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-operated hand-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) (B) (C) (D) (E) state city country continent 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. Questions5-7 refer to the phasediagrambelow of a pure substance. Questionsl-4 (4 Heisenberguncertaintyprinciple (B) Pauli exclusionprinciple K> Hund’s rule (principle of maximum multiplicity) 0) Shieldingeffect 03 Wave nature of matter P 1. Can be usedto predict that a gaseouscarbon atom in its groundstateis paramagnetic (atm) 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) (B) (C) (D) (E) 4. Predictsthat it is impossibleto determinesimultaneouslythe exact positionand the exact velocity of an electron Sublimation Condensation Solvation Fusion Freezing 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. (A) (B) (C) 0) (E) Liz I% N 02 FZ Questions11-13 (4 Pb (W Ca cc>zn 0% As (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 aqueoussolutionof anysolutethan it is for pure water? (A) PH (B) (C) (D) (E) Vapor pressure Freezing point Electrical conductivity Absorptionof visible light 15 In a moleculein which the central atom exhibits sp3d2 hybrid orbitals,the electronpairs are directed 16. Commercial vinegar was titrated with NaOH solutionto determinethe contentof acetic acid, HC2H302. For 20.0 milliliters of the vinegar, 26.7 milliliters of 0.600-molar NaOH solutionwas required.What was the concentrationof acetic acid in the vinegar if no other acid was present? (A) (B) (C) (D) (E) 1.60 A4 0.800 M 0.600 M 0.450 A4 0.200 M towardthe cornersof (A) (B) (C) (D) (E) a tetrahedron a square-based pyramid a trigonal bipyramid a square an octahedron 17. Relatively slow ratesof chemical reactionare associated with which of the following? (A) (B) (C) (D) (E) The presenceof a catalyst High temperature High concentrationof reactants Strong bondsin reactantmolecules Low activationenergy 18. 2 HZ0 + 4 Mn04- + 3 C102- + 4 MnOz + 3 ClOh- + 4 OHWhich speciesactsas an oxidizing agentin the reactionrepresented above? (A) (B) (C) (D) (E) Hz0 ClodClOzMn02 Mn04- 19. In which of the following compoundsis the massratio of chromium to oxygen closestto 1.62 to 1.00 ? (A) (B) (C) (D) (E) 20. Cr-03 CrOr CrO Cr,O CrzO, . . . Ag’ + . . . ASH,(~) + . . . OH- + . . . Ag(s) + . . . H3As03(aq) + . . . Hz0 When the equationaboveis balancedwith lowestwhole-numbercoefficients,the coefficient for OH- is (A) (B) (C) (D) (E) 2 4 5 6 7 2 1. Correct statementsaboutalpha particlesinclude which of the following? I. They havea massnumberof 4 and a charge of +2. II. They are more penetratingthan beta particles. III. They are helium nuclei. (A) (B) (C) (D) (E) I only III only I and II I and III II and III HSO,- + HZ0 =+ H30+ + SO:- 22. In the equilibrium representedabove,the species that act as basesinclude which of the following? I. HS04 II. HZ0 III. sod2(A) (B) (C) (D) (E) II only III only I and II I and III II and III Step 1: Ce4++ Mn2++ Ce3++ Mn3+ 23. Step 2: Ce4++ Mn3++ Ce3++ Mn4+ Step 3: Mn4++ Tl’ + T13++ Mn2+ The proposedstepsfor a catalyzedreaction betweenCe4+and Tl’ are representedabove.The productsof the overall catalyzedreactionare (A) (B) (C) (D) (E) Ce4+and Tl’ Ce3+and T13+ Ce3+and Mn3+ Ce3+and Mn4+ T13+and Mn2’ 24. A sampleof 0.0100 mole of oxygen gasis confined at 37” C and 0.216 atmosphere.What would be the pressureof this sampleat 15” C and the same volume? (A) (B) (C) (D) (E) 0.0876 atm 0.175 atm 0.201 atm 0.233 atm 0.533 atm 25. Hz(g) + $ Wg) + HzO@) AH” = -286 kJ 2 Na(s) + i O?(g) + NalO(s) AH” = -414 kJ Na(s)+$Ol(g)+~H~(g)+NaOH(s) AH”=-425kJ Basedon the informationabove,what is the standardenthalpy changefor the following reaction? NazO(s) + H,O(!?) + 2 NaOH(s) (A) -1,125 kJ (B) -978 kJ (C) -722 kJ (D) -150 kJ (E) +275 kJ 26. Which of the following actionswould be likely to changethe boiling point of a sampleof a pure liquid in an open container? I. Placing it in a smallercontainer II. Increasingthe numberof molesof the liquid in the container III. Moving the container and liquid to a higher altitude (A) (B) (C) (D) (E) I only II only III only II and III only I, II, and III 27. Which of the following setsof quantumnumbers (n, I, mp, ms) bestdescribesthe valenceelectron of highestenergy in a ground-stategallium atom (atomic number3 1) ? (A) 4, 0, 0, ; (B) 4, 0, 1, ; (C) 4, 1, 1, ; (D) 4, 1, 2,; (E) 4, 2, 0, ; 28. Given that a solutionis 5 percentsucroseby mass,what additionalinformation is necessaryto calculatethe molarity of the solution? I. The density of water II. The density of the solution III. The molar massof sucrose (A) (B) (C) (D) (E) I only II only III only I andII1 II andIII 29. When an aqueoussolutionof NaOH is addedto an aqueoussolutionof potassiumdichromate, K&O,, the dichromateion is convertedto (A) CrO:(B) Cfl2- (C) Cr3+ (D) CrzO&) (E) Cr(OH)&) ReactionCoordinate 30. The energy diagram for the reactionX + Y + Z is shownabove.The additionof a catalystto this reaction would causea changein which of the indicated energy differences? (A) (B) (C) (D) (E) 1 only II only III only I and II only I, II, and III q 17B 31. H2C204+ 2 Hz0 ti 2 H30+ + C20$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) (B) (C) (D) (E) 5.36 x lo-* 5.3 x 1O-5 2.8 x lOA 1.9 x 10-l’ 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) (B) (C) (D) (E) molecularmass density specific heat hydrogenbonding 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 hydrocarbonis (B) C2H4 CC> C3He CD) Cd-b (E) Cd-&o 34. CH3-CH2-CH2-CH2-CH3 X CH3-CH2-CH2-CH2-OH HO-CH2-CH2-CH2-OH Y z Basedon conceptsof polarity and hydrogenbonding,which of the following sequences correctly liststhe compoundsabovein the order of their increasingsolubility in water? (A) (B) (C) (D) (E) 2 Y Y X X < < < < < Y< X 2 <X x < z Z < Y Y< Z 35. For which of the following processeswould OS have a negativevalue? I. 2 Fe203(s) -+ 4 Fe(s) + 3 O?