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el ec_
l l Ven at on
ol enc.
: ul e
or i on
Ll g sccond-
sl l y nega-
r si der ed
t o
0i \ enon.
sl rLl ct t t res.
;i bi e Lervi s
)' - i
\' o:
' , 9, '
- ; \ e -
),' i l
. I
j - 1 a n f -
t nce"
Hort ' -
i ch, anl ong
For el ant '
: l . ruLrgh
t hl s
n. t he
si n-
vo nossi bl e
i or carbot l
i , r e r : , , I l i t hc
"i ep, , . : ! : i cr ' ; : : " - i 1- l Cng
: - l ' i : ; : .
' : , " 1 . . ' r
' ; t ' 1 - ,
" 1 ' ; .
: ; rn i . . . -. *. €: t ri i i : :
l i t he i -ar-: i l e; ,
: 1, . . : si l r.
: l n: i l ! e t i ran f ; cn: e i ei : -r: -
- : ' r i i
/ . - . i . . : . .
v ,
' n r i l i . - . .
t . : : . .
aei i r e.
j i i :
i i l l i ! n i i r i s i ; r ; l i . =
13.13 Mol ecul ar Structure: The VSEPR Model 627
i l l l atonl s have fonl al chargcs of 0. Hou.ever, i f the atoms ate arratl gecl as
al l the l -el vi s structures gi ve tl nreasonabl e formal charges. Consi der the fol -
l orvi ng possi bi l i ti es, where the formal charges are l i sted bel o"l ' each atom:
C: O- aj : . C: O: O.
C- O: O:
t .
: 1 i l
None of these Lervi s structures (r,l ' i th thei r resul ti ng formal charges) agrees
wi th our observati on that oxygen has a si gni fi cantl y greater el ectronegati vi tl
than carbon. That i s, i t doesn' t make sense that a compound woul d contai t.t
a negatively charged carbon atoln next to a positively ch:rrged oxy€len atolll.
As a fi nal note, there are several cauti ons about formal charge to keep
i n mi nd. Fi rst, al though formal charges are cl oser to actual atomi c charges i n
mol ecul es than are oxi dati on states, formal charges sti l l are onl y' es6l tt-t"r.t ot
charge-they shoul d nof bc taken as actual atol ni c charges. Second, the eval -
uati on of Lel vi s structures usi ng formal charge i dci rs can l ead to erroneous
predi cti ons.
In tfi i s same vei n, note the di fference be6veen a "correct," or val i d, Lervi s
structure and an electronic structure that accuratel.y accounts for a molecr"rle's
observed properties. A valid Lervis structure is one that obeys the rules u,e
have established for Lewis structures. However, this'is structure may or
may not gi ve an accLrrate pi cture of the mol ecul e ar-rd i ts properti es. Expcri -
ments must bc cai ri ed out to make the fi nal deci si ons on the correct descri p-
ti on of the bondi ng i n a rnol ecul e or pol yatomi c i on."-
! 5. E3 fs?cl*cuEes Struetusc: The VSEFR lVtcdel
The strucrures of mol ecul es pl av a very i mportant rol e i n determi ni ng thei r
cl-remical properties. As u'e u,ill see later, structure is parrticularly in'rportant
for bi ol ogi cal mol ecul es; a sl i ght change i n the structure of a l arge bi ortrol e-
cul e can compl etel v destrov i ts uscful ness to a cel l or may even change the
cel l frorn normal to cal l cerous.
Many accurate methods nog' exi st for determi ni ng mol ecul ar stfucture,
the three-di mensi onal arrangentent of the atoms i n a mol ecul e. These meth-
ods must be used i f preci se i nformati on about structure i s requi red. However,
i t i s often useful to predi ct the approxi mate mol ecul ar structure of a rnol e-
cul e. In thi s secti on u' e consi der a si mpl e mocl el that al l ou' s us to do thi s. Thi s
model , cal l ed the val ence shel l el ectron-pai r repul si on (VSEPR) model , i s use-
ful i n predi cti ng the geometri es of mol ecul es formed from nonmetal s. The
mai n postul ate of thi s rnodel i s that the strttcture around 4 gi uen atom i s de-
termined principalll, b1, ntinimizing electron-pair repttlsioizs. The idea is that
the bondi ng and nonbortdi ng pai rs around a gi ven atom shoul d be posi ti oned
' For
a di scussi on of t hi s i sst t c, see Gor don H. Pur ser ,
. 1.
Chet n. Ed. 76
\ 1999\ :
l 013'
628 Lnapt er I J Bondi ng: Cener al Concept s
as f at : r r pr r r t as pt i ssi bl e. To sce l r ou' t l i i s nr ocl cl n' or ks. u' e u i l l f i r si
cl qsi dr r
t he ni ol ecr r l c l l eCl z, n. hi ch has t l r e Lovi s st r ur ct r l l : e
, 91
- Ct l :
Nttte that the' re i rre nr-o prl i rs of el cctrons arouncl rhe bcrl l l i um atont.
\\,,| 1x,
ar r at t gcnr cr ) t oi t l r cse el cct r on
l t r r i r s
r r l l os' s t hcm t o be as f ar epar t as po\ sl -
bl c t o nr i ni nr i ze t he r epul si ons? Cl ear l r , t he bcst ar r r l nsenr ent pl accs t he pai Ls
on opposi t c si dcs oi t he ber l l l i unr at onr at 180 cl esr ces:
T' hi s i s the maxi tnr-ttn possi bl e separati on i or nvo el ectror.r prri rs.
u.r. have
deternri necl the opti munr arrrrngenl ent of the cl ectron pai rs arounci the ceu-
tral atol l r, \\' e ci l n spcci i v thc ni ol c-cul rrr stnl ctrl re of l Je(l l ' -thi rt i s, the posi -
t i ons of t he at ot ns. Si nce each cl cct r on pai r on ber vl l i unr i s shar ccl l i r h a chl o-
ri ue atol tt, the r-nol ecul e hrrs rr l i ncar structurc' ,r' i th:r borrcl i rngl c of 180 cl rqrees:
Cl Be- Cl l
' ...-]:
Next, Iet' s cor.rsi der BFs, u' hi ch l .ras the Le\\-i s structLl rc
: F:
F B- F
Here the boron atonr i s surrci unded br- thrcc prri rs of el ectrons. What :rrri rnse-
Inerrt u' i l l rl i ni nri ze the rcptrl si ons? The el ectron pai rs are farrl .rest api rrt at an-
gl es of 170 cl egr ecs:
:,. ,l
\ " . )
Si nce crl ch el cctron pai r i s sharecl n' i th a fl uori nc atcl nl , thc nrol cctrl rl r struc-
trl re rs
' l
Thi s i s a pl anar ( f l at ) ancl t r i r r ngul ar
as tri sonal pl anar.
