Chapter 1: Fundamental Concepts of Thermodynamics

Problem numbers in italics indicate that the solution is included in the Students Solutions Manual. Questions on Concepts Q1.1) The location of the boundary between the system and the surroundings is a choice
that must be made by the thermodynamicist. Consider a beaker of boiling water in an airtight room. Is the system open or closed if you place the boundary just outside the liquid water? Is the system open or closed if you place the boundary just inside the walls of the room? If the system boundaries are just outside of the liquid water, the system is open because water can escape from the top surface. The system is closed if the boundary is just inside the walls, because the room is airtight.

Q1.2) eal walls are ne!er totally adiabatic. "rder the following walls in increasing
order with respect to being diathermal# $%cm%thick concrete, $%cm%thick !acuum, $%cm% thick copper, $%cm%thick cork. $%cm%thick !acuum & $%cm%thick cork & $%cm%thick concrete & $%cm%thick copper

Q1.3) 'hy is the possibility of e(change of matter or energy appropriate to the !ariable
of interest a necessary condition for equilibrium between two systems? )quilibrium is a dynamic process in which the rates of two opposing processes are equal. *owe!er, if the rate in each direction is +ero, no e(change is possible, and therefore the system can not reach equilibrium.

Q1.4) ,t sufficiently high temperatures, the !an der 'aals equation has the form
RT . -ote that the attracti!e part of the potential has no influence in this Vm b e(pression. .ustify this beha!ior using the potential energy diagram in /igure $.0. P ,t high temperatures, the energy of the molecule is large as indicated by the colored rectangular area in the figure below.

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Chapter $1/undamental Concepts of Thermodynamics

In this case, the well depth is a small fraction of the total energy. Therefore, the particle is unaffected by the attracti!e part of the potential.

Q1.5) The parameter a in the !an der 'aals equation is greater for *2" than for *e.
'hat does this say about the form of the potential function in /igure $.0 for the two gases? It says that the depth of the attracti!e potential is greater for *2" than for *e.

Pro lems P1.1) , sealed flask with a capacity of $.33 dm4 contains 5.33 g of ethane. The flask is
so weak that it will burst if the pressure e(ceeds $.33 6 $30 Pa. ,t what temperature will the pressure of the gas e(ceed the bursting temperature? PV $.33 $30 Pa $34 m4 T= = = 724 8 5.33 g nR $ $ 9.4$:. mol 8 43.37 g mol$

P1.2) Consider a gas mi(ture in a 2.33%dm4 flask at 27.3;C. /or each of the following
mi(tures, calculate the partial pressure of each gas, the total pressure, and the composition of the mi(ture in mole percent. a< $.33 g *2 and $.33 g "2 b< $.33 g -2 and $.33 g "2 c< $.33 g C*: and $.33 g -*4

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Chapter $1/undamental Concepts of Thermodynamics a< $.33 2.3$0 mol 9.4$: . mol $ 8 $ 433 8 = 0.2: $35 Pa 4 4 V 2.33 $3 m nO2 RT $.33 42.33 mol 9.4$: . mol $ 8 $ 433 8 PO2 = = = 4.=3 $3: Pa 4 4 V 2.33 $3 m 5 Ptotal = 0.57 $3 Pa mol * 2 $.33 2.3$0 mol > * 2 = $33 = $33 = =:.$> mol * 2 + mol " 2 $.33 2.3$0 + $.33 42.33 PH 2 = = mol > "2 = $33 b< $.33 29.32 mol 9.4$: . mol$ 8 $ 433 8 = :.:5 $3: Pa 4 4 V 2.33 $3 m nO RT $.33 42.33 mol 9.4$: . mol $ 8 $ 433 8 PO2 = 2 = = 4.=3 $3: Pa V 2.33 $34 m 4 Ptotal = 9.45 $3: Pa mol - 2 $.33 29.32 mol > - 2 = $33 = $33 = 54.4> mol - 2 + mol " 2 $.33 29.32 + $.33 42.33 PN 2 = = mol > "2 = $33 c< $.33 $7.34 mol 9.4$: . mol $ 8 $ 433 8 PNH 4 = = = 7.42 $3: Pa 4 4 V 2.33 $3 m nCH : RT $.33 $0.3: mol 9.4$: . mol $ 8 $ 433 8 PCH : = = = 7.77 $3: Pa V 2.33 $34 m 4 Ptotal = $.5$ $35 Pa mol -* 4 $.33 $7.34 mol > -* 4 = $33 = $33 = :9.5> mol -* 4 + mol C* : $.33 $7.34 + $.33 $0.3: mol > "2 = $33 mol C* : $.33 $0.3: = $33 = 5$.5> mol -* 4 + mol C* : $.33 $7.34 + $.33 $0.3: nNH4 RT mol "2 $.33 42.33 = $33 = :0.7> mol - 2 + mol " 2 $.33 29.32 + $.33 42.33 nN2 RT mol "2 $.33 42.33 = $33 = 5.=> mol * 2 + mol " 2 $.33 2.3$0 + $.33 42.33 nH 2 RT