(g) II. Mg2++ 2 OH- + Mg(OH)&) III. (A) (B) (C) (D) (E) H?(g) + GH&) I. There must be enoughsamplein the tube to cover the entire light path. II. The instrumentmust be periodically reset using a standard. III. The solutionmustbe saturated. + GH&) I only I and II only I and III only II and III only I, II, and III Zn(s) + Cu2+4 36. (A) (B) (C) (D) (E) Zn*+ + Cu(s) An electrolytic cell basedon the reactionrepresentedabovewas constructedfrom zinc and copper half-cells. The observedvoltagewas foundto be 1.00 volt insteadof the standardcell potential,E”, of 1.10 volts. Which of the following could correctly accountfor this observation? (A) The copperelectrodewas larger than the zinc electrode. (B) The Zn” electrolyte was Zn(N03)2, while the Cu’+ electrolyte was CuS04. (C) The Zn” solutionwas more concentratedthan the Cu” solution. (D) The solutionsin the half-cells had different volumes. (E) The salt bridge containedKC1 as the electrolyte. 37. A sampleof 3.30 gramsof an ideal gas at 15O.O”C 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 (A) (B) (C) (D) (E) 0.0218 gram/mole grams/mole 16.2 grams/mole 37.0 grams/mole 45.8 grams/mole 71.6 38. Concentrationsof colored substances are commonly measuredby meansof a spectrophotometer. Which of the following would ensurethat correct values are obtainedfor the measuredabsorbance? l I only II only I and II only II and III only I, II, and III 39. Samplesof F2 gasand Xe gasare mixed in a containerof fixed volume. The initial partial pressureof the F2 gasis 8.0 atmospheresand that of the Xe gasis 1.7 atmospheres.When all of the Xe gasreacted,forming a solid compound,the pressureof the unreactedF2 gas was 4.6 atmospheres. The temperatureremainedconstant.What is the formula of the compound? (A) (B) (C) (D) (E) XeF XeF3 XeF4 XeF6 XeFs IL Vacuum Closed-endManometer 42. Mass of an empty container 3.0 grams Mass of the containerplus 25.0 grams the solid sample 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 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 28 millimeters of mercury. The partial pressureof O,(g) in the systemis (A) 28 mm Hg (B) 56 mm Hg (C) 133 mm Hg (D) 161 mm Hg (E) 189 mm Hg (C) 2.0 g/cm3 (D) 2.00 g/cm3 (E) 2.27 g/cm3 43. Which of the following pairs of compoundsare isomers? (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 brown gas rapidly forms, the scandiumdisappears, and the resultingliquid is brown-yellow but becomescolorlesswhen warmed. These observationsbest supportwhich of the following statements? (B) CH3-FH-CH3 and CH3-y=CH2 CH3. CH3 (C) CH3-0-CH3 :: and CH3-C-CH3 (A) Nitric acid is a strongacid. m In solutionscandiumnitrate is yellow and scandiumchloride is colorless. Nitric acid reactswith metals to form (0 hydrogen. 09 Scandiumreactswith nitric acid to form a brown gas. 03 Scandiumand nitric acid react in mole proportionsof 1 to 3. (D) CH3-OH and CH3-CH2-OH (E) CH4 and CH*=CH;! 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 25.0” C in a sealedcontainerof constant volume. Which of the following valuesfor the gas will decrease? I. The averagemolecularmassof the gas II. The averagedistancebetweenthe molecules III. The averagespeedof the molecules (A) (B) (C) (D) (E) I only II only III only I and III II and III 49. The isomerizationof cyclopropaneto propyleneis a first-order processwith a half-life of 19 minutes at 500”C. The time it takesfor the partial pressure of cyclopropaneto decreasefrom 1.0 atmosphere to 0.125 atmosphereat 500”C is closestto (A) 38 minutes (B) 57 minutes (C) 76 minutes (D) 152 minutes (E) 190 minutes 50, Which of the following acidscan be oxidized to form a strongeracid? 46. Which of the following solidsdissolvesin water to form a colorlesssolution? (A) (B) (C) (D) (E) Cc13 FeC13 coc12 CuC12 ZnCl? 47. Which of the following has the lowestconductivity? (A) (B) (C) (D) (E) @I HNO3 (c> H2co3 0% H3BO3 09 H2so3 4 HCl(g) + 02(g) * 2 Cl,(g) + 2H&?) Equal numbersof molesof HCl and O2 in a closed systemare allowedto reach equilibrium as representedby the equationabove.Which of the following mustbe true at equilibrium? I. [HCI] mustbe lessthan [Cl,]. II. PCls(g) + energy III. Some PC13and Cl2 are mixed in a containerat 200” C and the systemreachesequilibrium accordingto the equationabove.Which of the following causesan increasein the number of molesof PCls presentat equilibrium? (A) (B) (C) (D) (E) I. Decreasingthe volume of the container II. Raisingthe temperature III. Adding a mole of He gas at constantvolume (A) (B) (C) (D) (E) H3PQ 51. 0.1 A4CuSO4 0.1 it4 KOH 0.1 M BaC& 0.1 MI-IF 0.1 M HNO3 PC&(g > + C12(g) @ 48. (A) I only II only I and III only II and III only I, II, and III 121 II [02] mustbe greater than [HCl]. [Cl,] must equal [H,O]. I only II only I and III only II and III only I, II, and III 59. When a 1.00~gramsampleof limestonewas dissolvedin acid, 0.38 gram of CO* was generated. If the rock containedno carbonateother than CaC03, what was the percentof CaC03 by massin the limestone? 63. What is the maximum massof copper that could be plated out by electrolyzingaqueousCuC12for 16.0 hoursat a constantcurrentof 3.00 amperes? (1 faraday = 96,500 coulombs) (A) 28 grams (B) 57 grams (C) 64 grams (D) 114 grams (E) 128 grams (A) 17% (B) 51% (C) 64% (D) 86% (E) 100% 60. 