Chapter 9

The Basic of Chemical Bonding

The Basic of Chemical Bonding
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Summary Highlights
Summary Highlights

Ionic Bonding

Electronegativity and Polar Bonds

Reactivity and Electronegativity

Lewis Symbol and Lewis Structures

Formal Charges

Coordinate Covalent Bonding

Resonance
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!" Electron trans#er leads to the #ormation o# ionic com$ounds %
Lattice Energy& '
Lattice Energy& '
Com$ound Ions
Lattice
Energy )*+
mol
,"
-
LiCl Li
.
and Cl
,
/0
1aCl 1a
.
and Cl
,
22
3Cl 3
.
and Cl
,
245
LiF Li
.
and F
,
"4%%
CaCl
6

Ca
6.
and Cl
,
660
7lCl
%

7l
%.
and Cl
,
0/56
Ca8 Ca
6.
and 8
69
%/4"
7l
6
8
%

7l
%.
and 8
69
"0&5":

Formation o# gaseous ions #rom an ionic solid

7
;
B
y)s-
<;B
y.
)g-
. yB
;9
)g-
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!" Electron trans#er leads to the #ormation o# ionic com$ounds /
Born Haber Cycle #or 1aCl
Born Haber Cycle #or 1aCl
61a
)s-
. Cl
6)g-
< 61aCl
)s-

=hat has to ha$$en>
Sublime 1a? @H
sub
A "42!
*+Bmol
IoniCe 1a? IE
"
A /50!/
*+Bmol
Brea* Cl bond? D) E
Cl9Cl
-

A
"6"!% *+Bmol

IoniCe Cl? E7 A 9%/!

*+Bmol

Form bond? 9' A 922

*+Bmol
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!" Electron trans#er leads to the #ormation o# ionic com$ounds 0
' vs! Bond Formation Energy
' vs! Bond Formation Energy

Fhe #ormation o# one mole o# solid #rom gaseous ions

)ionic bond formation- is numerically the same as the
lattice energy
1a
.
)g-
. Cl
9
)g-
< 1aCl
)s-
. 22 *+

Since this is energy released& the value #or this $rocess

would be G'

Smaller ions have greater attractive #orces& as have those

with higher charges
kr
q q
U
6
"

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!" Electron trans#er leads to the #ormation o# ionic com$ounds :
Electron Con#igurations Ions
Electron Con#igurations Ions
"! Fhe #irst electrons to be lost by an atom or ion
are always those #rom the shell with the largest
value o# n
6! 7s electrons are removed #rom a given shell&
they come #rom the highest9energy occu$ied
subshell #irst be#ore any are removed #rom a
lower9energy subshell!
%! =ithin a given shell& the energies o# the
subshells vary as #ollows? s p d f!
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!" Electron trans#er leads to the #ormation o# ionic com$ounds 2
Electron Con#igurations 8# Cations
Electron Con#igurations 8# Cations

Hain Irou$ metals lose the electrons in their

highest energy subshell #irst to achieve the
$reviously #illed noble gas )the octet rule-

Irou$ Ia? J1oble gas coreKns

"

Form ". ions to be isoelectronic with noble gas core

element

Irou$ IIa? Jn!g!c!Kns

6

Forms 6. ions

Irou$ IIIa? Jn!g!c!Kns

6
n$
"

Forms %. ions
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!" Electron trans#er leads to the #ormation o# ionic com$ounds
Electron Con#iguration o# Cations
Electron Con#iguration o# Cations

Hain Irou$ metals lose the electrons in their

highest energy subshell #irst! Elements in grou$
IIIa below 7l also #orm ". ions!

Ia ? J7rK /s
6
%d
"4
/$
"
9 " e9 <

Ia
.
? J7rK /s
6
%d
"4
9 6 more e9 <

Ia
%.
? J7rK %d
"4
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!" Electron trans#er leads to the #ormation o# ionic com$ounds 5
Predicting Cation con#igurations
Predicting Cation con#igurations

Consider Bi& whose con#iguration is

JLeK:s
6
/#
"/
0d
"4
:$
%
! =hat ions are e;$ected>

Bi
.
& Bi
6.
& Bi
0.

Consider Fe& whose con#iguration is? J7rK/s

6
%d
:
!
=hat ions are e;$ected>

Fe
.
& Fe
6.
& Fe
%.
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!" Electron trans#er leads to the #ormation o# ionic com$ounds "4
Mour FurnN
Mour FurnN
=hich is a li*ely charge #or Sb ion>
7! 6.
B! %.
C! /.
E! 7ll are $ossible

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!" Electron trans#er leads to the #ormation o# ionic com$ounds ""
Predicting 7nion Con#igurations
Predicting 7nion Con#igurations

1on9metals gain electrons to become isoelectronic

with the ne;t larger noble gas

8? JHeK6s
6
6$
/
.>e
9
<>

8
69

1? JHeK6s
6
6$
%
.>e
9
<>

1
%9
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"6
"49" Lewis Fheory? 7n 8verview
"49" Lewis Fheory? 7n 8verview

Oalence e
9
$lay a
#undamental role in
chemical bonding!

e
9
trans#er leads to
ionic bonds.

