Study Guide and

Student Solutions Manual

for John McMurry's

Organic Chemistry
Sixth Edition

Susan McMurry
Cornell University

THOMSON
-aROOKYCOLE 1

Ausnlir. ~ Merico
~ Singapare.
a Spain. Urjrd Kingdom U n i d Sute
 \, Contents
COPYRIGHT O 2 W Broo!dalc. a divirian of BrooWCole-Thomron Loarning
10Davir Drirc Chapier I Strucere and Bonding I
Thomon Lcaming, Inc. Thomronhming" ir a
Belmont. CA 940U2.3098 Chapicr 2 Polar Covalent Bonds; Acids and Bases 17
irademsk "red hercin under liccnse.
USA Revisiu Urrir 1 36
Chaprcr 3 Organic Campounds: Alkanes and Cycloalkanes
ALL RIGHTS RESERVED. No p u l of rhis work Chaprer 4 Stereochemisiry of Alkaner and Cyclpalkaner
coveredby ihe copyighi herean may bereprduccd Asia
Thomron Loaming Chapier 5 An Ovewiew o f Organic Reaclioos 85
orured in any fom o;by any meanr-graphic. Review Uitir 2 102
elecironic. or mechanical. including bu1 no1limitcd lo 5 Shenian Wav Rol-Ol
Chapter 6 Alkenes: Stmciure and Reaciiviiy 106
pholocapying. recarding. iaping, Wcb disinbuiion. UICBuilding
Chapier 7 Alkcnes: Reaciions andSynrhcsis 128
infamatian nciwrks. or informalionrioragc and Singapare 068808 Chaprer 8 Alkynes: An Introduciionto Organic Synthesis
revicval rysiem-wihour ihe wiiicn prmirsion of Review Unii 3 175
Uic publirher. Aurlraliah'ev úaland Chapier 9 Stercochemisiry 178
Thomron kaming Chapier 10 Alkyl Halides 206
Printed in he UniiedSiater of America 102 Ddds SVeet Chapier II Reaciions of Alkyl Halides: Nucleophilic Subsiitutions and Eliminaiions 225
4 5 6 7 070605 Sauihbank. Victoria 3W6 Rtuieiu Unii 4 255
AusValia Chapier 12 Srmcture Determination: Mas8 Spectrometry and lnfrared Specuoscopy 259
Prinier: Globur Prinüng Chapier 13 Stmciure Deierminaiion: Nuclear Magnetic Resonance Spectroscopy 282
Corcr image: Rajndropr an Roch wiih Mapls Leaf by Csnsda Rovieiu Unir 5 308
Gran1V. FainilOcny Imagcs Nelron Chaprer 14 Conjugaird Dienes and Ullraviold S p e c t r ~ c o p ~ 31 1
1120 Birchmount Road Chapier 15 Benzene and Aromaiicity 334
Torania. Ontario MLK5G4 Chaprer 16 Chemisiry o f Benzene: Electrophilic Aromaiic Substiiution 352
Canada Rtvbiv Unir 6 390
Chapter 17 Alcohols aod Phenois 394
EuropeIMiddle 5 U S o u l h Africa Chapier 18 Erhers and Epoxides: Thiols and Sulfides 426
Thamson b m i n g Revieuz Unii 7 451
High Holbom Hourc Chapter 19 Aldehydes and Ketones: Nucleophilic Addition Reactions 456
Chapter 20 Carboxylic Acids and Nitñles 497
50151 BedfardRow Chapier 21 Carboxylic Acid Derivatives and Nucleophilic Acyl Substilurion Reactions 521
London WClR 4LR 8 553
k v i e i u U~tir
U n i d Kingdom Chapter 22 Carbonyl Alpha-Subsiiiuiion Reactions 557
Far permiiion la use material fromlhii fe$
contaet ur by: Chapier 23 Carbonyl Condensarion Reaciions 582
Phone: 1-800730-2214 htin America Chapter 24 Amines 616
Thamuin h m i n g Rev,'ew Unii 9 650
Fsr: 1-80073&2215
Scneca. 53 Chaprer 25 Biomolecules: Carbohydraies 653
Colonia Palanca Chapier 26 Biomolecules: Amino Acids. Pepiides. and Pmteins
l l 5 W Mexico D.F. Revieiu Usii 10 711
Merico Chapier 27 Biomolecules: Lipida 714
Chapter 28 Biomolecules: Heterocycles and Nucleic Acids 737
Spaiflortugal Chapler 29 The Organic Chemislry o f Meiahlic Pathways 760
Paraninfo Revhw Unir 11 783
CallclMagallanm. 25 Chapler 30 Orbitals and Organic Chemisiry: Pericyclic Reactions
28015 Madrid. Spain Chaoter 31 Svntheiic Polvmen 808
Ravfew Unir 1 2 . 824 '

Appendices

Funclional-Group Synthesis 827

Funciional-Grwp Reacrions 832
Reagenc; in Organic Chemis~ry 8 6 1
Name'Reactions i n Organic Chemirmy 843
Abbreviatians 851
lnfrared Absorpiion Freqilencies 854
Proton NMR Chemical Shiffr 857
-
Orgaoic Chcmical ~rodu:iioi i ó 0 1 858
Nobel Pnzr Winnen i n Chcminmy 860
Ansuen !o Revieu-Unit Q~esuons 869
Preface
Whal enlen your mind when you hear the wods "organic cheniisuy? Some of you may ihink,
"thc chemistrv of life." or "the chemistw of carbon." Ohcr resoonses mieht include "ore-med.
precqure. "~ifficult.' or mcnuiiuri& Al.nough formal y '[he study'Óf the comp'ounds of
cirbon. ihe cisc:pline )f organic chenisiry cncompsscc many sk:lls ihai are common !o otlicr
aru, uf ,i~dy Ornanic chem.str, ir a' m a h a Iibenl an as a scicnce. and ma!tery i f [he conrepis
and techniques of órganic ckmifiry can lead io impmved compctence in oiher fieids.
As you work on the problems that accompany the text. you will bring to [he iask many
problem-solvingtechniques. For example. planning an organic synthesis requires the skills of a
chess player: you musl plan your moves while looking several steps ahead, and you must kcep
vour plan flexible. StmcNrc-deteminationpmblems are tike detective oroblem. in which manv
clues'm~siocasscmbled to )ield he m c i likply ~ o l uon i Nrnung orpnic coiiipu~iidsis sim.lir b
rnc systrmaii: naming of oi,logical rpecimcns. in both caser, 3 rei o l rulcs nusi oe leirneo 2nd
ihen applied lo the specimenor compound uiider study.
The ixoblems in the Icxt fall into two cateaories: drill and comolex. Dnll omblems. which
appcar tiru;gliuui ihe iexi and rt ihc end of crCh chapier. tcsi yo^; knowlídk o f onc fa:[ or
iccnniqu- at a !.me You may need lo rely nn rr?morixari>nlo solvc ihcic pi~blcms.uh.ch )o1
shoild aork on fint. Morc mmpl:caied prcblerrs req~ireyou 1, recall fi:is fmm severa. pans of
[he text and then use one or more of cheprobleni-soivin~techniauesmentioned above AS each
majx type of pmblem-synhesis. nomcncl~iurcor s . m c ~ u r e d e r ~ i n a i i ~ nS -.nirod~cedn ihe
ieht. iSO UILO IS ciicilriely worked oit in 'his Soluridnr htnnudl