Nert. i et' s consi cl er the rri ethanc
, . : . ' 1 "
' l cl l ect t I c' *' h i ch i s ccl t t t t t t ot rl t ' cl i ' scri [ . t ed
nrol cct rl c. n' hi cl r l . ras t he l -eu, i s st ! ' i l df ure
I l - ( .
- H
r t
n. What
r s possl _
.hc pai rs
consi der
u' e have
t he cen-
he posi -
r a chl o-
rt at an-
rr struc-
escri bed
13. 13 Mol ecul ar St r uct ur e: The VSEPR Model 629
There are four pai rs of el ectrons around the central carbon atom. What
arrangement of these el ectron pai rs best n' ri ni mi zes the rcpul si ons? Fi rst, l et' s
try a square pl anar arrangement:
- 1 , -
carbon atom and the el ectron pai rs are centered i n the pl ane of the pa-
and the angl es benveen the pai rs are al l 90 degrees.
Is there another arrangel nent wi th angl es greater than 90
woul d put the el ectron pai rs even farther away from each other?
i s yes. The tetrahedral arrangement has angl es of 109.5 degrecs:
degrees that
The answer
It can be shown that thi s i s the maxi murn possi bl e separati on of four pai rs
around a given atom. This means that wheneuer
pairs of electrons are
present around an atom, they should alutays be arranged tetrahedrally.
Now that rve have obtai ned the el ectron-pai r arrangement that gi ves the
l east repul si ons, we can determi ne the posi ti ons of the atoms and thus the mo-
l ecul ar structure of CHa. In methane each of the four el ectron pai rs i s shared
between the carbon atom and a hydrogen atom. Thus the hydrogen atoms are
pl aced as shorvn i n Fi g. 13.I4, gi vi ng the mol ecul e a tetrahedral structure wi th
the carbon atom at the center.
Recal i that the fundamental i dea of the VSEPR model i s to fi nd the
arrangement of el ectron pai rs around the central atom that n-ri ni rni zes the el ec-
tron repul si ons. Then we can determi ne the mol ecul ar structtl re from knorv-
i ng hou' the el ectron pai rs are sharcd u' i th the peri pheral atoms.
Drar'v the Lervis structure for the molecule'
Count the el ectron pai rs around the central atom and arrange them i 1 the
r,vay that rni ni mi zes repul si ons (that i s, put the pai rs as far apart :1s pos-
si bl e) .
Determi ne the posi ti ons of the atorns from the rvays the el ectron pai rs are
share cl .
Name the molecule strLlcture fronr tl-re positions of the atrtnts.
FI GURE I 3. I 4
The molecular structure of methane. The
tel rahedral arrangement o[ el ectron pai rs
a tetrahedral anangement of
hydrogen atoms.
Steps for Using the VSEPR
\7e tvi l l now predi ct the structure of ammoni a
(NH3) usi ng thi s approach.
550 Chapter I 3 Bondi ng: General Concepts
FI GURE I 5. I 5
(a) The tetrahedral arrangement of el ectron
pai rs around the ni trogen atom i n the am-
moni a mol ecul e (b) Three of the el ectron
pairs around nitrogen are shared with hydro
gen atoms, as shown, and the fourth i s a
lone pair. Although the artangement of e/ec-
tron poirs is tetrahedral, as in the methane
mol ecul e, the hydrogen atoms i n the ammo
ni a mol ecul e occupy onl y three corners of
[he tetral redron. A l one pa;r occupi es l he
fourth corner. (c) Note that mol ecul ar geom-
etry i s tri gonal pyrami dal , not tetrahedral .
, t ]
( a) ( . b)
Drarv the Lervi s structurc.
l -
j Pr t r
i r . r l
Count the pai rs of el ectrons i rnd arrange them to rni ni mi zc rcpul si ons.
Thc NI-I
mol ccul e has four pai rs of el three bondi ng pai rs and one
n<l rrboncl i ng pai r. Fron.r the di scussi or.r of tl -re nrethane mol ectrl e, u,.c knou,
that tl -re best arrangentent of forrr el ectron pai rs i s:r tetrahedral arra_\.,
shon' n i n Fi g. 13. 1- 5( a) .
Determi ne the posi ti ons of the atoms.
The t hr ee H at oms shar e cl cct r on pai r s, as shor vn i n Fi g. 13. 15( b) "
Name the mol ecul ar structure.
It i s veri ' i mport:rnt to recogni ze th:rt the name of the rncl l ecr-rl ar structure
i s al rvavs l raseci on the posi ti ons of the dtotl ts. The pl of tl i e el ec-
tron pai rs determi nes the stmcture, but tl i e narne i s based or-r the posi ti ons
of the atoms. Thus i t i s i r-rcorrect to srr)' thi l t the NH3 rrrol ecul e i s tetrahecl ral .
It has a tetral -recl ral arrangcrnent of cl cctron pai rs but not a tetrahedrrrl
arrangel -nent of atoms. The r.nol ecul ar structure of ammoni a i s a tri gonal
pyrami d ( tri rrngul ar si dc i s di ffercnt fronr the other tl -rree). rather than
a tetrahcdron.
