Chemistry | S t r u c t u r e a n d B o n d i n g 1

Chapter 1: Structure and Bonding

1.1 The Origins of Chemistry 1.2 Principles of Atomic

• the chemistry of carbon
c ompo und s
• organic means “derived from
liv ing orga n i s ms ”
• sugar, urea , s ta rc h wa x e s, pl a nt
oils w ere c o ns i dered o rg a ni c
• be fore p eop l e a c c ep te d v it a l is m ,
t h e b e l i e f t h a t n a t u r a l p ro d u c t s
needed a vital force to create
th em he nc e, t he st ud y of o rga ni c
chemistry is the study of
c ompo und s wi t h v i ta l f orc e
• inorganic c he mi s t ry wa s th e s tudy
of gases, ro ck s , a nd m in e ra l
• Friedrich Wöhler converted
ammonium cyanate made from
ammon ia a n d c y a ni c a c id to urea
by h eating i t i n t he a b se n ce o f
ox yge n
• A L L o rg a n i c c o m p o u n d s c o n t a i n
on e o r m ore c a r bon
• N O T a l l c a r b o n c o m p o u n d s a re
orga nic
Struc ture
❖ Struc ture o f the A tom
• a t om s a re m a d e u p o f :
1. p rot on s
‣ p os i ti v e c h a rg e
2. n e u tro n s
‣ u n c h a rg e d
‣ found together with
the protons in the
nucleus
3. e l e c tron s
‣ n e g a ti v e c h a rg e
• p rot on s a n d n e u t ro n h a v e s im il a r
m a s s ( A to m i c Ma s s , M)
• e a c h e le m e n t i s d is t in g u is h e d b y
t h e n u m b e r o f p ro t o n s ( A t o m i c
N u m b e r, Z )
• a t om s w it h t h e sa m e n u m b e r o f
p rot on s b u t d iff e re n t n u m b e rs o f
n e u tro n s a re c a ll e d i s ot o pe s
• 14
C is ot op e i s r a d io a c t iv e , w ith a
h a l f - li fe ( t h e t im e i t t a k e s f or h a l f
of t h e n u c l e i t o d e c a y ) o f 5 7 3 0
years

Neutrons = M - Z

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 2

❖ Electron Shells and Orb itals • the 2s orbital has a smaller

• ele ctrons tha t a re b o und t o nuc l ei a m o u n t of e le c tro n d e n s it y c lo s e
are f ou nd in or bit a ls to the nucleus
• m o st of t h e e l e c t ron d e n s i ty is
f a r th e r a w a y, b e y on d a re g io n of
zero electron density called a
n o de
• p o rb i t a l s h a ve 2 lo b e s wi t h a
n o da l p l a n e a t t h e n u c l e u s .
• t h e t h re e 2p or b it a ls d iff e r on ly i n
t h e i r sp a ti a l or i e n t a t io n , so t h e y
have identical energies hence,
de g e n e ra t e o rb i ta l s
• the Heisenberg Uncertainty
Principle states that we can
N E V E R d e t e r m i n e e x a c t l y w h e re
th e e lec tro n i s; ne v e rth e le s s , we
can determine the electron
densit y, t he p ro ba bi li ty of f in di ng
th e e lect ron i n a p a rti c ul a r p a rt o f
th e o rbita l
• atomic o rb i ta l s a re group e d i nto
different shells at different
distances fro m t he n u c le u s • t h e P a u li Ex c l u si o n Pr i n c i p le te lls
• each shell is identified by a u s t h a t e a c h o r b i ta l c a n h ol d a
princ ipal q ua ntu m n u mbe r n, wi th m a x i m u m o f t w o e l e c t ro n s
n = 1 f or the l ow es t- e n ergy s hel l
c lose st t o t he n uc l e us
• as n increases, the shells are
farther from the nucleus, are
hi gh er i n e n e rg y, a n d c a n h o l d
m ore el ec tron s

• f irs t s hell ( n = 1 ) c a n ho l d two

ele ctrons, a n d th e se c o nd s hel l ( n
= 2 ) c an ho l d e ig h t
• f irs t elect ron s hel l c o n ta i ns j us t
th e 1s orb i ta l
• s orbitals are spherically
symmetrical, meaning that they
are nond ire ct i o na l