Here are several suggestions that may help you wiih problem solving:
l.The iexi i s organized inlo chapten that describe individual functional groups. As you
siudv each hnctional "eroun.
.. vtake sure rhar rord iundersraildrhe srrucrure and reacrivirv of
~hargrnu~. I n case your mernory of a s p e i f ~reaction fails you. yo" can rely on i o i r
general knowledge of functioiial groups for help.
2. Usr moleculor nlodels. I t isdifficult Lo visualk the three-dimensional strkture of an
ornanic molecule when lookina al a two-dimensional drawing. Models will help you lo
appreciate ihe stmctural aspecis of organic chemistry and are indispensable iools for
undentanding stcreochemislry
3. Every effort has been madc to make this SolutionsManual as clear. attractivc. and
error-frez as possible. Ncvenhelcss, you should use rlie SolurioruManual in moderarion.
TICprincipal use of ihis book should bc io check answers lo problems you have already
worked out. Thc Solulions Manual should not be used as a substitute for effort: at times.
shuggling with apmblcm ir [he only way to teach yourselt
4. Look Ihrosgh ihe nppendices ni ihe end of ihe Sofuiions Manual. Some of these
appcndices contain tables that may hclp you i n working problems; others present
infomation related to h e history of organic chemisiry.

r\lihough the Solurror~M ~ n u oirl wr.ticn lo iicompin) Orpunrc Chemisiry. ii conta'nc

sevcnl unique IP~?IIIP~~. Eicn cnrpicr of inc Solur~ouMdniu. kgins w.ih ar outl.ne o i h e !e\[ iiai
can be usedfor a concisc review o f the teac material and can alsi scne as a reference. After evew
few chlpicrs 3 Reiicw U i i l h u been insenea. In mosicases.ihecha~terrcovered i r ihe ~ c v i e i
Units arc rela& to each oihcr. 2nd [he uriU aic plained w appear~rap?rorimstel) dir place in !he
tcntbook wherc 3 fcsi mitht be aivcn. Each ~ n iI.SU t th: vocabularv for ihe chaplers cove:cd. [he
skills needed lo solve p r ~ b l e m ~ a scvcral
nd imponanl poinis that Ínight need ;inforcing or that
restate material in l h e tea: from a slightly different point of view. Finally. the small self-test that hxs
been includcd allows you to test yourse¡f on lhe material from more han onechapter
1 have tned 6 include many types of study aids in his Soluiions Mari&l. Nevenheless,
lhis book can only sewe as an adjunct lo the larger and more complete textbook. I f Organic
Chenlis,ry is the guidebaok to your study of organic chemisiry. ihen [he Solutions Ma~iualis [he
madmap thai shows you hoW to find what YOU need. Chapter 1 - Structure and Bonding
Ackoowledgmeots 1 would like io thank my husband, John McMurry. for offering me the
opponunity to wnte this book many years ago and for suppoiiingmy efforts while ihis edilion was
being prepared. Although many pwple at BrookslCole Publishing company have given me
encouragemeni dunng ihis project. special rhanks are due lo Alyssa White. 1 also would like io
acluiowledge the conuibutions of Daniel Singleton.John Scheffer. John Hogg and Byron Benneii, Chapter Oulline
whose comments, suggesiions and accuracy checks were indispensable.
l. Aiomic Structure (Sections 1.1 - 1.3).
A. lnlmduction to atomic stniciure [Section I .O.
1. Aioms consisl of a dense, positively chaiged nucleus surrounded by negarively
charged electrons.
a. The nucleus is made up of positively charged protons and uncharged neuirons.
b. The nucleus contains most of the mass of [he aiom.
c. Electrons move aboui the nucleus at a distance of aboui 10.'' m.
2 . The atomic number (Z) gives the number of protons in ihe nucleus~
3. The m a s number (A) gives the total number of protons and neuirons.
4 . Al1 atoms of a given element have the same valueof Z.
a. Atoms of a given elemeni can have different values of A.
b. Atoms of the same element wiih differeñivalues of A are called isotopes.
. ~.1.21.
B. Orbilals fSection
1. The distnbuiion of elecirons in an atom can be descnbed by a wave equation.
a. í h e solulion lo a wave equation is an orbital. represented by Y.
b. r2predicts h e volume of space jn which an electron is likely io be found
2. There are four different kinds of orbiials (s. p. d.J.
a. The s otbitals are soherical.
b. TheporbiWls uedumbbell-ihqed
¿ F o ~ ofthe
r fi\e dorbibls u e cio\er!erf.shloc~
3. An atom's electrons are oreanized into sliells.
.
3 Ihc shclls diffcrinth<numbcrs and kinds o! orbiwls ihcy have
-
b Elec-lons in diffcríni orbiwls hrrc differeni enciaies
c. Each orbiial can hold iwo electrons.
4 . n i e iwo lowest-energy electrons are in Ihe Isorbital.
a. The 2r orbital is the next in energy.
Eachp orbital has a region of zero densiiy. called a node.
b. The nexi rhree otbiwls are 2p,. 2py and Zp,. which have the same energy
l C. Eleclmn Configurarion (Section 1.3).
l . The ground-state elecuon configuration of an atom is a lisiing of the orbitals
l
occupied by the eleclmns of the atom.
!I 2. Rules for predicting the ground-state eleclmnconfiguraiion of an atom:
a. Otbitals with the lowest energy levels are filled first
The order of filling is 1s. 2s. 2p. 3s, 3p. 4s, 3d.
1
b. Only iwoelecirons can occupy each orbital. and they must be of oppositespin
c. If iwo or more orbitals have the same energy, one eleclmn occupies each until
al1 are half-full (Hund's rule). Only lhen does asecond electron ~ u p oney of
the orbibls.
All of h e electrons in a half-filled dhell have ihe same spin.
11. Chemlcal Bonding Theory (Sections 1.4 - 1.6).
A. Developmeni of chemical binding thwry (Section 1.4).
I. Kekulé and Couper pmposed that carbon has four "affinity units" - carbn is
lehavalent.
2. Oiher scientisls suggested ihat carbn can fonndouble bonds, uiple bonds and
1
I rings.
 Structure and Bonding 3

