Organic Chemistry, 6e (Bruice) Chapter 1 Electronic Structure and Bonding Acids and Bases 1) Atoms with the same

e number of protons but different numbers of neutrons are called ________. Answer: isotopes Section: 1-1 2) Which of the following elements does this electronic configuration represent? 1s2 2s2 2p A) ! ") # #) $ %) Al &) ' Answer: A Section: 1-2 () )ow man* unpaired electrons are present in the isolated carbon atom +atomic number , -)? A) none ") one #) two %) three &) four Answer: # Section: 1-2 .) Which of the following is the electronic configuration of the element !e? A) 1s2 2s2 2p- (s2 (p- .s2 (d") 1s2 2s2 2p- (s2 (p/ (d#) 1s2 2s2 2p/ (s2 (p- .s2 (d%) 1s2 2s2 2p- (s2 (p- .s2 .d&) 1s2 2s2 2p- (s2 (p- .s2 .pAnswer: A Section: 1-2 ) 0he atomic number of boron is . 0he correct electronic configuration of boron is: A) 1s22s( ") 1s22p( #) 1s22s22p1 %) 2s22p( &) 1s22s2(s1 Answer: # Section: 1-2

-) Which of the following statements correctl* describes the third electron shell that surrounds the nucleus of an atom? A) 0he third shell contains onl* s and p atomic orbitals. ") 0he ma1imum number of electrons that can occup* the third shell is 1/. #) 0he total number of atomic orbitals present in the third shell is 1-. %) 0he third shell can contain f orbitals. &) All third shell elements must ha2e d electrons. Answer: " Section: 1-2 3) Ar4 564 #l- are isoelectronic elements +elements with the same number of electrons). What orbital does the last electron occup*? Answer: (p orbital Section: 1-2 /) 0he compound meth*lamine4 #)($)24 contains a #-$ bond. 7n this bond4 which of the following best describes the charge on the nitrogen atom? A) 61 ") slightl* positi2e #) uncharged %) slightl* negati2e &) -1 Answer: % Section: 1-( 8) Which of the compounds below ha2e bonds that are predominantl* ionic? A) 5#l ") #!. #) $)( %) both A and " &) both " and # Answer: A Section: 1-( 19) What t*pe of bonding is most important in #)(#)2#)2#)2#)2#)(? A) ionic ") h*drogen #) co2alent %) polar Answer: # Section: 1-(

11) Which of the following contain+s) polar co2alent bonds? A) $)( ") $a2' #) )2 %) 5! &) both A and # Answer: A Section: 1-( 12) Which of the following co2alent bonds has the largest dipole moment? A) #-# ") #-) #) #-' %) )-$ &) )-! Answer: & Section: 1-( 1() :sing the s*mbol ;6and ;-4 indicate the direction of the polarit* in the indicated bond.

Answer:

Section: 1-( 1.) #o2alent bonds ma* be polar or nonpolar. What propert* of the atoms forming a gi2en bond determines this? Answer: electronegati2it* Section: 1-( 1 ) <ro2ide the mathematical e=uation for the dipole moment of a bond4 and identif* the 2ariables. Answer: > , e ? d4 where > is the bond dipole moment4 e is the amount of charge which is separated4 and d is the distance o2er which the charge is separated. Section: 1-(

1-) 0he formal charge on nitrogen in the compound below is ________.

A) 62 ") 61 #) 9 %) -1 &) -2 Answer: " Section: 1-. 13) Which of the following is the most li@el* electronic structure for #2)2? A)

")

#)

%) &)

)##)

Answer: % Section: 1-.

1/) Which of the following structures4 including formal charges4 is correct for diaAomethane4 #)2$2? A) :#)2$$: ") #) %) &)

Answer: % Section: 1-. 18) What are the formal charges on nitrogen and the starred o1*gen atom in the following molecule?

A) $ , -14 ' , 9 ") $ , 614 ' , -1 #) $ , 614 ' , 61 %) $ , -14 ' , -1 &) $, 614 ' , 9 Answer: & Section: 1-.

