1104
1104
1104
Law of Thermodynamics
Questions on Concepts
container. The temperature of the liquid is varied by 1C. The system consists solely of the liquid.
Does heat or work flow across the boundary between the system and surroundings? Justify your
answer.
The work on the resistor is done by the surroundings. Heat flows across the boundary between
the surroundings and the system because of the temperature difference between them.
Q2.2) Explain how a mass of water in the surroundings can be used to determine q for a process.
Calculate q if the temperature of a 1.00-kg water bath in the surroundings increases by 1.25C.
If heat flows across the boundary between the system and surroundings, it will lead to a
q
temperature change in the surroundings given by T C .Forthecaseofinterest,weobtain:
p
q q surroundings -m C p T 1000 g 4.19 J g -1 K -1 1.15 K 5.24 10 3 J
Q2.3) Explain the relationship between the terms exact differential and state function.
In order for a function to be a state function f (x,y), it must be possible to express the function as
f f
df dx dy
x y y x
1
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
Ifthatformexists,itiscalledtheexactdifferential.
Q2.4) Why is it incorrect to speak of the heat or work associated with a system?
Heat and work exist only during the transitions of a given system between states. At system in a
Q2.5) Two ideal gas systems undergo reversible expansion starting from the same P and V. At the
end of the expansion, the two systems have the same volume. The pressure in the system that has
undergone adiabatic expansion is lower than in the system that has undergone isothermal
In the system undergoing an adiabatic expansion, all work that is done comes from lowering of
U, and therefore of the temperature. On the other hand, some of the work that is done in an
isothermal expansion can come at the expense of the heat that has flown across the boundary
Q2.6) A cup of water at 278 K (the system) is placed in a microwave oven and the oven is turned
on for 1 minute during which it begins to boil. Which of q, w, and U are positive, negative, or
zero?
The heat, q, is positive since heat flows across the system-surrounding boundary into the system.
The work, w, is negative because the vaporized water does work on the surroundings. U is
Q2.7) What is wrong with the following statement?: because the well-insulated house stored a
lot of heat, the temperature didnt fall much when the furnace failed. Rewrite the sentence to
Heat can not be stored since it only exists in transitions. The sentence should be rephrased to:
2
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
Since the house is well insulated, the walls are nearly adiabatic. Therefore, the temperature of the
house did not fall rapidly when in contact with the surroundings at lower temperature, as it would
Q2.8) What is wrong with the following statement?: burns caused by steam at 100C can be
more severe than those caused by water at 100C because steam contains more heat than water.
Heat is not a substance that can be stored. When steam gets into contact with your skin it
condenses to the liquid phase. In doing so, energy is released that is absorbed by the skin. Hot
water does not release as much heat in the same situation since it does not undergo a phase
transition.
Q2.9) Describe how reversible and irreversible expansions differ by discussing the degree to
In a reversible expansion, the system and surroundings are always at equilibrium with one another.
Q2.10) A chemical reaction occurs in a constant volume enclosure separated from the
surroundings by diathermal walls. Can you say whether the temperature of the surroundings
No, the temperature will increase if the reaction is exothermic, decrease if the reaction is
endothermic, and not change if no energy evolution or consumption takes place in the reaction.
Problems
Problem numbers in RED indicate that the solution to the problem is given in the Student
Solutions Manual.
3
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
P2.1) 3.00 moles of an ideal gas at 27.0C expand isothermally from an initial volume of 20.0
dm3 to a final volume of 60.0 dm3. Calculate w for this process (a) for expansion against a
constant external pressure of 1.00 105 Pa and (b) for a reversible expansion.
w n R T
Vfinal
3.00 mol 8.314472 J K 1 mol 1 300 K ln
0.06 m 3
- 8.22 10 3 J
Vinitial 0.02 m 3
P2.2) A major league pitcher throws a baseball at a speed of 150. km/h. If the baseball weighs
220. g and its heat capacity is 2.0 J g1 K1, calculate the temperature rise of the ball when it is
stopped by the catchers mitt. Assume no heat is transferred to the catchers mitt. Assume also
that the catchers arm does not recoil when he or she catches the ball.