12(g) + 3 Cl2(g) + 2 ICl,(g) According to the data in the table below, what is the value of AH0 for the reactionrepresented above? Bond AverageBond Energy (kilojoules/mole) I-I Cl-Cl I-Cl 149 239 208 64. At 25” C, a sampleof NH3 (molar mass 17 grams) effusesat the rate of 0.050 mole per minute. Under the sameconditions,which of the following gases effusesat approximatelyone-half that rate? (A) (B) (C) (D) (E) O2 (molar mass32 grams) He (molar mass4.0 grams) CO2 (molar mass44 grams) Cl, (molar mass71 grams) C& (molar mass 16 grams) 65. Barium sulfate is LEAST solublein a O.Ol-molar solutionof which of the following? (A) -860 kJ (B) -382 kJ (C) +180 kJ (D) +450 kJ (E) +1,248 kJ (A) A12(S04)3 (W (Nb)2S04 (C> Na2S04 0) NH3 (E) BaC12 61. A l-molar solutionof which of the following salts has the highestpH ? (A) NflO3 @I Na2C03 (C> 66. What is the pH of a 1.0 x 10-2-molarsolutionof HCN ? (For HCN, Ka = 4.0 x lo-“.) (A) 10 (B) Between 7 and 10 WC1 (C) 7 (D) Between 4 and 7 (E) 4 (D) NaHSO‘, (E) Na2SQ 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 separatedin the laboratory using the techniqueof fractionalcrystallization.This fractionalcrystallization is possiblebecausesubstances X and Y have different (A) (B) (C) (D) (E) 70. To determinethe molar massof a solid monoprotic acid, a studenttitrated a weighedsampleof the acid with standardizedaqueousNaOH. Which of the following could explain why the student obtaineda molar massthat was too large? boiling points melting points densities crystalcolors solubilities I. Failure to rinse all acid from the weighingpaper into the titration vessel II. Addition of more water than was neededto dissolvethe acid III. Addition of somebasebeyondthe equivalence point 68. Which of the following moleculeshas a dipole momentof zero? (A) (B) (C) (D) (E) C6H6(benzene) NO SO1 NH3 HS (A) (B) (C) (D) (E) 71. . . . Fe(OH)z + . . . O2 + . . . Hz0 + . . . Fe(OH)3 If 1 mole of O2 oxidizesFe(OH)2 accordingto the reactionrepresentedabove,how many molesof Fe(OH)j can be formed? 69. Correct proceduresfor a titration include which of the following? I. Draining a pipet by touchingthe tip to the side of the containerusedfor the titration II. Rinsingthe buret with distilledwaterjustbefore filling it with the liquid to be titrated III. Swirling the solutionfrequentlyduringthe titration (A) (B) (C) (D) (E) I only III only I and II only II and III only I, II, and III (A) (B) (C) (D) (E) I only II only I and III only II and III only I, II, and III n 24 n 2 3 4 5 6 72. The nuclide 249 ,,Cm is radioactiveand decaysby the loss of one beta (p-) particle. The productnuclide is 74. A solutionof calcium hypochlorite,a common additiveto swimming-poolwater, is (A) basicbecauseof the hydrolysisof the OCl- ion (B) basic becauseCa(OH)2 is a weak and insoluble base (C) neutral if the concentrationis kept below 0.1 molar (D) acidic becauseof the hydrolysisof the Ca” ions (E) acidic becausethe acid HOC1 is formed (A) ‘;;Pu (B) “z:Arn (C) ‘ZiCrn (D) ‘;;&-I 73. 2 sol(g) + 02(g) + 2 SO3(g) When 0.40 mole of SO?and 0.60 mole of 02 are placed in an evacuatedl.OO-liter flask, the reaction representedaboveoccurs.After the reactants and the productreach equilibrium and the initial temperatureis restored,the flask is found to contain 0.30 mole of S03. Basedon theseresults,the equilibrium constant,K,, for the reactionis 75. A direct-currentpower supplyof low voltage(less than 10 volts) has lost the markingsthat indicate which outputterminal is positiveand which is negative.A chemistsuggeststhat the power supply terminalsbe connectedto a pair of platinumelectrodes that dip into O.l-molar KI solution.Which of the following correctly identifies the polaritiesof the power supplyterminals? (A) 20. (B) 10. (C) 6.7 (D) 2.0 (E) 1.2 (A) A gas will be evolvedonly at the positiveelectrode. (B) A gas will be evolvedonly at the negativeelectrode. (C) A brown color will appearin the solutionnear the negativeelectrode. (D) A metal will be depositedon the positiveelectrode. (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 m REVISED QUANTITATIVE ITEMS FROM THE 1994 CHEMISTRY EXAM There were a total of 20 quantitative questionsin the multiple-choice section of the 1994 AP Chemistry Exam. Below are 10 quantitative questionsfrom this group rewritten to conform to the new format being introduced in 1996, in which calculators will not be allowed for the multiple-choice questions.(The capital “R” following the questionnumber indicatesthat it is a Revised question.) The remaining quantitative questions from the 1994 exam are those for which students would not typically need a calculator, and therefore represent quantitative questionsthat would appear exactly as they are now on the new format of the exam. 24R. A sample of 0.010 mole of oxygen gas is confined at 127°C and 0.80 atmosphere.What would be the pressureof this sample at 27°C and the same volume? (A) (B) (C) (D) (E) 0.10 atm 0.20 atm 0.60 atm 0.80 atm 1.1 atm 25~ H,(g) + l/2 O,(g) - H,O@) AHO=_X 2 Na(s) + l/2 O,(g) - N$O(s) AP=y Na(s) + l/2 O,(g) + l/2 H,(g) - NaOH(s) AH0 = z Based on the information above, what is the enthalpy change for the following reaction? N%O(s) + H,O@) - 2 Na0I-W (A) (B) (C) (D) (E) 16R. Commercial vinegar was titrated with NaOH solution to determine the content of acetic acid, HC,H,O,. For 20.0 milliliters of the vinegar, 32.0 milliliters of 0.500-molar NaOH solution was required. What was the concentration of acetic acid in the vinegar if no other acid was present? (A) (B) (C) (D) (E) 1.60 M 0.800 M 0640M 0.600 M 0.400 M 19R. In which of the following compounds is the mass ratio of chromium to oxygen closest to 1.6 to l.O? (A) (B) (C) (D) (E) CrO, CrO, CrO Cr,O Cr,O, 31R. x+y+z x+y-z x+y-22 22-x-y z-x-y H,C,O, + 2 H,O = 2 H,O+ + C,O,2Oxalic acid, H&O,, is a diprotic acid with