29) %raw the 5e@ulB structure for each of the following: a. #)(#)2') b. #)(#)' c. +#)()(#6 Answer:

Section: 1-. 21) 0he 5e@ulB structure of pentane is shown below. %raw the condensed structural formula which corresponds to this Cewis structure.

Answer: #)(+#)2)(#)( Section: 1-. 22) %raw condensed structures for the four compounds with formula #()8$. Answer: #)(#)2#)2$)2 #)(#)2$)#)( +#)()2#)$)2 +#)()($ Section: 1-. 2() Write a Cewis structure for the molecule gi2en and show all formal charges. #)2#' Answer:

Section: 1-.
-

2.) &1pand the condensed structure below to show the co2alent bonds and the lone-pair electrons. +#)()2#)#)2#)' Answer:

Section: 1-. 2 ) %raw the Cewis structure for #)($26. Answer:

Section: 1-. 2-) )ow man* distinct and degenerate p orbitals e1ist in the second electron shell4 where n , 2? A) 9 ") 1 #) 2 %) ( &) . Answer: % Section: 123) %raw the shape of a 2p orbital. Answer:

Section: 12/) #onsider the interaction of two h*drogen 1s atomic orbitals of the same phase. Which of the statements below is an incorrect description of this interaction? A) A sigma bonding molecular orbital is formed. ") 0he molecular orbital formed is lower in energ* than a h*drogen 1s atomic orbital. #) 0he molecular orbital formed has a node between the atoms. %) 0he molecular orbital formed is c*lindricall* s*mmetric. &) A ma1imum of two electrons ma* occup* the molecular orbital formed. Answer: # Section: 1-3

28) "oth sigma +D) and pi +E) bonds can be formed b* o2erlapping p orbitals. %escribe the difference. Answer: Sigma bonds are formed from the o2erlap of atomic orbitals along a circular a1is of s*mmetrical nature4 i.e.4 head-on o2erlap. All single bonds are sigma bonds. <i bonds are formed from the o2erlap of atomic orbitals along a non-s*mmetrical +parallel) a1is4 i.e.4 side-to-side o2erlap. %ouble and triple bonds contain both sigma and pi bonds. Section: 1-(9) What @ind of molecular orbital +D4 DF4 E4 or EF) results when the two atomic orbitals shown below interact in the manner indicated?

Answer: DF Section: 1-(1) What @ind of molecular orbital +D4 DF4 E4 or EF) results when the two atomic orbitals shown below interact in the manner indicated?

Answer: D Section: 1-(2) What @ind of molecular orbital +D4 DF4 E4 or EF) results when the two atomic orbitals shown below interact in the manner indicated?

Answer: E Section: 1-(() What @ind of molecular orbital +D4 DF4 E4 or EF) results when the two atomic orbitals shown below interact in the manner indicated?

Answer: DF Section: 1--

(.) What @ind of molecular orbital +D4 DF4 E4 or EF) results when the two atomic orbitals shown below interact in the manner indicated?

Answer: EF Section: 1-( ) #hoose the correct h*bridiAation for the atom indicated in the molecule below. #)(#)2#)2#)( G A) sp ") sp2 #) sp( %) none of the abo2e Answer: # Section: 1-3 (-) What orbitals are used to form the co2alent bonds in butane +#)(#)2#)2#)()? Answer: 0he carbon-carbon D bonds are formed b* the o2erlap of two carbon sp( h*brid atomic orbitals. 0he carbon-h*drogen D bonds are formed b* the o2erlap of a carbon sp( h*brid atomic orbital and a h*drogen s orbital. Section: 1-3 (3) Which carbon+s) in the following molecule is +are) sp h*bridiAed?

