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1994

CHEMISTRY

Three hoursare allottedfor thisexamination:1 hourand30 minutesfor SectionI, whichconsistsof multiple-choice


questions,and 1 hourand30 minutesfor SectionII, whichconsistsof problemsandessayquestions.SectionI is printed
in thisexaminationbooklet;SectionII, in a separatebooklet.

Battery-operatedhand-heldcalculatorsmay be usedin bothsectionsof the examination.All calculatormemoriesmust


be clearedof bothprogramsanddata;no peripheraldevicessuchas magneticcardsor tapeswill be allowed.Calculators
may not be shared.
SECTION I
Time - 1 hourand30 minutes
Numberof questions
- 75
Percentof totalgrade- 45

This examinationcontains75 multiple-choicequestions.Therefore, pleasebe careful to fill in only the


ovalsthat are precededby numbers 1 through 75 on your answer sheet.

GeneralInstructions

DO NOT OPEN THIS BOOKLET UNTIL YOU ARE INSTRUCTED TO DO SO.

INDICATE ALL YOUR ANSWERS TO QUESTIONS IN SECTION I ON THE SEPARATE ANSWER SHEET.
No creditwill be givenfor anythingwrittenin thisexaminationbooklet,but you may usethebookletfor notesor
scratchwork.After you havedecidedwhichof the suggested answersis best,COMPLETELY fill in the corresponding
oval on the answersheet.Give only oneanswerto eachquestion.If you changean answer,be surethattheprevious
markis erasedcompletely.

Example: SampleAnswer

Chicagois a
(A) state
(B) city
(C) country
(D) continent
(E) village

Many candidates wonderwhetheror not to guesstheanswersto questions aboutwhichthey are not certain.In this
sectionof theexamination,asa correctionfor haphazardguessing, one-fourthof thenumberof questionsyou answer
incorrectlywill be subtracted
from the numberof questionsyou answercorrectly.It is improbable,therefore,thatmere
guessingwill improveyour scoresignificantly;it may evenlower your score,andit doestake time. If, however,you are
not sureof thecorrectanswerbut havesomeknowledgeof thequestionandare ableto eliminateoneor moreof the
answerchoicesas wrong,your chanceof gettingthe rightansweris improved,andit may be to your advantageto answer
sucha question.

Use your time effectively, workingasrapidlyas you canwithoutlosingaccuracy.Do not spendtoo muchtimeon
questionsthatare too difficult. Go on to otherquestions
andcomebackto the difficult oneslaterif you havetime. It is
not expectedthateveryonewill be ableto answerall the multiple-choicequestions.

Copyright 0 1994 by Educational Testing Service. All rights reserved.


Note: For all questionsinvolving solutionsand/or chemical equations,assumethat the systemis in pure water and at
G temperatureunlessotherwisestated.

Part A

Directions: Each set of letteredchoicesbelow refers to the numberedquestionsor statementsimmediately following


it. Select the one letteredchoice that bestanswerseach questionor bestfits each statementand then fill in the
correspondingoval on the answersheet.A choice may be used once, more than once, or not at all in each set.

Questionsl-4 Questions5-7 refer to the phasediagrambelow of a


pure substance.
(4 Heisenberguncertaintyprinciple
(B) Pauli exclusionprinciple
K> Hunds rule (principle of maximum multiplicity)
0) Shieldingeffect
03 Wave nature of matter
P
1. Can be usedto predict that a gaseouscarbon atom (atm)
in its groundstateis paramagnetic

2. Explains the experimentalphenomenonof electron


diffraction lb io do iio i30-
T (Q
3. Indicatesthat an atomic orbital can hold no more
than two electrons (A) Sublimation
(B) Condensation
(C) Solvation
4. Predictsthat it is impossibleto determinesimulta- (D) Fusion
neouslythe exact positionand the exact velocity of (E) Freezing
an electron

5. If the temperatureincreasesfrom 10 C to 60 C at a
constantpressureof 0.4 atmosphere,which of the
processesoccurs?

6. If the temperaturedecreasesfrom 110 C to 40 C at


a constantpressureof 1.1 atmospheres,which of
the processesoccurs?

7. If the pressureincreasesfrom 0.5 to 1.5 atmospheres


at a constanttemperatureof 50 C, which of the
processesoccurs?

q 11a
Questions8-10 refer to the following diatomic species. Questions11-13

(A) Liz (4 Pb
(B) I% (W Ca
(C) N cc>zn
0) 02 0% As
(E) FZ (E) Na

8. Has the largestbond-dissociation


energy 11. Utilized as a coating to protect Fe from corrosion

9. Has a bond order of 2 12. Is addedto silicon to enhanceits propertiesas a


semiconductor
10. Contains1 sigma(CT)and 2 pi (7~)bonds
13. Utilized as a shieldfrom sourcesof radiation
Part B

Directions: Each of the questionsor incompletestatementsbelow is followed by five suggestedanswersor completions.


Select the one that is bestin each caseand then fill in the correspondingoval on the answersheet.

14. Which of the following is lower for a l.O-molar 16. Commercial vinegar was titrated with NaOH
aqueoussolutionof anysolutethan it is for pure solutionto determinethe contentof acetic acid,
water? HC2H302. For 20.0 milliliters of the vinegar,
26.7 milliliters of 0.600-molar NaOH solutionwas
(A) PH required.What was the concentrationof acetic
(B) Vapor pressure
(C) Freezing point acid in the vinegar if no other acid was present?
(D) Electrical conductivity (A) 1.60 A4
(E) Absorptionof visible light (B) 0.800 M
(C) 0.600 M
15 In a moleculein which the central atom exhibits (D) 0.450 A4
sp3d2 hybrid orbitals,the electronpairs are directed (E) 0.200 M
towardthe cornersof
(A) a tetrahedron 17. Relatively slow ratesof chemical reactionare asso-
ciated with which of the following?
(B) a square-based pyramid
(C) a trigonal bipyramid (A) The presenceof a catalyst
(D) a square (B) High temperature
(E) an octahedron (C) High concentrationof reactants
(D) Strong bondsin reactantmolecules
(E) Low activationenergy
18. 2 HZ0 + 4 Mn04- + 3 C102- + 4 MnOz + 3 ClOh- + 4 OH-

Which speciesactsas an oxidizing agentin the reactionrepresented


above?
(A) Hz0
(B) Clod-
(C) ClOz-
(D) Mn02
(E) Mn04-

19. In which of the following compoundsis the massratio of chromium


to oxygen closestto 1.62 to 1.00 ?
(A) Cr-03
(B) CrOr
(C) CrO
(D) Cr,O
(E) CrzO,

20. . . . Ag + . . . ASH,(~) + . . . OH- + . . . Ag(s) + . . . H3As03(aq) + . . . Hz0

When the equationaboveis balancedwith lowestwhole-numbercoefficients,the


coefficient for OH- is
(A) 2
(B) 4
(C) 5
(D) 6
(E) 7
2 1. Correct statementsaboutalpha particlesinclude 23. Step 1: Ce4++ Mn2++ Ce3++ Mn3+
which of the following?
Step 2: Ce4++ Mn3++ Ce3++ Mn4+
I. They havea massnumberof 4 and a charge
of +2.
Step 3: Mn4++ Tl + T13++ Mn2+
II. They are more penetratingthan beta particles.
III. They are helium nuclei.
The proposedstepsfor a catalyzedreaction
(A) I only betweenCe4+and Tl are representedabove.The
(B) III only productsof the overall catalyzedreactionare
(C) I and II
(A) Ce4+and Tl
(D) I and III
(B) Ce3+and T13+
(E) II and III
(C) Ce3+and Mn3+
(D) Ce3+and Mn4+
22. HSO,- + HZ0 =+ H30+ + SO:- (E) T13+and Mn2

In the equilibrium representedabove,the species


24. A sampleof 0.0100 mole of oxygen gasis confined
that act as basesinclude which of the following?
at 37 C and 0.216 atmosphere.What would be the
I. HS04 pressureof this sampleat 15 C and the same
II. HZ0 volume?
III. sod2-
(A) 0.0876 atm
(A) II only (B) 0.175 atm
(B) III only (C) 0.201 atm
(C) I and II (D) 0.233 atm
(D) I and III (E) 0.533 atm
(E) II and III
25. Hz(g) + $ Wg) + HzO@) AH = -286 kJ

2 Na(s) + i O?(g) + NalO(s) AH = -414 kJ

Na(s)+$Ol(g)+~H~(g)+NaOH(s) AH=-425kJ

Basedon the informationabove,what is the standardenthalpy


changefor the following reaction?

NazO(s) + H,O(!?) + 2 NaOH(s)

(A) -1,125 kJ
(B) -978 kJ
(C) -722 kJ
(D) -150 kJ
(E) +275 kJ

26. Which of the following actionswould be likely to


changethe boiling point of a sampleof a pure
liquid in an open container?
I. Placing it in a smallercontainer
II. Increasingthe numberof molesof the liquid in
the container
III. Moving the container and liquid to a higher
altitude
(A) I only
(B) II only
(C) III only
(D) II and III only
(E) I, II, and III

27. Which of the following setsof quantumnumbers


(n, I, mp, ms) bestdescribesthe valenceelectron of
highestenergy in a ground-stategallium atom
(atomic number3 1) ?

