e&pansion of 1 mol of an ideal gas at an initial
pressure of ).'' bar from an initial temperature of .*' 0 to a final temperature of -'' 0.
3rite an e&pression for the wor done in the isothermal reversible e&pansion of the gas at
-'' 0 from an initial pressure of ).'' bar. 3hat value of the final pressure would give
the same value of w as the first part of this problem! #ssume that CP,m B *4)).
( )
1 1 -
\$
-
?8.-1. " mol 0 1*' 0 1.87?1' "
)
w U n C ) T

-
1 1
ln @ ln
1.87?1' "
ln '.7./7
1 mol?8.-1. " mol 0 ?-'' 0
'..7) './.. bar
i i re(ersi\$le
re(ersi\$le
f f
i
f re(ersi\$le
f i
P P w
w n)T
P P n)T
P n)T
P w
P P

P2.8\$ +n the adiabatic e&pansion of 1 mol of an ideal gas from an initial temperature of
)*C\$ the wor done on the surroundings is 1)'' ". +f CV,m B -4))\$ calculate q\$ w\$ U\$ and
*.
( )
\$
\$
\$
1 1
1 1
' because the process is adiabatic
1)'' "
1)'' " 7.* 8.-1. " mol 0 )/8 0

1.* 8.-1. " mol 0
)') 0
V m f i
V m i
f
V m
q
U w
U nC T T
U nC T
T
nC

)(*
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( ) ( ) ( )
( )
\$ \$
1 1
-
).* 8.-1. " mol 0 )') 0 )/8 0
).'' 1' "
P m f i V m f i
* nC T T n C ) T T

+

-2"+\$ #n ideal gas undergoes an e&pansion from the initial state described by Pi\$ Vi\$ T to
a final state described by Pf\$ Vf\$ T in a2 a process at the constant e&ternal pressure Pf and
b2 in a reversible process. Derive e&pressions for the largest mass that can be lifted
through a height in the surroundings in these processes.
( )
( )
2 @
2 ln @ ln
f f i
f f i
f f
i i
P V V
a w mg P V V m
g
V V
n)T
\$ w mg n)T m
V g V

-2"#,\$ #n automobile tire contains air at -)'

1'
-
Pa at )'C. The stem valve is
removed and the air is allowed to e&pand adiabatically against the constant e&ternal
pressure of 1''

1'
-
Pa until P , Pexternal. ,or air\$ CV,m B *4)). Calculate the final
temperature. #ssume ideal gas behavior.
( ) ( )
( )
\$
\$
because '\$
V m f i ext f i
f
i
V m f i ext
f i
q U w
nC T T P V V
n)T
n)T
nC T T P
P P

_

,
The factor n cancels out. ;earranging the equation
\$ \$
\$
\$
1 1 *
1 1
*
1 1 *
1 1
*
8.-1. " mol 0 1' Pa
).* 8.-1. " mol 0
-.)' 1' Pa

8.-1. " mol 0 1' Pa
).* 8.-1. " mol 0
1' Pa
'.8'. )-*
ext ext
V m f V m i
f i
ext
V m
f
i
ext
i
V m
f
f i f
)P )P
C T C T
P P
)P
C
T
P
)P
T
C
P
T T T

_
_
+ +

,
,
+

+
0
P2.11\$ -.*' moles of an ideal gas is e&panded from .*' 0 and an initial pressure of
)(>
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
*.'' bar to a final pressure of 1.'' bar\$ and CP,m B *4)). Calculate w for the following
two cases.
a2 The e&pansion is isothermal and reversible.
b2 The e&pansion is adiabatic and reversible.
3ithout resorting to equations\$ e&plain why the result to part 1b2 is greater than or less
than the result to part 1a2.
a2
1 1 -
ln ln
*.'' bar
-.*' mol?8.-1." mol 0 ?.*' 0?ln )1.1 1' "
1.'' bar
f
i
i f
V
P
w n)T n)T
V P

b2 6ecause q B '\$ w B U. +n order to calculate U\$ we first calculate Tf.
1
1 1
1 1
*
1
-
*
-
@ @
*.'' bar
'.*)*
1.'' bar
'.*)*?.*' 0 )-> 0
f f f f f
i i i
i i i f i f i f
f
i
f
T V T T T
P P P
T V T P T P T P
T
T
T