A) carbon 1 ") carbon 2 #) carbons 14 ( %) carbons . &) carbons .4 Answer: & Section: 1-8

(/) Which of the following is an sp2 h*bridiAed carbon? A) ") H #)(

#) %) A and " &) A4 " and # Answer: A Section: 1-19 (8) What is the predicted shape4 bond angle4 and h*bridiAation for 6#)(? A) trigonal planar4 129I4 sp2 ") trigonal planar4 129I4 sp( #) trigonal planar4 198. I4 sp2 %) trigonal p*ramidal4 129I4 sp2 &) trigonal p*ramidal4 198. I4 sp2 Answer: A Section: 1-19 .9) What orbitals o2erlap to create the )-# bond in #)(6? A) sp(-sp( ") sp2-sp( #) s-p %) s-sp2 &) s-sp( Answer: % Section: 1-19 .1) 0he lone-pair electrons of the meth*l anion occup* a+n) ________ orbital. A) s ") p #) sp %) sp2 &) sp( Answer: & Section: 1-19

19

.2) Which of the following is closest to the #-'-# bond angle in #)(-'-#)(? A) 1/9I ") 129I #) 198. I %) 89I &) 1-9I Answer: # Section: 1-11 .() &ach lone pair of electrons on the ' atom in methanol +#)(')) occupies a+n) ________ orbital. A) s ") p #) sp %) sp2 &) sp( Answer: & Section: 1-11 ..) 0he $-) single bond in meth*l amine +#)($)2) is a ________ bond formed b* the o2erlap of a+n) ________ orbital on $ and a+n) ________ orbital on ). A) DJ sp2J s ") D J sp( J s #) E J sp( J s %) E J sp2 J p &) E J p J p Answer: " Section: 1-12 . ) 0rieth*lamine K+#)(#)2)($L is a molecule in which the nitrogen atom is ________ h*bridiAed and the #$# bond angle is ________. A) sp24 M198. I ") sp24 N198. I #) sp(4 M198. I %) sp(4 N198. I &) sp4 198. I Answer: % Section: 1-12

11

.-) 0he $-) bond in the ammonium ion4 $).64 is formed b* the o2erlap of what two orbitals? A) sp(-sp( ") sp(-sp2 #) sp2-sp2 %) sp2-s &) sp(-s Answer: & Section: 1-12 .3) Among the h*drogen halides4 the strongest bond is found in ________ and the longest bond is found in ________. A) )!4 )! ") )!4 )7 #) )74 )! %) )74 )7 &) )#l4 )"r Answer: " Section: 1-1( ./) Which bond in the following molecule is the shortest?

A) bond 1 ") bond 2 #) bond ( %) bond . &) bond Answer: & Section: 1-1. .8) Which of the following species ha2e tetrahedral bond angles?

A) A4 % and & ") A4 %4 & and ! #) A and & %) % onl* &) A4 " and & Answer: " Section: 1-1.
12

9) 0he carbon-carbon double bond in ethene is ________ and ________ than the carbon-carbon triple bond in eth*ne. A) strongerJ shorter ") strongerJ longer #) wea@erJ shorter %) wea@erJ longer &) strongerJ more polar Answer: % Section: 1-1. 1) What is the #$$ bond angle in the compound shown below?

A) O-9I ") O89I #) O119I %) O129I &) O1/9I Answer: % Section: 1-1. 2) %raw the structure of a molecule which contains onl* carbon and h*drogen atoms +onl* three of which are carbon) and in which two of the carbons are sp2 h*bridiAed and the other is sp h*bridiAed. Answer: )2###)2 Section: 1-1. () Wh* is the #) bond in ethene +)2##)2) shorter and stronger than the #) bond in ethane+#)(#)()? Answer: 0he length and strength of a #) bond depends on the h*bridiAation of the carbon atom. 0he more s character in the h*brid orbital used b* carbon to form the bond4 the shorter and stronger the bond. 0his is because an s orbital is closer to the nucleus than is a p. &thene uses carbon sp2 h*brid orbitals +1P( s character) to ma@e its carbon-h*drogen bonds while ethane uses carbon sp( +1P. s character). Section: 1-1. .) Which of the following molecules does not e1hibit a net dipole moment of Aero? A) #'2 ") #). #) ##l. %) )2' &) S'( Answer: %
1(

Section: 1-1 ) Which of the following molecules has a net dipole moment of Aero? A)

")

#)

%)

&)

Answer: " Section: 1-1 -) Which of the following molecules has the smallest dipole moment? A) "r2 ") $)( #) )#l %) )"r &) )7 Answer: A Section: 1-1

1.