The kinetic energy, E kin 12 m v 2 , of the ball is transferred into heat, q p C p T , in the mitt:
E kin 12 m v 2 q p C p T
m v2
1 1
0.22 kg 41.667 2 m 2 s 2
T
2.0 J g -1K 1 220.0 g 0.43 K
2 2
Cp
P2.3) 3.00 moles of an ideal gas are compressed isothermally from 60.0 to 20.0 L using a
U 0 and H 0 since T 0
q w 2.03 10 4 J
P2.4) A system consisting of 57.5 g of liquid water at 298 K is heated using an immersion heater
at a constant pressure of 1.00 bar. If a current of 1.50 A passes through the 10.0-ohm resistor for
4
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
150 s, what is the final temperature of the water? The heat capacity for water can be found in
Appendix B.
q I 2 R t n C p,m R Tf Ti
Tf
I 2
R t n C p,m Ti
n C p, m
1.5 A 2 10 Ohm 150 s
57.5 g
75.291 J mol -1 K 1 298 K
18.02 g mol
-1
312 K
57.5 g 75.291 J mol -1 K 1
18.02 g mol -1
P2.5) Using the results from Problem P1.4, determine the average heat evolved by the oxidation
of foodstuffs in an average adult per hour per kilogram of body weight. Assume the weight of an
average adult is 70. kg. State any assumptions you make. Assume 420. kJ of heat are evolved per
Theaverageheatevolvedbytheoxidationoffoodstuffsisthen:
q avrg
q O2 n O2
1.1796 mol h 420 10
-1 3
J mol -1 7.08 kJ h -1 kg -1
m 70 kg
Weassumedthatalltheoxygenthatisinhaledisusedintheoxidationoffoodstuffs.
P2.6) Suppose an adult body were encased in a thermally insulating barrier. If as a result of this
barrier all the heat evolved by metabolism of foodstuffs were retained by the body, what would the
5
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
temperature of the body reach after 3 hours? Assume the heat capacity of the body is 4.18 J g1K
From P2.5 we know that the heat produced after 3 h would be:
q 3 h 7.08 kJ h -1 kg -1 3 h 21.24 kJ kg -1
Thenusing q C p T ,weobtain:
q C p T
q 3 h
2.124 x 104 J kg -1
5.08 K
Cp 4.18 J K -1 g-1 1000 g kg-1
P2.7) For 1.00 mol of an ideal gas, Pexternal = P = 200.0 103 Pa. The temperature is changed
H q p
P2.8) Consider the isothermal expansion of 5.25 mol of an ideal gas at 450. K from an initial
pressure of 15.0 bar to a final pressure of 3.50 bar. Describe the process that will result in the
greatest amount of work being done by the system with Pexternal 3.50 bar and calculate w.
Describe the process that will result in the least amount of work being done by the system with
Pexternal 3.50 bar and calculate w. What is the least amount of work done without restrictions on
6
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
Vf pf
w reversible n R T ln n R T ln
Vi pi
3.50 bar
Theleastamountofworkisdoneinasinglestageexpansionatconstantpressurewiththe
externalpressureequaltothefinalpressure:
1 1
w p external Vf Vi -n R T p external
p f pi
1 1
5.25 mol 8.314472 J K -1 mol -1 450 K 3.50 bar ln 15.1 10 J
3
Theleastamountofworkdonewithoutrestrictionsonthepressureiszero,whichoccurswhen
p external 0 .
P2.9) A hiker caught in a thunderstorm loses heat when her clothing becomes wet. She is packing
emergency rations that, if completely metabolized, will release 30. kJ of heat per gram of rations
consumed. How much rations must the hiker consume to avoid a reduction in body temperature
of 4.0 K as a result of heat loss? Assume the heat capacity of the body equals that of water.
q C p T ,weobtain:
q person q 4 K m 17000 J kg -1 55 kg 9.2 10 5 J
7
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
And finally the mass of rations that needs to be consumed is given by:
m rations
q person
9.2 10 J 5
31.0 g
q rations 3.0 10 4
J g -1
P2.10) A muscle fiber contracts by 2.0 cm and in doing so lifts a weight. Calculate the work
performed by the fiber and the weight lifted. Assume the muscle fiber obeys Hookes law with a
P2.11) Calculate H and U for the transformation of 1.00 mol of an ideal gas from 27.0C and
T
C P,m 20.9 0.042 in units of J K 1 mol1
K
P2.12) Calculate w for the adiabatic expansion of 1.00 mol of an ideal gas at an initial pressure of
2.00 bar from an initial temperature of 450. K to a final temperature of 300. K. Write an
expression for the work done in the isothermal reversible expansion of the gas at 300. K from an
initial pressure of 2.00 bar. What value of the final pressure would give the same value of w as the
8
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
3
w ad U n C p,m R T mol 8.314472 J K -1 mol-1 150 K 1.87 103 J
2
pi p w reversible
w reversible n R T ln and ln i
pf pf nRT
ln
pi
w reversible
1.87 103 J 0.7497
pf nRT
1 mol 8.314472 J K -1 mol-1 300 K
pi
2.12
pf
pi
pf 0.944
2.12
P2.13) In the adiabatic expansion of 1.00 mol of an ideal gas from an initial temperature of
25.0C, the work done on the surroundings is 1200. J. If CV,m = 3/2R, calculate q, w, U, and H.
