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Thermodnamics, , , page2
1970
Considerthefirstionizationofsulfurousacid:
H2SO3(aq) H
+
(aq) +HSO3
-
(aq)
Certain related thermodynamic data are provided
below:
H2SO3(aq) H
+
(aq) HSO3
-
(aq)
----------------- ---------- ------------------
H f kcal/mole -145.5 0 -151.9
S
cal/moleK
56 0 26
(a) Calculate the value of G at 25C for the
ionizationreaction.
(b) CalculatethevalueofKat25Cfortheionization
reaction.
(c) Account for the signs of S and H for the
ionizationreactionintermsofthemoleculesand
ionspresent.
Answer:
(a)
H H
f
_
( po dc ) H
f
_
( eacan )
=[-159.9]-[-145.5]kcal=-14.4kcal

S S
roducts
S
(reactants)
=(26-56)cal=-30cal/K
G = H-T S=-14400-(298)(-30)cal
=-5.46kcal
(b) K=e
- G/RT
=e
-(-5460/(1.9872)(298))
=10100
(c)
1971
Giventhefollowingdataforgraphiteanddiamondat
298K.
S(diamond) = 0.58cal/moledeg
S(graphite) = 1.37cal/moledeg
H f CO2(from graphite) = -94.48kilocalories/mole
H f CO2(fromdiamond) = -94.03kilocalories/mole
Consider the change: C(graphite) = C(diamond) at 298K
and1atmosphere.
(a) What are the values of S and H for the
conversionofgraphitetodiamond.
(b) Perform a calculation to show whether it is
thermodynamically feasible to produce diamond
fromgraphiteat298Kand1atmosphere.
(c) For the reaction, calculate the equilibrium
constantK eq at298K
Answer:
(a) S = S(dia.) - S(graph.) =(0.58-1.37)cal/K
=-0.79cal/K
CO2 C(dia.) +O2 H=+94.03kcal/mol
C(graph.) +O2 CO2 H =-94.48kcal/mol
C(graph.) C(dia.) H = -0.45kcal/mol
(b) G = H -T S =-450-(298)(-0.79)cal
= -223.52 cal/mol; a G < 0 indicates feasible
conditions
(c) K
eq
=e
- G/RT
=e
-(-223.52/(1.9872)(298))
=-0.686
1972
Br2 +2Fe
2+
(aq) 2Br
-
(aq) +2Fe
3+
(aq)
For the reaction above, the following da
available:
2Br
-
(aq) Br 2(l)+ 2e- E = -1.07 v
Fe
2+
(aq) Fe
3+
(aq)+ e- E = -0.77 v
S,cal/mole C
Br 2(l) 58.6 Fe
2+
(aq) -27.1
Br
-
(aq) 19.6 Fe
3+
(aq) -70.1
(a)Determine

S
(b)Determine G
(c)Determine H
Answer:
(a)

S S
roducts
S
(reactants)
=[(19.6)(2)+(-70.1)(2)]-[58.6+(-27.1)(2)]cal
=-105.4cal=-441J/K
(b) Ecell =[+1.07+(-0.77)]v=0.30v
G=-n E=-(2)(96500)(0.30v)=-57900J/mol
(c)

H =

G

+T

S =57900+298(-441)J
=-73.5kJ/mol
1974
WO3(s) +3H2(g) W(s) +3H2O(g)
Tungstenisobtainedcommerciallybythereductionof
WO3 withhydrogenaccordingtotheequationabove.
The following data related to this reaction
available:
WO3(s) H2O(g)
H f (kilocalories/mole) -200.84 -57.8
Gf (kilocalories/mole) -182.47 -54.6
(a) Whatisthevalueoftheequilibriumconstan
thesystemrepresentedabove?
(b) Calculate S at25Cforthereactionindicatedby
theequationabove.
(c) Find the temperature at which the r
mixtureisinequilibriumat1atmosphere.
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Thermodnamics, , , page3
Answer:
(a) G =[3(-54.6)+0]-[-182.47+0]=18.7kcal
Keq =e
- G/RT
=e
-(18700/(1.9872)(298))
=1.93 10
-8
(b) H =[3(-57.8)+0]-[-200.84+0]=27.44kcal
S =
H G
T
=
27440 18670
298
= 29 . 2
cal
mol K
(c)
) !