3) "!( has a dipole moment of Aero. <ropose a structure for "!( that is consistent with this information. Answer: "!( is trigonal planar.

Section: 1-1 /) %raw the 5e@ulB structure and show the direction of the dipole moment for #)2#l2. Answer:

Section: 1-1 8) Which of the following is not a conQugate acid-base pair? A) )2'4 )'") )2'4 )('6 #) )S'.-4 )2S'. %) -')4 '2&) $'(-4 $'2Answer: & Section: 1-1-9) What is the product formed from the following acid-base reaction?

A) #)('- 6 6$). ") #)2') 6 6$)( #) #)(')26 6 -$)2 %) #)($)2 6 )2' &) #). 6 $)2') Answer: A Section: 1-1-

-1) 0he conQugate acid of )2' is: A) )('") )(' #) )('6 %) )'&) )2'6 Answer: # Section: 1-1-2) Which of the following ions is the strongest acid? A) )") )'#) )S'.%) )2' &) )('6 Answer: & Section: 1-1-() Which species act as bases in the following reaction?

A) 1 and 2 ") ( and . #) 2 and . %) 1 and ( &) 2 and ( Answer: # Section: 1-1-.) What is the conQugate acid of $)(? A) 6$)( ") -$) #) 6$). %) -$)2 &) 6$)2 Answer: # Section: 1-1-

1-

- ) What is the conQugate acid of #)($)2? A) #)($)(6 ") #)($)#) $).6 %) $)2Answer: A Section: 1-1--) What is the conQugate base of #)($)2? A) #)($)(6 ") #)($)#) $).6 %) $)2Answer: " Section: 1-1-3) Ri2e the conQugate acid and the conQugate base for )S'.-. Answer: conQugate acid: )2S'. conQugate base: S'.2Section: 1-1-/) Write a completed e=uation for the acid-base pair shown below. )#'2) 6 -$)2 S Answer: )#'2) 6 -$)2 S )#'2- 6 $)( Section: 1-1-8) What is the p) of a 9.1 T solution of )#l? +$ote: p5a for )#l is --.) A) ") -#) 1 %) -/ &) -1 Answer: # Section: 1-13 39) 7f )2' has a p5a 2alue of 1 .3 and )! has a p5a 2alue of (.24 which is a stronger base4 )'or !-? &1plain. Answer: )'- is a stronger base than !- because )! is a stronger acid than )2'4 and the stronger the acid the wea@er its conQugate base. Section: 1-13
13

31) Which of the following is the strongest acid? A) #)(') ") #)(')26 #) )2$%) #)($)2 &) #)($)(6 Answer: " Section: 1-21 32) 0he p5a of #)(#'') is ../ and the p5a of )#'') is (./. Ri2en this information4 one @nows that ________. A) #)(#'') completel* ioniAes in water ") )#'') is a wea@er acid than #)(#'') #) )#''- is a wea@er base than #)(#''%) #)(#'') reacts with )'- while )#'') does not &) )#'') reacts with )'- while #)(#'') does not Answer: # Section: 1-21 3() Which of the following is the strongest acid? A) )! ") )2' #) : $)( %) #). &) #)(') Answer: A Section: 1-21 3.) Which of the following is the strongest acid? A) #)(#)2') ") #)('#)( #) #)($)#)( %) #)(##) &) #)(#)#)2 Answer: A Section: 1-21

1/

3 ) #onsider the set of compounds4 $)(4 )!4 and )2'. Uan@ these compounds in order of increasing acidit* and discuss *our rationale. Answer: $)( N )2' N )! When determining relati2e acidit*4 it is often useful to loo@ at the relati2e basicit* of the conQugate bases. 0he stronger the acid4 the wea@er +more stable4 less reacti2e) the conQugate base. 7n this case4 one would loo@ at the relati2e basicit* of !-4 ')-4 and $)2-. 0he relati2e strengths of these species can be gauged based on the electronegati2it* of the charged atom in each base. Since fluorine is the most electronegati2e4 !- is the most stable4 least reacti2e base in the group. 0his means that its conQugate acid4 )!4 is the strongest. Section: 1-21 3-) Which of the following is the strongest acid?