(A) 4, 0, 0, ;

(B) 4, 0, 1, ;

(C) 4, 1, 1, ;

(D) 4, 1, 2,;

(E) 4, 2, 0, ;
28. Given that a solutionis 5 percentsucroseby mass,what
additionalinformation is necessaryto calculatethe
molarity of the solution?
I. The density of water
II. The density of the solution
III. The molar massof sucrose
(A) I only
(B) II only
(C) III only
(D) I andII1
(E) II andIII

29. When an aqueoussolutionof NaOH is addedto


an aqueoussolutionof potassiumdichromate,
K&O,, the dichromateion is convertedto
(A) CrO:-
(B) Cfl2-

(C) Cr3+
(D) CrzO&)
(E) Cr(OH)&)

ReactionCoordinate

30. The energy diagram for the reactionX + Y + Z is


shownabove.The additionof a catalystto this reac-
tion would causea changein which of the indi-
cated energy differences?
(A) 1 only
(B) II only
(C) III only
(D) I and II only
(E) I, II, and III

q 17B
31. H2C204+ 2 Hz0 ti 2 H30+ + C20$-
Oxalic acid, H2C204, is a diprotic acid with
K1 = 5.36 x lo-* and K2 = 5.3 x 10m5.For the
reactionabove,what is the equilibrium constant?
(A) 5.36 x lo-*
(B) 5.3 x 1O-5
(C) 2.8 x lOA
(D) 1.9 x 10-l
(E) 1.9 x lo-l3

32. CH3CH20H boils at 78 C and CH30CH3 boils at


-24 C, althoughboth compoundshavethe same
composition.This difference in boiling pointsmay
be attributedto a difference in
(A) molecularmass
(B) density
(C) specific heat
(D) hydrogenbonding
(E) heat of combustion

33. A hydrocarbongaswith an empirical formula CH2


has a density of 1.88 gramsper liter at 0 C and 1.00
atmosphere.A possibleformula for the hydro-
carbonis

(B) C2H4

CC> C3He

CD) Cd-b

(E) Cd-&o

34. CH3-CH2-CH2-CH2-CH3 CH3-CH2-CH2-CH2-OH HO-CH2-CH2-CH2-OH

X Y z
Basedon conceptsof polarity and hydrogenbonding,which of the following sequences
correctly liststhe compoundsabovein the order of their increasingsolubility in water?
(A) 2 < Y< X
(B) Y < 2 <X
(C) Y < x < z
(D) X < Z < Y
(E) X < Y< Z
35. For which of the following processeswould OS 38. Concentrationsof colored substances are commonly
have a negativevalue? measuredby meansof a spectrophotometer. Which
of the following would ensurethat correct values
I. 2 Fe203(s) -+ 4 Fe(s) + 3 O?(g)
are obtainedfor the measuredabsorbance?
II. Mg2++ 2 OH- + Mg(OH)&)
I. There must be enoughsamplein the tube
III. H?(g) + GH&) + GH&) to cover the entire light path.
(A) I only II. The instrumentmust be periodically reset
(B) I and II only using a standard.
(C) I and III only III. The solutionmustbe saturated.
(D) II and III only (A) I only
(E) I, II, and III (B) II only
(C) I and II only
36. Zn(s) + Cu2+4 Zn*+ + Cu(s) (D) II and III only
(E) I, II, and III
An electrolytic cell basedon the reactionrepre-
sentedabovewas constructedfrom zinc and copper 39. Samplesof F2 gasand Xe gasare mixed in a
half-cells. The observedvoltagewas foundto be containerof fixed volume. The initial partial pres-
1.00 volt insteadof the standardcell potential,E, sureof the F2 gasis 8.0 atmospheresand that of
of 1.10 volts. Which of the following could correctly the Xe gasis 1.7 atmospheres.When all of the Xe
accountfor this observation? gasreacted,forming a solid compound,the pres-
(A) The copperelectrodewas larger than the zinc sureof the unreactedF2 gas was 4.6 atmospheres.
electrode. The temperatureremainedconstant.What is the
(B) The Zn electrolyte was Zn(N03)2, while the formula of the compound?
Cu+ electrolyte was CuS04. (A) XeF
(C) The Zn solutionwas more concentratedthan (B) XeF3
the Cu solution. (C) XeF4
(D) The solutionsin the half-cells had different (D) XeF6
volumes. (E) XeFs
(E) The salt bridge containedKC1 as the elec-
trolyte.

37. A sampleof 3.30 gramsof an ideal gas at 15O.OC


and 1.25 atmospherespressurehas a volume of
2.00 liters. What is the molar massof the gas?
The gasconstant,R, is 0.0821 (L atm)/(mol K).
l l

(A) 0.0218 gram/mole


(B) 16.2 grams/mole
(C) 37.0 grams/mole
(D) 45.8 grams/mole
(E) 71.6 grams/mole
IL Vacuum 42. Mass of an empty container 3.0 grams
Mass of the containerplus
the solid sample 25.0 grams
Volume of the solid sample 11.0 cubic
centimeters
The data abovewere gatheredin order to determine
the density of an unknown solid. The density of the
Closed-endManometer sampleshouldbe reported as
(A) 0.5 g/cm3
(B) 0.50 g/cm3
40. The systemshownaboveis at equilibrium at 28 C.
At this temperature,the vapor pressureof water is (C) 2.0 g/cm3
28 millimeters of mercury. The partial pressureof (D) 2.00 g/cm3
O,(g) in the systemis
(E) 2.27 g/cm3
(A) 28 mm Hg
(B) 56 mm Hg
43. Which of the following pairs of compoundsare
(C) 133 mm Hg
isomers?
(D) 161 mm Hg
(E) 189 mm Hg (A) CH3--Hz---- CHz--CH3 and CH3-CH-CH3
CH3

41. A strip of metallic scandium,SC, is placed in a


beaker containingconcentratednitric acid. A (B) CH3-FH-CH3 and CH3-y=CH2
brown gas rapidly forms, the scandiumdisappears,
CH3 CH3.
and the resultingliquid is brown-yellow but
becomescolorlesswhen warmed. These observa-
tionsbest supportwhich of the following state- ::
ments? (C) CH3-0-CH3 and CH3-C-CH3
(A) Nitric acid is a strongacid.
m In solutionscandiumnitrate is yellow and
scandiumchloride is colorless.
(D) CH3-OH and CH3-CH2-OH
(0 Nitric acid reactswith metals to form
hydrogen.
09 Scandiumreactswith nitric acid to form a
brown gas.
(E) CH4 and CH*=CH;!
03 Scandiumand nitric acid react in mole propor-
tionsof 1 to 3.
44. Which of the following solutionshas the lowest
freezing point?
(A) 0.20 m CaH1206,glucose
(B) 0.20 m NI-&Br
(C) 0.20 m ZnS04
(D) 0.20 m KMn04
(E) 0.20 m MgCl2
45. A sampleof an ideal gasis cooled from 50.0 C to 49. The isomerizationof cyclopropaneto propyleneis
25.0 C in a sealedcontainerof constantvolume. a first-order processwith a half-life of 19 minutes
Which of the following valuesfor the gas will at 500C. The time it takesfor the partial pressure
decrease? of cyclopropaneto decreasefrom 1.0 atmosphere
to 0.125 atmosphereat 500C is closestto
I. The averagemolecularmassof the gas
II. The averagedistancebetweenthe molecules (A) 38 minutes
III. The averagespeedof the molecules (B) 57 minutes
(C) 76 minutes
(A) I only
(D) 152 minutes
(B) II only
(E) 190 minutes
(C) III only
(D) I and III
(E) II and III 50, Which of the following acidscan be oxidized to
form a strongeracid?
46. Which of the following solidsdissolvesin water to (A) H3PQ

form a colorlesssolution?
@I HNO3

(A) Cc13
(c> H2co3
(B) FeC13
(C) coc12 0% H3BO3

(D) CuC12 09 H2so3


(E) ZnCl?

51. 4 HCl(g) + 02(g) * 2 Cl,(g) + 2H&?)


47. Which of the following has the lowestconductivity?
(A) 0.1 A4CuSO4 Equal numbersof molesof HCl and O2 in a closed
(B) 0.1 it4 KOH systemare allowedto reach equilibrium as repre-
(C) 0.1 M BaC& sentedby the equationabove.Which of the
(D) 0.1 MI-IF following mustbe true at equilibrium?
(E) 0.1 M HNO3 I. [HCI] mustbe lessthan [Cl,].
II. [02] mustbe greater than [HCl].
48. PC&(g > + C12(g) @ PCls(g) + energy
III. [Cl,] must equal [H,O].
Some PC13and Cl2 are mixed in a containerat (A) I only
200 C and the systemreachesequilibrium (B) II only
accordingto the equationabove.Which of the (C) I and III only
following causesan increasein the number of (D) II and III only
molesof PCls presentat equilibrium? (E) I, II, and III
I. Decreasingthe volume of the container
II. Raisingthe temperature
III. Adding a mole of He gas at constantvolume
(A) I only
(B) II only
(C) I and III only
(D) II and III only
(E) I, II, and III

121 II
59. When a 1.00~gramsampleof limestonewas 63. What is the maximum massof copper that could be
dissolvedin acid, 0.38 gram of CO* was generated. plated out by electrolyzingaqueousCuC12for
If the rock containedno carbonateother than 16.0 hoursat a constantcurrentof 3.00 amperes?
CaC03, what was the percentof CaC03 by massin (1 faraday = 96,500 coulombs)
the limestone? (A) 28 grams
(A) 17% (B) 57 grams
(B) 51% (C) 64 grams
(C) 64% (D) 114 grams
(D) 86% (E) 128 grams
(E) 100%
64. At 25 C, a sampleof NH3 (molar mass 17 grams)
60. 12(g) + 3 Cl2(g) + 2 ICl,(g) effusesat the rate of 0.050 mole per minute. Under
the sameconditions,which of the following gases
According to the data in the table below, what is effusesat approximatelyone-half that rate?
the value of AH0 for the reactionrepresented (A) O2 (molar mass32 grams)
above? (B) He (molar mass4.0 grams)
(C) CO2 (molar mass44 grams)
AverageBond Energy (D) Cl, (molar mass71 grams)
Bond (kilojoules/mole) (E) C& (molar mass 16 grams)
I-I 149
Cl-Cl 239 65. Barium sulfate is LEAST solublein a O.Ol-molar
I-Cl 208 solutionof which of the following?