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 3

❖ Electron Config uration ๏ Problem 1-1

• th e A uf bau Pr i nc i p le s h o w s u s h o w 1. N i t ro g e n h a s re l a t i v e l y s t a b l e
to “build up” electron i sot op e s ( h a lf - l if e g re a te r t h a n 1
c on figur ati o n of a n a to m’s g ro und s e c o n d ) o f m a s s n u m b e r s 1 3,
state ( most s ta b l e) 14, 15, 16, and 17. (All except
- f ill l ow o rb i ta l ene rg y f i r st 14
N a n d 1 5 N a re r a d io a c t iv e . )
be fore p ro c eedi ng Calculate how many protons
• th e vale nc e elec t ro ns a re tho s e a n d n e u t ro n s a re i n e a c h o f
ele ctrons i n t he o ut er mos t s hel l . t h e s e is ot op e s of n it ro g e n .
Carbo n ha s fo ur v a l enc e el ec tro ns , a. mass number 13
nitrogen ha s fi v e, a nd o x y gen ha s
six . N e u t ro n = M -Z
- th e c ol um n or g ro up num b er
of the periodic table G i ve n: A t omi c N u mb e r o f N = 7
c orre s po nds to t he num b er P ro to n = 7
of va l e nc e el e c tro n s N e u t ro n = 1 3 - 7 = 6
• H u n d ’s R u l e s t a t e s t h a t w h e n
Answer: 6 Neutrons
th ere are two o r m ore or bi ta l s o f
th e same e nerg y, el e c tro n s g o i nto
b. mass number 14
differen t o rb i ta ls ra th e r th a n pa i r
up in th e s a m e or bi ta l
- N e u t ro n = M -Z
f ill t he sa m e o rb i t a l ene rg y
f irs t be fo re proc e e di n g
G i ve n: A t omi c N u mb e r o f N = 7
P ro to n = 7
N e u t ro n = 1 4 - 7 = 7

Answer: 7 Neutrons

2. Write the electronic

c o n f i g u r a t ion s o f t h e th i rd - ro w
e l e m e n t s s h o w n i n t h e p a rt i a l
p e r i o d i c ta b le i n F i g u re 1 -6 .
a. Na

Answer: 1s 2 , 2s 2 , 2p 6 , 3s 1

b. Cl

Answer: 1s 2 , 2s 2 , 2p 6 , 3s 2 ,3p 5

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 4

1.3 Bond Formation: The Octet 1.4 Lewis Structures

Rule • a w a y t o sy m b o li ze th e b o n d in g i n
• G. N. Lew i s p ro pos ed s e v er a l new a covalent molecule is to use
theories describing how atoms L e w i s S t ru c t u re s
bond to get her t o f or m m o le c ul e • each valence electron is
• atoms transfer (ionic) or share symbolized by a dot, while a
(c ovalen t) el e c tro n s in such a way bonding pair of electrons is
as to attain a filled shell of s ym b ol iz e d b y a p a i r o f d ot s o r b y
ele ctrons a dash ( — )
• th e oc tet r ule i m p l i e s a f i l l e d s h e l l • t h e e t h a n e s t r u c t u re s h o w s t h e
of e ight v a l enc e el e c tron s most important characteristic of
• ele men ts i n th e th ird a nd h i gher c a r b o n — i ts a b i l it y t o f o r m st ron g
row s (su ch a s A l, Si , P, S , C l , a n d c a r b o n – c a r b on b on d s
above) can have an “expanded • nonbonding electrons are
octet” of more than eight valence-shell electrons that are
ele ctrons be ca u s e t hey ha v e l o w- n o t s h a re d b e tw e e n tw o a t om s ( a
ly ing d o rb i ta l s a v a i la b l e p a i r i s of te n ca l l e d a l o n e p a i r)
• th e go al i s t o a tt a i n no b le ga s • oxygen atoms, nitrogen atoms,
c on figur ati o n a n d t h e h a l o g e n s ( F, C l , B r, I )
u s u a ll y h a v e n on b on d i n g e le c tro n s
i n th e ir st a b l e c om p o u n d s
❖ Ionic Bonding • t h e s e lo n e p a i r s of n on b o nd i n g
• me tal w ith n onm e ta l e l e c tro n s of t e n se r ve a s re a c t i v e
a. Me ta l
si te s i n t h e i r p a re n t co m p o u n d s
‣ po s i ti ve ly c ha rge d
‣ lost e-
b. Non me ta l
‣ ne ga t i ve l y c ha rge d
‣ ga i n e -
• re sults in th e fo r m a ti on o f c r y s t a l
lat t ic e
• c ommon i n in org a n ic c o m pou nds
๏ Problem 1-2
1. D r a w L e w is s tr u c t u re s f o r t h e
f ol lo wi n g c o m p ou n d s .
❖ Covalent Bonding a. A m m o n ia , N H 3
• nonm etal w i th n o nme ta l
• weak e r bo nd
..
A n sw e r : H — N —H
|
H

b. Wa t e r, H 2 O
.. ..
A n sw e r : H— O — H

c. Bo ra n e , BH 3

A n sw e r : H— B— H
|
H

d. Bo ron F l u o r id e , BF 3
.. ..
A n sw e r : ..
F — B— F..
..