( %) & ) !
T= H/ S=27440/29.2=938K
1975B
2NO(g) +O2 2NO2(g)
Arateexpressionforthereactionaboveis:

d[O
2
]
d
= k [ NO ]
2
[O
2
]

H
f

S

G
f

kcal/mole cal/(mole)(K) kcal/mole

NO(g) 21.60 50.34 20.72
O2(g) 0 49.00 0
NO2(g) 8.09 57.47 12.39
(a) For the reaction above, find the rate constant at
25Ciftheinitialrate,asdefinedbytheequation
above, is 28 moles per liter-second when the
concentrationofnitricoxideis0.20moleperliter
andtheconcentrationofoxygenis0.10moleper
liter.
(b) Calculatetheequilibriumconstantforthereaction
at25C.
Answer:
(a)
k
ae
[ NO ]
2
[O
2
]

28
(0. 20 )
2
(0. 10 )
=7000mol
-2
L
2
sec
-1
(b) G =[2(12.39)]-[2(20.72)+0]=-16.66kcal
Keq =e
- G/RT
=e
-(-16660/(1.9872)(298))
=1.65 10
12
1975D
2Cu+S Cu2S
For the reaction above,

H,

G

, and

S are all
negative. Which of the substances would predominate
in an equilibrium mixture of copper, sulfur, and
copper(I) sulfide at 298K? Explain how you drew
your conclusion about the predominant substance
Copper(I) sulfide.The forward reaction involvesbond
formation and is, therefore, exothermic (H<0). The
forward reaction produces 1 molecule from 3 atoms
and,therefore,decreasesinentropy( S<0).Butsince
G is <0 and G = H -T S, this reacti
spontaneousatlowtemperatures.
Thismixturemustbeheatedbecausebothreactantsare
solidsandtheyreactonlywhenthecopperatomsand
sulfur atoms collide, an infrequent occurrence in the
solidstate.
1977B
CH3OH(l) +
3
/2 O2(g) 2H2O(l) +CO2(g)
The value of S for the reaction is -19.3 cal
degreeat25 C.
H f S
kcal/moleat25C cal/mole-degreea
------------------------- -----------------------
CH
3
OH
(l)
-57.0 30.3
H2O(l) -68.3 16.7
CO2(g) -94.0 51.1
(a) Calculate G for the complete combustio
methanolshownaboveat25C.
(b) Calculate the value for the equilibrium con
forthisreactionat25C.
(c) Calculate the standard absolute entropy,
moleofO2(g).
Answer:
(a)

$ &# ) (

& ( " (
=[2(-68.3)+(-94.0)]-[-57.0]=-173.6kcal
G = H -T S =-173.6+(298)(0.0193)kcal
=-167.8kcal
(b) K eq =e
- G/RT
=e
-(-167800/(1.9872)(298))
=1.15 10
123
(c)

S S
roducts

S
(reactants)
-19.3=[2(16.7)+51.1]-[30.3+
3
/2 X]
X=49.0cal/molK
1978B
StandardEntropy
Substance cal/degmole
N2(g) 45.8
H (g) 31.2
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your conclusion about the predominant substance
presentatequilibrium. Whymustamixtureofcopper
and sulfur be heated in order to produce copper (I)
sulfide?
Answer:
H2(g) 31.2
NH3(g) 46.0
Ammoniacanbeproducedbythefollowingreaction:
N2(g) +3H2(g) 2NH3(g)

