5/9/1

Exercises

THE SECOND LAW

51

In all of the these relations, choosing the inequality provides the criteria for spontaneous change. specified. Choosing the equal sign gives us the criteria for equilibrium under the conditions Assume that all gases are perfect and that data refer to 298.15 K unless

Exercises
otherwise stated.

3.8

03.5

500 K given that it is 146.22 J K mol at 298 K. (b) 70C. reversibly and isothermally as heat to a large block of iron at (a) 0C, 3.2(b) Calculate the molar entropy of a constant-volume sample of argon at (b) 100C. 3.2(a) Calculate the molar entropy of a1 constant-volume sample of neon at 1 250 K given that it is 154.84 J K mol 1 at 298 K. 500 KCalculate given that it is 146.22 K 1 molwhen at 298 K.of energy is transferred 3.1(b) the change inJentropy 50 kJ 3.3(a) Calculate S (for the system) when the state of 3.00at mol perfect gas reversibly and isothermally as heat to a large block of copper (a)of 0C, 3.2(b) Calculate the molar entropy of a constant-volume sample of argon at 5 atoms, changed from 25C and 1.00 atm to 125C and (b) 70C. for which Cp,m = 2 R,Jis Pressure, temperature, and volume are easily measured properties. 250 K given that it is 154.84 K1 mol1 at 298 K. 5.00 atm. How do you rationalize the sign of S? 3.2(a) Calculate the molar entropy of a constant-volume sample of neon at 3.3(a) Calculate S (for the system) when the state of 3.00 mol of perfect gas 1 500 K given that it is J K mol1 when 298the K. state of 2.00 mol diatomic 3.3(b ) Calculate 146.22 S (for system) 5 the 03.7 The relation (aG j ap)r = V shows that the Gibbs function of a system increases with p at constant T in at 7 atoms, for which Cp,m = 25C and 1.00 atm to 125C and 2 R, is changed from perfect gas molecules, for which Cp,m = , is changed from 25C and 2 Rof Calculate molar entropy of of a constant-volume sample of argon at 5.00 considers atm. How the do you rationalize the sign S? proportion to the magnitude of its volume. This makes good sense when 3.2(b) one the definition 1.50 atm to 135C and 7.00 atm. 1 How 1 do you rationalize the sign of S? 250 K given that it is 154.84 J K mol at 298 K. G, which is G = U + pV - TS. Hence, G is expected to increase with p 3.3(b in proportion to V when T is when the state of 2.00 mol diatomic ) Calculate S (for the system) 3.4(a) A sample consisting of 3.00 mol 7 of diatomic perfect gas at 3.3(a) Calculate S (for for the which system) when the state of 3.00 mol ofmolecules perfect gas perfect gas molecules, Cp constant. ,m = 2 R, is changed from 25C and 200 K is which compressed and adiabatically until its atm temperature reaches 5 atoms, for Cp,m =reversibly R, isatm. changed from 25C and 1.00 to 125C and 1.50 atm to 135C and 7.00 How do you rationalize the sign of S ? 2 1 1 250 K. Given that CV molof , calculate q, w, U, H, and S. ,m = 27.5 J K 5.00 atm. How do you rationalize the sign S? 3.4(a) A sample consisting of 3.00 mol of diatomic perfect gas molecules at 3.4(b) A sample consisting of 2.00 mol of diatomic perfect gas molecules at 3.3(b S (for the system) the stateuntil of 2.00 diatomic 200)KCalculate is compressed reversibly andwhen adiabatically itsmol temperature reaches 7 1 250 K is compressed reversibly and adiabatically until its temperature reaches 1 = perfect gas molecules, for which C R , is changed from 25C Solutions to exercises 250 K. Given that CV,m = 27.5 J K H, and S. p,m 2 1, calculate q, w, U, and 1 mol 300 K. to Given that CV7.00 27.5 J K mol , calculate q, w , sign U, of H, and ,m = atm. 1.50 atm 135C and How do you rationalize the S? S. 3.4(b) A sample consisting of 2.00 mol of diatomic perfect gas molecules at 3.5(a) Calculate H and of S3.00 when two copper blocks, each of mass 10.0 3.4(a) A sample consisting mol of diatomic perfect gas molecules at kg, tot 250 K is compressed Assume that all gases are perfect and that data refer to 298. 15K unless otherwise stated. reversibly and adiabatically until its temperature reaches one atcompressed 100C and the other at 0C, in contact in an isolated 1 are placed 1 200 KK. is reversibly and adiabatically until its temperature reaches 300 Given that C K mol , calculate q , w , U , H , and S. V,m = 27.5 J 1 1 1 copper is 0.385 J K g and may be container. heatJcapacity of 250 K. Given The that specic CV,m = 27.5 K 1 mol , calculate q, w, U, H, and S. E3.1(b) 3.5(a) Calculate H and Stemperature when two copper blocks, each of mass 10.0 kg, assumed constant over the range involved. tot 3.4(b) A sample consisting of 2.00 mol of diatomic perfect gas molecules at 52 STUDENT'S SOLUTIONS MANUAL one at 100C and the other at 0C, are placed in contact in an isolated 3.5(b) Calculate reversibly H and Stot when two iron blocks, each of mass 1.00 kg, one 250 K is compressed and adiabatically until its temperature reaches 1 1 container. The specic heat capacity of 1 copper is 0.385 J K g and may be 300 Given that CV J K1 mol , calculate q, win , an U, isolated H, andcontainer. S. atK. 200C and the other at 25C, are placed in contact For the first step ,m = 27.5 assumed constant over the temperature range involved. (a) The specic heat capacity of iron is 0.449 J K1 g1 and may be assumed 3.5(a) Calculate H and Stot when two copper blocks, each of mass 10.0 kg, AS dqrev Cp,m dT - C L Tf constant over the temperature rangetwo involved. 