A) 7 ") 77 #) 777 %) 7V &) V Answer: & Section: 1-22 33) &1plain wh* :$!( is a wea@er base than :$)(. Answer: !luorine has an electron withdrawing effect that reduces the a2ailabilit* of the pair of electrons on nitrogen. 0hus the basicit* of :$!( is less than that of :$)(. Section: 1-22

18

3/) Would *ou predict trifluoromethanesulfonic acid4 #!(S'()4 to be a stronger or wea@er acid than methanesulfonic acid4 #)(S'()? &1plain *our reasoning. Answer: 0rifluoromethanesulfonic acid is a stronger acid. #ompare the strengths of the conQugate bases and remember that the wea@er the base4 the stronger the conQugate acid. 7n the case of the trifluoro deri2ati2e4 the presence of the highl* electronegati2e fluorine atoms ser2es to delocaliAe the negati2e charge to a greater e1tent. 0his additional delocaliAation ma@es trifluoromethanesulfonate a wea@er base. Section: 1-22 38) Which of the following anions4 #)(#)"r#'2- or #)(#)!#'2- is the stronger base? &1plain *our choice. Answer: #)(#)"r#'2- is the stronger base. 0he more electronegati2e ! atom can more effecti2el* delocaliAe the negati2e charge 2ia induction. 0his greater delocaliAation stabiliAes #)(#)!#'2- relati2e to #)(#)"r#'2- and ma@es it a wea@er base. Section: 1-22 /9) 0he p5a of #)(#'') is ../. 7f the p) of an a=ueous solution of #)(#'') and #)(#''- is ../4 then one @nows ________. A) #)(#'') is completel* ioniAed ") K#)(#'')L M K#)(#''-L #) K#)(#'')L , K#)(#''-L %) K#)(#'')L N K#)(#''-L &) #)(#'') is completel* unioniAed Answer: # Section: 1-2 /1) When a small amount of he1anoic acid K#)(+#)2).#'2)4 p5aO../L4 is added to a separator* funnel which contains the organic sol2ent dieth*l ether and water with a p) of 2.94 it is found mainl* in the ________ phase as ________. A) etherJ #)(+#)2).#'2") waterJ #)(+#)2).#'2#) etherJ #)(+#)2).#'2) %) waterJ #)(+#)2).#'2) &) none of the abo2e Answer: # Section: 1-2

29

/2) When a small amount of he1anoic acid K#)(+#)2).#'2)4 p5aO../L4 is added to a separator* funnel which contains the organic sol2ent dieth*l ether and water with a p) of 12.94 it is found mainl* in the ________ phase as ________. A) etherJ #)(+#)2).#'2") waterJ #)(+#)2).#'2#) etherJ #)(+#)2).#'2) %) waterJ #)(+#)2).#'2) &) none of the abo2e Answer: " Section: 1-2 /() At what p) will 2 W of a compound with a p5a of .( be in its basic form? Answer: ../ Section: 1-2 /.) 0he amino acid gl*cine +)($6#)2#'2)) has two acidic )s4 one with p5a , 2.(. and the other with p5a,8.-9. %raw the structure of the form of gl*cine that predominates at a p) of 12. Answer:

Section: 1-2 / ) "uffering is used to maintain the p) of human blood in the relati2el* narrow 3.( - 3.. range. What acidPbase pair ser2es to buffer the blood? A) )2' P )'") )('6 P )2' #) )2#'( P )#'(%) $).6 P $)( &) )#l P #lAnswer: # Section: 1-2/-) &1plain wh* Al#l( is a Cewis acid. Answer: A Cewis acid is an electron pair acceptor. Aluminum in Al#l( has an empt* p orbital that can accommodate the pair of electrons pro2ided b* a Cewis base. Section: 1-23