Thermodnamics, , , page4
The Gibbs free energy of formation Gf ofNH3(g) is
-3.94kilocaloriespermole.
(a) CalculatethevalueforH forthereactionabove
298K.
(b) Cantheyieldofammoniabeincreasedbyraising
thetemperature?Explain.
(c) What is the equilibrium constant for the reaction
aboveat298K?
(d) If235millilitersofH2 gasmeasuredat25Cand
570millimetersHgwerecompletelyconvertedto
ammonia and the ammonia were dissolved in
sufficientwatertomake0.5000literofsolution,
what would be the molarity of the resulting
solution?
Answer:
(a)

S S
roducts

S
(reactants)
=[2(46.0)]-[45.8+3(31.2)]=-47.4cal/K
H = G +T S =-7.88+(298)(-0.0474)kcal
=-22.0kcal
(b) No, since H > 0, an increase in T shifts
equilibriumtoleftanddecreasesequilibriumyield
ofNH3.
(c) K
eq=e
- G/RT
=e
-(-7880/(1.9872)(298))
=6.01 10
5
(d)
n =
PV
R T
=
(570)( 235)
(62400 )( 298 )
= 0.00720 mo lH
2
0.00720 mol H
2

2mol NH 3
3 mol H
2

1
0.500 L

=0.00960 MNH3
1979B
H f S
Compound (kilocalories/mole) (calories/moleK)
H2O(l) -68.3 16.7
CO2(g) -94.1 51.1
O2(g) 0.0 49.0
C3H8 ? 64.5
(d) Calculate the entropy change, Scomb, f
reactionandaccountforthesign Scomb.
Answer:
(a) C3H8 +5O2(g) 3CO2(g) +4H2O(l)
(b)

# !

! #

(c)
H
comb .

3 H
f

CO
2
4 H
f

H
2
O H
f

C
3
H
-530.8kcal=[3(-94.1)+4(-68.3)-X]kcal
Hcomb. =-25.0kcal/mol
(d)
S
comb .

= [3S_CO
2
+ 4S_H
2
O ] [S _C
3
H
8
+ 5S
=[3(51.1)+4(16.7)]-[64.5+5(49.0)]
=-89.4cal/mol.K
Entropydecreasesduetolossofhighlydisordered
gaseousspeciesuponcombustion.
1980D
(a) Statethephysicalsignificanceofentropy.
(b) From each ofthe following pairs ofsubs
choose the one expected to have the
absolute entropy. Explain your choice in
case.Assume1moleofeachsubstance.
(1) Pb(s) or C(graphite) at the same temperature
andpressure.
(2) He(g) at 1 atmosphere or He(g) at
atmosphere,bothatthesametemperature.
(3) H2O(l) or CH3CH2OH(l) at the
temperatureandpressure.
(4) Mg(s) at 0C or Mg(s) at 150C both at the
samepressure.
Answer:
(a) Entropyisameasureofrandomness,disorder,et
inasystem.
(b) (1) Pb has greater molar entropy, Pb
metallic bonding, forms soft crystals
high amplitudes of vibration; graphi
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When 1.000 gram of propane gas, C
3
H
8
,isburnedat
25C and 1.00 atmosphere, H2O(l) and CO2(g) are
formedwiththeevolutionof12.03kilocalories.
(a) Write a balanced equation for the combustion
reaction.
(b) Calculate the molar enthalpy of combustion,
Hcomb,ofpropane.
(c) Calculate the standard molar enthalpy of
formation, H f,ofpropanegas.
stronger(covalent)bonds,ismorerigid,and
thusismoreordered.
(2) He(g) at 0.05 atmosphere has greater molar
entropy.Atlowerpressure(greatervolume)
Heatomshavemorespaceinwhichtomove
aresoaremorerandom.
(3) CH3CH2OH has greater molar e
Ethanolmoleculeshavemoreatomsandthus
more vibrations; water exhibits st
hydrogenbonding.