Descri be thc nrol ecul i rr structrl re of the \\' ater nrol ecul e .
Soi ut!*cr
The Leu' i s stnl cture for u' ater rs
There ar:e four pai rs of cl ectror-rs: tu,o bondi r.rg pai rs and tr.r,o nonboncl i ng
p:ri rs. To mi r.ri rni ze repul si or-rs, thcsc are bcst rrrranged i n a tetrahedral arral ' ,
as shou' n i n Fi g. 13. 16( a) . Al t hough HzC) has a t et r ahedr al ar r anger nent of
el ectron pai rs, i t i s r.rot rl terral -recl ral rnol ecul e. The atonrs i n thc [' l 2O rnol e-
cul e f or m a V- shape, as shou, n i n Fi g. 13. 16( b) and ( c) .
eJ L
1 ' \
j . :
- \
, { ' N: - 4
.,' ,! ,i
* . , - "
\ )
, ., :
' \
r. . 1
1 r' : . . '
H" l
( c )
k ,
Fronr l .xrtntl .rl c I 3. I
bec: r use of t he pr escnce
I n' e set' thrrt the Hl f) ccul c i s V-shapecl , or bent,
of t he l one pai r s. I f no l one pi r i r s n' cr c pr esr ' ut , t he
Fl c uRE
l 5' 16
(a) The tetrahedral arrangement of the four
, electron
patrs around oxygen in the water
(b) Two of the electron pairs are
between oxygen and the hydrogen
and two are lone pain. (c) The V-
molecular structure of the water
I 3. , l 3 Mol ecul ar St r uct ur e: The VSEpR Model
Bondi ng
*t \
( c)
cancel , and the mol ecul e
water very different from
' .
TBondi ng
i l ons.
; and one
lr.e knolv
array, as
) .
the el ec-
posi ti ons
rahedral .
her than
tbondi ng
' al
:ment of
O mol e-
or bent,
sent, the
From the previ ous di scussi on ' ve wourd predi ct that the H-X-H bond
angl e (r' vhere
X i s the cenrral atom) i n cH*, NH3, and H2o shoul d be the
a' gl e (109.5
degrees). Experi ments, horo,.ue., shJl v that rhe actual
bond angl es are those gi ven i n Fi g. 13.17. what si gni fi i ancc
cl o these resul ts
have for the vsEPR model ? one possi bl e poi nt oi vi ew i s that the observed
angles are close enough to the tetrahedral angle to bc satisfactor;,. The oppo-
si te vi eu' i s that the devi ati ons are si gni fi .rni enough
to requi re modi fi cati on
of the si mpl e model so that i t can more ac.u."tel y handl e si mi l ar cases. we
r'vill take the latter view.
Let's examine the following data:
mol ecul e rvoul d be l i near, the pol ar boncl s woul d
rvoul d have no di pol e rl omenr. Thi s woul d make
the pol ar substance so fami l i ar to us.
Number of l one pai rs 0 1
Bond angl e
109. 5. 107"
104. 5'
one i nterpretati on
of the trend observed here i s that l o' e pai rs requi re more
space tha. bondi ng pai rs; i n other rvords, as the ,.,.,mbei .f l o' e pai rs i ' -
creases, the bondi ng pai rs are i ncreasi ngl y
squeezed togetl .rer.
Thi s i nterpretati on see' s to make physi cal ,.nr. i f rve thi nk i n the fol -
l o*' i ng terms. A bondi ng pai r i s shared b.tnu..n tr,vo nucl ei , and the el ectrons
can be cl ose to ei ther nucl eus. Therefore they are rel ati ' el y confi ned betr,veen
the trvo nucl ei . A l one pai r i s l ocal i zed o' onl y one nucl eus, so both el ecrrons
are cl ose to that.ucl eus onh' , as shown schemati cal l ,v i n Fi g. 13.i g. Thesc
pi ct' res hel p us understand *' i rv a l one pai r ma1- requi re ,rr,rr. ,pr.. near an
at onr r l r an a bondi ng pai r .
Fl c uRE
t 5. t 7
The bond angl es i n the CHo, NH., and HrO
Note that the bond angle
bonding pairs decreases as the
of lone pairs
l -\
ros. s.
Ammonr a ril/ater
" P..r"
r dz"
H' -l-' H
104. 5'
652 Chapt er I 3 Bondi ng: Ceneral Concepts
. t '
As a rcsul t oi thcsc obsen,ati ons, l r,e nrakc the fol l on.i ng acl di ti ,,n
crri gi rral pcrsttrl ate of the VSEPR model : Lcntc
l tai rs
rL' qtti t' . tttor(.' roorl t
bontl i ng pdi rs ttnd tend to c()tnpress the ttngl es l tetutcen the bondtng, putrs.
So far n,e have consi dered cases u.i th trvcl , three, and four el ectron
pai r5
arouncl thc ccntral aron1. These are l ri zcd i n Tabl c i 3.8. For fi r.e
pai rs
of el cctrons therc are several possi bi c el ectron-pai r arrangenl entt. Th.. on.l th.t
pxr duces nr i ni mum r epul si on i s a t r i gonal bi pyr ami d. Nor c f r om Tabl e
l 3. g
t hat t l - r i s ar r : l ngemel ) f has nvo di f f cr ent angl cs, 90 degr ees and 120 degr ees.
As the nanre suggests, the stnl cture formed bi ' thi s arrangement of p.ri r-scon_
si sts of t*' o tri gonal -bi rsecl pt.rarni ds that share a common base. Si x pai rs
el crl n bcst be arranged around i r gi r.en atom to form :rn octi rhedral
structurc u' i th 9O-dcgree angl es, as shorvn i n Tabl e 13.8.
TABTE 13.8 Arrangements of El ectron Pai rs Around an Atom
yi el di ng
Mi ni mum
Repul si on
( b)
FI GURE I 3. I 8
(a) In a bonding pair of electrons the elec-
trons are shared by two nuclei. (b) In a lone
pair, since both electrons must be close to a
si ngl e nucl eus, they tend to take up more of
the space around that atom.
