CHEMISTRY122

KINETICSANDEQUILIBRIUMEXAMREVIEW

1. NH
4
Cl(s)NH
3
(g)+HCl(g)H=+42.1kilocalories

Supposethesubstancesinthereactionaboveareatequilibriumat600KinvolumeVandatpressure
P.StatewhetherthepartialpressureofNH
3
(g)willhaveincreased,decreased,orremainedthesame
whenequilibriumisreestablishedaftereachofthefollowingdisturbancesoftheoriginalsystem.
SomesolidNH
4
Clremainsintheflaskatalltimes.Justifyeachanswerwithaoneortwosentence
explanation.

(a) AsmallquantityofNH
4
Clisadded.
(b) Thetemperatureofthesystemisincreased.
(c) Thevolumeofthesystemisincreased.
(d) AquantityofgaseousHClisadded.
(e) AquantityofgaseousNH
3
isadded.

2. Ammoniumhydrogensulfideisacrystallinesolidthatdecomposesasfollows:

NH
4
HS(s)NH
3
(g)+H
2
S(g)

(a) Some solid NH

4
HS is placed in an evacuated vessel at 25C. After equilibrium is attained, the total
pressureinsidethevesselisfoundtobe0.659atmosphere.SomesolidNH
4
HSremainsinthevessel
atequilibrium.Forthisdecomposition,writetheexpressionforK
P
andcalculateitsnumericalvalue
at25C.

(b) Some extra NH

3
gas is injected into the vessel containing the sample described in part (a). When
equilibrium is reestablished at 25C, the partial pressure of NH
3
in the vessel is twice the partial
pressureofH
2
S.CalculatethenumericalvalueofthepartialpressureofNH
3
andthepartialpressure
ofH
2
SinthevesselaftertheNH
3
hasbeenaddedandtheequilibriumhasbeenreestablished.

(c) Inadifferentexperiment,NH
3
gasandH
2
Sgasareintroducedintoanempty1.00litervesselat25C.
Theinitialpartialpressureofeachgasis0.500atmospheres.Calculatethenumberofmolesofsolid
NH
4
HSthatispresentwhenequilibriumisestablished.

3. Sulfurylchloride,SO
2
Cl
2
,isahighlyreactivegaseouscompound.Whenheated,itdecomposesas
follows:SO
2
Cl
2(g)
SO
2
(g)+Cl
2
(g).Thisdecompositionisendothermic.Asampleof3.509gramsof
SO
2
Cl
2
isplacedinanevacuated1.00litrebulbandthetemperatureisraisedto375K.

(a) WhatwouldbethepressureinatmospheresinthebulbifnodissociationoftheSO
2
Cl
2(g)
occurred?

(b) When the system has come to equilibrium at 375K, the total pressure in the bulb is found to be 1.43
atmospheres.CalculatethepartialpressuresofSO
2
,Cl
2
,andSO
2
Cl
2
atequilibriumat375K.

(c) Give the expression for the equilibrium constant (either K

p
or K
c
) for the decomposition of SO
2
Cl
2(g)
at
375K.Calculatethevalueoftheequilibriumconstantyouhavegiven,andspecifyitsunits.

(d) If the temperature were raised to 500K, what effect would this have on the equilibrium constant?
Explainbriefly.





























4.
CO
2
(g)+H
2
(g)H
2
O(g)+CO(g)

WhenH
2
(g)ismixedwithCO
2
(g)at2,000K,equilibriumisachievedaccordingtotheequationabove.Inone
experiment,thefollowingequilibriumconcentrationsweremeasured.

[H
2
] =0.20mol/L
[CO
2
] =0.30mol/L
[H
2
O]=[CO] =0.55mol/L

(a) WhatisthemolefractionofCO(g)intheequilibriummixture?
(b) Usingtheequilibriumconcentrationsgivenabove,calculatethevalueofK
c
,theequilibriumconstant
forthereaction.
(c) DetermineK
p
intermsofK
c
forthissystem.
(d) When the system is cooled from 2,000 K to a lower temperature, 30.0 percent of the CO(g) is
convertedbacktoCO
2
(g).CalculatethevalueofK
c
atthislowertemperature
(e) Inadifferentexperiment,0.50moleofH
2
(g)ismixedwith0.50moleofCO
2
(g)ina3.0literreaction
vessel at 2,000 K. Calculate the equilibrium concentration, in moles per liter, of CO(g) at this
temperature.

5. Intheequationbelow,theforwardreactionisfirstorderinbothPCl
3
andCl
2
andthereversereaction
isfirstorderinPCl
5
.
PCl
3
(g)+Cl
2
(g)PCl
5
(g)

(a) Suppose that 2 moles of PCl

3
and 1 mole of Cl
2
are mixed in a closed container at constant
temperature.DrawagraphthatshowshowtheconcentrationsofPCl
3
,Cl
2
,andPCl
5
changewithtime
untilafterequilibriumhasbeenfirmlyestablished.
(b) Givetheinitialratelawfortheforwardreaction.
(c) Provide a molecular explanation for the dependence of the rate of the forward reaction on the
concentrationsofthereactants.
(d) Provide a molecular explanation for the dependence of the rate of the forward reaction on
temperature.