_ _ _
_ _ _

, , ,
, , ,
_

,

( )
1 1
-
\$
- 8.-1. " mol 0
-.*' mol? ? )-> 0 .*' 0 /.-.?1' "
)
V m
w U nC T

5ess wor is done on the surroundings in part 1b2 because in the adiabatic e&pansion\$ the
temperature falls and therefore the final volume is less than that in part 1a2.
-2"#2\$ #n ideal gas described by Ti B -'' 0\$ Pi B 1.'' bar\$ and Vi B 1'.' 5 is heated at
constant volume until P B 1'.' bar. +t then undergoes a reversible isothermal e&pansion
until P B 1.'' bar. +t is then restored to its original state by the e&traction of heat at
constant pressure. Depict this closed(cycle process in a P!V diagram. Calculate w for
each step and for the total process. 3hat values for w would you calculate if the cycle
were traversed in the opposite direction!
)(7
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
) 1 1
1.'' bar?1'.' 5
'..'1 mol
8.-1.*?1' 5bar mol 0 ?-'' 0
i i
i
PV
n
)T

The process can be described by
step 1: Pi\$Vi\$Ti C P1 B 1'.' bar\$Vi\$ T1
step ): P1\$Vi\$ T1 C Pi\$V) T1
step -: Pi\$ V)\$ T1 C Pi\$Vi\$Ti.
+n step 1\$ Pi\$Vi\$Ti C P1\$Vi\$ T1\$ w B ' because V is constant.
+n step )\$ P1\$Vi\$ T1 C Pi\$ V)\$ T1
6efore calculating the wor in step )\$ we first calculate T1.
1
1
1'.' bar
-'' 0? -''' 0
1.'' bar
i
i
P
T T
P

1 1
1 1 -
ln ln
1'.' bar
'..'1 mol? 8.-1. " mol 0 ? -''' 0?ln )-.'?1' "
1.'' bar
f
i
i f
V
P
w n)T n)T
V P

+n step -\$
( )
1
1 ) )
* - -
-
@ 1' 1'' 5
1' Pa 1' m
1.'' bar? ? 1' 5 1'' 5 ? /.''?1' "
bar 5
i
i i i
i
external
PV
PV PV V V
P
w P V

- - -
' )-.' 1' " /.'' 1' " 1..' 1' "
cycle
w +
+f the cycle were traversed in the opposite direction\$ the magnitude of each wor term
would be unchanged\$ but all signs would change.
)(8
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
P2.13\$ -.'' moles of an ideal gas with CV,m B -4)) initially at a temperature Ti B )/8 0
and Pi B 1.'' bar is enclosed in an adiabatic piston and cylinder assembly. The gas is
compressed by placing a >)*(g mass on the piston of diameter )'.' cm. Calculate the
wor done in this process and the distance that the piston travels. #ssume that the mass of
the piston is negligible.
( )
)
*
) )
>)* g?/.81ms
1./*?1' Pa
D? '.1'' m
external
- mg
P
. r

1 1
) -
*
-.'' mol?8.-1. " mol 0 ?)/8 0
7..- 1' m 7..- 5
1' Pa
i
i
n)T
V
P

,ollowing E&ample Problem ).>\$
1 1 *
1 1
\$
*
1 1 *
1 1
\$
*
8.-1. " mol 0 ?1./* 1' Pa
1)..7 " mol 0 A
1.'' 1' Pa
)/8 0
8.-1. " mol 0 ?1./* 1' Pa
1)..7 " mol 0 A
1./* 1' Pa
B .11 0
external
V m
i
f i
external
V m
f
)P
C
P
T T
)P
C
P

_ _
+

, ,
1 1
) -
*
-.'' mol?8.-1. " mol 0 ?.11 0
*.)* 1' m
1./*?1' Pa
f
f
n)T
V
P

( ) ( )
* ) - ) - -
1./*?1' Pa? *.)*?1' m 7..- 1' m ..)* 1' "
external f i
w P V V

-
()
..)*?1' "
'.>/ m
>)* g?/.81 ms
w

mg

-2"#&\$ # bottle at )1.'C contains an ideal gas at a pressure of 1)>.. ? 1'
-
Pa. The
rubber stopper closing the bottle is removed. The gas e&pands adiabatically against
Pexternal , 1'1./ ? 1'
-
Pa\$ and some gas is e&pelled from the bottle in the process. 3hen P
B Pexternal\$ the stopper is quicly replaced. The gas remaining in the bottle slowly warms
up to )1.'C. 3hat is the final pressure in the bottle for a monatomic gas\$ for which
CV,m B -4)), and a diatomic gas\$ for which CV,m B *4))!
+n this adiabatic e&pansion\$ U w
)(/
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( ) ( )
( )
\$
\$
\$ \$
\$
\$
1 1 -
1 1
-
8.-1. " mol 0 1'1./ 1' Pa
1.* 8.-1. " mol 0
1)>.. 1' Pa