Number of
El ect ron Pai rs
Arrangement of
Electror-r Pair s Exarnpl e
2 Linear
e .,..'
- ; t
Tri eonel pl an: rr
, , ,
- ' ; ' A ,
. :
L r r
Tet rahedrrrl
Tri gon. rl [ . rpvr. r nri da I
Oct al . redral
\ oo'
i t : . t .
, , n' { ' '
. ' , "
- - -
* H
13. ' l 3 Mol ecul ar St r uct ur e: The VSEPR Model 635
To use thc VSF.l ' }R rnodel to determi ue the geometri c structttres of mr.rl e-
cul es,
you shoul cl memori ze the rel ati onshi ps betu' een thc number of el ectrorl
pai rs and thei r best arrangemcnt.
t to
n pai rs
' e
pai rs
l e
13. 8
l egrees.
rs con-
' e
i ! :
' :-)
a a
a '
i ; . , .
when phosphorus reacts r,vi th excess chl ori ne gas, the compound phosphorus
p..,t".| rl o.i i e (PCl .5) i s formed. In the gaseous and l i qr-ri d states thi s substance
i or-rsi sts of PCl 5 mol ecul es, but i n the sol i d state i t corl si sts of a 1:1 mi xture
pCl +*
and Pi l l e
i ons. Predi ct the geometri c structures of PCl 5, PCl a*, and
PCl 6
Sol uti on
The tradi ti onal Lewi s structure for PCl 5 i s shown i n the margi n. Fi ve pai rs of
el ectrons around tfue phosphorus atom requi re a tri gonal bi pyrami dal arrange-
(see Tabl e 13.8). When the chl ori ne atoms are i ncl uded, a tri gonal bi pyra-
mi dal mol ecul e resul ts.
The Le$,i s structure for the PCl a* i on
+ 4(71
32 val ence el ec-
trons] i s shorvn i n the margi n. There are four pai rs of el ectrors
-surroundi ng
the phosphorus atom i n the PCl a+ i on. Thi s requi res a tetrahedral arra1rge-
-..,t of ihe pai.s, as shor,vn in the figure in the margin. Since each pair is
sharecl l vi th a chl ori ne atom, a tetrahedral PCl a* cati on resul ts.
Si nce phosphorus i s surrounded by si x pai rs of el ectrons, an octahedral
,r.nng.1n.n, i s requi red to mi ni mi ze repul si ons, as shown bel orv on the l eft'
Si nce each el cctron pai r i s shared rvi th a chl ori ne atom' an octahedral PCl 6-
ani on i s predi cted.
The tradi ti onal Lervi s structure for PCl 6-
+ 6(7) + 1
48 val ence el ec-
tronsr is
, ,c,) l l c,,
" : c. l :
/ t ' J ,
i _j
@t S
Tetrahedral PCl o- cati on.
654 Chapt er 13 Bondi ng: Gener al Concept s
I Jecause t he n. bl e
ha' c f i l l ed s anr l p val ence ci r bi t r r l s, t hc. r ' ar e
pect t cl t o l t c chet t r i cal l v r cact i ve. hr f act , f or nr anr ' \ - car s t hesc el cnr cnt s
r r . er e
cal l ecl i r t er t
I i r , sc, s
because ci f t hi s supposecl i nabi l i t l - t o f or m anr . cor npound5.
Ho$, el ' et , i n t he ear l r - 1 960s seVer al cor npouncl s Of kn- pt on, xcnor t r nn, l
, adon
\\' ere svnthesi zccl . For exampl e, :l fei rnr at the Argonne Nati or-ri ,rl [-abor:ator,]
procl ucecl the sti rbl e col orl css conrpouncl xenon fetri l f[uori dc (XeF*). pr:edrcr
i ts structure ancl cl eternri nc l vhether i t hrrs a di pol c mol l ent.
S*[ ut i *n The t r acl i t i onal Leu' i s st r uct ur e f or XeFa i s shor vn bel or v.
' ! . . . . , ' f '
' r
t o. ,
The r enon at om i n t hi s I r r ol ecul e i s sur r ounded bv si x pai r s of cl ecr r er - r s,
r e-
qurri ng an octal -redral i i rrangenrerrt:
t :
j:"' ' ' / ...,
' ,' .1
.' .
' \

! = . _ :
t :
\ , , . '
The strttcrrtre predi cted for thi s mol ecul e cl epends on hou' tl i e l onc pai rs
and bondi ng pai r s ar c ar r aneed. Consi der r he nvo possi bi l i t i es shur l . n i n Fi g.
13. 19. Ti r e bondi ng pai r s i r r c i ncl i cat ed Ln. t he pr esence of f l uor i nc ar onr s.
Si nce tl ' rc stnrcrure predi cte d di ffers i n rhe tl r o cases, we ni r.rsr deci de u' hi ch
ci f thcse arri rnser.nel l ts i s preferabl e. Tbe ker. i s ro l ook at the l one pai rs. In
t he st r ucr t i r c i n par t ( a)
t he l one pai r - l one pai r angl e i s 90 degr ecs; i n t he
st nl ct ur e i n par t
{ b) t hc l or . r e pai r s i l r e sepr l r at ed bv 180 degr ees. Si nce l one
pai rs recl tri re nl ore rool n than bondi ng p:ri rs, i 1 strucfrl re u,.i tl .r tu' o l one pai rs
at 90 cl egr ees i s unf al or r r bl c. Thus t he ar r angement i n Fi g. 13. 19( b) i s pr e-
terretl , and the rnol ecul ar stmctrl re i s precl i ctecl to bc scl trare pl rrnar. Note rhar
t l r i s nr ol ecul e i s nct t descr i bed as bei ng oct ahedr al . Ther e i s ar t oct dbedr t l
111' 1' 1171' 4t' rrtcttt ctf el ectrou
l r.l i r,s,
br-rt tl re a/orl s fornt i r square pl anar strti cture.