(A) -860 kJ (A) A12(S04)3

(B) -382 kJ (W (Nb)2S04


(C) +180 kJ
(D) +450 kJ (C> Na2S04

(E) +1,248 kJ 0) NH3

(E) BaC12
61. A l-molar solutionof which of the following salts
has the highestpH ?
66. What is the pH of a 1.0 x 10-2-molarsolutionof
(A) NflO3 HCN ? (For HCN, Ka = 4.0 x lo-.)
@I Na2C03 (A) 10
(B) Between 7 and 10
(C> WC1
(C) 7
(D) NaHSO, (D) Between 4 and 7
(E) Na2SQ (E) 4

62. The electron-dotstructure(Lewis structure)for


which of the following moleculeswould havetwo
unsharedpairs of electronson the central atom?
(A) H2S

(B) NH3

Cl cH4

(D) HCN
(E) COz

n 23 n
67. SubstancesX and Y that were in a solutionwere 70. To determinethe molar massof a solid mono-
separatedin the laboratory using the techniqueof protic acid, a studenttitrated a weighedsampleof
fractionalcrystallization.This fractionalcrystalliza- the acid with standardizedaqueousNaOH. Which
tion is possiblebecausesubstances X and Y have of the following could explain why the student
different obtaineda molar massthat was too large?
(A) boiling points I. Failure to rinse all acid from the weighingpaper
(B) melting points into the titration vessel
(C) densities II. Addition of more water than was neededto
(D) crystalcolors dissolvethe acid
(E) solubilities III. Addition of somebasebeyondthe equivalence
point
68. Which of the following moleculeshas a dipole (A) I only
momentof zero? (B) III only
(A) C6H6(benzene) (C) I and II only
(D) II and III only
(B) NO
(E) I, II, and III
(C) SO1
(D) NH3
(E) HS 71. . . . Fe(OH)z + . . . O2 + . . . Hz0 + . . . Fe(OH)3

69. Correct proceduresfor a titration include which of If 1 mole of O2 oxidizesFe(OH)2 accordingto the
the following? reactionrepresentedabove,how many molesof
Fe(OH)j can be formed?
I. Draining a pipet by touchingthe tip to the side
of the containerusedfor the titration (A) 2
II. Rinsingthe buret with distilledwaterjustbefore (B) 3
filling it with the liquid to be titrated (C) 4
III. Swirling the solutionfrequentlyduringthe titra- (D) 5
tion (E) 6
(A) I only
(B) II only
(C) I and III only
(D) II and III only
(E) I, II, and III

n 24 n
72. The nuclide 249
,,Cm is radioactiveand decaysby the 74. A solutionof calcium hypochlorite,a common
loss of one beta (p-) particle. The productnuclide is additiveto swimming-poolwater, is
(A) basicbecauseof the hydrolysisof the OCl- ion
(A) ;;Pu (B) basic becauseCa(OH)2 is a weak and insoluble
base
(B) z:Arn (C) neutral if the concentrationis kept below
0.1 molar
(C) ZiCrn (D) acidic becauseof the hydrolysisof the Ca
ions
(D) ;;&-I (E) acidic becausethe acid HOC1 is formed

75. A direct-currentpower supplyof low voltage(less


than 10 volts) has lost the markingsthat indicate
73. 2 sol(g) + 02(g) + 2 SO3(g)
which outputterminal is positiveand which is
negative.A chemistsuggeststhat the power supply
When 0.40 mole of SO?and 0.60 mole of 02 are
terminalsbe connectedto a pair of platinumelec-
placed in an evacuatedl.OO-liter flask, the reaction
trodes that dip into O.l-molar KI solution.Which
representedaboveoccurs.After the reactants
of the following correctly identifies the polaritiesof
and the productreach equilibrium and the initial
the power supplyterminals?
temperatureis restored,the flask is found to contain
0.30 mole of S03. Basedon theseresults,the equi- (A) A gas will be evolvedonly at the positiveelec-
librium constant,K,, for the reactionis trode.
(B) A gas will be evolvedonly at the negativeelec-
(A) 20.
trode.
(B) 10.
(C) A brown color will appearin the solutionnear
(C) 6.7
the negativeelectrode.
(D) 2.0
(D) A metal will be depositedon the positiveelec-
(E) 1.2
trode.
(E) None of the methodsabovewill identify the
polaritiesof the power supplyterminals.
c

STOP
END OF SECTION I

IF YOU FINISH BEFORE TIME IS CALLED, YOU MAY CHECK YOUR WORK ON THIS SECTION.
DO NOT GO ON TO SECTION II UNTIL YOU ARE TOLD TO DO SO.

n 25 n
24R. A sample of 0.010 mole of oxygen gas is confined
m REVISED QUANTITATIVE at 127C and 0.80 atmosphere.What would be the
ITEMS FROM THE 1994 pressureof this sample at 27C and the same
CHEMISTRY EXAM volume?

There were a total of 20 quantitative questionsin the (A) 0.10 atm


(B) 0.20 atm
multiple-choice section of the 1994 AP Chemistry
(C) 0.60 atm
Exam. Below are 10 quantitative questionsfrom this (D) 0.80 atm
group rewritten to conform to the new format being (E) 1.1 atm
introduced in 1996, in which calculators will not be
allowed for the multiple-choice questions.(The capi-
tal R following the questionnumber indicatesthat it 25~ H,(g) + l/2 O,(g) - H,O@) AHO=_X
is a Revised question.) The remaining quantitative
2 Na(s) + l/2 O,(g) - N$O(s) AP=y
questions from the 1994 exam are those for which
students would not typically need a calculator, and Na(s) + l/2 O,(g) + l/2 H,(g) - NaOH(s) AH0 = z
therefore represent quantitative questionsthat would
Based on the information above, what is the
appear exactly as they are now on the new format of
enthalpy change for the following reaction?
the exam.
N%O(s) + H,O@) - 2 Na0I-W

(A) x+y+z
16R. Commercial vinegar was titrated with NaOH solution (B) x+y-z
to determine the content of acetic acid, HC,H,O,. (C) x+y-22
For 20.0 milliliters of the vinegar, 32.0 milliliters of (D) 22-x-y
0.500-molar NaOH solution was required. What was (E) z-x-y
the concentration of acetic acid in the vinegar if no
other acid was present?

(A) 1.60 M 31R. H,C,O, + 2 H,O = 2 H,O+ + C,O,2-


(B) 0.800 M
(C) 0640M Oxalic acid, H&O,, is a diprotic acid with
(D) 0.600 M K, =5 X lo-*andK,=5 X10-5.Whichofthe
(E) 0.400 M following is equal to the equilibrium constant for the
reaction representedabove?
(A) 5 X lo-*
19R. In which of the following compounds is the mass (B) 5 X10-
ratio of chromium to oxygen closest to 1.6 to l.O? (C) 2.5 x 10
(D) 5 x1O-7
(A) CrO,
(E) 2.5 X10-*
(B) CrO,
(C) CrO
(D) Cr,O
(E) Cr,O,
37R. A sample of 3.0 grams of an ideal gas at 127C and 63R. Which of the following expressionsis correct for
1.O atmospherepressurehas a volume of 1.5 liters. the maximum mass of copper, in grams, that could
Which of the following expressionsis correct for the be plated out by electrolyzing aqueousCuCl, for
molar mass of the gas?The ideal gas constant, R, is 16 hours at a constant current of 3.0 amperes?
0.08 (L= atm)/(moleeK). (1 faraday = 96,500 coulombs)

(A) (16)(3,600)(3.0)(63.55)(2)
(A) (0.08)(400)
(96,500)
(3.0)( 1.O)(1.5)
(B) (16)(3,600)(3.0)(63.55)
(B) (1.0)(1.5)
(96,500)(2)
(3.0)(0.08)(400)
(C) (16)(3,600)(3.0)(63.55)
(C) (0.08)( 1.O)(1.5)
(96,500)
(3.0)(400)
(D) (16)(60)(3.0)(96,500)(2)
(D) (3.0)(0.08)(400)
(63.55)
(1.0)(1.5)
(E) (16)(60)(3.0)(96,500)
(E) (3.0)(0.08)( 1.5)
. (63.55)(2)
(1.0)(400)

73R. 2 SO,(g) + Q,(g) = 2 SO,(g)


59R. When a 1.25-gram sample of limestone was
dissolved in acid, 0.44 gram of CO, was generated. When 0.40 mole of SO, and 0.60 mole of 0, are
If the rock contained no carbonate other than placed in an evacuated l.OO-liter flask, the reaction
CaCO,, what was the percent of CaCO, by mass in representedabove occurs.After the reactants and the
the limestone? product reach equilibrium and the initial temperature
is restored, the flask is found to contain 0.30 mole of
(A) 35%
SO,. Based on these results, the expression for the
(B) 44%
equilibrium constant, K,, of the reaction is
(C) 67%
(D) 80% (A) (o.30)2
(E) 100%
(0.45)(0. 1o)2
(B) (o.30)2
(0.60)(0.40)2
60R. I,(g) + 3 Cl,(g) - 2 ICl,(g)
(C) (2 x 0.30)
According to the data in the table below, what is the
(0.45)(2 X 0.10)
value of AHo for the reaction representedabove?
(D) (0.30)
Average Bond Energy (0.45)(0.10)
Bond (kilojoules/mole) (E) (0.30)
(0.60)(0.40)
I-I 150

Cl - Cl 240
I Answers to
I - Cl 210 Revised Questions
I
(A) - 870kJ 16R. B
I
(B) -390kJ 19R. B
(C) + 180 kJ I 24R. C
(D) +45OkJ 25R. D
(E) +1,260 kJ 31R. C
37R. D
59R. D
60R. B
63R. B
73R. A
1994
CHEMISTRY
SECTION II
Time-l hour and 30 minutes
Percentof total grade-55
PartsA, B, and C: Suggestedtime-50 minutes
Part D: Suggestedtime--40 minutes
General Instructions
The suggestedtimeswill not be announced,and you may proceedfreely from one questionto the next. Do not
spendtoo long on any one problem.
Pagescontaininga periodic table and the electrochemicalseriesare printedon the greeninsertand in the pink
essaybooklet for your use.
You may write your answerswith either a pen or a pencil. Be sureto write CLEARLY andLEGIBLY. If you
make an error, you may savetime by crossingit out rather thantrying to eraseit.

When you are told to begin, open your booklet,carefully tear out the greeninsert, and start work. The questions
are also printed in your essaybooklet,but it may be easierto work from the insert when answeringquestions.
Writeall v0ur answers in the Dink essav booklet.Number vour answersas the auestionsare numberedin the
examinationbook.

n 29 n
INFORMATION IN THE FOLLOWING TABLES MAY BE USEFUL IN ANSWERING THE QUESTIONS IN
THIS SECTION OF THE EXAMINATION.