3 . Van', Hoff and Le Bel proposed thai the4 atoms [o which carbon foms bonds sil
ai the comen of a regular tetrahedmn.
4 . In a drawing of a icinhedrdl carbon, a wedged line represens 3 bond piniing
toward the i:ewer. and a dvhed Iine poinis behind ihe plane of ihe page.
B. Covalent bonds(Section 1.5).
l.Atoms bond together because Ihe resulting compound is more stable than the
indiridull aioms
a. Aioms icnd [o achiere hc elccbon confí:uraiion of the n m s t noble gas.
b Atoms in gmJps IA. 2A and 7A eiiher lose electrons or g ~ i nelecoons lo fom
ionic compounds.
c. Atoms in the middle of Ihe pericdic table $are eleckons by foming covalent
bonds.
: Thc number of covalent bonds fomed by an atom depends on the numkr of
elccrrons iiha 2nd on [he number 11needs io achieve an octel.
1 . Cobaleni bonds can be repmented two ways
a In Lewis siructJres. bonds are rcpresenled as pairs of dois
b. In line-bondsuuciures. bonds are rcprescnied as Iines dnwn beiwren tufo
aioms
4 Valence elccrrons not sed for bonding are called lone-p%rclectrons
Lone-oxirelccuon; are rcpresendeda dois
C. ~alenceTondtheory(Section1.6).
l. Covalentbonds are fotmed by the overlap of iwo atomic orbitals. each of which
contains oneelecoon. The two elecüons have opposite spins.
7-. -"Friih nf the hnnded atoms retains its atomic orbids, but the electron pair of the
overlapping orbitals i s shared by both atoms.
3. The greater the ohital overlap, the sbonger [he bond.
4. Ehylene iscomposed of a carbon-carbondouble bond and four o bonds fomed
between Ihe remaining foursp2 orbitals of carbon and the Is orbitals of hydrogen.
The double bond of ethylene is both shorter and shonger than Ihe C Z bond of
ethane.
.~ ~~-~~~
C. so Orbilals (Section 1.10)~
1'. Ifone carbon Zsorbikl combines wiIh one carbon 2p orbilal. two hybridsporbitlls
are formed, and twop orbitals are unchanged.
2. The hxosp orbirals are 180' apart. and the hvo p orbitals are perpendicularlo ihem
and to each other.
3. Two different types of bonds fom.
a. A o bond foms fmm the overlap of two sp orbiials.
b. Two n bonds form by sideways ovedap of four p orbitals.
c. This combination is hnown a a carbon-carhon triple bond.
4. Acetylene i s compsed of a carbon-carbon tiple bond and two obonds fomed
between the remainingtwo sp orbitals ofcarbon and the 1s orbitals of hydrogen.
The triple bond of acetylene is the smngest carbon-carbon bond.
D. Hybridization of nitrogen and oxygen [Section 1.11).
l . Covalent bonds between oher elements can be described by using hybrid orbitals.
2 . Both the nitrogen atom in ammonia and L e oxygen atom in waterfomsp3 hybrid
orbi1als.
Tne lone-pair eiectrons in Ihesecompundsoccupy spl orbifals.
3. Tne bond angles behxeen hydmgen and the cenuai atom is oflen less than 1 W
becausc he lone-pair elecuons take up more rmm than the o bond.
IV. Molecular orbilal Iheory (Section 1.12).
A. Molecular orbifais arise fmm a mathematical combination of alomic orbirals and belong
io Ihe enim molecule.~~

A,. - -..-.fnmed
Rnnds .......bv the head-on overlao of two atomic orbitals are cylindrically 1. Two 1s orbitals can combine in two different ways.
symmetrical aniare calledobonds. ' a. m e additive combination is a bonding M 0 and is lower inenergy than the two
5 . Bond süeneth i s the measure of the dount of energy needed lo break a bond. hydrogen 1s atomic orbitals.
6 Bond lcngti ir the optimum dismce bei~eennuclei. b. The subtractive combination is an antibonding M0 and i s higher inenergy han
7. Evew bond has x characteristic bond length and bond strength. the two hydmeen 1s atomic orbitals
2. A node is a kgioibetween nuclei whereelectrons aren't found.
111. Hybridization i~ections1.7 - 1.11).
A. spl Orbitals (Sections 1.7. 1.8). If a node occun beiween twonuclei. Ihe nuclei repel each other.
l. SmcNre of mcthane (Section 1.7). 3. The number of MOs in a molecule i s h e same as the number of atomic orbirals
a. When carbon f o m 4 bonds with hydrogen, one 2sprbital and three 2p orbiials combined.
combine to fom four equivalent atomic orbitals (sp hybrid orbiiais).
b. These orbilals are teaahedrally oriented.
c.. Recause these orbilals are unsymmetrical, they can f o m slronger bonds than
unhybridized orbitlls can.
d. These bonds have a specific geomehy and a bond angle of 109.5'.
7 rnirturp. nf ethane
-. ~ ~~. (Section 1.8).
a. Ethane has h e sime type of hybrid;wtion as occurs in methane
b. The C X bond i s formed by ovcrlap of t ~ sp'o orbiials.
cl Bond IengIhs. shengths and anglesaIe veryilose to hose of methane.
B. sp2 Orbitals (Section 1.9).
.. lf
l. ~.ane carbon 2F orbitll combines with twocarbon 2p orbifals. three hybrid sp2
~

orbitals m fomed, and one p orbital n m n s unchxnged.

rg
2. Tk three orbitals tic in a plme atangles of 120'. and [he p orbiral i s
wmendicdas
r - - r ~-~
to them.
3. Two different types of bond f o n krween two carbons.
a. A obond forms hom the overlap of iwo sp2 orbitals.
b. A n bond f o m by sideways oGrlap of two p orbitals.
c. This combination is known as a carbon-carbondouble bond
4 Chaplir 1
Siruclure and Bonding 5
Solutions to Prohlems
íc) Oxygen (atomc number 8) (d) Chlorine (aromic number 17)

1.1 (a) To find Ihe ground-state electronanfiguraiion o f an element, first locate its atomic 2p-K4-4- ' p - K - K t
number. For boron, the atomic number is 5 ; boron thus has 5 protons and 5 electrons.
Nexc assign the clcckons to Ihe proper energy levcls. slarting with [he lowest level. Fill
each level completely before assigning electmns lo a higher energy level.
25 % 3s 4-t
lS 6 * p + t + t + t
2 p + - -
2s St
Boron 2s # St
Ix St 1sZ2sZ2~'
[He] 2s2 2p4
1 2 6
1s 2s 2p 3s 3p
2 5

[Ne] 3s' 3pr

Remembet that anly IWO elenrons can occupy the same orbital. and lhat they must be of
1.2 Strdfegy: The elements of the periodie table are organized into groups thai are based on
opposite spin.
the numbcr of outcr-shell electrons each element has-For example. an element in group IA
has one outer-shell electron, and an element in p u p SA has five outer-shell electrons. To
A diffcreni way io reprcasiit ihe ground.siaie electrnn conhgiiration i c to simp.y write
find lhe number ofouter-shell Clectron~for a given element. use the penodic iable to locate
doun ihe ixcupied orbifals i n d to indic~tethe number olelecirons in each orbifal. For
irS group.
ejample. ihe elcctron conftguraiion 101boron is l r 2 2d 2p.
Solution:
Often. we are iderested only i n lhe elecrrons i n the outennost shell. We can rhen
(a) Polassium (group I A ) has one elecimn in its outcnnosc shell.
represent al1 filled levels by h e symbol for ihe noble gas having the same levels Iilled. In
(b) Aluminum (group 3A) has t h e outer-shell elecirons.
[he case of boron, the filled 1s energy levcl is ~ p r a e n t e dby [He], and the valence shell
(e) Kqpton is a noble gas and has eight electrons i n iis outenost shell
configuration is symbolized by [He] 2 s ' ~ ~ ' .
.
(b) Let's consideran element wifh many elecuons. Pliosphoms, wiih an atomic number of 1.3 Slralegy: A solid line reprr,eniq a h n d lyine in {he ~ h n ofine
e pxge,x~cdgcdbond
reprwentsa bond pinttng cui of Ihe plane ofihe prge t o u u d ine viewrr, rnd 3 Jashcd
15. has I S electmns. Assigning these toenergy levels:
b ~ n rcpresrnts
d J rond poirung oehind ihe pllne of the pige