P1.3) ?uppose that you measured the product PV of one mole of a dilute gas and found
that PV @ 22.=9 A atm at 3;C and 4$.$9 A atm at $33;C. ,ssume that the ideal gas law is !alid, with T @ tB;C< C a, and that the !alue of R is not known. Determine R and a from the measurements pro!ided. )(pressing the ideal gas law in the form PV @ RBt C a< @ mBt C a<,

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Chapter $1/undamental Concepts of Thermodynamics PV ( 4$.$9%22.=9) l atm mol = = 3.39233 atm mol$ o C $ = R o t ( $33%3) C
$

m=

PV 4$.$9l atm mol $ a= t = $33o C = 293.2o C $ o $ R .39233 atm mol C

P1.4) , compressed cylinder of gas contains $.53 $34 g of -2 gas at a pressure of 2.33
$37 Pa and a temperature of $7.$;C. 'hat !olume of gas has been released into the atmosphere if the final pressure in the cylinder is $.93 $35 Pa? ,ssume ideal beha!ior and that the gas temperature is unchanged. Aet ni and nf be the initial and final number of mols of -2 in the cylinder. ni RT n f RT = Pi Pf n f = ni Pf Pi = $.536$34g $.93 $35 Pa 6 = 3.:92 mol 29.3$g mol$ 2.33 $37 Pa

$.536$34g ni = = 54.55 mol 29.3$g mol$ The !olume of gas released into the atmosphere is gi!en by n f ni RT ( 54.55 3.:92) mol69.23576$32 A atm mol $8 $ 62=3.2 8 V= = P $atm

= $.20 $34 A

P1.5) , balloon filled with $3.53 A of ,r at $9.3;C and $ atm rises to a height in the
atmosphere where the pressure is 2:9 Torr and the temperature is E43.5;C. 'hat is the final !olume of the balloon? 703 Torr 6 ( 274.$5 43.5 ) 8 P T V f = i f Vi = 6$3.53 A = 20.9 A Pf Ti 2:9 Torr 6 ( 274.$5 + $9.3 ) 8

P1.!) Consider a 23.3%A sample of moist air at 03;C and $ atm in which the partial
pressure of water !apor is 3.$23 atm. ,ssume that dry air has the composition 79.3 mole percent -2, 2$.3 mole percent "2, and $.33 mole percent ,r. a< 'hat are the mole percentages of each of the gases in the sample? PH 2O b< The percent relati!e humidity is defined as > * @ F where PH 2O is the partial PH 2O
pressure of water in the sample and PH 2O @ 3.$=7 atm is the equilibrium !apor pressure of water at 03;C. The gas is compressed at 03;C until the relati!e humidity is $33>. 'hat !olume does the mi(ture now occupy?