X10-5.Whichofthe K, =5 X lo-*andK,=5 following is equal to the equilibrium constant for the reaction representedabove? (A) (B) (C) (D) (E) 5 X lo-* 5 X10-’ 2.5 x 10” 5 x1O-7 2.5 X10-* 37R. A sample of 3.0 grams of an ideal gas at 127°C and 1.O atmospherepressurehas a volume of 1.5 liters. Which of the following expressionsis correct for the molar mass of the gas?The ideal gas constant, R, is 0.08 (L= atm)/(moleeK). (A) (0.08)(400) (3.0)( 1.O)(1.5) (B) (1.0)(1.5) (3.0)(0.08)(400) (C) (0.08)( 1.O)(1.5) (3.0)(400) (D) (3.0)(0.08)(400) (1.0)(1.5) (E) (3.0)(0.08)( 1.5) (1.0)(400) 59R. When a 1.25-gram sample of limestone was dissolved in acid, 0.44 gram of CO, was generated. If the rock contained no carbonate other than CaCO,, what was the percent of CaCO, by mass in the limestone? (A) (B) (C) (D) (E) 35% 44% 67% 80% 100% 63R. Which of the following expressionsis correct for the maximum mass of copper, in grams, that could be plated out by electrolyzing aqueousCuCl, for 16 hours at a constant current of 3.0 amperes? (1 faraday = 96,500 coulombs) (A) (16)(3,600)(3.0)(63.55)(2) (96,500) (B) (16)(3,600)(3.0)(63.55) (96,500)(2) (C) (16)(3,600)(3.0)(63.55) (96,500) (D) (16)(60)(3.0)(96,500)(2) (63.55) (E) (16)(60)(3.0)(96,500) . (63.55)(2) 73R. 2 SO,(g) + Q,(g) = 2 SO,(g) When 0.40 mole of SO, and 0.60 mole of 0, are placed in an evacuated l.OO-liter flask, the reaction representedabove occurs.After the reactants and the product reach equilibrium and the initial temperature is restored, the flask is found to contain 0.30 mole of SO,. Based on these results, the expression for the equilibrium constant, K,, of the reaction is (A) (0.45)(0. 1o)2 (B) 60R. I,(g) + 3 Cl,(g) - (C) (D) Average Bond Energy (kilojoules/mole) I-I 150 Cl - Cl 240 I - Cl 210 (o.30)2 (0.60)(0.40)2 2 ICl,(g) According to the data in the table below, what is the value of AHo for the reaction representedabove? Bond (o.30)2 (2 x 0.30) (0.45)(2 X 0.10) (0.30) (0.45)(0.10) (E) (0.30) (0.60)(0.40) I Answers to Revised Questions I (A) (B) (C) (D) (E) - 870kJ -390kJ + 180 kJ +45OkJ +1,260 kJ I I 16R. 19R. 24R. 25R. 31R. 37R. 59R. 60R. 63R. 73R. B B C D C D D B B 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 THIS SECTION IN THE FOLLOWING TABLES MAY BE USEFUL OF THE EXAMINATION. IN ANSWERING THE QUESTIONS 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 Universal gas constant: In, = 2.303 log,, Planck’s constant It = 6.63 x 10 -34joule * set Boltzmann’s constant k = 1.38 x 10 “joule/K Avogadro’s number = 6.022 x 1013molecules/mole 0.059 1 In Q = ~ log Q At 25” C, RT n n3 STANDARD REDUCTION Li. POTENTIALS, E”, IN WATER SOLUTION + e AT 25” C (in V) Li(s) - 3.05 Cs’ + e K++e Cs(s) K(s) - 2.92 - 2.92 Rb‘ Rb(s) - 2.92 Ba(s) Ws) - 2.90 Q(s) - 2.87 -2.71 fe Ba2+ + 2e Sr“ + 2e Ca” Na’ + 2e + em Mg” + 2e Na(s) Mg(s) Be’ ’ + 2 e Be(s) - Al’ Al(s) - 1.66 + 3e - 2.89 - 2.37 1.I0 + 2e Mn(s) - 1.18 Zn” + 2 e Cr’ ’ + ?e Zn(s) -076 - 0.74 Mn” Fe” Cr-” Cr(s) Fe(s) Cr’ ’ + 2e + e Cd” + 2e Tl’ + e - 0.44 -0.41 Cd(s) - 0.40 Tl(s) - 0.34 - 0.28 Co” + 2e Co(s) Ni’. Sn’ + 2e + 2e Ni(s) - 0.25 Sri(s) Pb(s) -0.14 ’ Pb” 2H’ + 2e +2e Hz(g) H$ S(s) + 2 H ’ + 2 e Sn4 ’ + 2e Cu” + e Cu’+ + 2e Cu. +e -0.13 0.00 0.14 Sn’ + Cu’ 0.15 Cu(s) Cu(s) 0.34 0.52 0.15 I:(s) + 2 e Fe’+ + e 21 0.53 Fe” 0.77 Hg,’ ’ + 2e Ag’ +e Hg” + 2em 2 Hg(Q) 0.79 Ag(s) 0.80 Hg(Q) Hgz’ + 2 Br- 0.85 2 H,O I .23 1.36 2Hg” + 2e Br,(Q) + 2e O,(g) + 4H’ + 4e 2 Cl Au(s) 0.92 1.07 Cl,(g) + 2 e Au’* + 3 e Co’+ + e co:+ I .82 FJg) + 2 e 2F 2.87 n 31 n 1.50 IN 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. 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. (4 Predict whether a precipitateof MgF2 will form when 100.0 milliliters of a 3.00 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 concentrations and ratesof reactionare given in the table below. Initial Concentration (mom) Experiment [NOI 1 0.0060 0.0060 0.0010 0.0020 2 3 4 B321 Initial Rate of Formation of N2 (mol/L*min) 0.0010 0.0020 0.0060 0.0060 1.8 x 3.6 x 0.30 x 1.2 x 1O-4 1O-4 1o-4 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. II. III. NO + NO+=N202 N202 + H2 + H20 + N20 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 Equilibrium Vapor Pressure of Hz0 (25” C) 745 mm Hg I 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, what behaviorof water in the beaker will be observed?Explain why this occurs. Pure H2O 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) + At 298 K, the standardenthalpychange,AH’, 3 S(s) + 2 HzO(g) for the reactionrepresentedaboveis -145 kilojoules. 64 Predict the sign of the standardentropy change,ASo, for the reaction.Explain the basisfor your prediction. What change,if any, would occur in (b) At 298 K, the forward reaction(i.e., toward the right) is spontaneous. the value of AG” for this reactionas the temperatureis increased?Explain your reasoningusing thermodynamic principles. (4 What change,if any, would occur in the value of the equilibrium constant,Keq, for the situationdescribed in (b)? Explain your reasoning. can be predicted.Write the (4 The absolutetemperatureat which the forward reactionbecomesnonspontaneous 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 achieved a higher mean score on the test as a whole than candidates who did not answer that question correctly. An answer sheet gridded with the correct responsesappearson the next page. Listed below are the correct answersto the multiplechoice questionsand the percentageof AP candidates who attempted each question and answered it correctly. As a general rule, candidates who correctly Section I Answer Key and Percent Answering Correctly c Item No. 1 2 3 Correct Answer Percent Correct