1.* 8.-
V m f i ext f i
V m f i ext
f i
ext ext
V m f V m i
f i
ext
V m
f
i
ext
i
V m
f
nC T T P V V
n)T n)T
nC T T P
V V
)P )P
C T C T
P P
)P
C
T
P
)P
T
C
P

_

,
_
_
+ +

,
,
+

+

+

1 1 -
1 1
-
8.-1. " mol 0 1'1./ 1' Pa
1. " mol 0
1'1./ 1' Pa

+

'./)- \$ )71 0
f
f
i
T
T
T

Ence the stopper is put in place\$ the gas maes a transformation from
-
)1. 0\$ 1'1./ 1' Pa to )/. 0 and
i i f f
T P T P
- -
\$ but
)/. 0
1'1./ 1' Pa 11'.* 1' Pa
)71 0
f f
i i
i f
i f
f
f i
i
P V
PV
V V
T T
T
P P
T

The same calculation carried out for
\$
*
)
V m
C ) gives
-
'./.*\$ )78 0
1'7.8 1' Pa
f
f
i
f
T
T
T
P

-2"#'\$ # pellet of Fn of mass 1'.' g is dropped into a flas containing dilute %)GE. at a
pressure of P B 1.'' bar and temperature T B )/8 0. 3hat is the reaction that occurs!
Calculate w for the process.
Fn1s2 A %)GE.1aq2 C Fn
)A
1aq2 A GE.
)H
1aq2 A%)1g2
The volume of %) produced is given by
)(1'
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
1 1
- - )
1 *
)
* - -
1'.' g 1mol % 8.-1. " mol 0 )/8 0
? ? -.7/ 1' m
1mol Fn 1?1' Pa
>*.-/ g mol Fn
volume of % produced.
1?1' Pa?-.7/?1' m -7/ "
external
V
w P V
V
w

P2.16\$ 1 mol of an ideal gas for which CV,m B )'.8 " 0
H1
mol
H1
is heated from an initial
temperature of 'C to a final temperature of )7*C at constant volume. Calculate q\$ w\$
U, and * for this process.
w B ' because V B '
1 1 -
)'.8 " mol 0 ?)7* 0 *.7) 1' "
V
U q C T

( )
- 1 1 -
*.7)?1' " 8.-1. " mol 0 )7* 0 8.'1 1' " * U PV U ) T

+ + +
-2"#)\$ 1 mol of an ideal gas\$ for which CV,m B -4))\$ initially at )'.'C and 1.'' ? 1'
>
Pa
undergoes a two(stage transformation. ,or each of the stages described in the following
list\$ calculate the final pressure\$ as well as q\$ w\$ U, and *. #lso calculate q\$ w\$ U,
and * for the complete process.
a2 The gas is e&panded isothermally and reversibly until the volume doubles.
b2 6eginning at the end of the first stage\$ the temperature is raised to 8'.'C at constant
volume.
> 1 1 1
)
)
1 1 - )
1
-
a2 '.*'' 1' Pa
)
ln 8.-1. " mol 0 ln ) 1.>/ 1' "
' and ' because '
1.>/ 1' "
PV P
P
V
V
w n)T
V
U * T
q w

( )
( )
>
* 1 ) ) 1
)
1 ) 1
1 1
\$
1
\$ \$
-*- 0 ? '.*'' ? 1' Pa
b2 @ >.') ? 1' Pa
)/- 0
1.* 8.-1. " mol 0 -*- 0 )/- 0 7.8 "
' because '
7.8 "
-
8.-1. " mol 0
)
V m
P m V m
T T T P
P
P P T
U nC T
w V
q U
* nC T n C ) T

+ ( )
1
-
-*- 0 )/- 0
1.)* 1' "

,or the overall process\$
)(11
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
- -
- -
- -
1.>/ 1' " 7.8 " )... 1' "
1.>/ 1' " ' 1.>/ 1' "
' 7.8 " 7.8 "
' 1.)* 1' " 1.)* 1' "
q
w
U
*
+
+
+
+
-2"#*\$ 1 mol of an ideal gas with CV,m B -4)) initially at )/8 0 and 1.''