6. Thefollowingdataaboutthereactionabovewereobtainedfromthreeexperiments:

2A+2BC+D

Experiment [A] [B]

InitialRateofFormation
ofC(mole
.
liter
1
min
1
)
1 0.60 0.15 6.3x10
3
2 0.20 0.60 2.8x10
3
3 0.20 0.15 7.0x10
4

(a) Whatistherateequationforthereaction?
(b) Whatisthenumericalvalueoftherateconstantk?Whatareitsdimensions?
(c) Proposeareactionmechanismforthisreaction.






























7. Ethyl iodide reacts with a solution of sodium hydroxide to give ethyl alcohol according to the
equation.
CH
3
CH
2
I+OH

CH
3
CH
2
OH+I

The reaction is first order with respect to both ethyl iodide and hydroxide ion, and the overallrate
expressionforthereactionisasfollows:

rate=k[CH
3
CH
2
I][OH

Whatwouldyoudointhelaboratorytoobtaindatatoconfirmtheorderintherateexpressionfor
eitherofthereactants.

































8. Changingthetemperatureandnootherconditionschangestheratesofmostchemicalreactions.Two
factors are commonly cited as accounting for the increased rate of chemical reaction as the
temperature is increased. State briefly and discuss the two factors. Which of the two is more
important?

9. Forthereactionabove,therateconstantat380Cfortheforwardreactionis2.610
3
liter
2
/mole
2
sec
andthisreactionisfirstorderinO
2
andsecondorderinNO.

2NO(g)+O
2
(g)2NO
2
(g)

The rate constant for the reverse reaction at 380C is 4.1 liter/molesec and this reaction is second
orderinNO
2
.

(a) Write the equilibrium expression for the reaction as indicated by the equation above and calculate
thenumericalvaluefortheequilibriumconstantat380C.
(b) WhatistherateoftheproductionofNO
2
at380CiftheconcentrationofNOis0.0060mole/literand
theconcentrationofO
2
is0.29mole/liter?
(c) The system above is studied at another temperature. A 0.20 mole sample of NO
2
is placed in a 5.0
litercontainerandallowedtocometoequilibrium.Whenequilibriumisreached,15%oftheoriginal
NO
2
has decomposed to NO and O
2
. Calculate the value for the equilibrium constant at the second
temperature.




























10. Graphicalmethodsarefrequentlyusedtoanalyzedataandobtaindesiredquantities.
2 HI(g) H
2
(g) +I
2
(g)
Thefollowingdatagivethevalueoftherateconstantatvarioustemperaturesforthegasphasereaction
above.
T (K) k (litre/mol sec)
647 8.5810
-5
666 2.1910
-4
683 5.1110
-4
700 1.1710
-3
716 2.5010
-3

(a) Describe, without doing any calculations, how a graphical method can be used to obtain the activation energy
for this reaction.

A(g) B(g) +C(g)
ThefollowingdatagivethepartialpressureofAasafunctionoftimeandwereobtainedat100Cforthe
reactionabove.

P
A
(mm Hg) t (sec)
348 0
247 600
185 1200
105 2400
58 3600
Describe,withoutdoinganycalculations,howgraphscanbeusedtodeterminewhetherthisreactionis
firstorsecondorderinAandhowthesegraphsareusedtodeterminetherateconstant.




















11. Considerthefollowinggeneralequationforachemicalreaction.

A(g) +B(g) C(g) +D(g) H reaction =-10 kJ
(a) DescribethetwofactorsthatdeterminewhetheracollisionbetweenmoleculesofAandBresultsina
reaction.
(b) How would a decrease in temperature affect the rate of the reaction shown above? Explain your
answer.
(c) Write the rate law expression that would result if the reaction proceeded by the mechanism shown
below.
A +B [AB] (fast)
[AB] +B C +D (slow)
(d) Explain why a catalyst increases the rate of a reaction but does not change the value of the
equilibriumconstantforthatreaction.









































12. Thefollowingresultswereobtainedwhenthereactionrepresentedabovewasstudiedat25C.

2 ClO
2
(g) +F
2
(g) 2 ClO
2
F(g)


Experiment

Initial [ClO
2
], (mol
.
L
-1
)

Initial [F
2
], (mol
.
L
-1
)
Initial Rate of Increase of [ClO
2
F],
(mol
.
L
-1.
sec
-1
)
1 0.010 0.10 2.410
-3
2 0.010 0.40 9.610
-3
3 0.020 0.20 9.610
-3
(a) Writetheratelawexpressionforthereactionabove.
(b) Calculatethenumericalvalueoftherateconstantandspecifytheunits.
(c) Inexperiment2,whatistheinitialrateofdecreaseof[F
2
]?
(d) Whichofthefollowingreactionmechanismsisconsistentwiththeratelawdevelopedin(a).Justify
yourchoice.

I. ClO
2
+F
2
ClO
2
F
2
(fast)
ClO
2
F
2
ClO
2
F +F (slow)
ClO
2
+F ClO
2
F (fast)
II. F
2
2 F (slow)
2 (ClO
2
+F ClO
2
F) (fast)