3.5(b) Calculate H and Stot when iron blocks, each of mass 1.00 kg, one '-' I T --T- p,m n Ti one at 100C and the other at 0C, are placed in contact in an isolated at 200C and the other at 25C, are placed in contact in an container. (b) 1 isolated container. The specic heat capacity of copper is 0.385 J K initially g1 and be 3.6(a) Consider a system consisting of 2.0 mol CO2(g), atmay 25C and 7) (l35 + 273) K The specic heat capacity of iron is 0.449 J K1 g1 and may be assumed f>"SI = (2.00 mol) x ( - x (8.3l45JK- 1 mol - I) x In = 18.31K- 1 assumed over the range involved. 10 atmconstant and conned to atemperature cylinder of cross-section 10.0 cm2. It is allowed to 2 (25+273)K constant over the temperature range involved. expand adiabatically against an external pressure of 1.0 atm until the piston for the second E3.2(b) and At 250 K, the entropy is equal to its entropy at 298 K plus I'1.S where 3.5(b) Calculate H and Stot when two iron blocks, each of mass 1.00 kg, one has moved outwards through 20 placed cm. Assume that carbon dioxide be 3.6(a) Consider a system consisting of 2.0 mol COin atmay 25C and 2(g), at 200C and the other at 25C, are in contact an initially isolated container. 1 1 2 considered a perfect gas with Cis = cross-section 28.8 JK mol and calculate (a) q, to f>"Sz = dqrev = qrev 10 atm andheat conned to a cylinder of 10.0 cm .assumed It is allowed 1 1 V,m The specic capacity of iron 0.449 J K g and may be T T (b) w, (c) U , (d) T , (e) San . external expand adiabatically against pressure of 1.0 atm until the piston dqrev CV,m dT _ Cv mIn Tf constant over the temperature range involved. I'1.S - has moved outwards through 20 cm. Assume that carbon dioxide may be T T Pi ' Tj Vf 3.6(b) Consider a system consisting 2.0 of 1.5 mol initially at 15C and where qrev = - w = J pdV = nRT In - = nRT In 1 CO 1 initially 2(g), 3.6(a) Consider a system mol CO at 25C and considered a perfect gasconsisting with CV,m of = 28.8 J K mol calculate (a) q, 2(g), and Vi Pf 2 2 cm . The sample is 9.0 atm and conneda to a cylinder of cross-section 100.0 10 atm conned cylinder (b) w,and (c) U, (d) to T, (e) S. of cross-section 10.0 cm . It is allowed to Pi I I L50atm I 250K allowed to expand against adiabatically against an external pressure of the 1.5 piston atm until so f>"Sz = nR In - = (2.00 mol) x (8.3 145 J K- mol - ) x In = - 25 .61 Kexpand an external pressure of 1.0 atm until so S =Pf 154.841 K- ' mol - ' + [(20.786 - 8.3145) 1 K'mol-'] x I n - - adiabatically 7.00atm the piston has moved outwards through 15 cm.CO Assume that carbon dioxide 3.6(b) Consider a system consisting of 1.5 mol initially at 15C and 298K has moved outwards through 20 cm. Assume that carbon may be 2(g),dioxide 1 1 2 and calculate 1 28.8 1K may beand considered a perfect with CV,m mol 9.0 atm conned to a cylinder of cross-section 100.0 cm, . The is considered a perfect gas with Cgas K= molJ and calculate (a)sample q, f>"S = (18.3 - 25.6)JK- 1 = !-7.31K- 1 ! V,m = 28.8 J (a) , (b) w (c) T U (d) S. allowed to expand adiabatically an external pressure of 1.5 atm until (b) w,q (c) U ,, (d) ,, (e) ST . , (e) against S in = step 1152.651K-' mol - gained ' The heat lost 2 was more than the heat in step 1, resulting in a net loss of entropy. Or the the piston has moved outwards through 15 cm. Assume that carbon dioxide 3.7(a) The enthalpy of consisting vaporization of chloroform (CHCl )1 is 29.4 kJand mol1 at 3.6(b) Consider a system of 1.5 mol CO2J (g), initially 15C 3 ordering represented by confining the sample to a smaller volume in step 2 overcame the disordering may be considered a perfect gas with CV,m = 28.8 K1 mol , at and calculate its normal boiling point of 334.88 Calculate (a) the entropy of vaporization represented by the temperature rise in step I. A negative entropy change is allowed for a system as long 9.0 atm and conned to a cylinder ofK. cross-section 100.0 cm2. The sample is (a) q, (b) w, (c) U, (d) heating T, (e) S . E3.3(b) as an However the change occurred I'1.S > has by reversible at of chloroform atadiabatically this temperature and (b) the entropy change ofatm the until increase in entropy elsewhere results in f>"Stotal O. the same value as if the change happened allowed to expand against an external pressure of 1.5 surroundings. (step 2) constant pressure (step I) followed by reversible isothermal compression the piston has moved outwards through cm. Assume that carbon dioxide 3.7(a) The enthalpy of vaporization of15 chloroform (CHCl kJ mol1 at 3) is 29.4 E3.4(b) q = qrev =0 [adiabatic reversible process] 1 may be considered perfect withK. CV K1 mol , and of calculate its normal boilingapoint ofgas 334.88 Calculate (a) the entropy vaporization 1 ,m = 28.8 J 3.7(b) The enthalpy of vaporization of methanol is 35.27 kJ mol at its (a) , (b) w, (c) Uthis , (d)temperature T, (e) S. and (b) the entropy change of the ofq chloroform at normal boiling point of 64.1C. Calculate (a) the entropy of vaporization f>"S = dqrev = surroundings. i T of methanol at this temperature and (b) the entropy change of the 3.7(a) The enthalpy of vaporization of chloroform (CHCl kJ mol1 at 3) is 29.4 1 f>"U = nCv ,mf>"T = (2.00 mol ) x (27.5 J K- I mol-I) x (300 - 250) K its normal boiling point 334.88 K. Calculate (a) the entropy vaporization surroundings. 3.7(b) The enthalpy ofof vaporization of methanol is 35.27 kJ of mol at its of chloroform at this temperature and (b) the entropy change the normal boiling point of 64.1C. Calculate (a) the entropy ofof vaporization = 2750J = 1+2.75 kJ 1 surroundings. of methanol at this temperature and (b) the entropy change of the w = f>"U - q = 2.75 kJ - 0 = 12.75 kJ 1 surroundings. 3.7(b) The enthalpy of vaporization of methanol is 35.27 kJ mol1 at its