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Chapter $1/undamental Concepts of Thermodynamics c< 'hat fraction of the water will be condensed if the total pressure of the mi(ture is isothermally increased to 233 atm? a< mol > - 2 @ $33 mol > "2 @ $33 mol > ,r @ $33 PN 2 Ptotal PO2 Ptotal = $33 = $33 3.79 3.99 atm = 09.0> $ atm 3.2$ 3.99 atm = $9.5> $ atm

PAr 3.3$ 3.99 atm = $33 = 3.=> Ptotal $ atm PH 2O Ptotal = $33 3.$2 atm = $2.3> $ atm

mol > * 2 " @ $33 b< PH 2OV = nH 2O RT V

2OV = PH 2OV where the primed quantities refer to $33> * PH V = PH 2OV 2O PH = 3.$2 atm 23.3 A = $2.2 A 3.$=7 atm

c< If all the water remained in the gas phase, the partial pressure of water at a total pressure of 233 atm would be PH 2O = Ptotal mol fraction * 2 " @ 233 atm 3.$2 @ 2:.3 atm *owe!er, the partial pressure of water cannot be greater than 3.$=7 atm, and the e(cess will condense. The fraction that condenses is gi!en by 2:.3 atm 3.$=7 atm fraction condensed @ = 3.==2 2:.3 atm

P1.7) , mi(ture of 2.53 $3E4 g of "2, 4.5$ $3E4 mol of -2, and :.07 $323 molecules
of C" are placed into a !essel of !olume 4.53 A at 5.23;C. a< Calculate the total pressure in the !essel. b< Calculate the mole fractions and partial pressures of each gas. a< nO2 = ntotal Ptotal 2.536$34g :.07 $323 molecules 5 = 7.9$6$3 mol n = = 7.756$3: mol G CO 42.3 g mol $ 0.322 $324 molecules mol $ = nO2 + nN 2 + nCO = 7.9$6$35 mol + 4.5$6$34mol + 7.756$3 : mol = :.406$34mol nRT :.406$34mol69.4$:6$3 2 A bar mol$8 $ 279.4 8 = = = 2.996$32 bar V 4.53 A

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Chapter $1/undamental Concepts of Thermodynamics

b< 7.9$6$35 mol 4.5$6$34mol xO2 = = 3.3$7= G xN2 = = 3.934 G :.406$34 mol :.406$34 mol 7.756$3: mol xCO = = 3.$79 :.406$34mol PO2 = xO2 Ptotal = 3.3$7=62.996$32 bar = 5.$06$3 : bar PN 2 = xN 2 Ptotal = 3.93462.996$32 bar = 2.4$6$3 2 bar PCO = xCO Ptotal = 3.$7762.996$32 bar = 5.$36$3 4bar

P1.") Aiquid -2 has a density of 975.: kg mE4 at its normal boiling point. 'hat !olume
does a balloon occupy at $9.5;C and a pressure of $.33 atm if 2.33 6 $3E4 A of liquid -2 is injected into it? N Vliq nN 2 = 2 M N2 VN 2 = nN2 RT P =

N2Vliq RT M N2 P

975.: g A$ 62.336$34 A69.23576$3 2 A atm 8 $mol $ 6 ( 274.$5 C $9.5) 8 = 29.3$ g mol$ 6$ atm = $.53 A

P1.9) , rigid !essel of !olume 3.533 m4 containing *2 at 23.5;C and a pressure of 0$$
$34 Pa is connected to a second rigid !essel of !olume 3.753 m4 containing ,r at 4$.2;C at a pressure of :44 $34 Pa. , !al!e separating the two !essels is opened and both are cooled to a temperature of $:.5;C. 'hat is the final pressure in the !essels? PV 0$$ $34 Pa 3.533m4 nH 2 = = = $25 mol RT 9.4$: . mol $8 $ ( 274.$5 C 23.5) 8 nAr = P= PV :446$34Pa 63.753m4 = = $29 mol RT 9.4$:. mol$8 $6 ( 274.$5 C 4$.2) 8

$ $ nRT ( $25 C $29 ) mol69.4$:. mol 8 6 ( 274.$5 C $:.5 ) 8 = = :.9:6$35 Pa 4 V B3.533 C 3.753< m