Thermodnamics, , , page5
(4) Mg(s) at150Chasgreatermolarentropy.At
thehighertemperaturetheatomshavemore
kinetic energy and vibrate faster and, thus,
showgreaterrandomness.
1981D
PCl5(g) PCl3(g) +Cl2(g)
For the reaction above, H = +22.1 kilocalories per
moleat25C
(a) Does the tendency of reactions to proceed to a
stateofminimumenergy favor the formation of
theproductsofthisreaction?Explain
(b) Does the tendency of reactions to proceed to a
stateofmaximumentropyfavortheformationof
theproductsofthisreaction? Explain.
(c) State whether an increase in temperature drives
this reaction to the right, to the left, or has no
effect. Explain.
(d) State whether a decrease in the volume of the
systematconstanttemperaturedrivesthisreaction
totheright,totheleftorhasnoeffect. Explain?
Answer:
(a) No, since reaction is endothermic, the products
mustbeathigherenergythanthereactants.
lnKP =- H/RT+constant;ifH>0,lnK P isless
thanifH<0.

G =

H - T

S. Low free energy (

0) is not
favoredby H>0.
(b) Yes, S>0 since 1 mol gas yields 2 mol gas,
whichmeansincreaseddisorder.
Atequilibrium H=T Sandapositive Hmeans
apositive S.
(c) Application of heat favors more products.
Thedatainthetableaboveweredeterminedat25
(a) Calculate G forthereactionaboveat25C.
(b) CalculateK eq forthereactionaboveat25C.
(c) Calculate

S forthereactionaboveat25

C.
(d) Inthetableabove,therearenodataforH2
are the values of H f , Gf , and of the absolute
entropy,S,forH2 at25C?
Answer:
(a)

$ &# ) (

& ( " (
=-166.2-[-137.3+2(0)]=-28.9kJ/mol
(b)K eq=e
- G/RT
=e
-(-28900/(8.3143)(298))
=1.16 10
5
(c)
S_=
H_ G_
T
=
128100 ( 28900 )J
298 K
=-333J/K
(d) Both the standard enthalpy of formation and th
standardfreeenergyofformationofelements=0.

S S
roducts

S
(reactants)
-333J/K=126.8J/K-197.9J/K-2SH2
SH2 =131J/mol.K
1984B
StandardHeat of Absolut
Formation, H f, Entropy,
Substance in kJ mol
-1
inJmol
-1
------------------ ----------------------------- ------------------
C(s) 0.00 5.69
CO2(g) -393.5 213.6
H2(g) 0.00 130.6
H2O(l) -285.85 69.91
O2(g) 0.00 205.0
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(c) Application of heat favors more products.
PredictablefromLeChateliersprinciple.
T StermhereincreasesasTisincreasedresulting
inamorenegative G.
(d) Reduction of volume favors more reactants.
Predictable from LeChateliers principle.
Increasedpressureisreducedby2gasmolecules
combiningtogive1molecule.
1983B
CO(g) +2H2(g) CH3OH(l) H =-128.1kJ
H f Gf S
(kJmol
-1
) (kJ mol
-1
) (J mol
-1
K
-1
)
CO(g) -110.5 -137.3 +197.9
CH3OH(l) -238.6 -166.2 +126.8
O2(g) 0.00 205.0
C3H7COOH(l) ? 226.3
The enthalpy change for the combustion of butyric
acid at 25C, Hcomb, is -2,183.5 kilooules per mole.
Thecombustionreactionis
C
3
H
7
COOH
(l)
+5O
2
(g)
4

CO
2
(g)
+4

H
2
O
(l)
(a) From the above data, calculate the standar
offormation, H f,forbutyricacid.
(b) Write a correctly balanced equation f
formationofbutyricacidfromitselements.
(c) Calculate the standard entropy change,
theformationofbutyricacidat25C.Theentropy
change, S,forthecombustionreactionaboveis
-117.1JK
-1
at25C.
(d) Calculate the standard free energy of form