U
H C P, m Tfinal Tinitial C V, m R 32 R R U 52 U 2000 J
3R
C V, m 2
P2.14) According to a story told by Lord Kelvin, one day when walking down from Chamonix to
commence a tour of Mt. Blanc, whom should I meet walking up (the trail) but (James) Joule,
with a long thermometer in his hand, and a carriage with a lady in it not far off. He told me he had
been married since we parted from Oxford, and he was going to try for (the measurement of the)
Calculate the temperature difference between the top and bottom of this waterfall.
The decrease in potential energy (mgh) must equal the heat evolved as the water falls.
9
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
(mCp,mT). Note that the mass cancels. Heat is evolved so T increases, translating into a
m g h m C p, m T
T
gh
9.81 m s 2 30.0 m
18.02 10 -3 kg mol -1 0.0704 K
C p, m -1
75.3 J m K -1
P2.15) An ideal gas undergoes an expansion from the initial state described by Pi, Vi, T to a final
state described by Pf, Vf, T in (a) a process at the constant external pressure Pf and (b) in a
reversible process. Derive expressions for the largest mass that can be lifted through a height h in
p f Vf Vi
w m g h p f Vf Vi m
gh
V nRT V
w m g h n R T ln f m ln f
Vi gh Vi
P2.16) An automobile tire contains air at 320. 103 Pa at 20.0C. The stem valve is removed and
the air is allowed to expand adiabatically against the constant external pressure of 100. 103 Pa
until P = Pexternal. For air, CV,m = 5/2R. Calculate the final temperature. Assume ideal gas behavior.
Since q = 0, we have U = w
n C V, m Tf Ti p ext Vf Vi
n R Tf n R Ti
n C V, m Tf Ti p ext
pf pi
Thefactorsncancelout.Rearrangingtheequationgives:
10
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
R p ext R p ext
C V, m Tf C V, m Ti
pf pi
C V, m
R p ext
2.5 8.314472 J K -1 mol -1
8.314472 J K mol 10
-1 -1 5
Pa
Tf
pi 3.20 10 Pa
5
Ti
2.5 8.314472 J K -1 mol -1 8.314472 J K mol 10 Pa
-1 -1 5
R p ext
C V, m
pf 10 Pa
5
Tf 0.804 Ti 235 K
P2.17) Count Rumford observed that using cannon-boring machinery, a single horse could heat
11.6 kg of water (T = 273 K) to T = 355 K. in 2.5 hours. Assuming the same rate of work, how
high could a horse raise a 150.-kg weight in 1 minute? Assume the heat capacity of water is 4.18
kJ K1 kg1.
The rate of work, L, for warming the water sample can be calculated as the ratio of work and
time:
w C m T 4.18 kJ K -1 kg -1 11.6 kg 82 K
L 0.442 kJ s -1 442 J s -1
t t 9000 s
The rate of work for lifting the weight depends on the potential energy:
w mgh
L , where m, g, and h are mass, gravitational acceleration, and height, respectively.
t t
Solving for h yields:
h
Lt
442 J s -1 60 s
18.03 m
m g 150.0 kg 9.80665 m s -2
P2.18) Count Rumford also observed that nine burning candles generate heat at the same rate
that a single horse-driven cannon-boring piece of equipment generates heat. James Watt observed
that a single horse can raise a 330.-lb. weight 100. feet in 1 minute. Using the observations of
Watt and Rumford, determine the rate at which a candle generates heat. (Note: 1.00 m = 3.281
ft.)