Universal gas constant: R = 8.31 joules (mole - K) = 0.0821 liter-atm/(mole - K)


= 62.4 liter-mm Hg/(mole - K) = 1.99 calories/(mole - K)
= 8.3 1 (volt)(coulombs)/(mole - K)
1 faraday ( 3 ) = 96,500 coulombs = 23.060 calories/volt = 96,500 joules/volt
1 caloric = 4.184 joules
1 electron volt/atom = 23.1 kilocalories/mole = 96.5 kilojoules/mole
Speed of light in vacuum = 2.998 x lo8 m/set
In, = 2.303 log,,
Plancks constant It = 6.63 x 10 -34joule * set
Boltzmanns constant k = 1.38 x 10 joule/K
Avogadros number = 6.022 x 1013molecules/mole

0.059 1
At 25 C, RT In Q = ~ log Q
n3 n

STANDARD REDUCTION POTENTIALS, E, IN WATER SOLUTION AT 25 C (in V)

Li. + e Li(s) - 3.05


Cs + e Cs(s) - 2.92
K++e K(s) - 2.92
Rb fe Rb(s) - 2.92
Ba2+ + 2e Ba(s) - 2.90
Sr + 2e Ws) - 2.89
Ca + 2e Q(s) - 2.87
Na + em Na(s) -2.71
Mg + 2e Mg(s) - 2.37
Be + 2 e Be(s) - 1.I0
Al + 3e Al(s) - 1.66
Mn + 2e Mn(s) - 1.18
Zn + 2 e Zn(s) -076
Cr + ?e Cr(s) - 0.74
Fe + 2e Fe(s) - 0.44
Cr- + e Cr -0.41
Cd + 2e Cd(s) - 0.40
Tl + e Tl(s) - 0.34
Co + 2e Co(s) - 0.28
Ni. + 2e Ni(s) - 0.25
Sn + 2e Sri(s) -0.14
Pb + 2e Pb(s) -0.13
2H +2e Hz(g) 0.00
S(s) + 2 H + 2 e H$ 0.14
Sn4 + 2e Sn + 0.15
Cu + e Cu 0.15
Cu+ + 2e Cu(s) 0.34
Cu. +e Cu(s) 0.52
I:(s) + 2 e 21 0.53
Fe+ + e Fe 0.77
Hg, + 2e 2 Hg(Q) 0.79
Ag +e Ag(s) 0.80
Hg + 2em Hg(Q) 0.85
2Hg + 2e Hgz + 0.92
Br,(Q) + 2e 2 Br- 1.07
O,(g) + 4H + 4e 2 H,O I .23
Cl,(g) + 2 e 2 Cl 1.36
Au* + 3 e Au(s) 1.50
Co+ + e co:+ I .82
FJg) + 2 e 2F 2.87

n 31 n
CHEMISTRY
SECTION II
Time-l hour and 30 minutes

The percentagesgiven for the partsrepresentthe scoreweightingsfor this sectionof the examination.Spend about
50 minuteson Parts A, B, and C combinedand about40 minuteson Part D.

THE METHOD USED AND THE STEPS INVOLVED IN ARRIVING AT YOUR ANSWERS MUST BE SHOWN
CLEARLY. It is to your advantageto do this, sinceyou may obtain partial credit if you do and you will receive
little or no credit if you do not. Attention shouldbe paid to significantfigures.

Be sureto write your answersin the spaceprovided following each question.

Data necessaryfor the solutionof the problemsmay be found in the tableson the precedingpages.

Part A
(20 percent)

Solve the following problem.

1. MgW) + Mg*+(aq) + 2 F-(aq)

In a saturatedsolutionof MgF7 at 18 C, the concentrationof Mg*+ is 1.21 x 10m3


molar. The equilibrium is
representedby the equationabove.

(4 Write the expressionfor the solubility-productconstant,Ksp, and calculateits value at 18 C.

(b) Calculatethe equilibrium concentrationof Mg in 1.OOOliter of saturatedMgF2 solutionat 18 C to


which 0.100 mole of solid KF has been added.The KF dissolvescompletely.Assumethe volume change
is negligible.

(4 Predict whether a precipitateof MgF2 will form when 100.0 milliliters of a 3.00 x 10-3-molarMg(N03)2
solutionis mixed with 200.0 milliliters of a 2.00 x 10-3-molarNaF solutionat 18 C. Calculationsto support
your predictionmust be shown.

w At 27 C the concentrationof Mg in a saturatedsolutionof MgF2 is 1.17 x 10T3molar. Is the dissolvingof


MgF2 in water an endothermicor an exothermicprocess?Give an explanationto supportyour conclusion.

N 32 n
Part B
(20 percent)

Solve EITHER problem 2 OR problem 3 in this part. (A secondproblem will not be scored.)

2 2 NO(g) + 2 Hz(g) + N(g) + 2 I-W(g)

Experimentswere conductedto studythe rate of the reactionrepresentedby the equationabove.Initial concentra-


tions and ratesof reactionare given in the table below.

Initial Concentration Initial Rate of Formation


(mom) of N2
Experiment [NOI B321 (mol/L*min)

1 0.0060 0.0010 1.8 x 1O-4


2 0.0060 0.0020 3.6 x 1O-4
3 0.0010 0.0060 0.30 x 1o-4
4 0.0020 0.0060 1.2 x 1o-4

(a> (i) Determine the order for each of the reactants,NO and HZ, from the data given and show your reasoning.
(ii) Write the overall rate law for the reaction.

(b) Calculatethe value of the rate constant, k, for the reaction.Include units.

w For experiment2, calculatethe concentrationof NO remainingwhen exactly one-half of the original amount
of H2 had been consumed.

Cd)The following sequenceof elementarystepsis a proposedmechanismfor the reaction.

I. NO + NO+=N202
II. N202 + H2 + H20 + N20
III. N20 + H2 + N2 + H20

Basedon the data presented,which of the aboveis the rate-determiningstep?Show that the mechanismis
consistentwith

(i) the observedrate law for the reaction,and


(ii) the overall stoichiometryof the reaction.

q 33 n
rr Gas Sample

Water

3. A studentcollecteda sampleof hydrogengasby the displacementof water as shownby the diagram above.The
relevantdata are given in the following table.

GAS SAMPLE DATA


I
Volume of sample 90.0 mL
Temperature 25 c
Atmospheric
Pressure 745 mm Hg I

Equilibrium
Vapor Pressure
of Hz0 (25 C) 23.8 mm Hg

(a) Calculatethe numberof molesof hydrogengascollected.

(b) Calculatethe numberof moleculesof water vapor in the sampleof gas.

(c) Calculatethe ratio of the averagespeedof the hydrogenmoleculesto the averagespeedof the water vapor
moleculesin the sample.

(d) Which of the two gases,H2 or H20, deviatesmore from ideal behavior?Explain your answer.

n 34 n
Part C
( 15 percent)

4. Answer FIVE of the eight optionsin this part. (Answersto more than five optionswill not be scored.)

Give the formulas to showthe reactantsand the productsfor FIVE of the following chemical reactions.Each of
the reactionsoccursin aqueoussolutionunlessotherwiseindicated.Representsubstances in solutionas ions if the
substanceis extensivelyionized. Omit formulas for any ions or moleculesthat are unchangedby the reaction.In
all casesa reactionoccurs.You need not balance.

Example: A strip of magnesiumis addedto a solutionof silver nitrate.

Mg + Ag -+ Mg*+ + Ag

(4 Excesssodiumcyanidesolutionis addedto a solutionof silver nitrate.

0-9 Solutionsof manganese(I1)sulfate and ammonium sulfide are mixed.

(4 Phosphorus(V)oxide powder is sprinkledover distilledwater.

Cd)Solid ammoniumcarbonateis heated.

Cd Carbon dioxide gasis bubbledthrougha concentratedsolutionof potassiumhydroxide.

(0 A concentratedsolutionof hydrochloricacid is addedto solid potassiumpermanganate.

(g) A small piece of sodiummetal is addedto distilledwater.


(h) A solutionof potassiumdichromateis addedto an acidified solutionof iron(I1) chloride.
Part D
(45 percent)

Spendabout40 minuteson this part of the examination.Answeringthesequestionsprovidesan opportunity to


demonstrateyour ability to presentyour material in logical, coherent,and convincingEnglish.Your responseswill be
judged on the basisof accuracyand importanceof the detail cited and on the appropriateness of the descriptive
material used.Specific answersare preferableto broad, diffuse responses.Illustrativeexamplesand equationsmay be
helpful.

ANSWER THE FOLLOWING ESSAY QUESTION.

5 Discussthe following phenomenain terms of the chemical and physicalpropertiesof the substances
involvedand
generalprinciplesof chemical and physicalchange.

(a) As the systemshownon the right


approachesequilibrium, what change
occursto the volumeof water in
beaker A ? What happensto the
concentrationof the sugarsolution
in beaker B ? Explain why these
changesoccur.

(b) A bell jar connectedto a vacuumpump


is shownon the right. As the air
pressureunder the bell jar decreases, Pure
what behaviorof water in the beaker H2O
will be observed?Explain why this occurs.
To
Vacuum
Pump

(c) What will be observedon the surfaces


of zinc and silver stripsshortly after
they are placed in separatesolutionsof
CuS04, as shownon the right? Account for
theseobservations.

I, in Water
(d) A water solutionof I2 is shakenwith an
equal volume of a nonpolarsolventsuch
as TTE (trichlorotrifluoroethane).Describe
the appearanceof this systemafter shaking.
(A diagrammay be helpful.) Account for this
observation.

n 36 n
SELECT TWO OF THE FOUR ESSAY QUESTIONS, NUMBERED 6 THROUGH 9.
(Additional essayswill not be scored.)

6. 2 HIS(g) + SO*(g) + 3 S(s) + 2 HzO(g)

At 298 K, the standardenthalpychange,AH, for the reactionrepresentedaboveis -145 kilojoules.

64 Predict the sign of the standardentropy change,ASo, for the reaction.Explain the basisfor your prediction.

(b) At 298 K, the forward reaction(i.e., toward the right) is spontaneous.


What change,if any, would occur in
the value of AG for this reactionas the temperatureis increased?Explain your reasoningusing thermody-
namic principles.

(4 What change,if any, would occur in the value of the equilibrium constant,Keq, for the situationdescribed
in (b)? Explain your reasoning.

(4 The absolutetemperatureat which the forward reactionbecomesnonspontaneous


can be predicted.Write the
equationthat is usedto make the prediction.Why doesthis equationpredict only an approximatevalue for
the temperature?
7. A chemical reactionoccurswhen 100. milliliters of 0.200-molar HCl is addeddropwiseto 100. milliliters of
O.lOO-molarNa3P04 solution.