21

/3) Ri2e the electronic configuration for $-(. A) 1s22s2 ") 1s22s22p( #) 1s22s22p. %) 1s22s22p&) 1s22s22p-(s1 Answer: % Section: 1-2 //) Ri2e the electronic configuration for #a62. Answer: 1s22s22p-(s2(pSection: 1-2 /8) 7dentif* the least electronegati2e atom. A) < ") $a #) 7 %) " &) ' Answer: " Section: 1-( 89) Ri2e the number of nonbonding pairs of electrons in )2$'). A) 9 ") 1 #) 2 %) ( &) . Answer: % Section: 1-( 81) Ri2e the formal charge on nitrogen in $).. A) -2 ") -1 #) 9 %) 61 &) 62 Answer: % Section: 1-.

22

82) %etermine the number of pi bonds in #)(#$. A) 9 ") 1 #) 2 %) ( &) . Answer: # Section: 1-8 8() Ri2e the numbering of nonbonding electron pairs4 bonding electron pairs4 pi bonds4 and sigma bonds in #'2. Answer: . nonbonding electron pairs4 . bonding electrons pairs 4 2 pi bonds4 2 sigma bonds Section: 1-1. 8.) Ri2e the shape of the meth*l radical. A) trigonal p*ramidal ") tetrahedral #) bent %) linear &) trigonal planar Answer: & Section: 1-19 8 ) 7dentif* the h*bridiAation of carbon in )2#'. A) sp ") sp2 #) sp( %) sp. &) s(p Answer: " Section: 1-1. 8-) Ri2e the appro1imate bond angle around the carbon in )2#'. A) -9 ") 89 #) 198. %) 129 &) 1/9 Answer: % Section: 1-1.

2(

83) 7dentif* the h*bridiAation of the o1*gen in #)('#)(. A) sp ") sp2 #) sp( %) sp. &) sp Answer: # Section: 1-1. 8/) Ri2e the h*bridiAations of the carbons4 from left to right4 in #)(#),#)#l. Answer: sp(4 sp24 sp2 Section: 1-1. 88) Ri2e the h*bridiAation4 shape4 and bond angle for the carbon in #'2. Answer: sp4 linear4 1/9 Section: 1-1. 199) Ri2e the h*bridiAation4 shape4 and bond angle for each carbon in #)(#$. Answer: #)( - sp(4 tetrahedral4 198. J # - sp4 linear4 1/9 Section: 1-1. 191) 7dentif* the compound with the wea@est bond. A) )2 ") )! #) )#l %) )"r &) )7 Answer: & Section: 1-1. 192) 7dentif* the compound+s) that ha2e a dipole moment. A) #)($)2 ") #'2 #) #)('#)( %) +#)()2#,#+#)()2 &) "#l( Answer: A4 # Section: 1-1

2.

19() 7dentif* the compound with the highest p5a. A) #)($)2 ") #)(') #) #)(#'') %) )2' &) #)($)(6 Answer: A Section: 1-21 19.) 7dentif* the compound with the highest p5a. A) #)(#)( ") )##) #) #)2#)2 %) #)(') &) #)($)2 Answer: A Section: 1-21 19 ) 7dentif* the most acidic carbo1*lic acid. A) 7#)2#'') ") "r#)2#'') #) #)(#'') %) !#)2#'') &) #l#)2#'') Answer: % Section: 1-22 19-) %raw a resonance contributor and the resonance h*brid for )'#'2-. Answer: resonance contributor: resonance h*brid:

Section: 1-2(

193) )ow man* carbon-carbon s bonds are in the molecule shown?

A) 1 ") 2 #) ( %) . Answer: " Section: 1-3 19/) 0he h*drogenXhalogen bond becomes ________ and ________ as the siAe +atomic weight) of the halogen increases. A) longer4 wea@er ") longer4 stronger #) shorter4 wea@er %) shorter4 stronger Answer: A Section: 1-1(

2-