Al t hough each Xe- F bci ncl i s pol r r r ( f l t r or i ne has i l gr ear er el cct r onega-
t i vi t t ' r han r enon) , t he squar e pl ani r r ar r angemcnt of t hese boncl s car - r ses t he
pol ar i t i es r o cr r ncel .
i t
Xenon tetrafluoride crystals.
- f hLr s
Xcl - a hi r s no cl i pol e nl oul ent .
l l 3. ' l 3 Mol ecul ar St r uct ur e: The VSEPR Model 655
lts \\'ere
d radon
Predi ct
]e pal rs
i n Fi g.
: lr,hich
ai r s. I n
i n the
ce l one
l e pal rs
i s pre-
)te that
' ucture.
' onega-
rses the
I 5. I 9
possible electron-pair arrangement for XeFo.
Si nce
has l one pai rs 90
apart, it is less favorable than
(b), where the lone pairs are
l B0 degrees
lgads td the
( a)
| 80"
( b)
We can further rvith lone pairs
ture for 13 is
i l l ustrate the use of the VSEPR
b1' consi deri ng the tri i odi dc i on
model for mol ecul es or
( 1. - ) .
The Ler vi s st r r r c-
The central i odi ne atom has fi ve pai rs around i t, requi ri ng a tri gonal bi pyra-
mi dal arrangel nent. Several possi bl e arrangements of the l one pai rs are shorvn
i n Fi g. 13.20. Note that structl rres (a) and (b) have l one pai rs at 90 degrees,
rvhereas i n (c) al l l one pai rs are at 120 degrees. Thus srrucrure (c) i s preferred.
The resul ti ng mol ecul ar structure for 13- i s l i near.
Chemi cal St r uct ur e and Communi cat i on: Semi ochemi cal s
I n t hi s chapt cr u, e have st ressecl t he i mport rrnce ci f
bci r. rg abl e t o predi ct t hc t hree, cl i nrensi c-rnrrl srrurct ure
of a nol ecul e. N. l ol ccul ar srrucrl l re rs rmport ant be-
c, l use of i t s ef f ect on cl . renri cal react i vi n-. Thi s rs espc-
ci al l r. t rue i n bi ol ogi cal s)' st erns, t 4rere reacf i ons
must Lre ef f i ci ent and hi ghl v spcci f i c. Arnorrg t l . re hun-
dreds of t 1' pes of mol ecul es i n rhe f l ui ds of a n. pi ci rl
bi ol ogi cal svst em, t hc appropri arl . re. l cranrs must f i nd
and react onl l u' i t h each ot her-t her. rnust be very,
di scri mi r. rat i ng. T' hi s speci f i ci t l ' deper. rds pri n. rari l l ' on
strllcture. The n-rolecules are constructecl so tl-rat onlv
t he appropri at e part ners can approach each ot l . rer i n
: t r r l t v t l r l t l l l on s r er r et i on.
Mol ecul ar st r uct ur e i s al so cent r al f r t r t l r ose
r nol ecul es used as a nl eans of conr r nuni cat i on. Ex-
ar npl es of chen' r i cal communi cat i on occur r i ng i n hu-
mans ar e t he conducr i on of nen- e i mpnl ses acr oss
svnapses, t he cont rol of t he manuf act ure and st or-
age of kev chemi cal s i n cel l s, and t he senses of
sr nel l and t ast e. Pl ant s and ani nal s : r l so use chemi -
cal communi cat i on. For exampl e, ant s l a, v down a
chemi cal t rai l so rhi rt ot her ant s can f i nd a cert ai n
f ood suppl y. Ant s al so warn t hei r f el l orv l vorkers of
appr oachi ng danger b1' emi t t i ng cer r ai n chemi cal s.
tr' {olecules con\re,v messages bv fitting into appro-
pri at e recept or si t es i n a ven' speci f i c u' a), rvhi ch i s
detern.rirred b1' their structure. Wher"r a molecule oc-
cupi es a recept or si t e, chen. ri cal processes are
st i mul at ed t hat produce t he appropri at e response.
Sor-net i mes, recept ors can be f ool ed, as i n t he use of
art i f i ci al sweet eners-mol ecul es f i t t he si t es on t he
t ast e buds t hat st i mul at e a "srveet " response i n t he
brai n, but t hev are not met abol i zed i n t he same \ va\ :
as nat ural su€l ars. Si mi l ar decept i on i s usef ul i n i nsecr
cgl t rol . l t an i rrea i s spravecl rvi t h sl nt het i c
f el t l l e
sex at t r act i l l t t mol ecul es, t he nt al es of t hat spcui es
come so conf Lrsecl t hat nrat i ne cl oes not occLrr.
A setnictL:lternical is tt n' rolecule that deliveis
a nres-
sage l)en|een rtrcmbers of the same or different
of pl ant or ani nral .
-i ' here
ar: c t hree groups
of t hese
cl -rerni cal rnessengel : s: al l omoncs, kai ronrones,
pheromones. L.ach is of grcat ccological
An al kt rrt cne i s def i ned as a chemi cal t l -ri l t gi res
adapt i ve advant age t o t he pr odt r cer . For exanr pl e,
l ear. es of t l -re bl ack n. : rl nut t ree cont ai n a herbi ci cl e,
j ugl onc,
t hat i rppears af t er t l . re l e: rr. es f al l t o t f , c
grouncl .
Jugl ol re i s not t ori c t o grxss or. et r| . l i n
grai ns, but i t i s ef f ect i l e agai nst pl : l nt s such rl s appt e
t rees t hat vn' oul d c<t rnpet e f or t he avai l abl e n. at er
f ood suppl i es.
Ant i bi ot i cs ar e al so al l omones, si nce t he nr i er oor -
eani snrs producc t hern t o i nhi bi t ot her speci es f rom
grou' i ng near t hem.
r\' Iani' pltl.rts prodr.rce bad-tasting chemicals to pro-
tect thenseh' es from plirnt-eating insects ancl aniurals.
