Name: ____________________ Chemistry 1AA3 McMaster University Test 1

Student number: ______________ February 1, 2008

VERSION 1 ANSWERS in blue + SOLUTIONS

Instructors: P. Berti, P. Lock, J. Valliant Duration: 100 minutes This test contains 22 numbered pages printed on both sides. There are 25 multiple-choice questions appearing on pages numbered 3 to 18. Page 21 includes some useful data and equations. There is a periodic table on page 22. Pages 19 & 20 may be used for rough work. You may tear off the last pages to view the periodic table and to do your rough work. You must enter your name and student number on the question sheets, as well as on the answer sheet. Your invigilator will be checking your student card for identification. You are responsible for ensuring that your copy of the question paper is complete. Bring any discrepancy to the attention of your invigilator. Questions 1 to 20 are each worth 2 marks, questions 21 25 are each worth 3 marks; the total marks available are 55. There is no additional penalty for incorrect answers. BE SURE TO ENTER THE CORRECT VERSION OF YOUR TEST (shown near the top of page 1), IN THE SPACE PROVIDED ON THE ANSWER SHEET. ANSWER ALL QUESTIONS ON THE ANSWER SHEET, IN PENCIL. Instructions for entering multiple-choice answers are given on page 2. SELECT ONE AND ONLY ONE ANSWER FOR EACH QUESTION from the answers (A) through (E). No work written on the question sheets will be marked. The question sheets may be collected and reviewed in cases of suspected academic dishonesty. Academic dishonesty may include, among other actions, communication of any kind (verbal, visual, etc.) between students, sharing of materials between students, copying or looking at other students work. If you have a problem please ask the invigilator to deal with it for you. Do not make contact with other students directly. Try to keep your eyes on your own paper looking around the room may be interpreted as an attempt to copy.

Only Casio FX 991 electronic calculators may be used; but they must NOT be transferred between students. Use of periodic tables or any aids, other than those provided, is not allowed. Page 1 of 15

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You are writing VERSION 1 of this test. Make sure you have correctly entered your version number (1) in the correct column on your scan sheet (see p. 2 for details). Questions 1 through 20 are worth two (2) marks each.

1. The purpose of a recrystallization is:

(A) (B) (C) (D) (E)

To check the miscibility of two compounds. To dry a compound before taking the melting point. To purify a compound. To find out the boiling point of compound. To check the solubility of a compound.

SeeLabmanual,Lab6.

2. Octane, C8H18, undergoes complete combustion in excess oxygen to give carbon dioxide and water. How many litres (L) of CO2(g) are produced in the complete combustion of 18.0 g of octane at 50.0 C and 1.00 atm? (A) (B) (C) (D) (E) 4.18 L 33.4 L 5.29 L 16.6 L 31.9 L
Balanced reaction: C8H18(l) + 25/2 O2(g) 8 CO2(g) + 9 H2O(l)

mol octane = 18.0 g / 114.2302 g/mol = 0.1576mol mol CO2 = 0.1576 mol octane 8 mol CO2 / 1 mol octane = 1.261 mol CO2 From PV = nRT, V = nRT/P V = ( 1.261mol)(0.08206 L.atm/K.mol)(323.15 K) / (1.00 atm) V = 33.4 L

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3. Which of the following statements are TRUE for the molecule shown below?
CH3 H3C
5

CH3 CH3 C C
3 2

C
4

CH2
1

CH3

CH3

(i) (ii) (iii) (iv) (v) (A) (B) (C) (D) (E)

C(1) is sp2 hybridized. C(3) is a quaternary (4) carbon atom. The molecule is an alkyne. There are no secondary carbon atoms. There are six sp3 hybridized atoms. all of the above none of the above i, ii, iv iii, v i, ii
(i)TRUE (ii)TRUEattachedto4otherCatoms. (iii)FALSEalkene (iv)TRUEallmethylgroupsareprimary, andC(3)andC(4)arequaternary. (v)FALSEthereare8sp3hyrbidizedatoms

4. What is a correct name for the following compound?

O O
Thesecbutylgroupindicatesabutylsubstituent attachedfromasecondarysite. Theacetateandsecbutylarefromourlistof commonnames.

(A) (B) (C) (D) (E)

sec-butyl acetate butyl methyl carboxylic acid ethyl butanoate isobutyl acetate n-butyl acetate

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5. Atropine is a toxic alkaloid closely related to the drug cocaine. Which of the following statements concerning atropine is/are TRUE?
CO2Me N-Me O- C O

(i)

Atropine contains a tertiary amine.