Solution
3 p t t t
u
3s +t I
Chlorofon
Phosphoms 2p # # ft M

2sSt
IsSt

Notice rhat the 3pelectrons are al1 in different orbitals According to Hund's rule, we must
place onc e k k o n into each orbifal oí Ihe same energy level until al1 orbitals are Uf.filled,
The more conitse way b refresent ground-state elecbn configuration ior phosphoms:
1s' 2r2 zp6 3s' 3p3 or [Nel3s 3p3
Chapier L

Strategy: ldentify the group of ihe central element lo predici the number of covaleni bonds (d) NaH ~ a H:
the element can fom.
2 valence elecmns
Solution: (a) Gennanium (Group 4A) has four electrons in its valence shelland forms H
four bonds to achieve h e noble-gas conriguration of neon. A likely formula ts GeCl4, .H. 1
(e) CH3Li ..
H:C:Li
1
H-C-Li
Eleaeiil Grorrp Likely Formulo 8 valence elechons H H
(b) Al 3A AIH3 1.7 Fach of !he iwo carnons has 4 \alence elecirons. T U Oelecuons are used lo form ihe
(c) C 4A CH2CI2 carnon.cahon bond. 2nd h e 6elecirons mal reman can fonn oonds with a muimurn o f 6
(d) Si 4A SiF4 njdrogens. Tnus. thc fonnub C2H7is not possible.
(e) N 5A CHiNH2
l .8 Strategy: Connect the carbons and add hydrogens so lhat al1 carbons are bonded lo four
Strateev:
----~ Follow
~these
- , three steps for drawing [he Lewis stmcture of a molecule. different atoms.
(1) Delemine the number of valence, or outer-shell electrons for each atom in the H H H H H
I I I \ spl;,H
molecule. For chlorofonn. we know that carbon has four valence electrons. hydrogen H-C-C-C-H H..C-C Pmpane
has one valence elechon, and each chlorine ha. seven valence eleclnifls. 1 I I 'sp3 \
H H H .C-H
H' lZp3
H
The geometry amund al1 carbon atoms is tetrahedral. and al1 bond angla are appmximately
.. 109".
..
:ci. 7x3=&
1.9
26 total valence elechons
HH H H HH

.H.
-
(2) Next. use two electrons for each single bond.
H,
1,
/C,
1,'
/C, C,
1; H H H H H H
I I I I 1 I
H-C-C-C-C-C-C-H
I I I I 1 I
Hexane
CI:c:c1 1: 1: 1:
.. H H H H H H
~ ~

HH HH HH
CI
(3) Finally, use the remainingeleclnins to achieve an noble gas configurationfor al1 atoms.
Solution: H H
I I
Molecrrle Lewisslnrcture Line-bondslrucfirre H-C-C Propene
1 \\
H H H /C-H H tC-H
(a) CHCI3 H JpZ

The C3-H bonds are o bonds fonned by overlap of an spl orbital of carbon 3 with an s
.. orbital of hvdroeen.
(b) HS
I .H.
H:S:
H-S
I The CZ:H&~ CI-H bonds are o bonds formed by overlap of an sp2 orbital of carbon
with an s orbital of hvdroaen.
8 valence elecmns H
The C2-C3 bondis a; bond fonned by oveda of an sp3orbital of carcon 3 with an
H H
I I
sri2orbital of cahon 2. ?
There are two CI-C?. bonds. One is a o bond fonned by overlap of an sp2 orbiial of
(e) CH3NH2 H-C-N-H
I carbon 1 with an sp2orbital of carbon 2. Theother is a n bond formed by overlap of a p
H orbihl of carbon 1 with a p orbihl of carbon 2. All four atoms connected to the carbon-
14 valenceelechons d o n double bond lie in the same plane, and al1 bond angla between thae atoms are
120". The bond angle behueen hydmgen and thesp3-hybridized carbon is 109"
 3
a
E,"
3.
Y0s
m a
S-
2zr 5.
O
zg
z2
0 0
5%.
t4 %
10 Chapter 1 Strucluro and Bonding 11

Addilional Problems

1.21 Arofnic Nuniber of

Elemenl Nio~rber valence elearonr

(a) Calcium 20 2
(b) Chlorine 17 7
(c) Gemanium 32 4
(d) Swntium 38 2

1.22 Alornic Gro~rnd-siare

EIelnenr Nuniber Eleclron conjgurarion
l. 18 Cimc acid (C6Ha07) coniains seven oxygen atoms. each of which has hvo electron lone
pairs. Three of the oxygens f o m double bonds wilh carbon. (a) Pomsium 19 ls2 2s2 2p6 3s2 3p6 4s1
n (b) Sulfur
(c) Aluminum
(d) Bromine
16
13
35 '
~~a
ls2 2s22p6 3s2 3p4
is:2 ~ : 3 ~ 3pi ;
1s 2s 2p 3s 3p 4s 3dI04p5

1.23 (a) CHIOH (b) AICI] (c) CF2C12 (d) NIl

Ciüic acid

In hecompound acetonitnle, nitrogen has eighielectrons in its outer electron shell. Six are
+ used in the carbon-nitrogen tnple bond. and two are a nonbonding electron pair.
H\ r All carbons are sp2 hybridized. except for the carbon 1.25 The HJC-carbon is sp3 hybridized. and [he -CN carbon is sp hybridized
..
:o-C
1
C=C
\
-N:
H
1 indicated as sp3. The W o oxygen atoms and lhe n i w 1.26
1 \\ 11 \ J/ gen atom have lone pairelecmns, as shown.
c-c c-csd
H \ I I \
H H :o: H
Acetaminophen

Vinyl chloride has 18 valence elechons. Eight electrons are used for 4 single bonds. 4
electrons are used in the carbon-carbon double bond. and 6 elecbons are in lhe 3 lone vairs
that surround chlorine.
12 Chapler I