The Maxwell relations are relations between partial derivatives all of which are expressed in terms of when 25 kJ of energy is transferred 3.1(a) Calculate the change in entropy Assume that all gases are perfect and that data refer to 298.15 K unless functions of state (properties of the system). Partial derivatives can be thought of as a kind of shorthand reversibly and isothermally as heat to a large block of iron at (a) 0C, otherwise stated. (b) the 100C. entropy of the system for an experiment. Therefore, the partial derivative (aS j aV)T tells us how 3.1(a) Calculate the change in entropy when 25 kJ of energy is transferred volume under constant-temperature conditions. 3.1(b) But, Calculate the change in entropy whenblock 50 kJ of of iron energy transferred is not a changes when we change its as entropy reversibly and isothermally as heat to a large at is (a) 0C, reversibly and isothermally as heat to a large block of copper at (a) 0C, is important that the derivative property that can be measured directl (b) 100C. Prac4ce 3 y (there are no entropy meters), it Assume that all gases are perfect and that data refer to 298.15 K unless (b) 70C. measurable properties. (and hence the experiment) be transformed into a form that involves directly otherwise stated. the 3.1(b) Calculate change inThat entropy when 50 kJ of energy is transferred 3.2(a) Calculate the molar entropy ofaalarge constant-volume sample of0C, neon at is what the following Maxwell relation does for us. reversibly and isothermally heat to block copper at (a) 3.1(a) Calculate the change inas entropy when 25 kJ of of energy is transferred 1 1

Physical Chemistry

Second Law - Example 1 Exercises

3.8

3.8

3.8(a) 3.8

(b rea (c 298

3.9

(a

3.9 3.8(b) 3.9

rea reactio 29 298 K 3.1

3.9 3.1 rea 3.9(a)

rea rea (a 29 298 (b

3.1 rea 3.9(b) rea

Second Law - Example 1

Second Law Example 2

3.1 reactio 3.1 CH 3.10(b for ent reactio

reactio 3.1 3.1 298 K rea for 3.10(a

3.11(a CH 30 2 C en Cal forma

3.1 3.1

3 CH O 363 Ca entha Cal

3.1 3.1 3.11(b

-f

Second Law Example 2

W

Second Law Example 3

6 3054 sur Ca Calcu of m rev 3.1 3.12(b and sur 632 k of Calcu 3.1 rev sur 3.13(a an of a surrou 4.6 3.1 of ma irre sur revers exp of and (c 4.6 3.1 3.13(b irr obt surrou exp me of arg 3.1 4.60 d 3.1 ob irreve obt me expan pro

3.1 3.12(a 3.1

if

f>"H

= nCp.mf>"T

obtain ob ope metha pro calc and 3.14(b 3.1 obtain op propa cal an 3.15(a

3.1 3.14(a 3.1

Cp,m = CV ,m + R

(27.51 K- I mol-I + 8.3141 K- I mol-I)

35.814J K- I mol - I

So f>"H
E3.S(b)

(2.00 mol) x (35.8141 K- I mol - I) x (+50 K)

= 358l.41 = 13.58 kJ 1

normal boiling point of 64.1C. Calculate (a) the entropy of vaporization of methanol at this temperature and (b) the entropy change of the surroundings.

opera calcul and d

Since the masses are equal and the heat capacity is ass umed constant, the final temperature will be the average of the two initial temperatures,

The heat capacity of each block is C

= mCs

where Cs is the specific heat capacity

so f>"H (individual)

= mCsf>"T =

1.00 x 103 g x 0.4491 K- I g-I x (87.5K)

= 39kJ

5 atoms, for which Cp,m = 2 R, is changed from 25C and 1.00 atm to 125C and 5.00 atm. How do you rationalize the sign of S?

298 K.
3.10(a) Use standard Gibbs energies of formation to calculate the standard

5/9/1
LAW

3.3(b) Calculate S (for the system) when the state of 2.00 mol diatomic
7 perfect gas molecules, for which Cp,m = 2 R, is changed from 25C and 1.50 atm to 135C and 7.00 atm. How do you rationalize the sign of S?

reaction Gibbs energies at 298 K of the reactions in Exercise 3.8a.

3.10(b) Use standard Gibbs energies of formation to calculate the standard THE SECOND reaction Gibbs energies at 298 K of the reactions in Exercise 3.8b. 3.11(a) Calculate the standard Gibbs energy of the reaction 4 HCl(g) + O2(g) 2 Cl2(g) + 2 H2O(l) at 298 K, from the standard entropies and enthalpies of formation given in the Data section. 6. r W = v6.r W v6. r W [2.32] 3.11(b) Calculate the standard Gibbs energy of the reaction CO(g) + Products Reactants CH3OH(l) CH at 298 K, from the-standard entropies and 3COOH(l) = -484.5 kJ mol-I - (-238.66 kJ mol-I) (-110.53 kJ mol-I) enthalpies of formation given in the Data section.