1'
*
Pa
undergoes a reversible adiabatic compression. #t the end of the process\$ the pressure is
1.''

1'
>
Pa. Calculate the final temperature of the gas. Calculate q\$ w\$ U, and * for
this process.
( )
1
1 1
1 1
*
1
-
*
*
'..
-
>
@ @
1.''?1' Pa
'.1'' ).*1
1.''?1' Pa
).*1?)/8 0 7./ 0
f f f f f
i i i
i i i f i f i f
f
i
f
T V T T T
P P P
T V T P T P T P
T
T
T

_ _ _
_ _ _

, , ,
, , ,
_

,

q B ' because the process is adiabatic.
( )
( ) ( )
1 1
-
\$
- 1 1
-
-?8.-1. " mol 0
1 mol? 7./ 0 )/8 0 *.>) 1' "
)
*.>) 1' " 8.-1. " mol 0 7./ 0 )/8 0
/.-7 1' "
V m
w U nC T
* U PV U ) T
*

+ + +

P2.19\$ 1 mol of an ideal gas\$ for which CV,m B -4))\$ is subIected to two successive
changes in state:
a2 ,rom )*.'C and 1''

1'
-
Pa\$ the gas is e&panded isothermally against a constant
pressure of )'.'

1'
-
Pa to twice the initial volume.
b2 #t the end of the previous process\$ the gas is cooled at constant volume from )*.'C to
H)*.'C. Calculate q\$ w\$ U, and * for each of the stages. #lso calculate q\$ w\$ U, and
* for the complete process.
( ) ( )
1 1
) -
-
) -
- ) - ) -
8.-1. " mol 0 )/8 0
a2 )..8 1' m
1'' 1' Pa
) ../> 1' m
)'.' 1' Pa ../> 1' m )..8 1' m ./> "
and ' because '
./> "
i
i
f i
ext f i
n)T
V
P )
V V
w P V V
U * T
q w

)(1)
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( ) ( )
( ) ( ) ( )
( )
1 1
\$
\$ \$
1 1
-
b2 1.* 8.-1. " mol 0 ).8 0 )/8 0 >)- "
' because '
>)- "

).* 8.-1. " mol 0 ).8 0 )/8 0
1.'. 1' "
V m f i
P m f i V m f i
U nC T T
w V
q U
* nC T T n C ) T T

+

- -
' >)- " B >)- "
' ./> " B ./> "
./> " >)- " B 1)7 "
' 1.'. 1' " B 1.'. 1' "
total
total
total
total
U
w
q
*

-2"2,\$ The temperature of 1 mol of an ideal gas increases from 18.' to **.1C as the
gas is compressed adiabatically. Calculate q\$ w\$ U, and * for this process assuming
that CV,m B -4)).
q B ' because the process is adiabatic.
( )
( ) ( )
1 1
\$
1 1
-?8.-1. " mol 0
1 mol? ? **.1 C 18.' C .>- "
)
.>- " 8.-1. " mol 0 **.1 C 18.' C
771 "
V m
w U nC T
* U PV U ) T
*

+ + +

o o
o o
P2.21\$ # 1(mol sample of an ideal gas for which CV,m B -4)) undergoes the following
two(step process.
a2 ,rom an initial state of the gas described by T B )8.'C and P B ).''

1'
.
Pa\$ the gas
undergoes an isothermal e&pansion against a constant e&ternal pressure of 1.''

1'
.
Pa
until the volume has doubled.
b2 Gubsequently\$ the gas is cooled at constant volume. The temperature falls to H.'.*C.
Calculate q\$ w\$ U, and * for each step and for the overall process.
a2 ,or the first step\$ U B * B ' because the process is isothermal.
( )
1 1
) -
.
1 mol?8.-1. " mol 0 ? )7-.1* A )8.' 0
1.)* 1' m
).''?1' Pa
i
i
i
n)T
V
P

. ) - -
1.''?1' Pa?'.1)*?1' m 1.)*?1' "
external
w q P V

b2 ,or the second step\$ w B ' because V B '.
)(1-
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
( ) ( )
1 1
o o
1 1 o o
-
-?8.-1. " mol 0
1 mol? ? )8.' C A .'.* C 8*. "
)
8*. " A8.-1. " mol 0 ? )8.' C A .'.* C
1..) 1' "
V
q U C T
* U PV U ) T
*

+ +

,or the overall process\$ w B H
-
1.)*?1' "\$ q B 8*. A
-
1.)*?1' " B
-
).')?1' "\$ U B 8*. "\$
and * B 1..)