CH2OH CH

(ii) Atropine contains a primary alcohol. (iii) Atropine has two ether groups. (iv) The molecule is completely flat.

atropine

(A) (B) (C) (D) (E)

i, ii ii, iii iii, iv i none of them

(i)TRUE (ii)TRUE (iii)FALSEithas2estergroups (iv)FALSEtherearemanysp3hybridizedatomsin thestructure,tellingus(especiallywiththetricyclic groupontheleft)itisnotflat.

6. A compound with molecular formula C12H22 could not be: (A) (B) (C) (D) (E) a cyclic alkane a dialkene a cyclic alkene an alkyne a bicyclic alkane (i.e., 2 rings)
Acompletelysaturatedlongchainalkanewould havemolecularformulaCnH2n+2.Thusfor12Catoms, itwouldbeC12H26.Thereare4Hatomsmissing meaningthattherecouldbe2rings,2pibonds,ora combinationofboth,asrepresentedinanswers(B) to(E). AnswerAonlyshowslossof2Hintheformula,so thisdoesnotmatchthegivenformula.

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7. Which of the following statements about bonding and hybridization is/are TRUE?

(i) (ii) (iii) (iv)

The hybridization of C in CO2 is sp2. Carbon-carbon (pi) bonds are formed by the sideways overlap of p orbitals. Carbon-carbon (pi) bonds are stronger than carbon-carbon (sigma) bonds. Carbon-carbon double bonds are stronger than carbon-carbon single bonds.
(i)FALSEsphybridized (ii)TRUE (iii)FALSEoverlapisweaker,thuspibondsare weakerthansigmabonds. (iv)TRUEsinglebondrepresentsasigmabond, whereasdoublebondissigma+pi.

(A) (B) (C) (D) (E)

i, ii, iii ii, iv i, ii ii i, iii, iv

8. Which of the following statements are TRUE regarding the properties of alkanes? (i) (ii) Alkanes are miscible (mix well) with water. Alkanes burn in air to give H2O and CO2 with release of free energy.

(iii) Alkanes are nonpolar molecules. (iv) Alkanes react with Mg to give Grignard reagents. i, ii ii, iv i, iii ii, iii iii, iv
(i)FALSEalkanesarenonpolar(see(iii)). (ii)TRUEhydrocarboncombustionreactionsarespontaneous(G negative). (iii)TRUE (iv)FALSEalkylhalidesreactwithMgtogiveGrignardreagents.

(A) (B) (C) (D) (E)

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9. The molecule lupeol is shown in two representations: as a two-dimensional drawing, and as a three-dimensional structure. (Me = CH3, methyl).
HO
Me Me Me

Me

H
Me Me

Which of the following statements is/are TRUE?

HO H Me Me

Me Me

Me

Me

(i)

The molecule has five axial methyl groups and one equatorial hydroxyl group.

(ii) The molecule is tetracyclic. (iii) The oxygen atom is sp3 hybridized and its electron pair geometry is bent. (iv) The molecule possesses two equatorial methyl substituents. i, ii ii, iii iii, iv i iii
(i)TRUE (ii)FALSEthereare5rings,not4. (iii)FALSEtheOatomissp3hybridized,anditselectronpairgeometryis thereforebasedonthetetrahedron. (iv)FALSE1equatorialmethylgroup(and5axial).

(A) (B) (C) (D) (E)

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10. How do the following compounds relate to each other?

CH3 HC CH3 H2C CH3

(A) (B) (C) (D) (E)

Identical Structural isomers Geometric isomers Both (B) and (C) None of the above

ThesemoleculesareallC5H12,andallhavethe sameconnectivity(skeletalstructure).Theyare allidentical.

11. What is TRUE about the following molecule?

CH3 H
Thesubstituentsherearealleclipsingone another. Thetermconformationappliestothis molecule.Withrotationaboutsinglebonds itcouldalsoappearinastaggered conformation. Thetermconfigurationapplieswhenthere isgeometricisomerism(notthecasehere) whereonecannotconvertbetween geometricisomersbysimpleroationabout singlebonds.

H CH3

(A) (B) (C) (D) (E)

The molecule is in an eclipsed conformation The molecule is in a staggered conformation The molecule is in an eclipsed configuration The molecule is in a staggered configuration None of the above

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12. The functional groups present in the following molecule include:

O H

Thefunctionalgroupsare:
OCH3 OH

Aldehyde Ether Phenol Arene

(A) (B) (C) (D) (E)

Ester, aldehyde, ether, and phenol Aldehyde, phenol, and ester Alcohol, acid, and ether Alkyne, aryl, and aldehyde None of the above

13. How many structural isomers are there for a compound having the formula C2H2Cl2? (A) (B) (C) (D) (E) 1 2 3 4 5

Thereare2structuralisomers: 1,1dichloroetheneand1,2dichloroethene. Notethatthe1,2dichloroethenestructuralisomer canexistasbothEandZisomers,whichareapair ofgeometricisomers.