1.28 In molecular formulas of organic molecules. carbon is listed firsi, followed by hydmgen.
All oüier elemenk are listed in alphabetical order. H H
\ 1
Compound Molecrrlar Fomrrla C=C
1 \
(a) Aspinn C9H~04 H-C C-H Benzene
\\ 11
(b) Vitamin C CsHsO6 C-C,
(c) Nimune CIOHI~N~
(d) Glucose CaHiz06
1.29 T~ work a problem ofthis sort. you must examine al1 possiblest~cluresconsisten1 w t h All carbon atoms of benzene are sp2 hybridized. and al1 bond angles of benzene are I2O0,
he niles ofvalence. y o u must systematically consider al1 possible altachmenk, including Benzene is a planar molecule.
üiose that have branches. nngs and multiple bonds.
1.32 (a) The C - O C bond angle is approximately 109". and oxygen is spl-hybridized.
(b) TheC-N< bond angle is approximately 109". and nitrogen is sp3-hybndized.
(a) H H H (b) H H HI HI (c) The C-N-H bond angle is approximately l09", and nitrogen is sf3-hybndized.
I I I I I (d) R e O<-0 bond angle is approximately 120". and carbon is s p -hybndized.
H-C-C-C-H H-C-N-H H-C-C-O-H H-C-O-C-H
I l I I I I I I
H H H H H H H H 1.33 Examples
(a) CH3CH2CH=CHZ (b) H~C=CH-CH=CH~
- (c) H~C=CH-C=CH
(d) H H H H Br H
I l I I I I 1.34 (a) The4 valence electrons of carbon can fonn bonds with a maximum of 4 hydrogens.
H-C-C-C-Br H-C-C-C-H
I I I I I I Thus, it is not possible for the compound CH5 to exist.
H H H H H H (b) If you try to draw a molecule with ihe formula CzH6N. you will see that it is impossible
for both carbons and nitrogen lo have a complete octet of electrons. Therefore. CzH6N is
i unlikely lo exist.
H o (c) A com~oundwith the formula ClHsBrz doesn't have filled outer shells for al1 atoms
I H, 1 \ H,
H-C-C-H H-C=C-O-H ,c-c, 1.35
and is teus unlikely lo exist.
1 1 1 H H
H H H

H H H H H H H H
I I I I I I 1 I
H-C-C-C-H H-C-C-C-H H-C-C-N-C-H H-C-N-C-H
I l I I I I I I I I I I I
H H N H N H H H H H H C H
H' 'H H' H
' H'I'H
H

1 1.37
(a) (b)
H-O

(c)
H H H H H H H
H\ I l I 1'1 I I
C-CGN H-C-C-O-C-H H-C-C-C-C-H H, 1C-C \ H,
H-C
11 I I I I I I I
H H H H H H H HxC\ IC'H
\ c=c
H 1 \
 ,,
n r 1,
t-
"
* y o y*.
CY m
n
6- $-O"*.
+,
N
n 1
*. $l
 Chapter 2 -Polar Covalent Bonds; Acids and Bases
I
Chapter Outline
l. Polar covalent bonds (Sections 2.1 - 2.3).
Triplet methylene Singlet merliylene A. Electmnegativity (Section 2.1).
(plan4 1. Although some bonds are btally ionic and someare totally covaient, most chemicai
(linear) bonds are oolar covalent bonds.
ln mes¿ bonrir. electrons are aiinrcd to une atorn rnore ihan to the oiner r i ~ m
2 Bond polant) 1s d-e lo differences in elecnonegaii\ii) (EN)
A Look Ahead 3 E cmnis on ihe nnhi ride of the nenodic iable 3rc more e.ectroneeative lhan
elemenu on the leE side.
1.49 b. Carbon has a n of 2.5. ~ ~
7% c. Elernenrs with EN > 2.5 are more elecüonegative than carbon
d . Elements with EN < 2.5 are less eleclroneeative than carbon.
CH3CH2CH2CH3 CH3CHCH3
iwo compounds differ in ilie way that rhecarbon atoms are connected. bond.
a. If AEN < 0.4. a bond is nonpolar cavaleni.
-
3. ?he difference in EN between rwo elemenw can be used to predict the polarity of a

b. If &ENis between 0.4 and 2.0. a bond is polar covalent.

c . If aEN > 2.0, a bond is ionic.
d. The svmbols 6+ and 6 are used to indicate oartial charoes.
e. A crokred arrou ir used io indicaie bond pdanty.
Tne Uil of the a m a ir electron-por. snd the head of lhe m ~ iruelecimn-ncn
4. Elxuostatic mtenial mros m also uscd lo shou elecbon-nch (red) . . nnd electron.
poor (blue) kgions of m&ules.
One compou~dhas a double bond, and one has a ring 5. An indunive effect is an atom's ability [o polarize a bond.
B. Dipole moment (Section 2.2).
1.51 l . Dipole momeni is Ihe measure of a molecule's overall polarity.
CH3CH20H CH30CH3 2. Dipole moment (p) = Q x r, where Q = charge and r = distance between charges
Diple moment is rneasured in debyes (D).
The two compounds differ in the l0cati0n of the OXY,men atom. 3. Dipole moment can be used to measurecharge separation.
4 . Water and amrnonia have large values of D;methane and ethane have D = 0.
C. Formal charge (Seciion 2.3).
1. Formal charge (FC) indicates elecüon "ownership" in a molecule.
elecüons ] _ [# nonbonding]
H2c - - \i
2.
CH3CH2CH=CH2 CH3CH=CHCH3
] "
CH3
" , z r i #(FC) = [ - [ #of bonding
2 elecüons
The compounds differ in ihe way that the carbon aioms are connected and in the 3. Molecules that are neuiral overail bullhat have + and - charges on individual atoms
location of ihe double bond. are dipolar.
Ii. Resonance (Sections 2.4 - 2.6).
A. Chemical shuclures and resonante (Section 2.4).
l . Some molecules (CH3N@, for example) can be drawn as hvo (or rnore) different
Lewis
-~ shuclures.
~~

a Tnese shucnires are called resonance smictures.