P1.1#) , sample of propane BC4*9< placed in a closed !essel together with an amount of
"2 that is 4.33 times the amount needed to completely o(idi+e the propane to C"2 and *2" at constant temperature. Calculate the mole fraction of each component in the resulting mi(ture after o(idation assuming that the *2" is present as a gas. The reaction is C4*9Bg< C 5"2Bg< H 4C"2Bg< C :*2"Bg<. If m mol of propene are present initially, there must be $5m mol of "2. ,fter the reaction is complete, there are 4m mol of C"2, :m mol of *2", and $3m mol of "2. $%0

Chapter $1/undamental Concepts of Thermodynamics

xCO2 =

4m :m $3m = 3.$70 G xH 2O = = 3.245 G xO2 = = 3.599 $7m $7m $7m

P1.11) , glass bulb of !olume 3.$40 A contains 3.734$ g of gas at 75=.3 Torr and
==.5;C. 'hat is the molar mass of the gas? m PV RT n= = GM = m M RT PV 9.23576$32 A atm mol $8 $ 6 ( 274.$5 C ==.5 ) 8 M = 3.734$g 6 = $59 amu 75= atm63.$40 A 703

P1.12) The total pressure of a mi(ture of o(ygen and hydrogen is $.33 atm. The
mi(ture is ignited and the water is remo!ed. The remaining gas is pure hydrogen and e(erts a pressure of 3.:33 atm when measured at the same !alues of T and V as the original mi(ture. 'hat was the composition of the original mi(ture in mole percent? 2*2Bg< C "2Bg< H 2*2"Bl< o o nO initial moles nH 2 3 2
o at equilibrium nH 2 2 o nO 2

o o If the "2 is completely consumed, nO2 = 3 or = nO2 . The number of moles of *2 o o o remaining is nH 2 2 = nH 2 2nO2 . Aet P$ be the initial total pressure and P2 be the total pressure after all the "2 is consumed. RT RT o o o o P and P2 = nH 2nO $ = n H 2 + nO2 2 2 V V Di!iding the second equation by the first

o o nH nO P2 2 = o 2 o 2 o = xH 2 2 xO2 = $ xO2 2 xO2 = $ 4xO2 o P n + n nH 2 + nO2 $ H2 O2

P $ 3.:33 atm $ xO2 = $ 2 = $ = 3.23G 4 P 4 $.33 atm$ $

xH 2 = 3.93

P1.13) , gas sample is known to be a mi(ture of ethane and butane. , bulb of 233.3%
cm4 capacity is filled with the gas to a pressure of $33.3 6 $34 Pa at 23.3;C. If the weight of the gas in the bulb is 3.49:0 g, what is the mole percent of butane in the mi(ture?

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Chapter $1/undamental Concepts of Thermodynamics n$ = moles of ethane n2 = moles of butane PV $33.3 $34 Pa 3.233 $3 4m 4 = = 9.2$ $34mol $ $ RT 9.4$: . mol 8 2=4 8 The total mass is n$M $ + n2 M 2 = 3.49:0 g n$ + n2 = Di!iding this equation by n$ + n2 n$M $ nM 3.49:0 g + 2 2 = = :0.97 g mol $ n$ + n2 n$ + n2 9.2$ $34mol

x$M $ + x2 M 2 = ( $ x2 ) M $ + x2 M 2 = :0.97 g mol $ x2 = :0.97 g mol$ M $ :0.97 g mol $ 43.30= g mol $ = = 3.5== M 2 M$ 59.$24 g mol $ 43.30= g mol $