Write the two net ionic equationsfor the formation of the major products.

Identify the speciesthat acts as both a Bronstedacid and as a Bronstedbasein the equationsin (a). Draw the
Lewis electron-dotdiagram for this species.

Sketcha graph using the axes provided, showingthe shapeof the titration curve that resultswhen 100. milliliters
of the WC1solutionis addedslowly from a buret to the Na3P04 solution.Account for the shapeof the curve.

0 mL HCl

Write the equationfor the reactionthat occursif a few additionalmilliliters of the HCl solutionare addedto
the solutionresultingfrom the titration in (c).

n 38 n
8. For each of the following, use appropriatechemical principlesto explain the observation.

(a) Sodium chloride may be spreadon an icy sidewalkin order to melt the ice; equimolaramountsof calcium
chloride are even more effective.

(b) At room temperature,NH3 is a gas and HZ0 is a liquid, even thoughNH3 has a molar massof 17 gramsand
Hz0 has a molar massof 18 grams.

(c) C (graphite) is usedas a lubricant,whereasC (diamond) is usedas an abrasive.

Cd)Pouring vinegar onto the white residueinside a kettle usedfor boiling water resultsin a fizzing/bubbling
phenomenon.

n 39 n
9. Use principlesof atomic structureand/or chemicalbondingto answereach of the following.

(a) The radiusof the Ca atom is 0.197 nanometer;the radiusof the Ca2+ion is 0.099 nanometer.Accountfor
this difference.

(b) The lattice energy of CaO(s) is -3,460 kilojoulesper mole; the lattice energy for M20(s) is -2,240 kilojoules
per mole. Account for this difference.

Ionization Energy
(kJ/mol)

First Second

K 419 3,050

Ca 590 1,140

(c) Explain the difference betweenCa and K in regardto

(i) their first ionizationenergies,


(ii) their secondionizationenergies.

(d) The first ionizationenergy of Mg is 738 kilojoulesper mole and that of Al is 578 kilojoulesper mole.
Accountfor this difference.

END OF EXAMINATION

n 40 n
Chapter III

Answers to the
1994 AP Chemistry Examination

n SECTION I: MULTIPLE-CHOICE
answered an individual question in this section also
Listed below are the correct answersto the multiple- achieved a higher mean score on the test as a whole
choice questionsand the percentageof AP candidates than candidates who did not answer that question
who attempted each question and answered it cor- correctly. An answer sheet gridded with the correct
rectly. As a general rule, candidates who correctly responsesappearson the next page.

Section I Answer Key and Percent Answering Correctly

c Item
No.

1
Correct
Answer

C
Percent
Correct

32%
Item
No.

26
Correct
Answer

C
Percent
Correct

61%
Item
No.

51
Correct
Answer

D
Percent
Correct

29%
2 E 38% 27 C 48% 52 B 29%
3 B 44% 28 E 58% 53 E 55%
4 A 82% 29 A 36% 54 D 43%
5 A 73% 30 D 55% 55 C 35%
6 B 74% 31 C 39% 56 B 35%
7 B 66% 32 D 77% 57 A 46%
8 C 21% 33 C 52% 58 B 29%
9 D 47% 34 E 39% 59 D 29%
10 C 57% 35 D 54% 60 B 47%
11 C 52% 36 C 46% 61 B 21%
12 D 21% 37 D 81% 62 A 64%
13 A 78% 38 C 41% 63 B 24%
14 C 46% 39 C 38% 64 D 23%
15 E 50% 40 C 67% 65 A 21%
16 B 69% 41 D 58% 66 D 64%
17 D 82% 42 D 39% 67 E 25%
18 E 62% 43 A 55% 68 A 41%
19 B 83% 44 E 31% 69 C 36%
20 D 58% 45 C 44% 70 A 15%
21 D 58% 46 E 46% 71 C 33%
22 E : 62% 47 D 38% 72 E 53%
23 B 71% 48 A 35% 73 A 24%
24 C 76% 49 B 49% 74 A 34%
25 D 63% 50 E 58% 75 B 16%
H SECTION II: FREE-RESPONSE examination. Members of the AP Chemistry Develop-
ment Committee submit suggestedscoring standards
Report of the Chief Faculty Consultant with each question that they write. Scoring standards
Robert W. Gleason are discussedfurther when questionsare revised and
Middlebury College chosenby the committee to be included in an exami-
nation.At this stage,considerationis given to potential
Grading the Examination difficulties that might interfere with the reliable scoring
of a question,and the scoringstandardmay be revised
The free-response section of the AP Chemistry accordingly. Prior to the Reading, the chief faculty
Examination is read and scoredby faculty consultants consultantgeneratesa draft of the scoringstandardfor
- AP Chemistry teachersand college chemistry pro- each of the nine questionsin the free-responsesection,
fessors- who are under the direction of a chemistry taking into considerationissuesraisedduring previous
teacherdesignatedas the chief faculty consultant.The reviews.The generalscoringguidefor the free-response
faculty consultantsare from secondary schools and questionsis as follows:
colleges throughout the United States, and also from
Canada.The faculty consultantsdo not have accessto, Problems 9 pointseach
and therefore are not influenced by, the multiple- Chemical Reactions 3 pointseach (15 pointstotal)
choice section of the examination, which is scored Essays 8 points each
separatelyby machine. Studentscoreson both partsof
the examination are combined and used by the chief Two days before the Reading begins, the chief fac-
faculty consultant to determine the levels of student ulty consultantmeets with the table leaders to review
performance on the AP 1 to 5 grading scale. the draft standards,and the group reachesa consensus
on a possible standardfor each question. The table
The Reading leadersbreak into groupsto test the standardsagainst
a number of studentresponses.During this phase of
In June the faculty consultantsmeet for six days on a
the process,the standardsmay be modified somewhat.
college campusto score the free-responsesectionsof
Meeting again as a whole group, the chief faculty
the AP Chemistry Examination. The chief faculty
consultantand the table leadersreach anotherconsen-
consultantdivides the faculty consultantsinto groups,
suson the standards,after which each table leader is
each under the direction of a designatedfaculty con-
assignedto a particular questionand is also assigneda
sultantcalled a table leader. One or more table leaders
list of faculty consultantswith whom he or she will
with their group of faculty consultantsis assignedto
score the questionduring the Reading.
score each free-responsequestion, depending on the
On the first day of the Reading, the table leaders
number of studentswho chose to answer it. The table
train the faculty consultantsin applying the scoring
leaders train their groups to score their designated
standardsto a setof samplestudentresponsesselected
question, and scoring of student papers commences
for that purpose.During this process,the standardsare
according to standardsdeveloped as describedbelow.
refined and may be modified slightly once again.
Each answer booklet is circulated among the various
After the group is proficient in applying the scoring
groups until all the studentresponsesin that booklet
standards,the actual scoring of the student papers
have been scored. The finished booklets are then
begins. The final results of the rigorous standard-
removed from the Reading site and the scores are
setting procedure described above are standardsthat
enteredinto computersand matchedwith the students
canbe appliedreliably not only to the commonmethods
multiple-choice section scores.Composite scoresare
of solution seen in the studentresponses,but also to
calculated and theseand other data are provided to the
commonerrorsandto alternativeor unusualapproaches.
chief faculty consultantfor the grade-settingsession,
Becausevarious studentresponsesto a given ques-
which occurs shortly after the Reading is over.
tion are scoredover a six-day period by more than one
faculty consultant,it is important to monitor the appli-
Developing Free-Response cation of the standardsduring the Reading. This is
Scoring Standards done by having a certain number of student papers
Scoring standardsfor the free-responsequestionsare independently graded more than once, either by dif-
a consideration throughout the development of the ferent faculty consultants,or by the sameconsultantat
a later time. The original scores are concealed from n FREE-RESPONSE QUESTIONS,
subsequentfaculty consultants, and the two sets of SCORING GUIDES, AND SAMPLE
scoresare then compared. The checking of one con- STUDENT ANSWERS
sultant againstanother quickly identifies any remain-
ing ambiguities that may exist in the standardsand On the pages that follow are a selection of student
allows their further refinement, to help assurethat a responsesto each of the questionsthat made up the
students score is independent of the person scoring free-response section of the 1994 Advanced Place-
the paper. Checking a consultant against his or her ment Examination in Chemistry. Also included are
own work also helps assurethat a students score is the standardsthat were applied in the scoringprocess,
independentof what day or time the paper is scored. and an explanation of why each responsereceived the
Rarely is there a discrepancyof more than 1 point on score it did. For each question, two studentresponses
the scale. Other procedureshelp maintain consistent have been selected to illustrate a superior answer and
scoring standards.After the Reading is underway, the one of somewhatlower quality.
table leaders select and score another series of ques- From our experience in reading Advanced Place-
tions for yet another kind of consistencycheck. This ment Examinations we know that no set of scoring
one does not compare the faculty consultants with standardscan possiblyanticipatethe creativity of high
themselves,but rather it comparesthem with the other school studentsin developing solutions to problems.
faculty consultants in their group and individually Therefore, you should understandthat readers make
with the table leaders. every possibleeffort to give credit for every response
The philosophyof the faculty consultantsin scoring that reflects an understandingof basic principles of
the free-responsequestionsis to award credit for cor- chemistry regardless of how far the approach used
rect work. When questionsinvolve calculations,most deviates from what might be a more conventional
of the points awarded are given for setting up the route developed in the standards.
solution correctly rather than actually carrying out the In developing the standardsfor the 1994 AP Chem-
computation. Partial credit is awarded within each istry Exam, the chief faculty consultanthad the assis-
part of a question,so studentsshouldbe encouragedto tance of 11 faculty consultantswho served as table
show their work. Faculty consultantstry to determine leaders, and two test development specialists from
whether an incorrect answer to a previous part has ETS. The group met for two days prior to the Reading.
been correctly usedin a subsequentpart of a question. After a draft set of standardswas established, the
Full credit for the latter part may be awarded if the application of the standard for each question was
consultant can successfully trace the students work testedwith about 100 papers.The standardswere then
to make that determination. Students should also be reviewed in the light of that experience and either
encouragedto continue on to later parts of a question revised accordingly or adopted.
if they get stuck at some point. Parts of a questionare If a studentmade an error in part (a) of a four-part
often independentof each other; even when they are problem and the answer to part (a) was essential to
dependent, credit can be earned on later parts when working the rest of the problem, the reader of the
earlier answersare missing.Also, a students explana- paper was obliged to work through the solutionsto the
tion of what he or shewould do, if possible,could earn subsequentparts of the question with the erroneous
some credit. Finally, when final answersare numeri- answer to part a. Thus, every effort was made to
cal, studentsshouldpay attentionto significantfigures reward the students with points for the appropriate
since 1 point is deducted (once per problem) if the applicationof chemicalprinciples.Studentswere, how-
number of significant figures in a students answer ever, penalized for mathematical errors and errors in
differs by more than one from the appropriatenumber. significant figures (exceeding one too many or one too
few) to the maximum extent of 1 point for an error of
each kind on any one problem.

n 44 n
Question 1

This required problem provided studentswith an opportunity to demonstratetheir understandingof an ionic


equilibrium and the common ion effect, to make a prediction basedon their calculations,and to relate solubility
data to thermodynamics.