b. l ñ e m e smicmre oflhe molecule is intemxdiaie berween !he smiciures
c. The hueshucture is called aresonance hybrid.
2. Resonance shuctures differ only in lhe placement of n and nonbonding elecirons.
All atoms occupy the same positions.
3. Resonante is an importan1concept in organic chemisuy.
 X-3'H > rI-3'~ '!J-3'~ > JBBW-~CH > HO-3'~
:LI?IO~ puoq Bu!seai~u!jo l a p o u! ' s n u .N- isaB~1a q seq puoq ielod isou aqL pne
s!mq e oi aseq s!mq e uioq suon3ala jo iuauanoui a q smoqs mom p N n 3 v 'E
.ñ!s 3!seq auo ueqi ajoui aneq saseq s!mq J!W%JOLuew .q
0'1 = N3V E'I =N- n s e q s ~ m aie
q spuncduio3 ~!ueLo%u!uyumuaBoq~pue -ua%Lxoi s o ~.e
.suoliJa[a %u!puoquoujo j ~ edmq amq s!mq v 'z
S'Z = N3 :uoqle3 Z'I = N3 :un!sauaefi .spunodwo~~eiaui-uog!suw
S'E = ka uaMxo S.Z = ~3 :uopre3 pue spunoduio3 E dnoif) 'sppe ua%oleq'suope3 Waui apnpu! salduexx 'q
.uaao~pLq
S'I = N3V L'I = N3V 5.1 = N3V o] puoq lelod e lo (q!qlo LBlaua-m01 lue3en e laqi!a aneq Xeu p!3e S l M q V 'E
.J-d uoq3ala m slda33e p!3e s!mq V ' I
S'Z = NB :uoP3 8'0 = ~g :un!sseiod 0.1 = ~3 :wnwq '(1 1.z uog3a~)saseq pue sppe s!mq '3
O'P = N3 : a u W H S'Z = N3 :uoqie3 S'Z = N3 :UOpTe3 .jied
:uo!tnloS riniilaiaauoi
~~, e mim uioie uaBoniu e S U I ~ U O Jaseq 31W8~040adQVui
. aill 'q
.dnoB 0=3 coi IXWu W ~ i q ioi bpuoq uaBaipAq aneq ieqi SP!~V .I!
'N3VBu!seai3~!10 JapJOU! SJaMSUE aqi >(Wpue .uaBAxo oi papuoq uaBolphq U ~ ~ I U Oieqi J Sp!3V '1
N- a i e l n ~ p 3'luauiala 4 x 9 40 sa!i!~!ie%auari3alaaqi pug oi rz a i n a ! ~asn :W~VJ]S : s i.$ ~iueBjoio sadb uieu omi are a i a u 'e
E.Z . u0!]3áS) Samq $ ~ E ~ J OPUE Sp!JE 3!~~%10 '9
~ ~ i m ai qm ~
ueq alqms aiou ale uo!l3eai aseq-ppe ue JO s13npojd a q 'spom iaqlo u] 'q
Dad
q~!qe q1!m p!3e ue JO aseq aie8n.03 aqi qi!m SVWJ - ~ m01 d eq ~ mp!3e ÜV .e
.(67 uo!i3a~)Oxd uioq suo!iseaj aseq-p!3e %u!~!pid .S
,aseq %uonse S! p!3e yeam e JO
amq aiean-03 a q pue 'aseq yeam e S! p!3e BUO~ISeJo aseq aieBnluos aqL '3
'Z'Z ajnB!d asn '1.z ualqold u! s y .Dxdaanl e seq p!3e yeam E pue ' E ~~d~ e u i s a s p!3e
e q %UOJIS V .q
C~ Bol- = %d .e
2.z .
,. P ~aqL
.q18uans p!Je ssaldxa oi pasn ~lleuuouEI'SIUBISUOJ d .P
Li!p!~e jalpus aneq sppe j a v m pue 'slumsuos L11pl3a%nlaneq SP!3e %uoJIS 'E
.iueisuo3 Q!p!3e aql Lq pie3!pu! S! lalem u! p!Je ue JO q2uaqs aqL 'z
. ( r z uog3a~)Jalem q!m Llaialduio3 isoui[e ri3eai p!3e Zuons V ' 1
.(01.z - 8.1 uo!iaaS) qiBuaiis aseq pue p ! ~ v. e
,ppe a q j o aseq aieBn(uo3 aq] S! $1raso1 p!3e ue uaqm EilnsaJ l e q 13npold
a q :avq aqi 10 p!" aieBnpo3 aqi s! +H su!eB aseq e uaqm silnsaj i e q i~npoida u 'Z
-iumala aqi an!ieSauaiiqa a l w a q .+Hn d a m aseq ,bmoJ.paisu@la e iuo! ue saieuop p!3e bmo~-palsu!WV '1
'laqwnu aqi laBlel a u 'siamsue 1noL >1~aq3
01Z.Za j d ! ~
3sn 'ualqold s!q~BU!A~OSJaUv .(L.z uo!13aS) uo!i!uyap b m g - w s u 0 J a -V
1.Z :
' ( 1 1 ' ~- ~ isuo!iJaS) saseq pue S P ! ~ V'111
.pa]eiaua%aq uea suuo] a3ueuosai <sa3a!duioie-aaq asaq %u!z!u%o3ajLB 'E
'uon3aia
~~~
~,
'spuoq moqs slapoui I>!is-pue-llea 'Z
'alnJalou e u!q!m Bu!pmol3 aqi moqs slapou Bu!llg-a~ed~- 1 lm!q~odBu!puoquou e o] iua3ecpe puoq aldglnui E q!m Bu!dnma m o l e - w i LUV . l
-1n.v
,,L--;,--o,.
iinn-igr) ~ u~ ~~ ~
u o a3ueuosai
--., i %UIMEJD ioi anb~uqmilnjasn v 3
'(EI'Zuo!13aS) slapou JelnJalow
. .u .uuoj a3ueuovaj lenp!n!pu! Lue ueq~a l w s ajoti S! puqiq axieuow a~ '5
.umoqs aje suioie iaqio .J
'umoqs Lllensn i,uaie u o q m oi papuoq suioie uaBojpLH .q .hualenjo salu [euuou Laqo pue sajni3ruis s!mq p!leflq isnu s u u o ~a3ueuosaa 'p
.rvilxuni
,-,--a ?nueuosaj
--- .. alams aJou aql Salquasai
umoqs Ilensn i,uam suole uoqle3 .e
'II!IS laldu!s are sarni3Riis ieiaian~ 7
alnJa(ou leni3e a q j o a r n ) n ~ aql
~ s ?ualen!nbauou are SuuOJ & ~ u o s a l J l
..u
. -"
.]ualen!nba aq o] aneq 1,uopaln3aloui e JO s u u o ~a3ueuosaj iuajag!a ' E
'Si!Un H 3 PUB 2 ~ " 3~ 3 -suiolelou 'SuonJalaJo luauianoui aq] ale3!pu!ol pasn S! M m paNn3 V
u m i a q SPuoq alli moilr 1 . ~ p0 e~s p o q H-3moqs i,uop saini3~1spxuapuo3 . I
'(z1.z uo!lJas) salni3niis Ie3niiaw Buirnon .W .suaqJa[a 2u!puoquou1o u l!aqIjo luauaJe[d a q u! Lluo~a#!p SuuoJ a3ueuoiaa 'Z
J
. I ~ IOU ',í~eu!Beu! aie suuoj a3ueuosai lenp!n!pul ' I
'(5.z uo!i2aS) s u u o ~a3ueuosaj JOJ salna -a
 Polar Covalenl Dondr; i\cidr ond Ilarei iI

In an elec6ostatic poteiitial map, h e color ~d indicates regions oi a molecu!e thal are Solution:
2.4
elecrron-"ch. The map shows thai oxygen is the most electronegative atom in methyl
akohol. and the direction of polarity of the C-O bond is:
~~~~l charge (FC) = [#;:g:~] [
- # ~f bonding electrons ] _ [# nonbonding]
2 electrons
.6. 6 -2 = t l
Forsulfur: FC = 6 - 7
HO:
1 Melhylalcohol ! Foroxygen: FC = 6 - - 2- 6 =-1
2

2.8
of valence] _ [ U of bonding elccirons ] -
j Formal ch% (FC) = [ Itelcclrons 2
nonbonding]
electrons

The diple moment of C02 is zero because tk bond polaities of h e Iwo carbon-oxygen
bonds cancel. For carbon: FC - 4- a
--
2
-0 = 0 -
2.6 Strategy: For each bond, idedify h e more elecironegative element, and draw an arrow
ihat poinu from h e less electronegative element lo h e more electronegariveelement. 2
-
For nitrogeii 1: FC = 5 - 8 - O = +L

Estimatehe sum of the individual diple momenb lo an'iveat the dipole moment for h e
entire molecule. For iiiiragen 2 : FC = 5 - 4- q = -1
2
Solution:
-~ ~

i
(a) (b) Remembcr: Valence eleclmns are the eleclrons charactenstic ofa spccific element. Boridr,ig
eleclrons are those electrons involved in bonding to oher atoms. Notibondiag elecrmis are
O diple : those eleclrans in lone pairs.
mment moment

I 8 -0 = 0
Forcarbon 1: FC = 4- -
2
8 -0
Forcarbonl: FC = 4 - - : O
2
2.7 Strategy: To find the formal chargeof an atom in a molecule, follow ihese two steps: For nitrogen : FC = 5 - a -0
- = tl
2
(1) ihaw a Lewis smcnire of h e molecule.