Item No. Correct Answer Percent Correct Item No. Correct Answer Percent Correct C E 32% 38% 44% 82% 73% 74% 66% 21% 47% 57% 52% 21% 78% 46% 50% 69% 82% 62% 83% 58% 58% 62% 71% 76% 63% 26 C C E D B 29 A 30 32 D C D 33 C 34 E 35 D 61% 48% 58% 36% 55% 39% 77% 52% 39% 54% 46% 81% 41% 38% 67% 58% 39% 55% 31% 44% 46% 38% 35% 49% 58% 51 27 28 29% 29% 55% 43% 35% 35% 46% 29% 29% 47% 21% 64% 24% 23% 21% 64% 25% 41% 36% 15% 33% 53% 24% 34% 16% B 4 A 5 A 6 7 B B 8 C 9 D 10 11 C 12 D 13 A 14 C 15 E 16 B D 17 18 19 20 21 22 C E B D D E 23 24 B 25 D C : 31 36 C 37 38 D 39 C 40 C 41 D D 42 C 43 44 A 45 C 46 47 E D 48 A 49 B 50 E E 52 53 E 54 D 55 C 56 B 57 A 58 B 59 60 65 D B B A B D A 66 D 61 62 63 64 67 E 68 A 69 70 C A 71 72 C 73 74 A A 75 B E H SECTION II: FREE-RESPONSE Report of the Chief Faculty Consultant Robert W. Gleason Middlebury College Grading the Examination The free-response section of the AP Chemistry Examination is read and scoredby faculty consultants - AP Chemistry teachersand college chemistry professors- who are under the direction of a chemistry teacherdesignatedas the chief faculty consultant.The faculty consultantsare from secondary schools and colleges throughout the United States, and also from Canada.The faculty consultantsdo not have accessto, and therefore are not influenced by, the multiplechoice section of the examination, which is scored separatelyby machine. Studentscoreson both partsof the examination are combined and used by the chief faculty consultant to determine the levels of student performance on the AP 1 to 5 grading scale. The Reading In June the faculty consultantsmeet for six days on a college campusto score the free-responsesectionsof the AP Chemistry Examination. The chief faculty consultantdivides the faculty consultantsinto groups, each under the direction of a designatedfaculty consultantcalled a table leader. One or more table leaders with their group of faculty consultantsis assignedto score each free-responsequestion, depending on the number of studentswho chose to answer it. The table leaders train their groups to score their designated question, and scoring of student papers commences according to standardsdeveloped as describedbelow. Each answer booklet is circulated among the various groups until all the studentresponsesin that booklet have been scored. The finished booklets are then removed from the Reading site and the scores are enteredinto computersand matchedwith the students’ multiple-choice section scores.Composite scoresare calculated and theseand other data are provided to the chief faculty consultantfor the grade-settingsession, which occurs shortly after the Reading is over. Developing Free-Response Scoring Standards Scoring standardsfor the free-responsequestionsare a consideration throughout the development of the examination. Members of the AP Chemistry Development Committee submit suggestedscoring standards with each question that they write. Scoring standards are discussedfurther when questionsare revised and chosenby the committee to be included in an examination.At this stage,considerationis given to potential difficulties that might interfere with the reliable scoring of a question,and the scoringstandardmay be revised accordingly. Prior to the Reading, the chief faculty consultantgeneratesa draft of the scoringstandardfor each of the nine questionsin the free-responsesection, taking into considerationissuesraisedduring previous reviews.The generalscoringguidefor the free-response questionsis as follows: Problems 9 pointseach Chemical Reactions 3 pointseach (15 pointstotal) Essays 8 points each Two days before the Reading begins, the chief faculty consultantmeets with the table leaders to review the draft standards,and the group reachesa consensus on a possible standardfor each question. The table leadersbreak into groupsto test the standardsagainst a number of studentresponses.During this phase of the process,the standardsmay be modified somewhat. Meeting again as a whole group, the chief faculty consultantand the table leadersreach anotherconsensuson the standards,after which each table leader is assignedto a particular questionand is also assigneda list of faculty consultantswith whom he or she will score the questionduring the Reading. On the first day of the Reading, the table leaders train the faculty consultantsin applying the scoring standardsto a setof samplestudentresponsesselected for that purpose.During this process,the standardsare refined and may be modified slightly once again. After the group is proficient in applying the scoring standards,the actual scoring of the student papers begins. The final results of the rigorous standardsetting procedure described above are standardsthat canbe appliedreliably not only to the commonmethods of solution seen in the studentresponses,but also to commonerrorsandto alternativeor unusualapproaches. Becausevarious studentresponsesto a given question are scoredover a six-day period by more than one faculty consultant,it is important to monitor the application of the standardsduring the Reading. This is done by having a certain number of student papers independently graded more than once, either by different faculty consultants,or by the sameconsultantat a later time. The original scores are concealed from subsequentfaculty consultants, and the two sets of scoresare then compared. The checking of one consultant againstanother quickly identifies any remaining ambiguities that may exist in the standardsand allows their further refinement, to help assurethat a student’s score is independent of the person scoring the paper. Checking a consultant against his or