11
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
m = 330.0 lb = 149.685 kg
h = 100 ft = 30.479 m
Since this heat is equivalent to the heat that nine candles generate, the heat evolved by one candle
is:
q 1 candle
q 9 candles
44754.948 J min -1
4972.8 J min -1
number of candles 9
P2.19) 3.50 moles of an ideal gas are expanded from 450. K and an initial pressure of 5.00 bar to
a final pressure of 1.00 bar, and CP,m = 5/2R. Calculate w for the following two cases:
Without resorting to equations, explain why the result for part (b) is greater than or less than the
Vi
n R T 3.50 mol 8.314472 J K 1 mol 1 450 K
0.0262 m 3
pi
5.00 10 Pa
5
Vf
n R T 3.50 mol 8.314472 J K 1 mol 1 450 K
0.1310 m 3
pf
1.00 10 5 Pa
w for an isothermal, reversible process is then given by:
12
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
w n R T ln
Vfinal
3.50 mol 8.314472 J K 1 mol 1 450 K ln
0.1310 m 3
Vinitial
0.0262 m
3
w -21076 J -21.1 kJ
b) For an adiabatic, reversible process:
Tfinal V
ln - 1 ln final , where C P, m /C V, m
Tinitial Vinitial
ln
Tfinal T p
- 1 ln final initial
- 1 ln
p initial
Tinitial Tinitial p final p final
Therefore:
- 1 p initial
Tfinal Exp ln ln Tinitial
p final
With C P, m 52 R, and C V, m 32 R , the final temperature is:
5 bar
Tfinal Exp 0.4 ln ln 450 K 236 K
1 bar
And finally w for an adiabatic process and for 3.5 moles of gas:
Less work is done on the surroundings in part b) because in the adiabatic expansion, the
temperature falls and therefore the final volume is less that that in part a).
P2.20) An ideal gas described by Ti = 300. K, Pi = 1.00 bar, and Vi = 10.0 L is heated at constant
volume until P = 10.0 bar. It then undergoes a reversible isothermal expansion until P = 1.00 bar.
It is then restored to its original state by the extraction of heat at constant pressure. Depict this
closed-cycle process in a PV diagram. Calculate w for each step and for the total process. What
values for w would you calculate if the cycle were traversed in the opposite direction?
13
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
n
p i Vi
1.00 bar 10.0 L 0.401 mol
R Ti
8.314472 10 -2 L bar K 1 mol 1 300 K
The process in the diagram above is described by the steps:
T1 Ti
p1
300 K
10.0 bar 3000 K
pi 1.00 bar
Vf pf
w 2 n R T ln n R T ln
Vi pi
0.401 mol 8.314472 J K -1 mol -1 3000 K ln 10.0 bar
23.0 10 J
3
1.00 bar
p 1 Vi
p 1 Vi p i V2 and V2 10Vi 100L
pi
Andthework:
Andfortheentirecircle:
P2.21) 3.00 mols of an ideal gas with CV,m=3/2R initially at a temperature Ti = 298 K and Pi =
14
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
1.00 bar are enclosed in an adiabatic piston and cylinder assembly. The gas is compressed by
placing a 625-kg mass on the piston of diameter 20.0 cm. Calculate the work done in this process
and the distance that the piston travels. Assume that the mass of the piston is negligible.
The constant pressure during compression pconst, which is also the final pressure, pf, can be
calculated using the gravitational acceleration. Pressure is force divided by area:
p f p const
F mg
mg
2
625 kg 9.80667 m s 2 195084.2 Pa
A A 4d
4
0.2 m 2
For a adiabatic, non-reversible compression:
n R Tf n R Ti
nC V, m Tf Ti p const Vf Vi p const
pf pi
To calculate the distance the cylinder moved, we need the final volume of the piston:
Vf
n R Tf
3.0 mol 8.314472 J K 1 mol 1 411.34 K 0.05259 m 3
pf 195084.2 Pa
The height of the cylinder that the gas filled initially is then:
hi
Vi
0.07433 m 3
2.367 m
A
0.0314 m 2
The reduced height of the cylinder filled with gas after compression is:
hf
h i Vf
2.367 m 0.0526 m 3
1.675 m
Vi
0.07433 m 3
That means the piston moved the difference in height:
h h i - h f 2.367 m - 1.675 m 0.69 m
P2.22) A bottle at 21.0C contains an ideal gas at a pressure of 126.4 103 Pa. The rubber
15
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
stopper closing the bottle is removed. The gas expands adiabatically against Pexternal = 101.9 103
Pa, and some gas is expelled from the bottle in the process. When P = Pexternal, the stopper is
quickly replaced. The gas remaining in the bottle slowly warms up to 21.0C. What is the final
pressure in the bottle for a monatomic gas, for which CV,m = 3/2R, and a diatomic gas, for which
CV,m = 5/2R?
In an adiabatic expansion U = w:
n C V, m Tf Ti p ext Vf Vi
n R Tf n R Ti
n C V, m Tf Ti p ext
pf pi
Thefactorsncancelout.Rearrangingtheequationgives:
R p ext R p ext
C V, m Tf C V, m Ti
pf pi
1.5 8.314472 J K mol 8.314472 J K mol 101 .9 10 Pa
-1 -1 3
R p ext
C V, m -1 -1
Tf pi 126.4 10 Pa
3
Ti
1.5 8.314472 J K -1 mol -1 8.314472 J K mol 101.9 10 Pa
-1 -1 3
R p ext
C V, m
pf 101.9 10 Pa
3
Tf 0.923 Ti 271 K
pi Vi p f Vf
Ti Tf
With Vi = Vf:
16
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
pf
Tf
pi
294 K 101.9 103 Pa 110.5 103 Pa
Ti 271 K
5
Thesamecalculationcarriedoutfor C V, m R gives:
2
Tf
0.945, Tf 278 K
Ti
p f 107.8 103 Pa
P2.23) A pellet of Zn of mass 10.0 g is dropped into a flask containing dilute H2SO4 at a pressure
of P = 1.00 bar and temperature of T = 298 K. What is the reaction that occurs? Calculate w for
the process.