1'
-
".
-2"22\$ # cylindrical vessel with rigid adiabatic walls is separated into two parts by a
frictionless adiabatic piston. Each part contains *'.' 5 of an ideal monatomic gas with
CV,m B -4)). +nitially\$ Ti B )/8 0 and Pi B 1.'' bar in each part. %eat is slowly
introduced into the left part using an electrical heater until the piston has moved
sufficiently to the right to result in a final pressure Pf B 7.*' bar in the right part.
Consider the compression of the gas in the right part to be a reversible process.
a2 Calculate the wor done on the right part in this process and the final temperature in
the right part.
b2 Calculate the final temperature in the left part and the amount of heat that flowed into
this part.
The number of moles of gas in each part is given by
) 1 1
1.'' bar?*'.' 5
).') mol
8.-1.*?1' 5bar mol 0 ?)/8 0
i i
i
PV
n
)T

a2 3e first calculate the final temperature in the right side.

1
1 1
1 1
*
1
-
*
-
@ @
1.''bar
).).
7.*' bar
).).?)/8 0 >>7 0
f f f f f
i i i
i i i f i f i f
f
i
f
T V T T T
P P P
T V T P T P T P
T
T
T

_ _ _
_ _ _

, , ,
, , ,
_

,

( )
1 1
-
\$
-?8.-1. " mol 0
).') mol? >>7 0 )/8 0 /.-' 1' "
)
V m
U w nC T

b2 3e first calculate the final volume of the right part.
) 1 1
).') mol?8.-1.?1' 5bar mol 0 ?>>7 0
1../ 5
7.*' bar
rf
rf
rf
)T
V
P

Therefore\$ Vlf B 1''.' 5 H 1../ 5 B 8*.1 5.
)(1.
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
-
) 1 1
1 1 - -
\$
7.*' bar?8*.1 5
-.8' 1' 0
).') mol?8.-1.?1' 5bar mol 0
).') mol?8.-1." mol 0 ? -.8' 1' 0 )/8 0 *8.8 1' "
lf lf
lf
V m
P V
T
n)
U nC T

,rom part 1a2\$ w B H/.-'

1'
-
"
q B U H w B *8.-

1'
-
" A /.-'

1'
-
" B >7.-

1'
-
"
P2.23\$ # vessel containing 1 mol of an ideal gas with Pi B 1.'' bar and CP,m B *4)) is in
thermal contact with a water bath. Treat the vessel\$ gas\$ and water bath as being in
thermal equilibrium\$ initially at )/8 0\$ and as separated by adiabatic walls from the rest
of the universe. The vessel\$ gas\$ and water bath have an average heat capacity of
CP B 7*'' " 0
H1
. The gas is compressed reversibly to Pf B 1'.* bar. 3hat is the
temperature of the system after thermal equilibrium has been established!
#ssume initially that the temperature rise is so small that the reversible compression can
be thought of as an isothermal reversible process. +f the answer substantiates this
assumption\$ it is valid.
1 1
1 1 -
-
1
ln ln
1.'' bar
1 mol? 8.-1. " mol 0 ? )/8 0?ln *.8- 1' "
1'.* bar
*.8-?1' "
'.777 0
7*'' " 0
)// 0
f
i
i f
com\$ined system P
com\$ined system
P
f
V
P
w n)T n)T
V P
U C T
U
T
C
T

## The result Iustifies the assumption.

-2"2&\$ The heat capacity of solid lead o&ide is given by
- 1 1
\$
...-* 1..7 1' in units of " 0 mol .
P m
T
C
/

+ Calculate the change in enthalpy of
1 mol of PbE1s2 if it is cooled from *'' 0 to -'' 0 at constant pressure.
)(1*
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
\$
-''
-
*''
-'' 0
)
-
*'' 0
-
...-* 1..7 1'
0 0
B ...-* -'' 0 *'' 0
1..7 1'

) 0
887' " 117 "
8.// 1' "