ScoringStandards

(4 Ksp - [Mg*+J[F-]* (1 pt.>


- (1.21 x 103)(2 x 1.21 x 103)2
- 7.09 x 10-9 U pt.1
Note: if number of significant figures in final answer differs by
more than one from the appropriate number, 1 point is
deducted ONCE PER PROBLEM.

(W - [M$+](2x + O.lOO)* 2x << 0.100 (1 pt.) for proper


KsP
substitution
7.09 x 10-9 - [Mg*+](o 010)2
IMg*+l - (7.09 x io+)/(lo-2)
- 7.09 x 10-7 M

Note: OK if 0.102 is used for [F-j, then Ksp - 6.76 x 10

Cc> IQ*+] .- 100.0 x 3.00 x 103 - 300 . 0 x [Mg2+]

Q -
[F] : 200.0

Ion Product
I%*+1
x 2.00
WI
-
-
-
-
x 1O-3
-
1.00

1.33

[Mg*+][F']*
x 1O'3 M

- 300.0
x loo3 M

(1.00 x 103)(1.33
1.77 x 10'9
x [F-l

x lo-S)*
I** (1 pt.)

correct

(1 pt.>
if both
concentrations are

Since Q < Ksp , no precipitate will form (1 ptJ

Note: conclusion must be consistent with Q value.


** Correct substitution and calculation of the wrong
concentration values earns the second point, but not
the first.
(d) Solubility of MgF, decreases with increasing
temperature, thus dissolution process is exothermic (1 pt.>

MgFz(s) + Mg2+ + 2 F- + Q (cr H)

Reason:
EITHER

i) Increased temperature puts a stress on the system


(Le Chatelier). The system will reduce the stress
by shifting the equilibrium in the endothermic (left)
direction
(1 pt*)
0%

ii) a data supported argument such as comparing ion


concentrations, calculating second Ksp and giving
proper interpretations. i

n 46m
Comment:This paper earned all of the 9 possiblepoints. Although the studentdid not explicitly indicate that the
simplifying approximationwas being made in part b, it clearly was; and the substitutionand calculationwere made
correctly. The calculationsin part c were clear and correct and the conclusionbased on the relationship between
Q, and K,, was unambiguous.The analysisand conclusion in part d were straightforward and to the point.
Sample Student Response 2

Comment:In part a of this question,the studentlost a point for failing to squarethe concentrationof the fluoride
ion in the calculation. This was a common flaw in part a. Although the studenthad an incorrect value for K,, in
part a, he or sheearnedfull credit in part b for usingit correctly in the calculations.The studentlost a point in part
c for the mathematicserror made in calculating Q,. Although the analysisin part d is somewhatunusual,it is clear
the studentunderstandsthe implications of raising the temperatureon a systemin equilibrium in which the forward
reaction is exothermic, thus full credit was awarded for this part. The total score for this paper was 7.
Question 2
Studentsfrequently did parts a and b correctly (although many omitted units in part b). Credit was given in (ii) of
part a if the rate law given was consistentwith the kinetic orders of (i). The fact that the initial concentrationsof
the reactantsin part c were not equal led many studentsto miss this part. Many studentswho lost points in part c
simply failed to take advantage of the simple stoichiometry but tried to plug concentrationsinto the rate law.
Part d was difficult for many studentswho tried to show that the reaction stoichiometry was consistentwith the
rate-determining step. Many studentswho correctly chose Step II of the mechanismas the rate-determining step
simply statedthat because2N0 = N202, then [N202] = [NO]2 and lost a point as a result.

ScoringStandards

(a) (i) From exps. 1 and 2: Doubling [HZ] while keeping [NO]
constant doubles the rate, therefore the reaction (1 pt.) for order and
is first order in [HZ]. jus tification
From exps. 3 and 4: Doubling [NO] while keeping [Hz ]
constant quadruples the rate, therefore the reaction (1 pt.) for order and
is second order in [NO]. jus tification

(ii) Rate - k[Hz I WI2 (1 pt.>

Note: full credit earned for (ii) as long as rate expression


is consistent with orders in (i).

(b) k - [Hz;:O]L
1.8 x 10s4 M/min
From exp. 1: k -
(1.0 x 1O-3 M)(6.0 x 1O-3 M)2 (1 pt.) for value
- 5.0 X lo3 !I'* min'l (2 pt.) for units

Note: same result from initial rate data from all 4 experiments

(c) Stoichiometry: NO:H2 is 1:l


When 0.0010 mole of Hz had reacted, it must have
reacted with 0.0010 mole of NO; thus
[NO] remaining - 0.0060 - 0.0010 - 0.0050 M. (1 pt.>
IN202 1
(d) (i) For I: Keq -
INW

For II: Rate = w, I [NZOZ


1
IN2021 - KeqlNOl'
Rate - WH21[W2 (1 pt.1
Note: there must be some clear algebraic manipulation
showing that [N202] is proportional (NOT equal) to [NO]*.

Step II is the rate-determining step. (1 pt.1

(ii) I: NO + NO N2O2
II: N2O2 + H2 - H,O + N20
III: N,O + H, - N2 + H,O (1 pt.>

I + II + III: 2 NO + 2 H2 - N2+ 2H20


SampleStudent Response1
Comment:In part a, the kinetic ordersderived are well justified and the rate law is consistentwith them. In part
b, the studentderives an expressionfor the rate constantfrom the rate law and even specifies the number of the
experiment from which he or she takesthe experimental data in evaluating k. In part c, the studentsystematically
tabulatesthe concentrationsof the reactantsin a fashion similar to that used in equilibrium problems and clearly
recognizesthe stoichiometricratio of hydrogen to nitric oxide. The studentearnsall 3 of the possiblepoints in part
d by choosing the secondstep of the mechanism as the rate-determining step, showing that its rate is consistent
with the rate law, and demonstratingthat the sumof the three stepsin the mechanismis equal to the overall reaction
stoichiometry. This was an excellent answer that received a perfect score of 9.
Sample Student Response 2

Comment:Although the studentexpressesthe rate law in part (ii) of a as a proportionality, the equation is written
correctly in part b and full credit is given in part a. The solutionto part b is clear and straightforward.The student
runs into trouble in part c by substitutingconcentrationsinto the rate expression(a common error) and failing to
note the 1:1 stoichiometry in the reaction. In part d, a point was deductedbecausethe studentdid not showthat the
mechanismwas consistentwith the reaction stoichiometry. The total score for this answer was 7.
Question3
Although the difficulty of this question was judged by the readersto be similar to that of question 2, significantly
lessthan half of the examineeschoseto work on this problem. Points were frequently lost in part a when students
failed to consider the water vapor in the collected gas. Failure to read part b carefully led many studentsto
calculate the number of molecules of hydrogen rather than water vapor. In part c credit was awarded for answers
derived from equating the average kinetic energies of the gas molecules or by calculating the root-mean-square
speedsof the molecules of the two gases.In part d many studentscited the difference in the massesof the two
molecules and lost credit for the explanation part of the question.

Scoring Standards

(721)(0.090)
(a) z2 - -$ - - 3.49 x low3 mol Hz
(62.4)(298)
25C - 298 K (1 pt.>
745 - 24 - 721 mm Hg (1 pt.>
calculation of moles of Hz (1 pt.>

(23*8)(o*ogo) _ 1 15 x 10-4 mol H 0


tb) (62.4) (298) 2 (1 pt.1

(1.15 x 10B4)(6.03 x 1023) - 6.92 x 1019 molecules H20 (1 pt.>

(c) The average kinetic energies are equal, so

(+ )H,O - (+&H2 .

(1 pt.) for formula


(1 pt.) for calculatiorz

Note: credit also given for correct use of vrms 3RT


- -
M

(d) H20 deviates more from ideal behavior. (1 pt.>


Explanation:
EITHER
i) The volume of the Hz0 molecule is larger

I
than that of the Hz molecule
W (1 pt.>
ii) The intermolecular forces among Hz0 molecules are
stronger than those among Hz molecules
Sample Student Response 1

Comment:In part a, the conversionof Celsiustemperatureto Kelvins, the application of Daltons Law, and the use
of the ideal gasequation were all done correctly. In part b, the studentclearly recognized the relationshipbetween
the pressureof a gas and the number of moles presentand made the correct calculation usingNA. The solution to
part c is clear and straightforward.The analysisin part d wanderssomewhat,but credit was awarded becausethe
studentwas aware that the hydrogen bonding in water is an intermolecular force and that ideal gasesexperience no
intermolecular forces. This responsereceived a score of 9 points.

n 55m
Sample Student Response 2

Comment:The correct answerswere obtained in both parts a and b in routine fashion. Although the answer in
part b was expressedin too many significant figures, no points were deductedbecausethe number of significant
figures given exceeded the appropriate number by only one. The student earned no credit in part c since the
responsereflected no recognition of the relationshipbetween molecular speedand the squareroot of the molecular
mass nor the inverse relationship between molecular mass and speed. In part d, the studentcorrectly identifies
water as the gasthat deviatesmore from ideal behavior, but, like many students,attributedthat greater deviation to
waters larger molar mass.The total score was 6 points.
Question4
The ability to write the formulas of chemical speciesfrom their namesand knowing the reactionsthat commonly
encounteredchemical systemsundergoapparentlycontinuesto confoundAP Chemistrystudents. Historically,the
performanceof studentson the requiredequationquestionhas reflectedtheir lack of exposureto enough
descriptivechemistry.The performancesof studentson this years requiredequationquestion,however,were
significantlyimprovedover1993(meanscoresof5.3 versus4.4). Only0.7% of thestudents takingtheexamination
hadperfectscoresof 15 on thisquestion.