..

|
F
..
..
..

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 5

1.5 Multiple Bonding 1.6 Electronegativity and Bond

• ele ctrons b et wee n two a t om s ha s : Polarity
a. Sin gl e Bo nd • a b o n d wi th t h e e l e c t ron s s h a red
‣ s ha re s o ne pa i r e q u a ll y b e tw e e n t h e t w o a to m s i s
b. Do u bl e B o nd c a ll e d a n o n p ol a r c o v a l e n t bo n d
‣ s ha re of t wo p a i rs • an unequally shared pair of
c. Tri p l e B o nd bonding electrons is called a
‣ s ha re of t hree pa i rs po l a r co v a l e n t bo nd
- w h e n c a r b on i s b on d e d to
chlorine the bonding
e l e c tro n s a re a tt r a c t e d m o re
strongly to the chlorine
a t om
- carbon: positive charge,
c h l or in e : n e g a t iv e c h a rg e

• the number of bonds an atom

usu ally fo r ms i s c a ll ed it s v a lenc e
(e.g. carbon is tetravalent,
n i t ro g e n i s t r i v a l e n t , o x y g e n i s
divalen t, a nd hy d ro g en a nd the
haloge ns a re mo n ov a l e nt )

• we symbolize the bond polarity

using an arrowhead at the
n e g a ti v e e n d of t h e p o la r b on d
a n d a p lu s si g n a t t h e p o si ti v e e n d
• t h e b o n d p ol a r it y i s m e a su re d b y
i ts d i po l e m o m e n t ( m )

๏ Problem 1-3 µ=𝛿xd

1. Draw Lew i s s tr uc t ures f or t he • μ = d ip ol e m o m e n t
f ollowin g c om po und s . • 𝛿 = p a rt i a l c h a rg e
a. N2 • d = b on d l e n g t h
.. ..
An swe r : N — N
b. Wa ter, H 2 O

An swe r : H— O — H
.. ..

c. Bo ra ne , BH 3

An swe r : H— B— H
|
H

d. Bo ro n Fl u or id e , BF 3
.. ..
An swe r : ..
F—B —F..
..

..

|
..
F
..
..

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 6
• an electrostatic potential map ๏ Problem 1-5
( EPM ) use s co l o r t o re p re se nt the 1. Use electronegativities to
c alcu late d c ha rge di st r ib u ti o n i n predict the direction of the
th e molecul e dipole moments of the
- red : el e ct ro n- r i c h reg i on s (- ) f ol lo wi n g b on d s.
- blue-purple: electron-poor a. C —C l
re gio n (+ )
- o rang e , y el lo w, a nd g reen: G i ve n : C= 2 . 5 ,
intermediate levels of Cl= 3.2
ele c tro s t a ti c po te n ti a l
A n sw e r : C— C l , ΔE N = 0 . 7 , p ol a r
→

b. N — Cl

G i ve n : N = 3 ,
Cl= 3.2

• el ect ro neg a t i v it ies i s a g u id e i n A n sw e r : N — Cl , Δ E N = 0. 2 , no np o l a r

predicting whe th er a 1 g iv e n bo nd
→
will be po l a r and the 2 d i rec t i o n o f
its dipo le m ome n t c. N—O
• th e Paulin g E l ec tron e ga t iv i ty Sc a l e
is use fu l f or pre di c ti ng t he p ol a ri ty G i ve n : N = 3 ,
of co vale nt bon d s. O= 3 . 4
• e l e c t ro n e g a t i v i t i e s i n c re a s e f ro m
left to ri g ht a c ros s th e p eri o di c A n sw e r : N — O , ΔE N = 0 . 4 , n o n po l a r
table →
d. B— C l

G i ve n : B= 2 ,
Cl= 3.2

A n sw e r : B— Cl , Δ E N = 1 . 2 , po l a r
→
.. ..