2-
Zn (s) H 2 SO 4 (aq) Zn 2 (aq) SO 4 (aq) H 2 (g)
VH2
10 g
8.314472 J K mol 298 K 3.79 10
-1 -1
-4
m3
65.39 g mol -1
110 Pa
5
Assumingthat Vf Vi VH 2 ,theworkis:
P2.24) One mole of an ideal gas for which CV,m = 20.8 J K1 mol1 is heated from an initial
17
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
q U C V T 20.8 J K 1 mol 1 275 K 1.0 mol 5720.0 J 5.72 kJ
H C p T n R C V T
8.314472 J K 1
mol 1 1.0 mol 20.8 J K 1 mol 1 1.0 mol 273 K 8006.0 J 8.0 kJ
P2.25) One mole of an ideal gas, for which CV,m = 3/2R, initially at 20.0C and 1.00 106 Pa
undergoes a two-stage transformation. For each of the stages described in the following list,
calculate the final pressure, as well as q, w, U, and H. Also calculate q, w, U, and H for the
complete process.
a. The gas is expanded isothermally and reversibly until the volume doubles.
b. Beginning at the end of the first stage, the temperature is raised to 80.0C at constant
volume.
p1 V1 p1
a) p 2 0.500 10 6 Pa
V2 2
Vf
w n R T ln
1.0 mol 8.314472 J K -1 mol -1 293.15 K ln 2 1.69 10 3 J
Vi
U H 0 because T 0
q w 1.69 10 3 J
T1 T2 T2 p1 0.500 10 6 Pa 353 K
b) p
, and therefore 2 6.02 10 5 Pa
p1 p 2 T1 293 K
w=0becauseV=0
U=748J
q=
18
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
q 1.69 10 3 J 748 J 2.44 10 3 J
w 1.69 10 3 J 0 J 1.69 10 3 J
U 748 J 0 J 748 J
H 1.25 10 3 J 0 J 1.25 10 3 J
P2.26) One mole of an ideal gas, for which CV,m = 3/2R, initially at 298 K and 1.00 105 Pa
undergoes a reversible adiabatic compression. At the end of the process, the pressure is 1.00 106
Pa. Calculate the final temperature of the gas. Calculate q, w, U, and H for this process.
1 1 1
Tf Vf T pi
f
Ti Vi Ti pf
1
Tf p
i
Ti pf
1
Tf p
i
Ti pf
5
1
3
Tf 1.00 10 5 Pa 5
0.100
0 .4
2.51
3
1.00 10 Pa
6
Ti
19
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
P2.27) The temperature of 1 mol of an ideal gas increases from 18.0 to 55.1C as the gas is
compressed adiabatically. Calculate q, w, U, and H for this process assuming that CV,m = 3/2R.
H U p V U R T 463 J 8.314472 J K -1 mol -1 55.1 C - 18.0 C 771 J
P2.28) A 1.00-mol sample of an ideal gas for which CV,m = 3/2R undergoes the following two-step
process: (1) From an initial state of the gas described by T = 28.0C and P = 2.00 104 Pa, the
gas undergoes an isothermal expansion against a constant external pressure of 1.00 104 Pa until
the volume has doubled. (2) Subsequently, the gas is cooled at constant volume. The temperature
falls to 40.5C. Calculate q, w, U, and H for each step and for the overall process.