54

STUDENT'S SOLUTIONS MANUAL

3.4(a) A sample consisting of 3.00 mol of diatomic perfect gas molecules at E3.11(b) 200 K is compressed reversibly and adiabatically until its temperature reaches 1 1 282 .9) K. Given CV 27.5 JK , calculate q, w, U, H, and S. /'<,.S =250 ( 1.5 mol ) x that (28.8 JK -1 mol I) x mol In ? ? ,m = { ( _8L 3.4(b) A sample consisting of 2.00 mol of diatomic perfect gas molecules at 250 K is compressed reversibly and adiabatically until its temperature reaches +(8.314J K- I mol - I) x In ( 5.44)} 300 K. Given that CV,m = 27.5 J K1 mol1, calculate 3.942 q, w, U, H, and S.

Second Law Example 3

Second Law Example 4

E3.7(b)

one at 100C and the other at 0C, are placed in contact in an isolated 1 1 container. The specic heat capacity of copper and may be (a) /'<,. vap H 35.27 x 103 J mol - I _ is I 0.385 I J K g_ I I the temperature range /'<,. vapS = assumed = constant (64. 1 + over 273.15) K = + I 04.58 J K involved. = 104.6 J K

3.5(a) Calculate H and Stot when two copper blocks, each of mass 10.0 kg,

----y:;;-

3.12(a) The standard enthalpy of combustion of solid phenol (C6H5OH) is 3054 kJ mol1 at 298 K and its standard molar entropy is 144.0 J K1 mol1. CalculateProducts the standardReactants Gibbs energy of formation of phenol at 298 K.

= -135.31kJmol- 1

3.5(b) Calculate H and Stot when two iron blocks, each of mass 1.00 kg, one (b) If vaporization occurs reversibly, generally assumed at 200C and the otheras atis 25C, are placed in contact in an isolated container. EXERCISES 113

= 159.8JK- I mol- I -126.8JK- I mol-I -197.67JK- I mol-I 3.12(b) The standard enthalpy of combustion of solid urea (CO(NH2)2) is 1 1 1 I and 632 kJ at 298 = mol -164.67 J K-K mol -its I standard molar entropy is 104.60 J K mol .
6. r c B- = 6. r W - T 6. r SB3.13(a) Calculate the change in the entropies of the system and the 1 I = -135.31kJmol(298K) (-I64.67JKsurroundings, and the total- change inxentropy, when amol-I) sample of nitrogen gas

The specic heat capacity of iron is 0.449 J K1 g1 and may be assumed involved. /'<,.Ssysconstant + /'<,.Ssur over = 0 the sotemperature /'<,.Ssur = 1- range 104.6 J K- I I
THE SECOND LAW 55

Calculate the standard Gibbs energy of formation of urea at 298 K.

E3.8(b) E3.11(b)

(a)

3.6(a) Consider a system consisting of 2.0 mol CO2(g), initially at 25C and /'<,.rS & = atm and conned aq) + to a cylinder s) s) aq) 10 of cross-section 10.0 cm2. It is allowed to

rred

expand adiabatically against an external pressure of 1.0 atm until the piston II + 33.15 - through 41.63 + 20 99.6] J K- I molthat - I =carbon 1-21.0J K- Imol= [-112.1 E3.12(b) has moved outwards cm. dioxide may be 3.8(a) Calculate theW standard entropy atAssume 298 K of 6. r W = L v6.r - L reaction v6. r W [2.32] 1 1 considered a perfect gas with C = 28.8 J K mol and calculate (a) q, V,m Products Reactants 2 CH (b) (a) 2 CH (b) w, (c) + UO , (d) T, (e) S 3CHO(g) 2(g) 3.COOH(l)

of mass 14 g at 298 K and 1.00 bar doubles its volume in (a) an isothermal = -135.31kJ mol - I + 49.072 kJ mol-I = 1-86.2 kJ mol-II reversible expansion, (b) an isothermal irreversible expansion against pex = 0, (c) anreaction adiabatic expansion. The and formation of reversible urea is
3.13(b) Calculate the change in the entropies of the system and the surroundings, and the total change in entropy, when the volume of a sample of argon gas of mass 21 g at 298 K and 1.50 bar increases from 1.20 dm3 to dm3 inreaction (a) an isothermal reversible expansion, (b) an isothermal The 4.60 combustion is irreversible expansion against pex = 0, and (c) an adiabatic reversible expansion.

rred C, E3.9(b)

(b) 2 AgCl(s) + Br2(l) 2 AgBr(s) + Cl2(g) 1 I mol 3.6(b) Consider a system of 1.5-mol 15C = -135.31kJmol2(g), initially = [( 12 x 213 .74) + ( II xconsisting 69.91 ) - 360.2 ( 12CO x 205.14)] J K- at -I and (c) Hg(l) + atm Cl2(g) HgCl2(s) 9.0 and conned to a cylinder of cross-section 100.0 cm2. The sample is 1 l allowed to expandmol adiabatically against an K external pressure of 1.5 atm until = 1+5 12.0JK- 1 entropy 3.8(b) Calculate reaction at 298 of Products the standard Reactants the piston has moved outwards through 15 cm. Assume that carbon dioxide I mol-I -197.67JK- I mol-I = 159.8JK- I mol- I -126.8JK2+ 2+ (a) Zn(s) + Cu (aq) Zn (aq) + Cu(s) may be considered a perfect gas with CV,m = 28.8 J K1 mol1, and calculate (a) /'<,.rW = /'<,.rW(Zn2+, I mol - I aq) - /'<,.rW(Cu 2+ , aq) = -164.67 K- w (a) q, J (b) , (c) U, (d) T, (e) S. (b) C 12H22O11(s) + 12 O2(g) 12 CO2(g) + 11 H2O(l)

= -484.5 kJ mol-I - g) (-238.66 kJ mol-I) - (-110.53 kJ mol-I) /'<,.rS & = 12S:' (C0 2, +

- 12S:'(0 2, g)