(2) Usehe formula in Section 2.3 to detennine formal charge for each atom. The periodic
tnble shows the number of valence eleclrons of h e elemed. and h e Lewis smcture shows
h e number of bonding and nonbonding electrms.
 Polar Covalrnl Bonds; Acids and Esser 23

(c)
H3C-NEC:
L.. "
. ::C:
= H:C:N: . 2

] - pnelectmns
2.9 2 . 1 1 Strategy: When an dcid lores a proion. the product i s inc con~ugaicbase of ine acid
[ h f ~ ~ l e n c -[#o'
e] bonding electrom onbodk] Wher. a basc gains 3 pmton. ihc protuct ir thc conjugate icid of ihe basc
Formal charge (FC) = elecirons 2
Solution:

Acid Base Conjugate Conjugate

base acid

Foroxygenl: FC = 6 -
2.12 Recall from Secrion 2 8 di1a snong acid nas a rmall pK, 2nd a ~ e a ac:d
k has a lage pK,
4 Accordiiigl). plcnc acid (pK, = O 38) 1s a suonger acid ihan formic acid (pK, = 3.75)
7 -4 =O
2.13 HO-H i s a stronger acid than HzN-H. Since HzN- is a stronger base than HO-. the
conjugate acid of HzN- (HlN-H) is a weaker acid than the conjugate acid of HO-
(HO-H).

2.14 Strategy: Use Table2.3 to fni d the sirength of each acid. A reaction takes place as written
i f the sironger acid is the reactant.
2
For oxygen 4: FC = 6 - -
2 - 6 = -1 Solution:
Oxygen atoms 3 and 4 each have a formal charge of -1 (a) 7
H-CN + CH3CW ~ a 'i + 4 + CH~COOH
~ a -U
2.10 Strategy: Look for thrwatom groupings that contain a multiple bond next to an atom pK, = 9.3 pK. = 4.7
with a p orbital. Exchangethe posiiions of thebond and the elecmns in h e p orbital to Weaker acid Sironger acid
draw the resonance form of each grouping.
Remember that the lower the pK,, the stronger the acid. 7hus CH,COOH, not HCN, is
Solution: the stmnger acid. and [he above reaction will no[ take place in the direction written.
(a) Nimate anion has 3 three-atomgroupings and thus has 3 resonance forms:

- - ..- .. -
/f:v )
.,N:.. ..,N;
ip: :si
+N.,
(b) CH3CH20-H + ~a~
7
CH3CH20- Na* + HCN

-:o 2:- -:o.. 2: :o 0:- pK, = 16 I pK, = 9.3

Weaker acid Stmnger acid
Using the same reasoning as in past (a). wecan seethat the above reaction will noioccur.
24 Chapler 2 Polar Covalent Bonds; Aeidr and Bares 15

(b) H
.. 8 - 0 = -1
--
-
H:C:H
.. .. ..H
CI Aluminum: FC = 3
2
.. 7 /C\ CI:E : ..
N : C:H
..
H ~ ~ '+ ~ -:
' NH2~ ~ ~H3C cH2:- Nat + :NH3 8 -0 =+I
pK, = 36
CI H:C:H
.. Nitrogen: . FC = 5 --
2
pK, = 19 H
Sironger acid Weaker acid The fomal charge of -1 for aluminum indicales that iihas a nei negauvecharge; ihe fomal
charge + I for nitrogen indicates ihat it has a net positive charge.
Theabove reaction will take place as wntlen.
For c l k t y , electron dok have been left off Fand CI in Ihe above stnictures.
2.16 ~~t~~ -9.31 into a calculator and use h e MV LOG funcrion to amve at the answer
K, = 4.9 x 2.19 The niuogen on the left 1s rnorc elecrron-nch and more b s i c The indicaid hydmgen .S
2.17 strategy: Locate [he eleclron pair(s) of the Lewis base and draw a c u r v d arrow from the rnost elczimn-pool (bluer!) and 1s mosi 3cid.c.
elecuon pairto the Lewis acid. 'The electron pair rnoves horn h e atom al [he tail of [he
anow (Lewis base) to h e atorn at h e poinl of [he arrow (Lewis acidl.

solution:( ~ ~ 1 ~ : dots have been ornitted frorn CI- l o reduce clutter.)

2.20 Strategy: Remernber that the end of a line represenk a carbon atom with 3 hydrogens, a
two-way intersection represents a carbon atom with 2 hydrogens. a bree-way intersection
represenrs a carbon with 1 hydrogen and a four-way interseclion represenk a carbon with
no hydrogens.

Solutian:

..
H
m e famal charge of-1 for bomn indicates hat bomn has a net negative charge; oxygen
has a net positive charge.
X Y
X Y
X
Sa = %' = %'
! + " r
30 Chapier 2 Polar Covaleni Bonds; Acids and Bar- 31
2.42
(a)
.. .. (b) .. .. ..
H H (c)
:E:$:?!: H:C:C: N : H
.. .. .. ..
H:B:H
:E,:
.. H H H H

"1.-

~h~ last
resonante swcture is a minar contributor because iis carbon l ~ k ascomplete

(a) CH3OH + HzSO, ;=t CH~OH,~+ HSO;

shonger stmnger weaker weaker
base acid acid base
(b) CH30H + NaNH2 ;=t C H 3 0 - ~ a ++ N H ~
suonger stronger weaker weaker
aeid base base acid
(c) CH~NH~+CI- NaOH Z=? CH3NH2 + H20 + NaCl
stmnger stronger weaker weaker
2.38 ~h~ two stmctures are not resonante fonns because the position of the carbon atoms is acid base base acid

2.39
different in the two fomis.

.. -.. 2.44 As i n Problem 2.35. rnolecules are shown as line-bond slmctures wirh lone-pair eleckons
indicated. Only calcularions for atoms with non-zero formal charge are shown.