V
nRT 1mol 8.314472 J K 1 mol 1 301.15K
0.1251 m 3
p
2.00 10 4 Pa
And:
q w 0.1251 m 3 1.00 10 4 Pa 1251 J
H U 0
20
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
q U n C V T 3
2
8.314472 J K 1
mol 1 68.5 K 1.0 mol 854.3 J
H n C p T n R 32 n R T 52 n R 52 8.314472 J K 1 mol 1 1.0 mol 68.5 K 1423.9 J
For the overall process:
w tot w 1 w 2 1251 J
U tot U 1 U 2 854.3 J
H tot H 1 H 2 1423.9 J
P2.29) A cylindrical vessel with rigid adiabatic walls is separated into two parts by a frictionless
adiabatic piston. Each part contains 50.0 L of an ideal monatomic gas with CV,m = 3/2R. Initially,
Ti = 298 K and Pi = 1.00 bar in each part. Heat 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 =
7.50 bar in the right part. Consider the compression of the gas in the right part to be a reversible
process.
a. Calculate the work done on the right part in this process and the final temperature in the
right part.
b. Calculate the final temperature in the left part and the amount of heat that flowed into this
part.
n
p i Vi
1.00 bar 50.0 L 2.02 mol
R Ti 8.314472 10 -2 L bar K 1 mol 1 298 K
1 1 1
Tf Vf T pi
f
Ti Vi Ti pf
21
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
1
Tf p
i
Ti pf
1
Tf p
i
Ti pf
5
1
3
Tf 1.00 bar 5
3 2.24
Ti 7 .50 bar
Vrf 14.9 L
p rf 7.50 bar
Tlf
plf Vlf
7.50 bar 85.1 L 3800 K
nR 2.02 mol 8.314472 10-2 bar L K 1 mol 1
P2.30) A vessel containing 1.00 mol of an ideal gas with Pi = 1.00 bar and CP,m = 5/2R is in
thermal contact with a water bath. Treat the vessel, gas, and water bath as being in thermal
equilibrium, initially at 298 K, and as separated by adiabatic walls from the rest of the universe.
22
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
The vessel, gas, and water bath have an average heat capacity of CP = 7500. J K1. The gas is
compressed reversibly to Pf = 10.5 bar. What is the temperature of the system after thermal
Tf
q
Ti
9671.6 J 298 K 299.3 K
C p system 7500 J K 1
P2.31) DNA can be modeled as an elastic rod that can be twisted or bent. Suppose a DNA
molecule of length L is bent such that it lies on the arc of a circle of radius Rc. The reversible work
BL
wbend where B is the bending force constant. The DNA
2R 2 c
in a nucleosome particle is about 680 in length. Nucleosomal DNA is bent around a protein
complex called the histone octamer into a circle of radius 55 . Calculate the reversible work
involved in bending the DNA around the histone octamer if the force constant B = 2.00 1028 J
m1.
w bend
BL
2.00 10 -28 J m -1 680 10 -10 m
2.25 10 -19 J m -2
2 R c2
2 55 10 m -10 2
P2.32) Compare the energy of DNA bending calculated in Problem 2.31 to the thermal energy kB
23
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
T, where kB is Boltzmanns constant. Assume T = 310. K. Propose a source for the excess energy
E thermal k B T 1.38 10 -23 J K -1 310 K 4.278 10 -21 J
The ratio between the energy from P2.31 and the thermal energy is:
E bend
2.25 10 -19 J
52.6
E thermal
4.278 10 - 21 J
The energy source could be the formation of intermolecular interactions.
P2.33) The reversible work involved in twisting a short DNA molecule depends quadratically on
f/L, the angle of twist per unit length, where the twist angle is expressed in units of radians. The
2
CL
wtwist . A DNA oligomer 20 base pairs in length
2 L
reversible work involved in this twisting deformation. Assume C = 2.5 1028 J m. Assume also
2
36 Pi rad
w twist
CL
2
2.5 10 - 28
J m 20 3.4 10 -10 m 180
7.26 10 - 21 J
2 L 2
20 3.4 10 -10
m
P2.34) The formalism of Youngs modulus is sometimes used to calculate the reversible work
rod of cross-sectional area A0 and length L0. As a result of this force, the rod changes in length by
24
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
a. Derive Hookes law from the Youngs modulus expression just given.
b. Using your result from part (a), show that the reversible work involved in changing by L
2
1 L
is w EA0 L0 .
2 L0
a) Hookes law says that the force with which a mass on a spring opposes displacement is directly
Fkd
F L0
E
A 0 L
E L A 0
F k L ,
L0
E A0
k
L0
L L 2
1 1 E A0 1 L
w twist F ds k L ds k L2 L2 E A 0 L 0
0 0
2 2 L0 2 L0
25
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
T
C P,m 44.35 1.47 103 in units of J K 1 mol1
K
Calculate the change in enthalpy of 1 mol of PbO(s) if it is cooled from 500 to 300 K at constant
pressure.
H n C p T 44.35 1.47 10 -3 300 J K 1 mol 1 1.0 mol 300 K - 500 K - 8.96 10 3 J
P2.36) Consider the adiabatic expansion of 0.500 mol of an ideal monatomic gas with CV,m =
a. Calculate the final temperature if the gas undergoes a reversible adiabatic expansion to a
b. Calculate the final temperature if the same gas undergoes an adiabatic expansion against an
c. Explain the difference in your results for parts (a) and (b).