The f ami l i : rr compound ni cot i nc derers ani ni al s f roni
eat i ng t he t obi rcco pl anr. The rni l l i pede sends an un-
mi st akabl e "back of f " message l rv squi rt i ng a predi rt or
rvi t h benzal del . rvcj e and hydrogen cy' ani de.
Def ensc i s not t he onl v use of al l omones. hon, -
ever. Fl ou' ers use scent t o at t ract pol l i nat i ng i nsect s.
Honevbees, f or i nsrance, are gui decl t o al f al i a f l orv-
ers bt ' a seri es of su. eet -scent ed cornpounds.
Kdi romones i rre che mi cal r. nessengers t hat bri ng
advant ageol rs ne\ \ : s t o t he r: ecei ver. For exampl e,
t he f l or: rl scent s are kai romones f rom t he honey-
becs' r' i ei vpoi nt . Nl an1. predat ors are gLri ded br-
kai romones en' ri t t ed bv t hei r f oocl . For exampl e,
FI GURE I 5. 20
Three possible arrangements of the electron
pai rs i n the l ,- i on. Arrangement (c) i s
preferred because there are no 9O-degree
l one pai r l one pai r i nteracti ons.
\ .
13. 13 Mol ecul ar St r uct ur e: The VSEPR Model 637
i al e
es be-
i ves
l "
i de,
" r r . L
) r and
i roor-
) pro-
nal s.
Ll n-
)rl ng
) ' , , "
cppl c
ski ns
exudc a chemi cal that attracts the
.oati ng
moth l arva. In some cases kai romones hel p
Certai n mari ne moi l usks can pi ck up
of thei r predators, the sea stars' and
ml ke
t hei r escaPc'
are chemi cal s that affect receptors of
species as the donor. That is, they are spe-
a species. Releaser pheromones cause an
reaction in the receptor, whereas prirnet
cause long-term effects. Examples of re-
pheromones are the sex attractants of insects,
in some species by the males and in others
6y the females. Sex pheromones have also been found
i n
Pl ants
and mammal s.
Al arm
pheromones are hi ghl y vol ati l e compounds
(ones easi l y changed to a gas) rel eased to warn of
Honeybees produce isoamyl acetate
(C7HMO2) in their sting glands. Because of its high
this compound does not linger after the
state of alert is over. Social behavior in insects is
by the use of trail pheromones, which
are used to indicate a food source. Social insects such
as bees, ants, wasps, and termi tes use these sub-
stances. Si nce trai l pheromones are l ess vol ati l e com-
pounds, the i ndi cators persi st for some ti me.
I' ri nter pheromones, whi ch cause l ong-term be-
havi orai changes, are harder to i sol ate and i denti fy.
One exampl e, however, i s the "queen substance"
produced by queen honeybees. Al l the eggs i n a
col ony are l ai d by one queen bee. If she i s removed
from the hi ve or di es, the worker bees are acti vated
by the absence of the queen substance and begi n to
feed royal
j el l y
to bee l arvae to rai se a new queen.
The queen substance al so prevents the devel opment
of the rvorkers' ovari es, so that onl y the queen her-
sel f can produce eggs.
Many studi es of i nsect pheromones are now undcr
r,vay in the hope that they rvill provide a method of
control l i ng i nsects that i s n.rore effi ci ent and safer than
the current chemi cal Desti ci des. I
Honeybees are attracted to these alfalfa flowers by sweet-scented
compounds the flowers emit
The VSEPR Model and Mul t i Pl e Bonds
So far i n our treatment of the VSEPR nodel , we have not col si dered ani t mol -
ecul es r,vi th rnul ti pl e bonds. To see hor,v these mol ecul es are handl ed by thi s
model , l et' s consi der the NO3 i on, rvhi ch requi res three resonance structufes
t o de: cr i be i r s el ect r oni c st r uct ur c:
: o
l z*
l sr
. t
i l l
N |
- .
l- [
' o,]
-["' \]
658 Chapt er 13 Bondi ng: Cener al Concept s
Smel l i ng and Tast i ng El ect roni cal l y
Tl -re hLrrnan nose and t ongue are excel l ent cl t ral i t l --
cont rol sensors. For exarl pl e, \ ve c: t l -t t el l r' vhct hcr
f ood i s spoi l ecl bv i t s di sagrecal t l e odor ancl t ast e.
Because i t ' s i nrpract i cal t o use l t unrans as scnsors i t t
i r-rdust ri al set t i ngs, ser, eral conrpaui es are nor' , ' cl e-
vel opi ng el ect r oni c noses.
Cl ' ano Sci cnces has cl evel cl ped a hand-hcl d el ec-
t roni c nose (cal l ecl a Cvranose) t hat can i dent i f v spe-
ci f i c odors bv t he "snrel l pri nt " t hev crei l t e i n t he 32
sensors of t he i nst rument . Each sensor i s composcd
of conduct i ve carbon bl ack cornbi ned rvi t h a non-
conducting pol,vmer. In the presence of the chemicals
associated with an odor, the pol,vmer su' ells, tl.rerebl
di srupt i ng t he conduct i ve pat h$ravs and i ncreasrng
t he resi st ance. The devi ce i s "t rai ned" t o det ect par-
t i cul ar odors by subj ect i ng i t t o knorvn sources of
t hose odors and st ori ng t he el ect ri cal si gnal s i n t he
machi ne' s dat abase. When t he "nose" i s t hen ex-
posed to an odor in an industrial settir.rg, it identifies
the odor bv comparing the input signals rvith its
database. The C1' ranose is used in the food and bct' -
erage industries to monitor the condition of ran'
rnat eri al s and t he qual i t v of t he f i ni shed product . I n
the chemical industr,v it is used to pir.rpoint leaks
and to identify manufacturing odors.