ScoringStandards

Guiding principles :

1) Each reaction is worth a total of 3 points


2) Reactants +l point; products +2 points
3) Ignore balancing and states
4) Inappropriate ionization - maximum 1 point penalty per equation

(a) CN + Ag+ - Ag(CN)z


Note: any complex ion of Ag with cyanide with consistent charge earns 3 points;
AgCN given as product earns 1 product point

w Mn*+ + 3 - Mns

Note: If Mg used instead of Mn, maximum possible score is 2 points

(4 PbOjO (or PZOS) + Hz0 - H3 PO4

Note: Acidic species (H+ or oxyacid of phosphorus) earns 1 product point;


P in +5 oxidation state in oxyanion earns 1 product point;
anions of oxyacids of phosphorus require H+ for full credit
for products

W lNH4)ZcC3 - NH3 + Hz0 + CO2

Note: Any one product earns 1 point; all three earns 2 product points
NH4OH+ co* earns 1 product point
NH3 + HtCO3 earns 1 product point

(e) CO, + OH- - HC%

Note: C+2 + H20 as products earns 2 product points


Caj2 alone as product earns 1 product point
HCOj - + Hz0 earns 1 product point
(f) Ii+ + Cl' + KMrlO& - K+ + Mn*+ + Cl2 + Hz0

Note: HCl and MnO4' acceptable as reactants


Any valid redox product earns 1 point
All four products earns 2 points
K+ and/or Hz0 only as products earns no credit
If both H+ and Hz0 omitted, then maximum of 2 points possible

W Na + Hz0 - Hz0 + Na+ + OH'

Note: All three products earns 2 product points


Any vaid redox product earns 1 product point

W Crz+2' + Fe2+ + H+' - Cr3+ + Fe3+ + Hz0


Note: All three products earns 2 product points
Any valid redox product earns 1 product point
Hz0 only earns no credit
If Cl' - Cl, instead of Fe2+ - Fe3+, then maximum
of 2 points possible

n s8m
Sample Student Response 1

Comment:This responsefailed to earn a perfect scorefor omitting the water in equationh. This was a common
error in the redox reactions.The total score for this answer was 14 points.

Sample Student Response2

Comment:A point was lost in equation g for failure to represent sodium hydroxide as an ionized species. In
equation a, a point was deducted for the failure to recognize that a complex ion was formed (see the Scoring
Standards).In equationd, a productpoint was deductedfor the hydroxide ion (ratherthan water). In equatione, the
c?udentlost a point for the incorrectchargeon the carbonateion product.The scorefor this responsewas 11 points.

n 59 n
Question5
For this requiredessayquestioninvolving simulatedlaboratoryexercises,studentswere asked to explain the result
of a change in conditions on an illustrated experimental situation. The committee hoped it would encourage a
significant increasein the laboratory componentin AP Chemistry courses.

ScoringStandards

(a) Volume decreases in beaker A; the concentration


decreases in beaker B (either observation earns 1 point (1 pt.>
provided other one is not wrong)

The vapor pressure


pressure
of pure Hz0 is greater
of Hz0 in solution,
than the vapor
1
OR, 7 (1 pt.>
the rate of evaporation of Hz0 molecules from pure Hz0 is
greater than that from the sugar solution, while the
condensation rates are the same. J

(b) The water will begin to boil (or evaporate).

The external pressure on the water will become equal


to the vapor pressure of the water, causing it to boil,

OR,
the drop in external pressure causes the boiling point
7 (1 pt.>

to drop to the temperature of the water. /

(c) Solid copper is deposited on the zinc strip; the zinc (1 pt.>
strip goes into solution. No reaction occurs with silver.

Zinc is a better reducing agent or a more active metal


than copper and will be oxidized. Silver is a less (1 pt.>
reactive metal than copper is.

(d) Two layers will form, one of which is colored. (1 pt.>


Iodine is nonpolar and will dissolve in TTE.
Water-is polar and will not dissolve in TTE. (1 pt.>

Note: placement of 12 must be correctly indicated for 2nd point.

n 60 H
Sample StudentResponse1

n 61 n
Comment:The responsein part a presentsan unusualcombination of a reference to an increasein entropy and the
differential rates of evaporation of pure water and an aqueoussolution of sugar.In part b, the responsedoes not
match the standardsbut clearly indicates that the student understandswhat is required for this system to reach
equilibrium and why this one never can. The students responseto part c essentially embodies the ideas in the
standards.The responseto part d quite simply covers all of the bases.One would have to look hard for a place to
deduct points from this response,which received the maximum score of 8 points.
SampleStudent Response2

Comment: This paper earned a score of 6. The responsein part a was seen in many papers.The awarding of the
observation point was routine, but simply stating that there is a tendency for the concentrationsof the two
systemsto become equal was insufficient to earn the explanation point. Both the observation point and the
explanation point were clearly articulated in the responseto part b. The students responsein part c also clearly
earnscredit for both the observation and explanation points. In part d a point was lost since there was a clear
statementthat the solutionswould separateand two layers would form. Failure to specify that the iodine will be in
the TTE cost this studenta point.
Question6
The importance of thermodynamicsin even an introductory chemistry course is reflected by the fact that it is
almosta standardessaytopic on theAP ChemistryExamination.In part a of thisquestion,students weregiventhe
opportunityto relatetheentropychangefor a reactionto thestoichiometry
andto thephasechangethattakesplace
as reactantsare convertedto products.Parts b and c gave the student an opportunity to demonstrate an
understandingof the implicationsof a change in the temperatureon the spontaneityof a reaction and the K,, of a
systemat equilibrium. In each of the parts a, b, andc, the writingof an equationalonewasnot suffkientto earn
the explanationpoint;the studentwasrequiredto connecttheequationto the issueto beexplained.In part d, a
knowledgeof the Gibbs-Helmholtzequationand the dependenceof the enthalpy and entropy changeson
temperaturewere required.Pointswere not deductedfor sloppinessor confusionrelativeto the differences
betweenthe standardandnonstandard valuesof changesin freeenergy,entropy,or enthalpy.

ScoringStandards

(a) Statement that ASo is negative (1 pt.>

3 moles of gas - 2 moles of gas plus solid,


(3 moles - 2 moles earns no points)
0%
2 gases - 1 gas + solid, (1 pt.>
0%
use of A@ -A@ - TAS" with Ati - 0
Note: If statement is that AS0 is positive, then explanation of
3 moles gas - 5 moles of gas earns I point
(3 moles - 5 moles earns no points)
If correct explanation for ASo being negative is given
but wrong sign is stated, 1 point is earned.

(b) A@ is less negative, goes to 0, goes +, gets larger (1 pt.>


Explanation using A8 - A@ - TAS (1 PU
Note: if answer to (a) is that ASo is positive, then full
credit can be earned here for correct reasoning based
on that assumption. An explanation that uses
Le Ch&teli.er's principle based on sign of @ is NOT
valid here since system not at equilibrium.
(4 &q decreases (exponent - more negative) as 2' increases
CR. (1 pt.>
Keq g oes from > 1, to 1, to < 1, as T increases

Correct explanation using the equation


A# - -RT In Keq (or In&/K;!) - AH%l/T2 - WI)
OR. (1 pt.>
higher 2' favors the reverse reaction (Le Chatelier)
because the forward reaction is exothermic

Note: if answer for (a) is that AS0 is positive then statement


that Ke will decrease or increase depending on the relative
magnitu 3e of T and A8 change earns 2 points. Recognition that
BOTH A@ and T are changing in A8 - -RT In Keq is necessary.
Or, ignoring part (a), use of AHO< 0 explanation to correctly
predict that Qq will decrease earns 2 points.

(d) Since A@ - 0 at this point, the equation is T - f@/AS.


W - & - TAS is NOT sufficient without Afl - 0.) (1 pt.>

Prediction is not exact because & and/or AS0 vary with T (1 pt.)

General Note: For parts (a), (b), and (c), just writing an equation is not
sufficient for the "explanation" point. To earn credit, the
student must connect the equation to issue to be explained.
Sample Student Response 1
Comment:Full credit is given for part a sincethe studentcorrectly evaluatesthe changein disorderasthe reactants
are converted to products. In part b, the student appropriately discussesthe Gibbs-Helmholtz equation and
correctly notes how the two state functions will change as temperature is increased.The answer in part c could
have been clearer; nonetheless,the answerdoes reflect an understandingof the relationshipbetween temperature,
K,,, and free energy change,so both points were awarded.In part d, the studentcorrectly notesthat at the change-
over point the free energy change becomes zero and that both changes in entropy and enthalpy are slightly
temperature dependent.The total score for this answer was 8

Sample Student Response2

Comment:This paper earned4 of the possible8 points. No points were given in part a, becausethe studentfailed
to recognize that changes in phase are more important in determining changesin entropy than changes in the
number of moles of products versusthe number of moles of reactants.Full credit was given in part b, since the
analysisusingthe Gibbs-Helmholtz equation is correct usingthe incorrect sign of entropy changefrom part a. No
points were awarded in part c, althoughthere is somemerit in the analysisof the exothermic nature of the reaction
and the effect of increasingthe temperature on the position of the equilibrium. In fact, the studentdid not answer
the question,What is the changein the value of the equilibrium constant? Two points were awarded in part d for
the correct use of the Gibbs-Helmholtz equation and the recognition that (at least) one of the state functions is
dependenton temperature.
Question7
The students performanceon this question is reflected in the liberal nature of the scoring standards.It seemsthat
most studentsare not exposedappropriately to titration curvesor taught the propertiesof polyprotic acids.

Scoring Standards

(a) POb3' + H+ * HPObt'


only (2 p-4
HP04*- + H+ _ H2P0,-

Note: any proton transfer to any PxOY species earns 1 point.

L 2-
w

3
:;: explicit 32 e
explicit 2 - charge (somewhere)
H : 'b' 0.;:b': (2 pts*>
** l * not more than 1 double P-O bond
53':
.#

Note: HPOb*- (formula only) or other PxOr species with


correct diagram earns 1 point.