1 1 1
Tf Vf T pi
f
Ti Vi Ti pf
1
Tf p
i
Ti pf
1
Tf p
i
Ti pf
26
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
5
1
3
Tf 3.25 bar 5
3 0.626
Ti 1.00 bar
b) The final temperature for the expansion against an external pressure can be obtained by using
n C V, m Tf Ti p ext Vf Vi
n R Tf n R Ti
n C V, m Tf Ti p ext
pf pi
Thefactorsncancelout.Rearrangingtheequationgives:
R p ext R p ext
C V, m Tf C V, m Ti
pf pi
8.314472 J K 3.25mol 1.00 bar
-1 -1
R p ext
C V, m 1.5 8.314472 J K -1 mol -1
Tf pi bar
Ti
8.314472 J K mol 1.00 bar
-1 -1
R p ext
C V, m 1.5 8.314472 J K -1 mol -1
pf 1.00 bar
Tf 0.723 Ti 217 K
P2.37) The relationship between Youngs modulus and the bending force constant for a
deformable cylinder is B = EI, where, I = R4/4 and R is the radius of the cylinder.
a. Calculate the Youngs modulus associated with a DNA of radius 10. (1 = 1010 m).
b. Suppose a DNA molecule 100 base pairs in length is extended by 10. . Calculate the
27
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
E
B
4B
4 2.00 10 -28 J m 1
2.55 10 8 J m -3
I R 4
10 10 m
-10
4
b) Assuming 3 10 -10 m per base pair for the DNA, the work is given by:
w
E A 0 L2
2
10 10 -10 m 2.55 10 8 J m -3 10 10 -10 m 2
4.45 10 -22 J
2 L0 2 300 10 -10 m
c) The thermal energy at 310 K is:
E thermal k T 1.38 10 -23 J K -1 310 K 4.28 10 -21 J
P2.38) The Youngs modulus of muscle fiber is approximately 3.12 107 Pa. If a muscle fiber
2.00 cm in length and 0.100 cm in diameter is suspended with a weight M hanging at its end,
calculate the weight M required to extend the length of the fiber by 10%.
E L A 0
F k L ,
L0
We set this force equal to the force exerted by the weight in the earths gravitational field
E L A 0
gm
L0
2 2
E L A 0 E L r 2
d
E L 7
3.12 10 Pa 0.1 0.02 m
0.001 m
m 2 2 0.25 kg
L0 g L0 g L0 g 0.02 m 9.81 m s 2
P2.39) An ideal gas undergoes a single-stage expansion against a constant external pressure
28
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
a. What is the largest mass m that can be lifted through the height h in this expansion?
b. The system is restored to its initial state in a single-state compression. What is the smallest
mass m that must fall through the height h to restore the system to its initial state?
c. If h = 10.0 cm, Pi = 1.00 106 Pa, Pf = 0.500 106 Pa, T = 300. K, and n = 1.00 mol,
w m g h p ext Vf Vi
p ext Vf Vi
m
gh
For a final volume of Vf, the external pressure can not be larger than pf:
p f Vf Vi
m max
gh
w m g h p ext Vi Vf
p ext Vi Vf
m
gh
For a final volume of Vi, the external pressure can not be larger than pi:
p i Vi Vf
m min
gh
c) Vi
n R Ti 1.0 mol 8.314472 J K 1 mol 1 300 K
2.49 10 -3 m 3
pi
1.00 10 6 Pa
p i Vi p f Vf
29
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
Vf
p i Vi
1.00 10 6 Pa 2.49 10 -3 m 3
4.98 10 -3 m 3
pf
0.500 10 Pa
6
p f Vf Vi 0.500 10 6 Pa 4.98 10 -3 m 3 2.49 10 -3 m 3
m max 1.27 10 3 kg
gh 9.81 m s -2 0.100 m
m min
p f Vf Vi
1.00 106 Pa 4.98 10-3 m 3 2.49 10-3 m 3 2.54 103 kg
gh 9.81 m s-2 0.100 m
P2.40) Calculate q, w, U, and H if 1.00 mol of an ideal gas with CV,m = 3/2R undergoes a
reversible adiabatic expansion from an initial volume Vi = 5.25 m3 to a final volume Vf = 25.5 m3.
V
C p,m nR C V, m nR 32 R
Tfinal Exp 1 ln final ln Tinitial , 3 5
3
Vinitial C V, m C V, m 2 R
25.5 m 3
Tfinal Exp 53 1 ln 3
ln 300 K 104.6 K
5.25 m
P2.41) A nearly flat bicycle tire becomes noticeably warmer after it has been pumped up.