her own work also helps assurethat a student’s score is independentof what day or time the paper is scored. Rarely is there a discrepancyof more than 1 point on the scale. Other procedureshelp maintain consistent scoring standards.After the Reading is underway, the table leaders select and score another series of questions for yet another kind of consistencycheck. This one does not compare the faculty consultants with themselves,but rather it comparesthem with the other faculty consultants in their group and individually with the table leaders. The philosophyof the faculty consultantsin scoring the free-responsequestionsis to award credit for correct work. When questionsinvolve calculations,most of the points awarded are given for setting up the solution correctly rather than actually carrying out the computation. Partial credit is awarded within each part of a question,so studentsshouldbe encouragedto show their work. Faculty consultantstry to determine whether an incorrect answer to a previous part has been correctly usedin a subsequentpart of a question. Full credit for the latter part may be awarded if the consultant can successfully trace the student’s work to make that determination. Students should also be encouragedto continue on to later parts of a question if they get stuck at some point. Parts of a questionare often independentof each other; even when they are dependent, credit can be earned on later parts when earlier answersare missing.Also, a student’s explanation of what he or shewould do, if possible,could earn some credit. Finally, when final answersare numerical, studentsshouldpay attentionto significantfigures since 1 point is deducted (once per problem) if the number of significant figures in a student’s answer differs by more than one from the appropriatenumber. n FREE-RESPONSE QUESTIONS, SCORING GUIDES, AND SAMPLE STUDENT ANSWERS On the pages that follow are a selection of student responsesto each of the questionsthat made up the free-response section of the 1994 Advanced Placement Examination in Chemistry. Also included are the standardsthat were applied in the scoringprocess, and an explanation of why each responsereceived the score it did. For each question, two studentresponses have been selected to illustrate a superior answer and one of somewhatlower quality. From our experience in reading Advanced Placement Examinations we know that no set of scoring standardscan possiblyanticipatethe creativity of high school studentsin developing solutions to problems. Therefore, you should understandthat readers make every possibleeffort to give credit for every response that reflects an understandingof basic principles of chemistry regardless of how far the approach used deviates from what might be a more conventional route developed in the standards. In developing the standardsfor the 1994 AP Chemistry Exam, the chief faculty consultanthad the assistance of 11 faculty consultantswho served as table leaders, and two test development specialists from ETS. The group met for two days prior to the Reading. After a draft set of standardswas established, the application of the standard for each question was testedwith about 100 papers.The standardswere then reviewed in the light of that experience and either revised accordingly or adopted. If a studentmade an error in part (a) of a four-part problem and the answer to part (a) was essential to working the rest of the problem, the reader of the paper was obliged to work through the solutionsto the subsequentparts of the question with the erroneous answer to part a. Thus, every effort was made to reward the students with points for the appropriate applicationof chemicalprinciples.Studentswere, however, penalized for mathematical errors and errors in 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 Ksp - (4 [Mg*+J[F-]* (1.21 7.09 - x 1.21 x 10’3)2 U pt.1 if number of significant figures in final answer differs more than one from the appropriate number, 1 point is deducted ONCE PER PROBLEM. Note: (W KsP 7.09 x 10-9 IMg*+l OK if Note: Cc> (1 pt.> x 10’3)(2 x 10-9 IQ*+] .- - [M$+](2x - [Mg*+](o 010)2 (7.09 x io+)/(lo-2) 7.09 x 10-7 M 0.102 is used for 100.0 x 3.00 I%*+1 [F”] : 200.0 x 2.00 WI Q - Ion Product ** Correct [F-j, then Ksp - 6.76 300 . 0 x [Mg2+] - - x 1O'3 M 1.00 x 1O-3 - - x loo3 M 1.33 300.0 - [Mg*+][F']* (1.00 x 10’3)(1.33 - 1.77 will must be consistent substitution concentration the first. x [F-l x lo-S)* x 10'9 no precipitate (1 pt.) for substitution 2x << 0.100 x 103 - Since Q < Ksp , Note: conclusion + O.lOO)* by x 10” I** form with and calculation (1 pt.) if both concentrations are correct (1 pt.> (1 ptJ Q value. of the wrong values earns the second point, proper but not (d) Solubility of MgF, decreases thus dissolution temperature, MgFz(s) + Mg2+ + with increasing process is exothermic 2 F- + Q (cr (1 pt.> H) Reason: EITHER i) Increased temperature puts a stress on the system The system will reduce the stress (Le Chatelier). 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. n 46m i 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) Doubling [HZ] while keeping From exps. 1 and 2: constant doubles the rate, therefore the reaction is first order in [HZ]. (i) Doubling From exps. 3 and 4: constant quadruples the rate, is second order in [NO]. (ii) Note: Rate - k[Hz From exp. (c) (1 pt.) for order and jus tification (1 pt.) for order and jus tification (1 pt.