CO(NH2 )z (S)

--+ C02Cg)

+ 2H20(l) + N2(g)

3.14(a) the non-expansion work per mole 6. c H = Calculate 6.rW(C02, g)maximum + 26.rW(H20, 1) - 6.rW(CO(NH2h. s) that may be

eon at

gon at
E3.12(b)

ect gas C and

E3.10(b) mic

1 I its normal boiling point 334.88 K. Calculate (a) the entropy -135.31kJmolx of (-I64.67JKmol-I) Gibbs - (298K) reaction = enthalpies, and calculate the standard reaction energies at of vaporization /'<,.rG & = -218.66kJmol- 1 - (298 .15K) x (-2 1.0JK - 1 mol - I) = 1-212.40kJmol - 1 I of chloroform at this temperature and (b) the entropy change of the 298 K. = -135.31kJ mol - I + 49.072 kJ mol-I = 1-86.2 kJ mol-II surroundings. 3.9(b) Combine the reaction entropies calculated in Exercise 3.8b with the (b) The formation reaction of urea is-5645 kJ /'<,.rW = /'<,. c H t> = mo l- I 3.7(b) The enthalpy of vaporization of methanol isenergies 35.27 kJat mol1 at its reaction enthalpies, and calculate the standard reaction Gibbs normal boiling point of 64.1C. Calculate (a) the entropy of vaporization I 298 K. /'<,.rG& = -5645 kJ mol - I - (298.15 K) x (5 12.0J K - mol - I) = 1-5798 kJ mol - I I of methanol at this temperature and (b) the entropy change of the 3.10(a) Use surroundings. standard Gibbs energies of formation to calculate the standard (a) The combustion reaction is&(Zn 2+ reaction Gibbs at 298 Kof /'<,.rG the reactions in Exercise 3.8a. /'<,.rG & = energies /'<,.rG , aq) &(C u 2+ , aq)

= - 153.89 - 64.77 kJ mol - I = -2 18.66kJmol - 1 6. r c B- = 6.3.7(a) 6. r SBr W - TThe enthalpy of vaporization ofin chloroform (CHCl is 29.4 kJ mol1 at 3.9(a) Combine the reaction entropies calculated Exercise 3.8a with 3)the

obtained from a fuel cell in which the chemical reaction is the combustion of methane at 298 K. s) = 6.rWCC02 , g) + 26.rW(H20, I) - 6.cH(CO(NH2)z , s) 6.rW(COCNH2h.

Second Law Example 4

3.14(b) Calculate the non-expansion work perkJ mole be kJ mol - I) =maximum -393 .51 kJ mol-I + (2) x (-285.83 mol that - I) -may C -632 obtained from a fuel cell in which the chemical reaction is the combustion of = -333.17kJmol- 1 propane at 298 K.

Second Law Example 4

3.15(a) Calculate the e ciency of a primitive steam 6. rSB- =(a) S!CCO(NH2)z, s)Carnot - S!CC, gr) - !S!(02 , g) - S!(N2 , g) -engine 2S!CH2, g) operating on steam at 100C and discharging at 60C. (b) Repeat the = 104.60J K- I mol-I - 5.740J K- I mol - I - !(205.138J K- I mol-I) calculation for a modern steam turbine that operates with steam at 300C - 191.61 K- I mol - I - 2(130.684J K- I mol-I) and discharges at J 80C.

= -456.687JK- I mol-I
6.rcB- = 6.rW - T 6. rS B-

S?

les at reaches S.

reaction energies 298 K of the in Exercise 3.8b. 6. c H =Gibbs 6.rW(C02, g) + at 26.rW(H20, 1) - reactions 6.rW(CO(NH2h. s)

1= 3.10(b) Use standard Gibbs energies of-formation to calculate CO(NH2 )z (S) --+ C02Cg) + 2H20(l) + N2(g) =+-147.06 - 65.49kJmol 1-2 12.55kJmOI - 1the standard

3.11(a) Calculate the standard Gibbs energy of the 4 HCl(g) + O2(g) (b) /'<,.rGt> = I 2/'<,.r Gt> (C0 2, g) + + 1126.rW(H20, /'<,.rG &(H20 , I)-reaction -6.cH(CO(NH2)z /'<,.rG &(C 12H220 - 12/'<,.rG&(02, g) 6.rW(COCNH2h. s) = 6.rWCC02 , g) I) , s) 11 , s)

= -333.17kJmol -

(298K) x C -456.687JK - I mol-I )

2 Cl2(g) + 2 H2O(l) at 298 K, from the standard entropies and enthalpies of -393 .51 kJ mol-I + (2) x (-285.83 kJ mol - I) - C -632 kJ mol - I) x= (-394.36) + II = [12 formation given in the Data section . x (-237. 13) - (-1543) - 12 x 0] kJ mol - I
1 = 1-5798kJmol3.11(b) Calculate the standard Gibbs energy of the reaction CO(g) +
= -333.17kJmol- 1

= -333.17kJ mol-I = 1-197kJmol- 1 1

+ 136.093 kJ mol - I

ules at reaches S.

10.0 kg,

COMMENT. In each case these values of L'. rG& agree closely with the calculated values in Exercise 3.9(b). - 191.61 J K- I mol - I - 2(130.684J K- I mol-I) 3.12(a) The standard enthalpy of combustion of solid phenol (C H OH) is
1 I mol-I 3054 kJ at 298 K and its standard molar entropy is 144.0 J K1 mol1. =mol -456.687JKCalculate the standard Gibbs energy of formation of phenol at 298 K. 6 5

CH6. CH3COOH(l) at 298 from ,the entropies and s) - S!CC, gr) -K, !S!(02 g) - standard S!(N2 , g) 2S!CH2, g) rSB- = S!CCO(NH2)z, 3OH(l) I mol enthalpies of formation given in the Data section . = 104.60J K- I mol-I - 5.740J KK- I mol-I) I - !(205.138J

may be

0 kg, one ntainer. d

3.12(b) The standard enthalpy of combustion of solid urea (CO(NH2)2) is

1

6.rcB- = 6.rW - T 6. rS B-

= -333.17kJmol -456.687JK - mol-I ) - (298K) x C 1 632 kJ mol at 298 K and its standard molar entropy is 104.60 J K1 mol1. = the -333.17kJ mol-I + 136.093 kJ of molformation -I Calculate standard Gibbs energy of urea at 298 K.