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14. Which of the following statements about saturated hydrocarbons is/are TRUE? (A) (B) (C) (D) (E) They contain at least one -bond.
Saturatedhydrocarbons,bydefinition,haveall bondingelectronsinsigmabonds,thus(A)isFALSE All C-C-C bond angles are 120o. and(D)isTRUE.AllCatomswillbesp3hybridized, thus(B)isFALSE.Saturatedhydrocarbonsdisplaya They have high boiling points. widerangeofboilingpoints,frommethane(CH4,a All electrons participate in -bonds. greenhousegasandagasatroomtemperature,b.p. 162C),tohexane(liquidatroomtemperature, Both (C) and (D). b.p.68.7C,seep.1081,Petrucci),allthewayup to,forexample,triacontane(C30H62,solidatroom temperature,b.p.450C).Answer(C)isthusFALSE theydisplayarangeofboilingpoints,some extremelylow.

15. For cyclohexane which of the following statements is/are FALSE? (A) The bond angles at carbon are around 109o and the carbon atoms are sp3 hybridized. The molecule adopts the chair conformation, rather than a planar conformation, to reduce bond angle strain. Cyclohexane is a saturated hydrocarbon. A Newman projection of the planar configuration of cyclohexane would show less eclipsing interactions between H-atoms than in the chair conformation. Both (B) and (D)
(A)TRUE (B)TRUEinaplanarconformationthebondangleswouldbe120. (C)TRUEallelectronsofinterestareengagedinsigmabonds.Notethat thereisadifferencebetweenamoleculethatissaturated(e.g.youcannot doanadditionreactionwithit),versusamoleculewithadegreeof unsaturation(itsformulashows2lessHthananlinearalkane). (D)FALSEAllHatomswouldbeengagedineclipsinginteractions.

(B)

(C) (D)

(E)

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16. What are the reaction conditions i and ii?

i ii OH
Step(i)showsthehydrationofanalkene;werequire thepresenceofwateranddiluteacidcatalysta 10%aqueoussolutionofH2SO4providesthis. Step(ii)showsthedehydrationofanalcohol.This reactionispromotedwiththepresenceofheatand astrongdehydratingagent;concentratedH2SO4is anexcellentreagentforremovalofwater.The symbolrepresentsheat.

i (A) 10% H2SO4

ii conc. H2SO4,

(B) conc. H2SO4, 10% H2SO4 (C) conc. H2SO4 (D) conc. H2SO4 (E) 10% H2SO4 conc. H2SO4, HBr, conc. H2SO4, h

17. Which of the following molecules have the Z configuration?

Br

Br

Br I

F Cl (iv)

(i)

(ii)

(iii)

(A) (B) (C) (D) (E)

iii, iv i, ii iv i i, iv

Thealkeneconfigurationisassignedbyprioritizingthegroupsat eachendofthedoublebond.Whenthepriority1groupsareonthe samesideofthedoublebond,itisaZconfiguration;ontheopposite side=E.Seeclassnotesforareviewonhowtoassignpriorities basedonatomicnumber. (i)isE(Br,CH3onoppositesides) (ii)isneitherEnorZ(2CH3groupsatoneend) (iii)isZ(CH3andFonsameside) (iv)isZ(I,Clonsameside)

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18. Which hybridization state of carbon is not shown in this diagram?

Energy

2p 2s

hybridize

(A) (B) (C) (D) (E)

sp sp2 sp3 p2 unhybridized ground state

Picture1showsanunhybridizedgroundstateCatom. Picture2showsansp3hybridizedCatom. Pictures3showsansp2hybridizedCatom.

19. Which hybrid orbital has the highest energy? (A) (B) (C) (D) (E) sp3 sp2 sp 2s 2p
Thesp3hybridorbitalhasthegreatestamountofp orbitalcharacter.Sincetheporbitalssitathigher energythans,themoreporbitalcharacterthehigher theenergyofthehybridorbitalthatresultsfromthe combinationofsandporbitals.