Anot l . rer t ype of el ect roni c nose was devel opcd
at Lund University in Srveder.r specificall,v to detect
t he odors associ at ed r' vi t h spoi l ed f i sh. I n t hi s case
t he sensor uses t wo enzvmes l i nked t o a pol l ' rner t o
det ect t he presence of i rmi nes such as hi st ami r. re,
put resci ne, and cadaveri ne. Such ami nes are pro-
duced by mi crobes as f i sh spoi l .
A compi rnv cal l ed Al pha l vI . O. S. has recent l r'
i nt roduced r, r' l "rat i t ct rl l s t he "rvorl d' s f i rst commer-
ci al el ect roni c t ongue, " a dei ' i ce used t o i dent i f i '
vari ous t ast es associ i t t ed u' i t h l i qui ds. Li ke t he
Cvri rnosc t hc el ect roni c t ongue n-rust f i rst be
A Cyranose sensor (an "electronic nose").
"t rai ned" bv exposi ng i t s probe t o knou' n l i qLri d
charact eri st i cs t o record t hei r "f i ngerpri nt s. " Once
progranrn-red, t he "t ongue" ci t n recogni ze t ast es
such as s\ \ reet ness, sol rrness, bi t t erness, and sal t i -
ness and can det ect ranci di t v and vari ot t s t 1' pes of
cont ami nat i on. The el ect roni c t ot rgue i s of part i cu-
l ar i nt erest t o t he pharnraceut i cal i ndust n' , t vhel e t t
i s hoped i t can rcduce t he neecl f or human t ast l ng
panel s.
Humans i rnd ani rl al s are st i l l t he best
"smel l ers" ant l t ast ers. but comput ers are r: rpi dl v
cat chi ng up. E
The NOr i or . r i s knor , r ' n t o be pl anar - r ' i t h 120 dcgr ee bond ar . r gl cs:
13. 13 Mol ecul ar St r uct ur e: The VSEPR Model 659
Thi s pl anar stfucture i s the one expected for three pai rs of el ectrons
ar:ound a central aton.r, r"' hi ch means rhat d doubl e bctnd shoul d be cotutted
cts one effecti ue
l tai r
i n usi ng the VSEPR model . Thi s rnakes sense because the
two pai rs of el ectrons i nr' ol ved i n the doubl e bond are not i ndependent pai rs.
Both of the el ectron pai rs must be i n the space between the nucl ei of the tr,vo
atoms to form the doubl e bond. In other l vords, the doubl e bond acts as one
center of el ectron cl ensi ty to repel the other pai rs of el ectrons. The same hol ds
true for tri pl e bonds. Thi s l eads us to another general rul e: For the VSEPR
model multiple bonds cowrtt cts one effectiue electron pair.
The mol ecul ar strLl cture of ni trate al so i l l ustrates one more i mportant
potrtt: \Yhen a mol ecul e exhi bi ts resonance, dnJ, o11e of the resottdnce strLtc-
tures calr be used to predict the moleuilar structlrre using the VSEPR model.
These rul es are i l l ustrated i n Exarnpl e 13' i 4.
Predi ct the mol ecul ar structure of the sul fur di oxi de mol ecul e. Is thi s mol e-
cul e expected to have a di pol e moment?
Sol uti on
Fi rst, we must determi ne the Lewi s structure for the S02 mol ecul e, whi ch has
18 val ence el ectrons. The expected resonance structures are
To determi ne the mol ecul ar structure, we must coul l t the el ectron pai rs around
the sul fur atom. In each resonance structure the sul fur has one l one pai r, one
pai r i n a si ngl e bond, and one doubl e bond. Counti ng the doubl e bond as one
pai r yi el ds three effecti ve pai rs around the sul fur. Accordi ng to Tabl e 13.8, a
tri gonal pl anar arrangement i s requi red, yi el di ng a V-shaped mol ecul e:
Tl rus the srructure of the SO2 mol ecul e i s expected to be V-shaped wi th a 120-
degree bond angl e. The rnol ecul e has a di pol e nomenr di rected as shown:
Si nce the mol ecul e i s V-shapcd, the pol ar bonds do not cancel .
It shoul d be noted at thi s poi nt that l one pai rs ori ented at l east 120 c1e-
€i rees
from other pai rs do not produce si gni fi cant di storti ons of bond angl es.
For exampl e, the al gl e i n the SO2 mol ecul e i s actual l y qui te cl ose to 120 de-
grees. We rvill follow the general principle t1tat an angle of 120 degrees
iidnt ln,rt pairs with enottgh space so that distortions do not occur. Angles
l ess tban 120 desrees are di stotted when l one pai rs are present'
640 Chapt er 13 Bondi ng: Gener al Concept s
( c )
The molecular structure of methanol. (a) The
arrangement of electron pairs and atoms
around the carbon atom. (b) The arrange-
ment of bondi ng and l one pai rs around the
oxygen atom. (c) The molecular strurture.
Mol ecul es Cont ai ni ng No Si ngl e Cent ral At om
So far u' e har.c c<l nsi de red rnol ecul cs ccl nsi sti ng of one central atonr srl rrounded
br- other aroms. The \ISEPR model can be readi l v ertended ro nore
coni pl i -
cat ed r . nol e' cul es, such as met hanol ( CHr oH) . Thi s r nol ecul e i s r epr esel t cdbr ,
the fol l ou' i ng I-ovi s structrl re:
The VSEPR Model
The fol l orvi ng rul es are hel pful i n usi ng the VSEPR model
cul ar st r uct ur e.
precl i ct
nrol e-
Determi ne the Lcu.i s structurc(s) for thc i nol ecul e.
For mol ecul es r,vi tl -r resonance structures, use anv of the structLl res to Dre-
di ct tl "re mol ecul ar structure.
Sum the el ectron pai rs around the central atom.
wher.r counti ng pai rs, count each rnul ti pl e boncl as a si ngl e effecti ve pai r.