mole > @ 5=.=>

P1.14) 'hen .ulius Caesar e(pired, his last e(halation had a !olume of 533 cm4 and
contained $.33 mole percent argon. ,ssume that T @ 433 8 and P @ $.33 atm at the location of his demise. ,ssume further that T and P currently ha!e the same !alues throughout the )arthIs atmosphere. If all of his e(haled C"2 molecules are now uniformly distributed throughout the atmosphere Bwhich for our calculation is taken to ha!e a thickness of $.33 km<, how many inhalations of 533 cm4 must we make to inhale one of the ,r molecules e(haled in CaesarIs last breath? ,ssume the radius of the )arth to be 0.47 6 $30 m. J*int# Calculate the number of ,r atoms in the atmosphere in the simplified geometry of a plane of area equal to that of the )arthKs surface and a height equal to the thickness of the atmosphere. ?ee Problem P$.$5 for the dependence of the barometric pressure on the height abo!e the )arthKs surface.L % o Ad where N % o is the The total number of ,r atoms in the atmosphere is N Ar = N Ar Ar
3

% is gi!en by number of ,r atoms per m4 at the surface of the earth. N

o Ar 24 5 % o = N A PAr = 0.324 $3 3.3$33 $ $3 Pa = 2.:$ $324 m 4 N Ar RT 9.4$: . 8 $ mol$ 433 8

The total number of ,r atoms in the atmosphere is M g Ar o % % % o A RT N Ar = N Ar Ad = N Ar e RT Ad = N Ar M Ar g 3 3 = 2.:$ $324 m 4 : 0.47 $30 m 9.4$: . mol $ 8 $ 433 8 4=.= $34 kg =.9$ m s 2

= 7.95 $3:$ The fraction of these atoms that came from CaesarKs last breath, f, is gi!en by

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Chapter $1/undamental Concepts of Thermodynamics % o V 2.:$ $324 m 4 3.533 $3 4 m4 N f = Ar = = $.54 $322 :$ N Ar 7.95 $3 The number of ,r atoms that we inhale with each breath is PV $32 $ $35 Pa 3.533 $34 m 4 24 N = NA = 0.324 $3 = $.2$ $323 $ $ RT 9.4$: . mol 8 433 8 The number of these that came from CaesarKs last breath is fN fN = $.54 $322 $.2$ $323 = $.95 $32 The reciprocal of this result, or 5:, is the number of breaths needed to inhale one ,r atom that Caesar e(haled in his last breath.

P1.15) The barometric pressure falls off with height abo!e sea le!el in the )arthIs
3 atmosphere as P = P 3 e RT where Pi is the partial pressure at the height , Pi is the i i partial pressure of component i at sea le!el, g is the acceleration of gra!ity, R is the gas constant, and T is the absolute temperature. Consider an atmosphere that has the composition x N 2 = 3.033 and xCO2 = 3.:33 and that T @ 433 8. -ear sea le!el, the total pressure is $.33 bar. Calculate the mole fractions of the two components at a height of 53.3 km. 'hy is the composition different from its !alue at sea le!el? Mg i 29.3: $34 kg =.9$ m s 2 53 $34 m 3 5 RT PN 2 = PN2 e = 3.033 $.3$25 $3 Pa e(p 9.4$: . mol $ 8 $ 433 8 Mi g

= 2:2 Pa PCO2 = P e
3 CO2 Mig RT

::.3: $34 kg =.9$ m s 2 53 $34 m = 3.:33 $.3$25 $3 Pa e(p 9.4$: . mol$ 8 $ 433 8
5

xCO2

= 0.=4 Pa PCO2 0.=4 = = = 3.329 PCO2 + PN 2 0.=4 + 2:2

xN2 = $ xCO2 = 3.=72

The mole fraction of C"2 at the high altitude is much reduced relati!e to its !alue at sea le!el because it has a larger molecular mass than -2.