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 7

1.7 Formal Charges 1.8 Ionic Structures

• formal charges (FC) provide a • b on d s b e t w e e n a t om s w it h ve ry
method for keeping track of l a rg e e l e c t ro n e g a t i vi t y d i ff e re n c e s
ele ctrons, b ut th ey m a y or ma y no t (about 2 or more) are usually
c orre spo nd t o rea l c ha rges drawn as ionic
• hel ps u s det er mi n e w hi c h a to ms
bear most of the charge in a
c harged mo l ec u le ; i t a l so h e l ps us
to see ch a rged a to ms i n m o le c ul es
th at are n eut ra l ov e ra l l

FC = valence e- -
(bond line + nonbonding e-) ๏
1.
Problem 1-6
D r a w L e w is s tr u c t u re s f o r t h e
f ol lo wi n g c om p o u n d s a n d io n s,
๏ Solved Probl em 1-1 showing appropriate formal
1. Comput e t he fo r ma l c h a rg e (FC) c h a rg e s .
on ea c h a t om i n th e f ol lo wi ng a. [ C H 3O H 2] +
struc tu res .
a. Me th a ne, C H 4 H
| ..
[ ]
+
Giv en: valen ce e l ec t ron = 4 , H —C — O — H
A n sw e r : | |
bond line = 4, H H
nonbonding electron = 0
b. N H 4C l
H
| NH4 FC= 5-(4+0) = +1
H—C—H
| CL FC= 7-(0+8) = -1
H
FC= 4- ( 4+0) H

[ ] [ ]
| + .. -
An sw er : 0 H —N — H Cl
..
..
..
A n sw e r : |
b. Hy dro ni um Io n, H 3 O + H

Giv en: valen ce e l ec t ron = 6 , c. N a OC H 3

bond line = 3,
nonbonding electron = 4 Na FC= 1-(0+0) = +1

.. ..
H—O—H
O FC= 6-(1+6) = -1

| H
H

[ ][ ]-
+ .. |
FC= 6- ( 3+4) A n sw e r : Na O
..— C— H
..

|
An sw er : +1 H

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 8
1.9 Resonance
• whe n two o r m o re v a l e nc e- bo nd
struc tu re s a re pos si bl e , di ff eri ng
on ly in the pl a c em e nt o f el ec tro ns,
the molecule will usually show
c hara cter i s ti c s of b o th st r uc t ures
• th e diff eren t s t ru c tu re s a re c a l l ed
resonance structures or
reso na nce fo r ms b ec a us e t hey a re
NOT different compounds, just
differen t wa y s of dr a wi ng t he s a m e
c ompo und
• th e a ctual mo l ec ul e is s a i d to be a
reso na nce hy b r i d of it s res o na nc e
f or ms
❖ Resonance Hybrid
• w e s a w t h a t t h e i o n [ H 2C N H 2] +
might be rep res e nt ed by ei ther o f
th e f ollowi n g res o na nc e f o r m s :
• in the actual molecule, the
positive charge is delocalized
(sprea d out ) ov er b o th t he c a rbo n
atom a nd the ni trog e n a t om
• to give the structure, with a
positive c ha rge on n it roge n a nd a n
oc tet on ca r bo n
• the combined representation
attempts to combine the two
resonance forms into a single
pictu re , w i th t he c h a rg e s ha red by
c arbon an d n it roge n .
• th is mak es t he i on more s ta bl e
t h a n i t w o u l d b e i f t h e e n t i re
c harge were l oc a l iz ed o nl y on the
c arbon or o nl y o n th e n i t ro gen, we
c a l l t h i s a re s o n a n c e - s t a b i l i z e d
c atio n
• resonance stabilization plays a
c r u c ia l ro le in c om p o u n d s h a v in g
d ou b le b o n d s
• i n t h e a c id it y o f a c e ti c a c i d , it
loses a proton, the resulting
a c e t a t e i o n h a s a n e g a t i ve c h a rg e
delocalized over both of the
ox y g e n a to m s
• e a c h ox y g e n a t o m b e a r s h a lf of
the negative charge, and this
d e l o c a l iz a ti o n s ta b il iz e s th e io n.
Ea c h o f th e c a r b o n – o xy g e n b o nd s
i s h a lf w a y b e t we e n a si n g l e b on d
a n d a d ou b le b o n d , a n d th e y a re
s a id t o h a v e a bo n d o rde r o f 1 1 / 2
• remember that individual
re s on a n c e f or m s d o N O T e x i st
• the molecule does NOT
“resonate” between these
s tr u c t u re s BUT i t is a h y b r i d wi t h
s o m e c h a r a c t e r is ti c s of b o t h
- a n a n a lo g y i s a m u le , w h ic h
i s a h yb ri d of a h o rs e a n d a
d on k e y
- the mule does not
| a t e ” b e tw e e n l o o k i n g
“ re s on
l ik e a h o r se a n d l ook i n g l i ke
a donkey; it looks like a
m u l e a l l t h e t i m e , w i th t h e
b roa d b a c k o f th e h or se a n d
t h e l on g e a r s o f t h e d on k e y
© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 9