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20. Allene is a rather exotic molecule, where the central carbon atom forms double bonds to two other carbon atoms (as seen below in the structure on the left). The p-orbitals are shown below in the structure on the right.
C

H2C C CH2

C
Which of the following structures for allene is correct?
Wecanseeinthefigureattopright: (a)thatthe2terminalCatomsaresp2hybridized,sothe approximateHCHbondanglesare120.Thiseliminates answers(C)and(D)asINCORRECT. (b)thatthereare2adjacentpibonds.Thiseliminatesanswer (E)asINCORRECT. Weknowthatporbitalsmustbeat90tooneanother,andso the2pibondscannotbecoplanar.Wealsoknowthatthe2H atomsattachedtoeachCattheendofthemoleculemustbe inaplaneat90tothepibondconnectedtothatCatom.So, ifthe2pibondscannotbecoplanar,thenthe2setsofH atomsalsocannotbecoplanar.Thiseliminatesanswer(B)as INCORRECTandsoweareleftwithanswer(A)asCORRECT. Foradditionalfollowuponthisquestionpleasesee recommendedtextquestion#24fromCh.11.

H C C C H
120

(A)

H C C C

H
120

(B)

H C C C H
109.5

(C)

H C C C

H
109.5

(D)

H C C C
(E)

H H

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Questions 21-25 are worth three (3) marks each.

21. How many sigma () bonds, pi () bonds and lone pairs of electrons are there in a molecule of methyl acrylate, CH2CHCOOCH3? Sigma bonds Pi bonds Lone pairs of electrons

(A) (B) (C) (D) (E)

8 6 9 7 11

2 3 4 2 2

4 1
Thestructureis: H2C=CHC(O)OCH3

4 1 4

Thereare2pibonds(1eachinthealkeneand thecarbonyloftheestergroup).Thereare4 lonepairsofelectrons(2pairsoneachOatom). Thereare11sigmabondsrequiredtoholdthe skeletonofthemoleculetogether.

22. Which of the following statements are TRUE? (i) Grignard reagents can be synthesized from alkanes by reaction of an alkane with a halogen and heat, followed by addition of Mg in ether. (ii) The reaction mechanism of a halogen with an alkane involves a charged (ionic) intermediate. (iii) Possible products of the reaction of ethane with chlorine in the presence of light include CH3CH2Cl, HCl, and a small amount of CH3(CH2)2CH3. (iv) The bond in Br2 is more easily broken than the bond in I2. (A) (B) (C) (D) (E) i, ii i, iii ii, iv i, iv iii, iv
(i)TRUE:alkane+X2andheatorlightproduceshaloalkane;additionofMginether tohaloalkaneproducesGrignardreagent. (ii)FALSE:themechanismisaradicalchainmechanism(nocationsoranions). (iii)TRUE:CH3CH3+Cl2willproduceCH3CH2ClalongwithHCl,andsinceethyl radicalsareproducedinthereaction,thecombinationof2ethylradicals(ina terminationstep)wouldproducebutane. (iv)FALSE:ThebondinI2islonger;weexpectitisaweakerbondthanBrBr.

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23. For the following molecule, look down the C-C bond from A to B in the direction that is indicated by the arrow. Which of the following Newman projections is/are correct for this bond?

OH A B MeO

Note: Ph = a phenyl substituent PhOMe = a phenyl substituent bearing a para-methoxy group

H HO Et Ph H PhOMe H H

PhOMe Et OH Ph

Ph HO Et H H PhOMe

(A)

(B)

(C)

(D) Both (B) and (C); they are simply rotational isomers (E) None of the above Answer: C
(A)INCORRECT:Differentmolecule. (B)INCORRECT:ThisistheviewfromBtoA. (C)CORRECT. (D)INCORRECT.BandCarenotrotationalisomers.Theyare thesamemoleculeinthesameconformation,viewedfrom differentdirections. (E)INCORRECT(see(C)).

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24. Which one of the reactions below correctly follows Markovnikov's rule?

HCl

Cl

(A)
2 HBr Br

Markovnikovsruleappliesinmechanisms whereweexpectcationicintermediatesin theadditionofasymmetricreagentsto alkenes. (A)DoesnotfollowMarkovnikovsrule (B)Markovnikovsruledoesnotapply

(B)

Br

(C)

H2C CH2

catalyst

H3C CH3

(C)Markovnikovsruledoesnotapply (D)CORRECT

HI

(D)

(E)Markovnikovsruledoesnotapply(this reactionwillnotoccur)

MeMgBr

(E)

25. Which one of the following statements is CORRECT?

4
(A)FALSE:Eisomer.

(A) 1 is a Z-isomer. (B) 2 and 3 are geometric isomers. (C) 1 and 3 are geometric isomers. (D) 2 and 4 are structural isomers. (E) 2 and 3 are structural isomers.

(B)FALSE:2and3arethesamemolecule,withasingle bondrotationbetweenatoms2and3. (C)TRUE:1isEand3isZatposition3. (D)FALSE:2and4aredifferentmolecules(different molecularformulae). (E)FALSE:see(B)above.

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