P1.16) ,ssume that air has a mean molar mass of 29.= g molE$ and that the atmosphere
has a uniform temperature of 25.3;C. Calculate the barometric pressure at Den!er, for which @ $033 m. Mse the information contained in Problem P$.$5. Mg i 29.= $3 4 kg =.9$ m s 2 $033 m : P = P 3e RT = $35 Pa e(p = 9.4: $3 Pa $ $ 9.4$: . mol 8 433 8

P1.1$) Calculate the pressure e(erted by ,r for a molar !olume $.:2 A at 433 8 using
the !an der 'aals equation of state. The !an der 'aals parameters a and b for ,r are

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Chapter $1/undamental Concepts of Thermodynamics $.455 bar dm0 molE2 and 3.3423 dm4 molE$, respecti!ely. Is the attracti!e or repulsi!e portion of the potential dominant under these conditions? RT a P= 2 Vm b Vm = 9.4$:6$32 bar dm 4mol $8 $ 64338 $.455 bar dm 0 mol 2 = $7.4 bar 2 $.:2 dm 4mol$ 3.342$dm4 mol $ $.:2 dm4 mol $

Pideal =

RT 9.4$:5 $3 6A bar mol 8 6433 8 = = $7.0 bar V $.:2 A

Necause P & Pideal, the attracti!e part of the potential dominates.

P1.18) Calculate the pressure e(erted by ben+ene for a molar !olume $.:2 A at 7=3 8
using the edlich%8wong equation of state# RT a $ nRT n2a $ P= = . The edlich%8wong Vm b T Vm ( Vm + b ) V nb T V ( V + nb ) parameters a and b for ben+ene are :52.3 bar dm0 molE2 8$12 and 3.3927$ dm4 molE$, respecti!ely. Is the attracti!e or repulsi!e portion of the potential dominant under these conditions? RT a $ P= Vm b T Vm ( Vm + b ) = 9.4$:6$32 bar dm 4mol $8 $ 67=3 8 $.:2 dm4 mol$ 3.3927$dm4 mol$ :52.3 bar dm mol 8 $ 4 $ 4 $.:2 dm mol 6 $.:2 dm mol $ C 3.3927$dm4mol $ 7=3 8
0 2 $ 2

P = :$.0 bar RT 9.4$:56$32 6A bar mol$8 $ 67=3 8 Pideal = = = :0.4 bar V $.:2 A Necause P & Pideal, the attracti!e part of the potential dominates.

P1.1%) De!ise a temperature scale, abbre!iated O, for which the magnitude of the ideal
gas constant is $.33 . OE$ molE$. Aet T and T represent the 8el!in and O scales, and in each of these scales. Then PV = nRT = nR T T = R T = 9.4$:T R and R represent the gas constant

The temperature on the O scale is the !alue in 8 multiplied by 9.4$:. $%$3

Chapter $1/undamental Concepts of Thermodynamics

P1.2#) , mi(ture of o(ygen and hydrogen is analy+ed by passing it o!er hot copper
o(ide and through a drying tube. *ydrogen reduces the Cu" according to the reaction Cu" C *2 H Cu C *2" and o(ygen reo(idi+es the copper formed according to Cu C $12 "2 H Cu". ,t 25;C and 753 Torr, $33.3 cm4 of the mi(ture yields 9:.5 cm4 of dry o(ygen measured at 25;C and 753 Torr after passage o!er Cu" and the drying agent. 'hat is the original composition of the mi(ture? Two equilibria must be considered# Cu"Bs< C *2Bg< H *2"Bl< C Cu o nO at equilibrium 2 Cu Bs< C P "2Bg< H Cu" $ o nO at equilibrium 2 2
o In the final state, only "2 is present. Therefore = nO2 . In an e(cess of "2, all the $ o o o copper is o(idi+ed. Therefore = 0 or = nO2 . 'e conclude that nO2 = nO2 nH 2 . 2 Aet V$ and V2 be the initial and final !olumes. RT $ o RT o o o V$ = nH + nO V2 = nO nH 2 2 2 P 2 2 P

Di!iding the second equation by the first yields o o nO V2 $ nH 2 $ o $ o 4 o o o = o 2 o = xO xH = $ xH xH = $ xH o o 2 2 2 2 V$ nH 2 + nO2 2 nH 2 + nO2 2 2 2 2

o xH = 2

2 V2 2 9:.5 cm 4 $ = $ = 3.$34G 4 4 V$ 4 $33.3 cm

o o xO = $ xH @ 3.9=7 2 2

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