= 1-197kJmol1 3.13(a) Calculate the change in the entropies of the system and the

C and ed to piston y be q,

surroundings, and the total change in entropy, when a sample of nitrogen gas of mass 14 g at 298 K and 1.00 bar doubles its volume in (a) an isothermal reversible expansion, (b) an isothermal irreversible expansion against pex = 0, and (c) an adiabatic reversible expansion.
3.13(b) Calculate the change in the entropies of the system and the

Second Law Example 5

Second Law Example 5

56 STUDENT'S SOLUTIONS MANUAL

C and mple is m until ioxide ulate

surroundings, and the total change in entropy, when the volume of a sample of argon gas of mass 21 g at 298 K and 1.50 bar increases from 1.20 dm3 to 4.60 dm3 in (a) an isothermal reversible expansion, (b) an isothermal irreversible expansion against pex = 0, and (c) an adiabatic reversible expansion.
3.14(a) Calculate the maximum non-expansion work per mole that may be

E3.13(b)

(a)

= nR In (Vf) [3 .13] = (
Vi

21 g I) x (8.314J K- 1 mol-I) In 2 39.95gmol-

= 3.029JK- 1 = 13.0JK- I = = (b)

= 1-3.0JK- I 1[reversible]

@]
=

mol1 at rization

obtained from a fuel cell in which the chemical reaction is the combustion of methane at 298 K.
3.14(b) Calculate the maximum non-expansion work per mole that may be

= 1+3.0JK- I 1[S is a state function]

@] [no change in surroundings]

= @] @] [No heat is transfered to the surroundings]

obtained from a fuel cell in which the chemical reaction is the combustion of propane at 298 K.
3.15(a) (a) Calculate the Carnot eciency of a primitive steam engine

= 1+3 .0JK- I 1 (c) qrev = 0 so = =

E3.14(b)

ts ion

operating on steam at 100C and discharging at 60C. (b) Repeat the calculation for a modern steam turbine that operates with steam at 300C and discharges at 80C.

@]

C3Hg(g) + 502(g) --+ 3C02(g) + 4H20(l) = g) + I) l ) -

g) - 0 1(-23.49kJmol- l )

= 3(-394.36kJmol- l ) + 4(-237.13 kJmol-

5/9/1

Exercises
56
56

STUDENT'S SOLUTIONS MANUAL

114

3 THE SECOND LAW

STUDENT'S SOLUTIONS MANUAL

E3.13(b) 3(b) (a)

(a)

= nR In (Vf) [3 .13] = ( 21 g I) x (8.314J K- 1 mol-I) In 2 Vi = ( = nR In (Vf) [3 .13] 21 g 39.95gmolI) x (8.314J K- 1 mol-I) In 2 Vi 39.95gmol= 3.029JK- 1 = 13.0JK- I = 3.029JK- 1 = 13.0JK- I

I Second Law I Example 5

@]
= =

= (b)

@]

= 1-3.0JK- I 1[reversible] = 1-3.0JK- I 1[reversible]

Assume that all gases are perfect and that data refer to 298.15 K unless 3.15(b) A certain heat engine operates between 1000 K and 500 K. (a) What is otherwise stated. the maximum eciency of the engine? (b) Calculate the maximum work that 3.1(a) the change inof entropy when 25 kJ of energy is transferred can be Calculate done by for each 1.0 kJ heat supplied by the hot source. (c) How much heatand is discharged into cold sink in block a reversible process for each reversibly isothermally asthe heat to a large of iron at (a) 0C, 1.0 kJ supplied by the hot source? (b) 100C.

3.8(a) 3.19(a)

pressu (a)

Second Law Example 6

(b) 3.19(b)

(c) pressu

(b)

(c)

= 1+3.0JK- I 1[S is a state function] = 1+3.0JK- I 1[S is a state function] = @] [no change in surroundings] = @] [no change in surroundings] = 1+3 .0JK- I 1 = 1+3 .0JK- I 1 (c) qrev = 0 so = @] = @] qrev = 0 so = heat @] [No heat is transfered to the surroundings] = @] [No is transfered to the surroundings]
=

to 60 cm3.and Calculate G for as the process. reversibly isothermally heat to a large block of copper at (a) 0C, (b) 70C. 3.16(b) Suppose that 2.5 mmol Ar(g) occupies 72 dm3 at 298 K and expands 3 to 100 dm . Calculate G for the process. 3.2(a) Calculate the molar entropy of a constant-volume sample of neon at 500 K given that it is 146.22 J K1 mol1 at 298 K. 3.17(a) The change in the Gibbs energy of a certain constant-pressure process was found to t the G/Jof =a 85.40 + 36.5(T/K). Calculate the value 3.2(b) Calculate theexpression molar entropy constant-volume sample of argon at of K S for thethat process. 250 given it is 154.84 J K1 mol1 at 298 K.
3.17(b)Calculate The change in the Gibbs energy of the a certain constant-pressure process 3.3(a) S (for the system) when state of 3.00 mol of perfect gas
5 was found to t the expression G/J = 73.1 + 42.8(T/K). Calculate the value atoms, for which Cp,m = 2 R, is changed from 25C and 1.00 atm to 125C and of S for the process. 5.00 atm. How do you rationalize the sign of S?
3

3 3.16(a)Calculate Suppose the that 3.0 mmol N2(g) occupies at 300is Ktransferred and expands 3.1(b) change in entropy when 5036 kJcm of energy

3.8(b) 3.20(a)

3.9(a) Calcul reactio the sam 298 K.