(c) Graph goes from upper left to lower right (pH decreases) (1 pm
Two protons Two "buffers" in either (1 pt.>
transferred Two "equivalence" direction
c 7
Explain/correctly label at least one "buffer" or
"equivalence" region (1 PC*>

w H2P04- + *H+ H3f04 (1 pt.1


Note: other proton transfer earns 1 point if
consistent with product in part (a)
Sample Student Response 1

(c) Sketch a graphusing the axes provided, showingthe shapeof the titrationkurve that resultswhen 100. milliliters
of the HCl solutionis added slowly from a buret to the Na3P04 soiution.Account for the shapeof the curve.

0 nL HCI

(d) Write the equationfor the reaction that occursif a few additionalmilliliters of the HCl solutionare addedto
the solutionresultingfrom the titration in (c). $ H-,?OY * Ofl
Y I- t I@
!-Jr3

Comment:This was one of a very few perfect responses(a score of 8 points) to this question. Both points were
clearly earned in part a and in part b. The nature of this students titration curve (part c) reflects a real
understandingof the nature of this system,the somewhatdiffuse equivalencepoints, and the buffering regions.The
responseto part d is exactly right.
.

SampleStudent Response2

0 rnL HCI
1s
(d) Write the equationfor the reaction that occursif a few additional milliliters of the HCl solution are addedto
the solution resulting from the titration in (c).

Comment:The studentclearlyearnsthetwo pointsin part a, buthe or shefailsto identifytheamphotericspecies,


andthe Lewisstructurehaslittle validityin referenceto the octetrule.This studentearnsa pointin part c for the
shapeof the titrationcurveandanotherpointfor identifyingtheequivalence pointsasdropsoccurringwith the
formationof eachsuccessive moleof acid.The studentwasalsoawardeda pointin part d for correctlywritingthe
appropriateequationfor a total scoreof 5.
Question8
This questiongave the studentsan opportunity to relatechemicalprinciplestoeverydayexperiences.Theattempt
tomakechemistryrelevant"hasbecomemoreandmoreapparentinrecentyearsandthattrendisreflectedineach
ofthe four parts to this question.

ScoringStandards

(a) The addition of a solute lowers the freezing point (1 pt.1


of water.

A mole of NaCl contains (dissociates into) 2 moles of


ions/particles, whereas a mole of CaC12 contains (dissociates (1 pt.)
into) 3 moles of ions. Therefore CaC12 is more effective.

w Hydrogen bonding is the most important intermolecular


attractive force between molecules of Hz0 and between (1 pt*)
molecules of NHs.

Water is a liquid because the hydrogen-bonding forces are


stronger between adjacent Hz0 molecules than between adjacent (1 l-4
NH3 molecules.

Further explanations for the stronger hydrogen bonding in Hz0


include the larger dipole moment (or more polar character)
of Hz0 compared to NH, and the fact that 0 is more electronegative
than N is.

(c) Graphite's structure consists of 2-dimensional sheets


of covalently bonded carbon atoms. The attractive forces
between sheets (layers) are weak London (dispersion) forces, (1 pt.1
which allow the sheets to slide easily over one another.
Note: must indicate layers and sliding to earn point.

Diamond consists of an extended 3-dimensional covalent network


of carbon atoms. This makes diamond a very hard substance. (1 pt.)

(d) Vinegar, a dilute solution of acteic acid, reacts with the


white solid, which contains metal carbonates, (1 pt.1
in a neutralization reaction to form gaseous CO2. (1 PW

n 7i n
Comment:Since studentswere not required to relate freezing-point depressionto vapor-pressurelowering, the
statementthat the added salt lowers the freezing point of water earned the first point in part a. The secondpoint in
this part was awarded for the clear recognition of the difference in the i factor for the two solutes.Mentioning
hydrogen bonding and relating the strength of the hydrogen bonds in the two molecules to electronegativity in
oxygen and nitrogen earnedboth points in part b. In part c, the responseclearly earnedthe first point in explaining
the lubricating properties of graphite as a function of sliding layers and, even though the three-dimensionalnature
of the covalent network was not mentioned, the secondpoint was also awarded.The responseto part d is right on
the mark. The total score was 8 points.

n 72 n
Sample Student Response 2

Comment: Although the responseis rather cryptic, since the student notes in part a that the freezing point is
reduced by dissolved solutesand that calcium chloride producesmore ions in solution than sodium chloride, the
responseearned both points. In part b, the studentlosesa point for mistakenly identifying hydrogen bonding as an
intramolecular force and in part c, a point was deductedbecausethe studentfailed to note the covalent network
structure of diamond. In part d, the studentgets back on track by concisely explaining the effervescence when
vinegar is added to the white residue in a tea kettle.
Question9
Atomic structureandchemicalbonding,frequentlythe topicsof essayquestionson theAP Chemistry Examina-
tion, were the foci in this question. In addressingthe four parts, studentswere required to relate differences in
atomic size, crystal-lattice energy, and ionization energy to chemical principles.The fact that very few students
scoredwell on part b is indicative,perhaps,thatthistopicis oftenglossedoverin AP coursesand shouldreceive
more attention.

ScoringStandards

(a) Cat+ has fewer electrons, thus it is smaller than Ca (1 pt.)


The outermost electron in Ca is in a 4s orbital, whereas
the outermost electron in Ca*+ in in a 3p orbital (1 pt.)

Note: The first point is earned for indicating the loss of


electrons, the second point for indicating the outermost
electrons are in different shells -- must account for
the magnitude of the size difference between Ca and Ca2+.

(b) ZI for CaO is more negative than U for K20, so it is more (1 pt.)
difficult to break up the CaO lattice (stronger bonds in CaO).
Ca*+ is smaller than @, so internuclear separations (between
cations and 02-)are less,
OR, (1 pt.>
Ca*+ is more highly charged than K+, thus cation--02 bonds
are stronger

Note: understanding what "lattice energy" is earns 1 point; size


or charge explanation needed for the second point. Responses
that use Lewis structures or otherwise indicate molecules rather
than ionic lattice earn no points.

n 74 n
(c) (i) Ca has more protons e is smaller. The outermost
electrons are more strongly held by the nuclear charge
of Ca.

(ii) The outermost electrons in Ca are in the 4s, which is


a higher energy orbital (more shielded) than the 3p
electron in K.

Note: for (i), the idea of attraction between nucleus


and electrons must be present; for (ii), a
"noble-gas configuration" argument must be tied
to an energy argument in order to earn credit.

(d) The highest energy (outermost) electron in Al is in


a 3p orbital, whereas that electron in Mg is in a 3s orbital. (1 pt*)

The 3p electron in Al is of higher energy (is more shielded)


than is the 3s electron in Mg. (1 pt*)

Note: noting that different orbitals are involved earns the first
point; a correct energy argument earns the second point.
Responses that attribute the greater stability of Ca over K
(or K+ over Ca+,or Mg over Al) to the stability of a completely
filled (vs. half or partially filled) orbital earn NO credit.
SampleStudent Response2

Comment:Thisresponseearned 4 points. Both points in part a were given for noting that electronsare lost in the
ionization while implying that the nuclear chargeremainsthe same,increasingthe force of attractionof the nucleus
per electron. In part b, the studentlost both points sinceit is clear he or shedoesnot understandthe nature of lattice
energy. In part c, the studentearned only 1 of the 2 points, for invoking a common error in responsesto this
question(that filled subshellsare especially stable) in the first part. The point for part c (ii) was awarded since the
studentclearly knew that the secondelectron lost from potassiumcomes from a 3p orbital. In part d, a point was
earned by noting the electron configurationsof the speciesinvolved, but the explanationpoint was lost by using the
same fallacious argument as in part c.
Chapter IV

Statistical Information

n SECTION II SCORES at each score point is listed, along with the total num-
ber of candidatesattempting that essay.
Table 4.1 shows the score distribution for the free- Question 2 had the highest mean as percent of
responsesectionof the 1994 AP Chemistry Examina- maximum possible score, indicating that the score
tion. Studentswere required to complete Questions 1, earned by this questions typical studentwas closer to
4, and 5, and then had to choosea fourth questionfrom the questions highest score than for any other ques-
Questions2 and 3, and two more from Questions6-9. tion. Question 1 had the greatest standarddeviation,
Questions l-3 were scored on a 9-point scale, Ques- indicating that the scorestended to be spreadout more
tion 4 on a 15-point scale, and Questions5-9 on an 8- than for the other questions,
point scale. For each question,the number of students

Table 4.1 - Section II Scores

Score
Question 1
(9)*
Question 2
(9) T Question 3
(9)
Question 4
(15)
Question 5
(8)
Question 6
(8)
Question 7
(8)
Question 8
(8)
Question 9
(8)

16
15 215
14 527
13 710
12 892
11 1,226
10 1,473
9 1,532 357 800 1,740
8 2,116 1,155 735 2,165 486 337 35 165 41
7 2,618 2,210 963 2,344 938 1,787 57 412 175
6 2,674 3,398 1,096 2,593 1,722 2,300 101 712 293
5 2,525 4,390 1,401 2,880 2,601 2,320 152 1,242 846
4 2,518 3,102 1,543 3,183 3,840 2,573 268 1,673 1,839
3 2,863 1,459 1,578 3,325 5,197 2,470 825 2,165 3,446
2 3,87 1 1,137 1,356 3,406 6,131 2,992 2,162 2,396 5,104
1 4,94 1 798 1,018 2,107 5,642 2,072 2,99 1 2,78 1 4,760
0 3,983 1,111 624 1,750 3,076 1,598 887 3,191 1,422
NR** 1,989 1,226 173 1,094 1,997 2,305 1,840 283 242
I I
Number of
Candidates 3 1,630 19,117 1 11,114 31,630 31,630 18,449 7,478 14,737 1 17,926
t(
x,t
x(
I *
:(219/
3.45 1 4.71 1 4.32 2.61 3.60 1 1.73 2.41 1 2.24

* Numbers
__ in brackets
- indicate the maximum possiblescore.
*y No response.Studentsgave either no responseor a responsenot on the topic. Responsesthat fall into this category were not included in the calculation
of number of candidates, mean, standard deviation, or means as a percentageof maximum.
18060-12162*S35M20*255118