Approximate this process as a reversible adiabatic compression. Assume the initial pressure and
temperature of the air before it is put in the tire to be Pi = 1.00 bar and Ti = 298 K, respectively.
The final volume of the air in the tire is Vf = 1.00 L and the final pressure is Pf = 5.00 bar.
Calculate the final temperature of the air in the tire. Assume that CV,m = 5/2R
30
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
1 1 1
Tf Vf T pi
f
Ti Vi Ti pf
1
Tf p
i
Ti pf
1
Tf p
i
Ti pf
7
1
5
Tf 1.00 bar 7
5 1.58
Ti 5.00 bar
P2.42) One mole of an ideal gas with CV,m = 3/2R is expanded adiabatically against a constant
external pressure of 1.00 bar. The initial temperature and pressure are Ti = 300. K and Pi = 25.0
bar, respectively. The final pressure is Pf = 1.00 bar. Calculate q, w, U, and H for the process.
R Tf
C V, m Tf - Ti Vf - Vi R Tf Vi 1
Vf Vf
Solving for Tf results in:
31
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
Tf
R Ti p f
C V, m Ti
8.314472 J K 1 mol 1 300 K 1 10 5 Pa 3
5 300 K 184.8 K
p i C V, m R C V, m R
25 10 5 Pa 52 8.314472 J K 1 mol 1
For an adiabatic process:
P2.43) One mole of N2 in a state defined by Ti = 300. K and Vi = 2.50 L undergoes an isothermal
reversible expansion until Vf = 23.0 L. Calculate w assuming (a) that the gas is described by the
ideal gas law and (b) that the gas is described by the van der Waals equation of state. What is the
percent error in using the ideal gas law instead of the van der Waals equation? The van der Waals
Vf
w reversible n R T ln
1.0 mol 8.314472 J K -1 mol -1 300 K ln
23.0 L
5.54 10 J
3
Vi 2.50 L
Vf Vf
RT a Vf
RT
Vf
a
w p external dV dV
dV
dV
Vi Vi
Vm b Vm 2 Vi
Vm b Vi Vm
2
Vf y
RT f
RT
dV dy R T ln Vf b ln Vi b
Vi Vm b yi y
Therefore,theworkisgivenby:
32
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
Vf b 1 1
w reversible n R T ln a
Vi b Vi Vf
23.0 L 0.0380 L
1.0 mol 8.314472 J K -1 mol-1 300 K ln
2.50 L 0.0380 L
1.366 L2 bar
10 Pa
5
10 6 m 6 L2
1
1
5.52 103 J
1 bar 2.50 10 -3
m 3
23 . 0 10 -3
m
3
0.4%
5.52 10 J 3
P2.44) One mole of an ideal gas, for which CV,m = 3/2R, is subjected to two successive changes in
state: (1) From 25.0C and 100. 103 Pa, the gas is expanded isothermally against a constant
pressure of 20.0 103 Pa to twice the initial volume. (2) At the end of the previous process, the
gas is cooled at constant volume from 25.0 to 25.0C. Calculate q, w, U, and H for each of
H C p T n R 32 n R T 52 n R 52 8.314472 J K 1 mol 1 1.0 mol 50.0 K - 1039.3 J
For the overall process:
33
Chapter 2/Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics
w tot w 1 w 2 495.8 J
U tot U 1 U 2 623.6 J
H tot H 1 H 2 - 1039.3 J
P2.45) The adhesion of leukocytes (white blood cells) to target cells is a crucial aspect of the
bodys immune system. The force required to detach leukocytes from a substrate can be measured
with an atomic force microscope (AFM). The work of de-adhesion is proportional to the cell
substrate contact area Ac, which in turn is related to Youngs modulus, the force F applied to the
2/3
RF
cell by the AFM, and the radius R of the cell by Ac . Assuming R = 5.00 106 m
E
and F = 2.00 107 N, calculate the change in contact area when Youngs modulus is reduced
from 1.40 to 0.30 kPa. By what amount does the work of de-adhesion change when Youngs
5.00 10 5.00 10
2 2 2 2
R F R F 6
m 2.00 10 7 N 6
m 2.00 10 7 N
3 3 3 3
A c
E1 E2 1400 Pa 300 Pa
2.51 10 10
m 2
7.01 10 10
m 2
4.50 10 10
m 2
Sincetheworkisproportionalthecellsubstratearea,theworkratioistheratioofthetwoareas:
F2 7.01 10 m
10 2
2.78
F1 2.51 1010 m 2
34