3.20(b)

Calcul (a) the sam (b)

@]

@]

reactio 3.21(b) 298 K. pressu

3.21(a) 3.9(b) the pre

C3Hg(g) + --+ 502(g) --+ 3C02(g) + 4H20(l) E3.14(b) C3Hg(g) + 502(g) 3C02(g) + 4H20(l) 4(b)
=

3.18(a) Calculate the change in Gibbs energy 35 g of ethanol density 3.3(b ) Calculate S (for the system) when theof state of 2.00 mol (mass diatomic

3.10(a 3.22(a) reactio

g) +

g) +
l

I) -

I) l

g) - 0
l

g) - 0
l

l ) + 4(-237.13 = 3(-394.36kJmol) - 1(-23.49kJmol) + 4(-237.13 = 3(-394.36kJmolkJmol- )kJmol) - 1(-23.49kJmol-

7 0.789 g gas cm molecules, ) when the pressure ispincreased isothermally from 1 atm to perfect for which C ,m = 2 R, is changed from 25C and 3000atm atm. 1.50 to 135C and 7.00 atm. How do you rationalize the sign of S?

= -2108.11 kJ mol-IkJ mol-I = -2108.11 The maximum non-expansion work is 12108.11 kJ mol-IIkJ since IWaddl = IWaddl = The maximum non-expansion work is 12108.11 mol-II since =500 0.500 K = 0.500 Th 1000 K 1000 K ,--_--, ,--_--, Th (b) Maximum work = f lqhl = (0.500) x (1.0 kJ) 0.50 For the first step (b) Maximum work = f lqhl = (0.500) x =(1.0 kJ)kJ = 0.50 kJ (c) f max = frey I%I-Iqc,minl (c) f =and frey Iwmaxl and = Iwmaxl = I%I-Iqc,minl
AS - max dqrev Cp,m dT - C L Tf '-' I T --T- p,m n Ti Iqc,minl = 1%1 - Iwmaxl Iqc,minl = 1%1 - Iwmaxl 7) x (8.3l45JK- 1 mol - I) f>"SI == (2.00 1.0mol) kJ -x 0.50 kJ (2 kJ - 0.50 kJ = 1.0

3.18(b)ACalculate the change Gibbs of 25 g of methanol (mass at 3.4(a) sample consisting ofin 3.00 molenergy of diatomic perfect gas molecules density g cm3)reversibly when the and pressure is increased isothermally from 200 K is0.791 compressed adiabatically until its temperature reaches 100 K. kPa to 100 MPa. 250 Given that CV,m = 27.5 J K1 mol1, calculate q, w, U, H, and S.

3.11(a pressu 2C format

3.22(b)

when i 3.10(b 298 K. reactio

(a) 5(b) E3.15(b)

f =STUDENT'S 1 _ f Tc 1MANUAL _ 500 K_ 52 SOLUTIONS (a) = [3.10] 1 _ Tc=[3.10] = 1

I II Second Law Example 6 I

II I

3.4(b) A sample consisting of 2.00 mol of diatomic perfect gas molecules at

Problems* Second aw copper Example 3.5(a) Calculate H and S L when two blocks, each 7 of mass 10.0 kg,
tot

250 K is compressed reversibly and adiabatically until its temperature reaches 300 K. Given that CV,m = 27.5 J K1 mol1, calculate q, w, U, H, and S.

3.11(b

CH3O enthal

x In (l35 + 273) K (25+273)K

18.31K- 1

one at 100C and the other at 0C, are placed in contact in an isolated 1 unless Assume that allspecic gases are perfect and of that data refer to 298 K otherwise container. The heat capacity copper is 0.385 J K g1 and may be stated. constant over the temperature range involved. assumed

3.12(a

and for the = second 0.5kJ

6(b) E3.16(b)

7(b) E3.17(b)

[3T .56] = nRTln [Boyle's law] = nRTln [3 .56] = nRTln [Boyle's law] Vf Pi I 3 where qrev = w = J pdV = nRT In = nRT In = (2.5 x 10- mol) x (8.314JKmol-I) x (298 K) x In = 1-2.0J Vi Pf I = (2.5 x 10- 3 mol) x (8.314JK- mol-I) x (298 K) x In = 1-2.0J Pi I I L50atm so f>"Sz = nR In - = (2.00 mol) x (8.3 145 J K- mol - ) x In = - 25 .61 K- I 7.00atm = -S Pf [3.50] ; hence = -Sf, and = -Si = -S [3.50] ; hence = -Sf, and = -Si f>"S = (18.3 - 25.6)JK- 1 = !-7.31K- 1 ! =_(aCGf-GJ) The heat lost in step 2 was more than the heat gained in step 1, resulting in a net loss of entropy. Or the =_(aCGf-GJ)
T

f = nRTln
f>"Sz =

= I 0.5kJ I

dqrev = qrev

ordering represented by confining the sample to a smaller volume in step 2 overcame the disordering represented by the temperature rise in step I. A negative entropy change is allowed for a system as long = = (-73 .1 J +42.8J x as an increase in entropy elsewhere results in T f>"Stotal > O.
E3.4(b)

= qrev = 0 [adiabatic reversible = 1-42.8 J K- I 1 process]

=

+(aGi) aT p p +(aGi) aT aTp aT p aT p aT p aa = = - aa (-73 .1 J +42.8J x T

x (27.5 J K- I mol-I) x (300 - 250) K

f>"S
f>"U

if
i

dqrev

I = = 1-42.8 J K- 1

= nCv ,mf>"T = (2.00 mol )

f>"U - q

= 2750J = 1+2.75 kJ 1

= 2.75 kJ -

= 12.75 kJ 1
35.814J K- I mol - I

f>"H

= nCp.mf>"T

Cp,m = CV ,m + R

So f>"H
E3.S(b)