_ _
+

, ,

1
_
+
1

,
1
]

f
i
T
" m
T
* n C dT
T T
d
T
-2"2'\$ Consider the adiabatic e&pansion of '.*'' mol of an ideal monatomic gas with
CV,m B -4)). The initial state is described by P B -.)* bar and T B -'' 0.
a2 Calculate the final temperature if the gas undergoes a reversible adiabatic e&pansion to
a final pressure P B 1.'' bar.
b2 Calculate the final temperature if the same gas undergoes an adiabatic e&pansion
against an e&ternal pressure of P B 1.'' bar to a final pressure P B 1.'' bar.
E&plain the difference in your results for parts 1a2 and 1b2.
a2
1
1 1
1 1
*
1
-
*
-
@ @
-.)*bar
'.>)>
1.'' bar
'.>)> -'' 0 188 0
f f f f f
i i i
i i i f i f i f
f
i
f
T V T T T
P P P
T V T P T P T P
T
T
T

_ _ _
_ _ _

, , ,
, , ,
_

,

b2
( ) ( )
\$ V m f i external f i
U nC T T P V V
)(1>
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
\$
\$ \$
1 1
1 1
\$
\$
8.-1. " mol 0 ?1.''bar
1.*?8.-1. " mol 0 A
-'' 0
f
i
V m f i external
f i
external external
f V m i V m
f i
external
V m
i
f i
external
V m
f
T
T
nC T T n)P
P P
n)P n)P
T nC T nC
P P
)P
C
P
T T
)P
C
P

_

,
_
_
+ +

,
,
_
+

+

,
1 1
1 1
-.)*bar
8.-1. " mol 0 ?1.''bar
1.*?8.-1. " mol 0 A
1.''bar
)17 0
f
T

_

,

Jore wor is done on the surroundings in the reversible e&pansion\$ and therefore U and
the temperature decrease more than for the irreversible e&pansion.
-2"2(\$ #n ideal gas undergoes a single(stage e&pansion against a constant e&ternal
pressure Pexternal at constant temperature from T\$ Pi\$ Vi\$ to T\$ Pf\$ Vf.
a2 3hat is the largest mass m that can be lifted through the height in this e&pansion!
b2 The system is restored to its initial state in a single(state compression. 3hat is the
smallest mass m# that must fall through the height to restore the system to its initial
state!
c2 +f B 1'.' cm\$ Pi B 1.''

1'
>
Pa\$ Pf B '.*''

1'
>
Pa \$ T B -'' 0\$ and n B 1.'' mol\$
calculate the values of the masses in parts 1a2 and 1b2.
Consider the e&pansion
( )
( )
a2

ext f i
ext f i
w mg P V V
P V V
m
g

## for the final volume to be

\$
f
V
the e&ternal pressure can be no bigger than
f
P
( )
ma&
f f i
P V V
m
g

## b2 Consider the compression

( )
ext i f
P V V
m
g

for the final volume to be
\$
i
V
the pressure can be no smaller than
i
P
( )
K
min
i i f
P V V
m
g

)(17
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
c2
1 1
- -
>
> - -
- -
>
1.'' mol? 8.-1. " mol 0 ? -'' 0
)../ 1' m
1.''?1' Pa
1.'' ? 1' Pa ? )../ ? 1' m
../8 1' m
'.*'' ? 1' Pa
i
i
f f i i
i i
f
f
n)T
V
P
P V PV
PV
V
P

( )
> - - - -
-
ma& )
'.*'' 1' Pa ../8 1' m )../ 1' m
1.)7 1' g
/.81 m s '.1'' m
m

( )
> - - - -
-
min )
1.'' 1' Pa )../ 1' m ../8 1' m
).*. 1' g
/.81 m s '.1'' m
m

P2.27\$ Calculate q\$ w\$ U, and * if 1.'' mol of an ideal gas with CV,m B -4))
undergoes a reversible adiabatic e&pansion from an initial volume Vi B *.)* m
-
to a final
volume Vf B )*.* m
-
. The initial temperature is -'' 0.
q B ' because the process is adiabatic.
1
*
1
-
)*.*
'.-./
*.)*
'.-./?-'' 0 1'* 0
f f
i i
f
i
f
T V
T V
T
0
T 0
T

,
_

,

( )
( )
1 1
-
\$
- 1 1
-
- 8.-1. " mol 0
1.'' mol? ? 1'* 0 -'' 0 )..- 1' "
)
)..-?1' " A 1.'' mol?8.-1. " mol 0 ? 1'* 0 -'' 0
..'* 1' "
V n
U w nC T
* U n) T
*