❖ Major and Minor Resonance 1.10 Structural Formulas

Contributors • st ru c tu ra l f o rm u l a s a ct u a lly s ho w
• we c all the mo re s ta b le res ona nc e w h ic h a to m s a re b o n d e d t o wh ic h,
f or m the ma jo r c o nt r ib ut o r , a nd t h e re a re t w o m a j or ty p e s:
th e less s t a bl e f o r m i s t he mino r 1. L e w is S tr u c t u re s
c ont ribut o r 2. C o n d e n s e d S t r u c t u r a l
• lower-energy (more stable) F o r m u la
resonance forms are closer
representations of the actual ❖ Condensed Structural
molecule or ion than are the Form ulas
higher-energ y (l es s s ta b l e) o nes • i n a c on d e n se d st r u c t u r a l f or m u la ,
• on ly elect ro ns c a n b e del oc a l i z ed each central atom is shown
• the following general rules will t og e t h e r wi th t h e a t o m s t h a t a re
hel p us to d ra w rea l is ti c re s on a nc e b on d e d t o i t
struc tu re s : • n o n b o n d i n g e l e c t ro n s a re r a re l y
1. Seco n d- row el eme n ts (B , C , shown in condensed structural
N, O, F) can never have f or m u l a s
more t ha n ei g ht el e c tro n s in
th ei r v a l e nc e s he ll s
2. On ly t he p la c e m ent o f th e
electrons may be shifted
from one structure to
anoth er. El ec tron s in d o ubl e
bonds and nonbonding
electrons (lone pairs) are
mos t co mm o nl y s hi f te d
3. N u c l e i c a n n o t b e m o v e d ,
and all bond angles must
re ma i n the sa m e
4. Sigma bon ds a re v e ry s ta b le ,
and th ey a re ra re l y i nv o l v ed
in res o na n ce
5. T h e m a j o r r e s o n a n c e
c on tr ib ut or i s t he o ne wi th
th e l ow es t e nergy. Th e b e st ๏ Problem 1-11
c on tr ib ut or s g ene ra l ly ha v e 1. D r a w L e w is s tr u c t u re s f o r t h e
th e mo s t oc te ts s a ti s f i ed , a s f ol lo wi n g co n d e n s e d st r u c t u ra l
man y bo nds a s p o ss ib l e, 
 f or m u l a s.
and as little charge a. C H 3 ( C H 2 ) 3 C H ( CH 3 ) 2
sepa ra t i on a s pos si bl e
6. Ele c tron ega t i v e a t oms s uc h H H H H H H H
as N , O, a nd ha l oge n s o f te n | | | | | | |
hel p to de l oc a l i z e pos it i v e H - C -C - C- C- C -C - C- H
A n sw e r : | | | | | | |
c harge s , but t hey c a n b ea r a H H H H H H H
posi ti ve c ha rge o nl y i f th e y
have o c te ts
7. R e s o n a n c e s t a b i l i z a t i o n i s
most important when it
serves to delocalize a
c harge o r a ra d ic a l o v er tw o
or mo re a to m s

© Na ta sha Licong
 Chemistry | S t r u c t u r e a n d B o n d i n g 1 0

❖ Line–Angle Formulas
• line–angle formula, sometimes
c a l l e d a s k e l e t a l s t r u c t u re o r a
stick f igure
• of ten used f o r c y c li c c om p ounds
and occasionally for noncyclic
on es
• bonds are repres e nt ed b y l i nes ,
and car bo n a to m s a re a s su m ed to
be present wherever two lines
1
me et or a l i ne 2 b eg ins o r 3 end s
• hydro gen a t om s a re n ot us ua l l y
drawn un le s s t hey a re bon d ed to
an atom th a t i s d ra w n



© Na ta sha Licong