Determi ne the arrangernent of the pai rs that mi ni nri zes cl ectron pl i r re-
pul si ons. These arrangenl ents are shorvn i n Tabl e 13.8.
l -one pai rs rcqui re more space than bondi ng pai rs. Chocl se al l arrange-
ment thi l t gi "' es the l pai rs as nruch room as possi bl e, al though i t ap-
pcars tl l at an angl e of at l east 120 cl egrees benveen l one pai rs provi des
enough space. Recogni ze that l one pai rs at angl es l ess than I20 degrees
may produce di storti ons from ti .re i deal i zed stmcture.
The mol ecul ar structure can be predi cted from the arrangernent of pai rs around
the carbon and ox1' gen atoms. Note that there are four pai rs of el ectrons
around the carbon, rvhi ch cal l s for a tetrahedral i rrrangentent, as i n
Fi g. 13. 21( a) . The or , vger r al so has f our pai r s, r ecl ui r i ng a r et r ahcdr al ar r ange-
ment. Ho\\' evcr; i r-r thi s case the tetrahedron u' i l l be sl i ghtl ,v di stortecl b1' rhe
space r equi r enr ent s of t he l one pai r s
[ Fi g.
13. 21( b) ] . The over al l gconr er nc
ar r ansement f or t he r nol ecul e i s shou' r . r i n Fi g. 13. 21( c) .
The VSEPR Model-How Well Does lt Work?
The \/SEPR rnri dcl i s ven. si mpi e. There are onl r- a fer.,' rul es to rernember; r' et
the model correctl v predi cts the mol ecul :rr strLrctures of most mol ecul e s formed
from nonmetal l i c cl ements. N,{ol ecul es of anr-si ze ci ,rn be treatecl bv appl vi ng
the VSEPR ntocl el to ei rch appropri ate atonl (those l roncl ed ro ar l east two
<l ther atonrs) i n tl -re mol ecul e. Thus rve can use thi s nrodel to predi ct the
strl l ctures of n.rol ecul es n' i rh hundrecl s of atonrs. If does, hor,r,ever, fai l i n a ferv
i nstances. For exi rnrpl e, phosphi ne (PH:), n' hi ci r has i r Len.i s strucfure anal o-
t o r l t , t f of anr nr oni n.
t l
I { H
( a)
( b)
woul d be predi cted to have a mol ecul ar structure si mi l ar to that for NH3 wi th
pl i -
rul es have to be added to the model .
I b.l
Thi s exampl e agai n i l l ustrates the poi nt that si mpl e model s wi l l certai nl y
have excepti ons. In i ntroductory chemi strl ' we want to use si mpl e model s that
fi t the maj ori ty of cases; we are wi l l i ng to accept a few fai l ures rather than
compl i cate the model . The amazi ng thi ng about the VSEPR model i s that such
a simple n-rodel correctly
predicts the structures of so many molecules.
Disca!ssion Questions
ol e-
questions are designed to be considered by groups of
in class. Often these questions r' vork u' ell for intro-
duci ng
a part i cul ar t opi c i n cl ass.
1. Explain the electronegativity trends across a rou' and
down a col umn of t he peri odi c t abl e. Cornpare t hese
trends r.vith those of ionization energ.v and aton' ric radii.
Hor' v are they all related?
2. The ionic compound AB is forn' red. The charges on the
i ons may be +1,
-I ' 12, -2;
or even l arger.
' What
are the factors that determine the charge for an ion
i n an i oni c compound?
3. Usi ng onl y t he peri odi c t abl e, predi ct t he most st abl e i on
f or Na, Mg, Al , S, Cl , K, Ca, and Ga. Arrange t hese f rom
l argest t o smal l est radi us and expl ai n why t he radi us
vari es as i t does. Cornpare your predi ct i ons wi t h Fi g. 13. 7.
4. The bond energv f or t he C-H bond i s about 413 kJ/ nol
in CHa but 380 kJ/mol in CHBr:. Although these values
are relatively close in magnitude, they are different.
Explain why they are different. Does the fact that the C-
H bond energy in CHBI3 is lower make an,v sense? \Vhv?
5. Consider the following statement: "Because oxygen seems
to prefer a negative two charge, the second electron affin-
itf is more negative than the first." Indicate everything that
is correct in this statement. Indicate everything that is in-
correct. Correct the incorrect information, and explain.
6. Vhi ch has t he great er bond l engt hs: NO2- or NO3-? Ex-
pl ai n.
7. The following ions are best described with resonance
structures. Draw the resonance structures, and using for-
mal charge arguments, predict the "best" Lewis structure
for each ion.
a. NCO
b. cNo-
8. Vould you expect the electronegativity of titanium to be
t he same i n t he speci es Ti , Ti 2*, Ti 3*, and Ti a*? Expl ai n.
9. The second electron affinity values for both oxygen and
sulfur are unfavorable
(endotl.rermic). Explain.
10. Arrange the following molecules from most to least po-
l ar and expl ai n your order: CH4, CF2CI 2' CF2H2, CCl a,
and CCI 2H2.
n o i r
I re-
,i dcs
' n
i n
,. the
i e t I l C
l . . i n o
t the
r few
nal o-
A bl ue exerci se number i ndi cat es t hat t he answer t o t hat ex-
erci se appears at t he back of t hi s book and a sol ut i on appears
in the Solutions Guide.
Ch.-"mical Bonds and Electronegativity
-t Explain the differencc betr,veen the {ollorving pairs of
t erms.
a. electronegativit,v and electron affinity
b. coval ent bond and pol ar coval errt bor. rd
c. pol ar coval ent bond and i oni c bond
12. Use Coul omb' s l arv,
o, o,
\ ' =
Vr v 2 : 2. 3
l r l 0
' ' J
n' n(
to calculate the energy of interaction for the following
two arrangements of charges' each having a magnitude
equal t o t he cl ect ron cherge.
1 X 10- .
l 0
r n 1 x 1 0 - l o m
b . I
x l 0 - ' n m r \ J l I
Y l 0
r " n r
V ^
" ' J
I x l o
r ' ) * \ z ^ , {
| x l o
r or n
f ,