+

-2"2*\$ # nearly flat bicycle tire becomes noticeably warmer after it has been pumped
up. #ppro&imate this process as a reversible adiabatic compression. Tae the initial
pressure and temperature of the air before it is put in the tire to be Pi B 1.'' bar and
Ti B )/8 0. The final volume of the air in the tire is Vf B 1.'' 5 and the final pressure is
Pf B *.'' bar. Calculate the final temperature of the air in the tire. #ssume that CV,m B
*4)).
)(18
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
( )
1
1 1
1 1
7
1
*
7
'.)8*
*
@ @
1.''bar
'.)'' 1.*8
*.'' bar
1./'?-'' 0 .7* 0
f f f f f
i i i
i i i f i f i f
f
i
f
T V T T T
P P P
T V T P T P T P
T
T
T

_ _ _
_ _ _

, , ,
, , ,
_

,

P2.29\$ 1 mol of an ideal gas with CV,m B -4)) is e&panded adiabatically against a
constant e&ternal pressure of 1.'' bar. The initial temperature and pressure are Ti B -''
0 and Pi B )*.' bar. The final pressure is Pf B 1.'' bar. Calculate q\$ w\$ U, and * for
the process.
( ) ( )
\$ V m f i external f i
U nC T T P V V w
q B ' because the process is adiabatic.
( )
\$
\$ \$
1 1
1 1
\$
\$
8.-1. " mol 0 ?1.''bar
1.*?8.-1. " mol 0 A
)
-'' 0
f
i
V m f i external
f i
external external
f V m i V m
f i
external
V m
i
f i
external
V m
f
T
T
nC T T n)P
P P
n)P n)P
T nC T nC
P P
)P
C
P
T T
)P
C
P

_

,
_
_
+ +

,
,
_
+

+

,
1 1
1 1
*.'bar
8.-1. " mol 0 ?1.''bar
1.*?8.-1. " mol 0 A
1.''bar
18* 0
f
T

_

,

( )
( )
1 1
-
\$
- 1 1
-
-?8.-1. " mol 0
1.'' mol? 18* 0 -'' 0 1..- 1' "
)
1..-?1' " A 1.'' mol?8.-1." mol 0 18* 0 -'' 0
).-/?1' "
V n
U w nC T
* U n) T
*

+

-2"%,\$ Ene mole of =) in a state defined by Ti B -'' 0 and Vi B ).*' 5 undergoes an
isothermal reversible e&pansion until Vf B )-.' 5. Calculate w assuming a2 that the gas is
described by the ideal gas law and b2 that the gas is described by the van der 3aals
equation of state. 3hat is the percent error in using the ideal gas law instead of the van
der 3aals equation! The van der 3aals parameters for =) are tabulated in Table 7...
a2 for the ideal gas
1 1 -
)-.' 5
ln 1mol?8.-1. " mol 0 ?-'' 0 ?ln *.*. 1' "
).*' 5
f
re(ersi\$le
i
V
w n)T
V

)(1/
Chapter )4 %eat\$ 3or\$ +nternal Energy\$ Enthalpy\$ and the ,irst 5aw of Thermodynamics
b2 for the van der 3aals gas
)
)
_

,
_ _
+

, ,

f f
i i
f f
i i
V V
external
m m V V
V V
m m V V
)T a
w P dV dV
V \$ V
)T a
dV dV
V \$ V
The first integral is solved by maing the substitution y B Vm H \$.
( ) ( ) ln ln
f f
i i
V y
f i
m V y
)T )T
dV dy )T V \$ V \$
V \$ y
_ _
1
+ +

]

, ,

Therefore\$ the wor is given by
( )
( )
1 1
* > >
)
) - - - -
-
1 1
ln
)-.' 5 '.'-8' 5
1 mol?8.-1. " mol 0 ?-'' 0 ?ln
).*' 5 '.'-8' 5
1' Pa 1' m 1 1
1.->> 5 bar? ?
bar 5 ).*'?1' m )-.'?1' m
*.*> 1' " .8.7 " *.
f
i i f
V \$
w n)T a
V \$ V V
w

_
+

_
+

,
+
-
*) 1' "
Percent error B
- -
-
*.*)?1' " A *.*.?1' "
1'' '..L
*.*) 1' "

)()'