> for (ii) as long as rate orders in (i). expression [Hz;:O]L 1: k - Note: [NO] while keeping [Hz ] therefore the reaction I WI2 full credit earned is consistent with (b) k - [NO] same result Stoichiometry: (1.0 5.0 1.8 x 10s4 M/min x 1O-3 M)(6.0 x 1O-3 M)2 X lo3 !I'* from initial NO:H2 is rate min'l data for value (2 pt.) for units 4 experiments 1:l When 0.0010 mole of Hz had reacted, it reacted with 0.0010 mole of NO; thus [NO] remaining from all (1 pt.) - 0.0060 - 0.0010 must have - 0.0050 M. (1 pt.> 1 IN202 (d) (i) For I: Keq - Rate For II: = IN2021 Rate Note: w, I [NZOZ 1 KeqlNOl' (1 pt.1 WH21[W2 there must be some clear algebraic showing that [N202] is proportional Step II is (ii) the I: II: III: I - INW + II + III: rate-determining NO + NO step. to [NO]*. (1 pt.1 N2O2 N2O2 + H2 - H,O N,O H, - N2 2 NO + 2 H2 - N2+ + manipulation (NOT equal) + + N20 H,O 2H20 (1 pt.> 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 (a) z2 - -$ (721)(0.090) (62.4)(298) - - 3.49 x low3 mol Hz 25°C 298 K 745 - 24 721 mm Hg calculation of moles of Hz (23*8)(o*ogo) (62.4) (298) tb) (1.15 (c) x _ (+ (1 pt.> (1 pt.> mol H 0 x 1023) kinetic )H,O - energies - (+&H2 (1 pt.1 2 ’ 10B4)(6.03 The average 1 15 x 10-4 (1 pt.> 6.92 x 1019 molecules are equal, H20 (1 pt.> so . (1 pt.) (1 pt.) Note: (d) credit also H20 deviates given for correct more from ideal use of vrms - - 3RT M behavior. (1 pt.> Explanation: EITHER i) The volume of the Hz0 molecule than that of the Hz molecule is larger W ii) The intermolecular forces among Hz0 molecules stronger than those among Hz molecules are I (1 pt.> for for formula calculatiorz Sample Student Response 1 Comment:In part a, the conversionof Celsiustemperatureto Kelvins, the application of Dalton’s 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 water’s 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 Historically,the encounteredchemical systemsundergoapparentlycontinuesto confoundAP Chemistrystudents. performanceof studentson the required“equation”questionhas reflectedtheir lack of exposureto enough descriptivechemistry.The performancesof studentson this year’s requiredequationquestion,however,were significantlyimprovedover1993(meanscoresof5.3 versus4.4). Only0.7% of thestudents takingtheexamination hadperfectscoresof 15 on thisquestion. ScoringStandards Guiding principles : Each reaction is worth a total of 3 points +l point; products +2 points 3) Ignore balancing and states 4) Inappropriate ionization - maximum 1 point 1) 2) Reactants (a) CN’ Note: w any complex ion of Ag with cyanide with consistent AgCN given as product earns 1 product point If 3’ - + of Mn, maximum possible Hz0 - score CO, Note: charge earns is 2 points Acidic species (H+ or oxyacid of phosphorus) earns 1 product P in +5 oxidation state in oxyanion earns 1 product point; anions of oxyacids of phosphorus require H+ for full credit for products - NH3 + Any one product + OH- - C+2’ + H20 Caj2’ alone HCOj - + Hz0 3 points; H3 PO4 Hz0 earns + all 1 point; three earns 2 product points HC%’ as products as product earns earns earns 1 product point; CO2 NH4OH+ co* earns 1 product point NH3 + HtCO3 earns 1 product point (e) equation Mns Mg used instead lNH4)ZcC3 Note: per Ag(CN)z’ PbOjO (or PZOS) Note: W Ag+ - Mn*+ + Note: (4 + penalty 1 product point point 2 product points (f) Ii+ Note: W Na Note: W + + KMrlO& - K+ + Mn*+ + Cl2 + Hz0 as reactants HCl and MnO4' acceptable 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 + Hz0 - Hz0 + Na+ + possible OH' All three products earns 2 product points Any vaid redox product earns 1 product point Crz+2' Note: Cl' All Any Hz0 If of + Fe2+ + H+' - Cr3+ + Fe3+ + Hz0 three products earns 2 product points valid redox product earns 1 product point only earns no credit instead of Fe2+ Fe3+, then maximum Cl' Cl, 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 “product”point 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 provided other one is not wrong) The vapor pressure of pure Hz0 is greater pressure of Hz0 in solution, than 1 point (1 pt.> 1 the vapor 7 (1 pt.> 7 (1 pt.> OR, 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. (b) The water will The external to the vapor begin pressure pressure to boil (or J evaporate). on the water will become equal of the water, causing it to boil, OR, the drop in external pressure causes the boiling to drop to the temperature of the water. (c) (d) Solid strip copper is goes into deposited solution. on the zinc No reaction point / strip; the zinc occurs with silver. (1 pt.> Zinc is a better reducing agent or a more active metal than copper and will be oxidized. Silver is a less reactive metal than copper is. (1 pt.> Two layers (1 pt.> will form, one of which is colored. Iodine is nonpolar and will dissolve Water-is polar and will not dissolve Note: placement of 12 must be correctly in TTE. in TTE. indicated n 60 H (1 pt.> for 2nd point. 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 student’s 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 student’s 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 weregiventhe almosta standardessaytopic on theAP ChemistryExamination.In part a of thisquestion,students 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 “explanation”point;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 Note: (b) A@ -A@ Ati - 0 If statement is that AS0 is positive, then explanation 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. A@ is less Explanation Note: - TAS" with goes to 0, goes +, gets larger negative, using A8 - A@ - TAS” 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. of (1 pt.> (1 PU (4 decreases &q (exponent - more negative) as 2' increases CR. (1 pt.> g oes Keq Correct A# - from > 1, to 1, to < 1, as T increases explanation using the equation In Keq (or In&/K;!) - AH%l/T2 -RT - WI) OR. (1 pt.