(2.00 mol) x (35.8141 K- I mol - I) x (+50 K)

= = Second Law Example 7

(27.51 K- I mol-I + 8.3141 K- I mol-I)

= 358l.41 = 13.58 kJ 1

Since the masses are equal and the heat capacity is ass umed constant, the final temperature will be the average of the two initial temperatures,

3.5(b) Calculate H and Stot when two iron blocks, each of mass 1.00 kg, one Numerical problems at 200C and the other at 25C, are placed in contact in an isolated container. The heat capacity of iron is 0.449 J K1 (a) g1 between and mayliquid be assumed 3.1 specic Calculate the dierence in molar entropy water and constant over the temperature 3.13(a ice at 5C, (b) between liquid range water involved. and its vapour at 95C and 1.00 atm. 3.5 A surrou The dierences in heat capacities on of melting and on(g), vaporization are 3.6(a) Consider a system consisting 2.0 mol CO initially at 25C and substan 2 1 1 1 of mas 37.3 J Kand mol and 41.9 J K1 mol , respectively. Distinguish 10 atm conned to a cylinder of cross-section 10.0 cm2. It is between allowed to to a pr the entropy changes of the sample, the surroundings, and the total system, reversi expand adiabatically against an external pressure of 1.0 atm until the piston 300 K ( and discuss the spontaneity of the transitions at the two temperatures. and (c has moved outwards through 20 cm. Assume that carbon dioxide may be (Step 3 considered a perfect gas CV,m = 28.8 J K1 mol1 andCHCl calculate (a) q, 3.2 The heat capacity ofwith chloroform (trichloromethane, 3.13(b Determ 3) in the range 1 1 2 (b) (c)330 UK , (d) T, (e) S . 240w K, to is given by C /(J K mol ) = 91.47 + 7.5 10 ( T /K). In a surrou cycle a p,m particular experiment, 1.00 mol CHCl is heated from 273 K to 300 K. of argo 3.6(b) Consider a system consisting of31.5 mol CO2(g), initially at 15C and 3.6 1.0 Calculate the change in molar entropy of the sample. 4.60 dm 9.0 atm and conned to a cylinder of cross-section 100.0 cm2. The sample is an init irrever 1 3.3 A block of copper of mass 2.00 kg (C = 24.44pressure J K1 mol ) and allowed to expand adiabatically against an external of 1.5 atm until (a) rev p,m expans temperature 0C is introduced an insulated container in carbon which there is the piston has moved outwardsinto through 15 cm. Assume that dioxide Determ 1 1.00 mol H2O(g) ata100C and 1.00 atm. (a) Assuming all the steam is may be considered perfect gas with CV,m = 28.8 J K1 mol , and calculate 3.14(a 3.7 Th condensed water, what will be (a) q, (b) w,to (c) U, (d) T , (e) the S. nal temperature of the system, the heat obtain its heat transferred from water to copper, and the entropy change of the water, 1 metha 3.7(a) The enthalpy of vaporization of chloroform (CHCl3) is 29.4 kJ mol at Calcula copper, and the total system? (b) In fact, some water vapour is present at its normal boiling point of 334.88 K. Calculate (a) the entropy of vaporization 3.14(b equilibrium. From the vapour pressure of water at the temperature calculated 3.8 A of chloroform at this temperature and (b) the entropy change of the obtain in (a), and assuming that the heat capacities of both gaseous and liquid water with an surroundings. THE SECOND LAW propan are constant and given by their values at that temperature, obtain an improved 1.00 A 1 entropies. value of the nal temperature, the heat transferred, and the various taking 3.7(b) The enthalpy of vaporization of methanol is 35.27 kJ mol at its 3.15(a These twowill enthalpy changes add up to zero: I(a) 6. H tot = 0 I (Hint . You need to plausible approximations.) copper normal boiling point ofmake 64.1C. Calculate the entropy of vaporization operat Calcula of methanol at this temperature and (b) the entropy change of the calcula 3.4 Consider a perfect gas contained in a cylinder and separated by a 6.S = mCs In 200 C = 473.2 K; 2S C = 298.2 K; 112.5 C = 38S.7 K surroundings. and Fin di frictionless adiabatic piston into two sections A and B. All changes in B is 3.9

3054 = 2.00 Calcul the righ (a) SA 3.12(b system 632 k whethe Calcul from th

Second Law Example 7

(i);

The heat capacity of each block is C

= mCs

isothermal; that is, a thermostat surrounds B to keep its temperature constant. There is 2.00 each section. Initially, TA = T= 300 VIA = VB 6.S1 = mol ( 1.00of x the 103 gas g) xin (0.449J K- I g- I) x In IIS .5JK, KB=
1.00 x 103 g x 0.4491 K- I g-I x (87.5K)

substan brough

where Cs is the specific heat capacity

so f>"H (individual)

= mCsf>"T =

= 39kJ

* Problems denoted with the symbol were supplied by Charles Trapp, Carmen Giunta,
6.S2 = (1.00 x 10 3 g) x (0.449 J K- I g- I)
X

38S.7) In ( 473.2

-9 1.802J K- I

E3.6(b)

(a)

q = 0 [adiabatic]
w

(b)

-Pex6.V

= =

- ( I.Satm) x

(.

1.0 I x 10 pa) x (lOO.Ocm 2 ) x (lScm) x

-6--3

Im

-227.2 J 230 J

= 1-230 J I = 1-230 J I

(c)

6.U 6.U
6. T

= q+w=0= nCv.m6.T

(d)

6.U -227.2 J =- = - - -------:-