CH~OH t HCI S CH~OH; + CT

(a) CH3 2 - 6 = -1
I .. Oxygen: FC = 6 - -
H3C-N-O: 2
I Nitrogen: FC = 5 - -
8 - 0 = +I
CH3 2

(b)
..1 2 3 4 - 4 = -1
Nitrogen 1: FC = 5 - -
H3C-N-N-N: 2
8
Nitrogen 2: FC = 5 - - -0 = +,
2
6 -2 = O
Nitrogen 3: FC = 5 - -
2
.! 1 ?. Nikogen 1: FC = 5 -
6 -2
- =0
The O-H hydrogen of aceric acid is moreacidic than the C-H hydrogens. n i e -OH , H3C-N=N=N: 2
oxygen is electronegative, and, consequently, the +H bond is more s h n g l y ~olanzed
han ~i~ -C-Hbonds. In addition, the aceiate anion is stabilized by resmance.
Nitrogen 2: FC = 5- T8 - O = +l

2.41
Lewis acids: AIBr3, BHq HF, Tic14
.. ..
Lewis bases: CH3CH2NH2, H3-.-CH3
31 Chaplcr 2 Polar Covalenl Bonds; Aeids and Bases 33
2.45 ~h~ substanceswith the largest values of pK, are [he leasi acidic. 2.54 Sodium bicarbonatc reacts with acetic acid lo producc carbonic acid. whicli breaks dawn to

'
f o m COZ. Bubbles of CO? indicare the presence of an acid stronger !han carbonic acid. in
Lemr acidic * Mosr ocidic this case aceiic acid. Phenol does no1react with sodium bicarbonare.
o o
bOH
O
II Il Il 2.55 Reacrions (a) and (c) are rcaclions belwecn Bensled-Lowv acids and bases; the stronger
CH3CCH3 < < CH3CCH2CCH3 < CHsOH acid and strongcr base are idenlificd. Reacrions (b) and (d) occur beiween Lewis acids and
bases.

2.46 To reaci completely (> 99.9%) with NaOH, an acid musl have a pK, at lcast 3 unils
srnaller (han the pK, of H20.Thus, al1 subsiances in Ihe previous problem except acetone
(a)
CHQOH
base
+ H'
acid
- cH38H2

react completely with NaOH.

2.4 7 The stronger the acid (smallcr pK,), the weaker its conjugate base. Since N&+ is a
stronger acid [han CHINHlt. NH3i s a weaker base [han CHlNH2.

2.48
7%
H~C-C-O-K~
I
+ ~~0 - y 3
H3C-C-OH
1
-0H

'33 C"3
pKa = 15.7 pKa = 18
acid base
-
srronger acid weaker acid

m e mclion rakes place as written because water is a stronger acid than lerl-bulyl alcohol
n u s , a solution of potassium rerr-butoxide in water can't be prepared.

base acid

2.50 (a) Acelone: K,= 5 x
2.51 (a) Nifrornelhane: pK, = 10.30
(b) Fomic acid: K, = 1.8 x
(b) ActYlic acid: pKa=4.25
2.56 Pain (a) and (d) represent resonance stniclures; pairs (b) and (c) do not. I n arder for rwo
StnicNres to be resonance foms. al1 aloms must be in the same position in al1 resonance
forms.
lo4

2.52
Fonicacid + H20 _Ke
+ Fomale- + HjO+
[ 0.050 MI 1x1 Lxl
x2
K, = 1.8 10-4 = -
0.050 - x

~f le[ 0.050 - x = 0.050, then x = 3.0 x 10'; and pH = 2.52. Ifyou calculate X
3
exactly, then x = 2.9 x 10- and pH = 2.54.

2.53 Only acetic acid will reaci with sodium bicarbonate. Acetic acid is the only substance in
problem 2.45 (ha1is a suonger acid than carbonic acid.
 S
.
Y 2
2 " 6=
a
B
-
O
35
w L.
I
\
+ O==U
. \
I
o
Y k o r o
 --

Review Unit 1: Bonds and Bond Polarity Points lo Remember:

In order for ciroon. <iilh ialence che;! eleciron conrigurli.on of 23'2p?. io f o m four spj
h) bnd orbiiils. ii is necessq hit one e eciron bc promored from !he 2s cubshc I lo h e~-Zn
Major Topics Covered (with vocabulary:) s~bshe.,Allhough i h i prommion requires encr:) .~heres~longh j brid orbrials are ablc ti
~

form sironger bonds. and compounds conlaining ihese oonds ire more siable
Aioniic S!ruciiire:
aiomic numkr mass number wave equation orbital shell node eleciron configuration ' Assigning formal charge lo aioms in a molecule is helpful in showing where the elecirons in a
bond are located. Even if a bond is polar covalent, in some molecules rhe elecimns "klong"
Che,iiicol Bo~idintTheory: more to one of the atoms than the oher. This "ownership" is useful for prediciing the
covaleni bond Lewis smicture lone-pair electrons line-bond stmcture valence-bond lheory outcomes ofchemical reaclions. as we will see in later chapten.
sigma (o) bond bond slrengh bond length molecular orbiial theory bonding M 0
antibonding M 0 * Resonante swctures are representations of rhedistribulion of n and nonbonding electrons in a
molecule. Electmns don't move around in the molecule. and the molecule doesn't change back
Hybridizaiion: and forth, from simciure to stmcture. Rather, resonance stmciures are an attempt to show. by
sp] hybrid orbital bond angle spl hybrid orbital pi (n)bond sp hybnd orbiial conventional line-bond drawings. the electron distribution o f a molecule that can't be
represented by any one structure.
Polar covalenr bonds:
polar covalenl bond elecuonegativity (EN) e\ecVosL?tic porential maps inductive effect * As in general chemistiy, acid-base reactions are of f u n d a m t a l imponance in organic
dipole momenr formal charge dipolar m0iecUle chemisy. Organic acids and bases. as well as inorganic acids and bases, occur frquenily in
reactions. and large numbers of reactions are catalyzed by Bmnsled acids and bases and Lewis
Resoimce: acids and bases.
resonance form resonance h~brid

1
Acidr ond Baces: Seli-Test:
Br0nsted-Lowry acid BrBnsted-Lowry base conjugale acid conjugaie base acidity constant

Chemical Srnrctures:
.
K, pK, organic acid organic base Lcwis acid Lewis base

condensed sinicture skeletal stmcture space-filling models ball-and-siick models

Types o i Problems:

Afrer siirdying rltese clnprers yoi~shorild be oble lo:

- Predict h e ground state elecuonic configuration of atoms.
- Draw h w i s electmn-dot smciures of simple compounds.
- m i c t and describe h e hybndizauonof bonds in simple compounds. A B C
- Predict bond angles and shapes of molecules. Ricinine Oxaflozuie 1,3,4-Oxadiazole
(a toxic component (an antidepressant)
- predic[ hdirection of polxity of a chemical bond, and predict the dipole moment of a simple ofcastor beans)
compound.
- Calculate formal charge for atoms in a molecule. For A (ricinine) and B (oxaflozane): Add al1 missing electron lone pain. Identify h e '
- Draw resonance forms of molecules. hybndization of al1 carbons. Indicate [he direction of bond polarity for al1 bonds with A E N 2 0.5.
- Predict the relative acidmase smnglhs of Br@ns!ed acids and bases In each compound. which bond is h e most polar? Conve A and B to molecular formulas.
-
-
Predict the direction of Bransted acidmare reaCtiOnS.
Calculate: pKa from Ka. and vice versa.
P
Draw a resonance structure for B. Which atom (or atoms) of B can act as a Lewis base?
nH nf a snlution of a weak acid.
r-: -.:- -
- ldentify Lewis acids and b a s a Add mssing rleclron lonr pmn lo C 1s it possible lo drau rcsonance forms for C.' Ifco.
- D~~ chemical s m chom ~ molecular
~ ~ formulas, and viceversa d n u at leasi onc reronanw form. and descnbe 11
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