> higher 2' favors the reverse reaction (Le Chatelier) because the forward reaction is exothermic Note: (d) 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. Since A@ - 0 at this W - & Prediction General Note: - TAS” is point, the equation is T - f@/AS”. NOT sufficient without Afl - 0.) is not exact because & and/or AS0 vary with T (1 pt.> (1 pt.) 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 “changeover” 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 student’s 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 POb3' (a) + H+ * HPObt' HP04*- + H+ _ H2P0,- transfer to any only Note: any proton :;: H : 'b' 0.;:b': ** 53': .# Note: l * 3 HPOb*- (formula correct (c) diagram explicit 32 e’ explicit 2 - charge (somewhere) not more than 1 double P-O bond only) earns Graph goes from upper left Two protons transferred Note: H2P04- + or other 1 point. to lower right H+ at least (2 pts*> PxOr species with Two "buffers" Two "equivalence" c Explain/correctly label "equivalence" region w PxOY species earns 1 point. 2- L w (2 p-4 (1 in either direction (1 pt.> 7 one "buffer" * H3f04 other proton transfer earns 1 point if consistent with product in part (a) pm (pH decreases) or (1 PC*> (1 pt.1 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. t 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 student’s 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 pointsas“drops”occurringwith 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 tomakechemistry“relevant"hasbecomemoreandmoreapparentinrecentyearsandthattrendisreflectedineach ofthe four parts to this question. ScoringStandards (a) w The addition of water. of a solute lowers the freezing point (1 pt.1 A mole of NaCl contains (dissociates into) 2 moles of ions/particles, whereas a mole of CaC12 contains (dissociates into) 3 moles of ions. Therefore CaC12 is more effective. (1 pt.) Hydrogen bonding is the most important intermolecular attractive force between molecules of Hz0 and between molecules of NHs. (1 pt*) Water is a liquid because the hydrogen-bonding forces are stronger between adjacent Hz0 molecules than between adjacent NH3 molecules. (1 l-4 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 forces of covalently bonded carbon atoms. The attractive between sheets (layers) are weak London (dispersion) forces, which allow the sheets to slide easily over one another. Note: (d) must indicate layers and sliding (1 pt.1 to earn point. Diamond consists of an extended 3-dimensional covalent network of carbon atoms. This makes diamond a very hard substance. (1 pt.) Vinegar, a dilute solution of acteic acid, reacts white solid, which contains metal carbonates, (1 pt.1 in a neutralization reaction to form gaseous CO2. n 7i n with the (1 PW 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 Examination, 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 The outermost the outermost Note: The first electrons, electrons, electron electron thus it is smaller Ca than in Ca is in a 4s orbital, in Ca*+ in in a 3p orbital (1 pt.) whereas (1 pt.) point is earned for indicating the loss of 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 difficult to break up the CaO lattice (stronger bonds in CaO). Ca*+ is smaller cations and 02-)are than @, so internuclear separations (between less, OR, (1 pt.> Ca*+ is more highly are (1 pt.) charged than K+, thus cation--02’ bonds 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) (ii) Note: (d) Ca has more protons e is smaller. The outermost electrons are more strongly held by the nuclear charge of Ca. The outermost electrons a higher energy orbital electron in K. in Ca are in the 4s, which is (more shielded) than the 3p 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. 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 point; that different orbitals are involved earns the first 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 Table 4.1 shows the score distribution for the freeresponsesectionof the 1994 AP Chemistry Examination. Studentswere required to complete Questions 1, 4, and 5, and then had to choosea fourth questionfrom Questions2 and 3, and two more from Questions6-9. Questions l-3 were scored on a 9-point scale, Question 4 on a 15-point scale, and Questions5-9 on an 8point scale. For each question,the number of students Table 4.1 Score Question 1 (9)* Question 2 (9) T Question 3 (9) at each score point is listed, along with the total number of candidatesattempting that essay. Question 2 had the highest mean as percent of maximum possible score, indicating that the score earned by this question’s typical studentwas closer to the question’s highest score than for any other question. Question 1 had the greatest standarddeviation, indicating that the scorestended to be spreadout more than for the other questions, Section II Scores Question 4 (15) Question 5 (8) Question 6 (8) Question 7 (8) Question 8 (8) Question 9 (8) 16 15 14 215 13 12 710 892 11 1,226 527 10 1,532 357 800 8 2,116 2,618 2,674 1,155 2,210 735 7 9 1,473 1,740 2,165 2,344 486 337 35 938 1,787 57 165 412 41 175 3,398 963 1,096 2,593 1,722 2,300 4,390 1,401 2,880 2,601 2,320 101 152 712 1,242 293 2,525 2,518 2,863 3,102 1,543 3,183 3,840 2,573 268 1,673 1,839 1,459 1,578 3,325 5,197 2,470 825 2,165 1,137 798 1,356 1,018 3,406 2,107 6,131 5,642 2,992 2,072 0 NR** 3,983 1,989 1,111 624 173 1,750 1,094 3,076 1,997 1,598 2,305 2,162 2,99 1 887 3,446 5,104 1 3,87 1 4,94 1 1 11,114 31,630 31,630 18,449 6 5 4 3 2 1,226 I Number of Candidates 3 1,630 19,117 x,t x( 1 2,396 2,78 1 1,840 3,191 283 7,478 14,737 4,760 1,422 242 I t( I * 3.45 846 4.71 1 4.32 2.61 1 17,926 :(219/ 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