Sharing o# e
9
leads to
covalent bonds.

e
-
are trans#erred o#
shared to give each atom
a noble gas con#iguration

the octet.
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"%
Lewis Symbols
Lewis Symbols

7 chemical symbol re$resents the nucleus and the

core e
9
!

Eots around the symbol re$resent valence e

-
.
Si

7s

Sb

Bi

7l

Se

7r

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!6 Lewis symbols hel$ *ee$ trac* o# valence electrons "/
Lewis Structures 8# 7toms?
Lewis Structures 8# 7toms?

Fhe element symbol is imagined to have a bo;

around it! Fhe valence e9 are distributed around
the #our sides o# the bo;!

For the PaQ grou$ elements& the grou$ number is

the number o# valence e9!

For& 7l& a grou$ IIIa element& there are % valence

e
9
! Its Lewis structure is
7l
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!6 Lewis symbols hel$ *ee$ trac* o# valence electrons "0
Fhe 8ctet Rule
Fhe 8ctet Rule

Stable atoms tend to have #ull or e;actly hal#9#ull

sublevels!

S$ecial stability is achieved in the noble gases&

which have #ull sublevels!

Fhe Poctet ruleQ9 atoms will lose or gain e9 in

order to have e9 surrounding them as have the
noble gases!

H and He will need only 6 e9& thus #ollow the

Pduet ruleQ!
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!6 Lewis symbols hel$ *ee$ trac* o# valence electrons ":
Lewis Structures For Honatomic Ions
Lewis Structures For Honatomic Ions

Because ions are #ormed by the gain or loss o# e9& the

Lewis structure indicates this change in the number o#
valence e9

=e subtract the charge on the ion #rom the number o#

valence e9 and show these around the element symbol

=e enclose the symbol in brac*ets and indicate the

charge

#or 1a
.
ion "9"A4

#or 8
69
ion& :9)96-A
J 1a K
.
J 8 K
69

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!6 Lewis symbols hel$ *ee$ trac* o# valence electrons "2
Mour FurnN
Mour FurnN
How many electrons are to be shown on 1
%9
>
7! %
B! 0
C!
E! 1one o# these
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!6! Lewis symbols hel$ *ee$ trac* o# valence electrons "
Chemical Bonds
Chemical Bonds

Ionic bonds result #rom attractive #orces between

o$$ositely charged $articles

Hetal 9 nonmetal bonds are ionic because?

metals have low ioniCation energies and easily lose e

9
to be
stable

non9metals have low electron a##inities

the #ormation o# the lattice stabiliCes the ions!

Na
+
Cl
-
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!6! Lewis symbols hel$ *ee$ trac* o# valence electrons "5
Ionic Com$ounds
Ionic Com$ounds

Ionic crystals: e;ist in a %9

dimensional array o# cations and
anions called a lattice structure

Ionic chemical formulas? always

written as em$irical #ormula
)smallest whole number ratio o#
cation to anion-
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!6! Lewis symbols hel$ *ee$ trac* o# valence electrons 64
Ionic Com$ounds G Lewis Structures
Ionic Com$ounds G Lewis Structures
Ionic com$ounds are #ormed by the attraction
between o$$ositely charged ions

show each ion& se$arately& alternating charges

#or the ionic com$ound 3
6
S?
[ K ]
+
[ S ]
2-
[ K ]
+
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!6! Lewis symbols hel$ *ee$ trac* o# valence electrons 6"
Mour FurnN
Mour FurnN
=hich o# the #ollowing correctly describes a #ormula unit
7
6
8>
7! J7
.
KJ 8
69
KJ 7
.
K
B! J 8
69
KJ 7
.
K J 8
69
K
C! J 7
.
K J 7
.
K J 8
69
K
E! 7ll o# these are $ossible
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!% Covalent bonds are #ormed by electron sharing 66
Chemical Bonds
Chemical Bonds

Covalent bonds #orm when atoms share valence electrons in

the region o# s$ace created by orbital overla$

1onmetal 9 nonmetal bonds are shared or covalent bonds

because neither element easily loses e
9

SymboliCed by a line between the atoms

Hay include u$ to three $airs o# e

9
?

two $airs #orm a double bond LAM

three $airs #orm a tri$le bond LRM

H
H
:
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!% Covalent bonds are #ormed by electron sharing 6%
Potential Energy vs! Internuclear Eistance In H
Potential Energy vs! Internuclear Eistance In H
6 6
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!% Covalent bonds are #ormed by electron sharing 6/
Bond Eissociation Energy& E
Bond Eissociation Energy& E

Fhe energy needed to brea* one mole o# a bond in

a covalent molecule in the gas $hase is called
bond dissociation energy& and is symboliCed E

E varies with bond ty$e )single& double& tri$le-

E varies with the atoms involved

Fhe #ormation o# bonds stabiliCes the structure

energetically
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!% Covalent bonds are #ormed by electron sharing 60
Holecules 8#ten 8bey Fhe 8ctet Rule
Holecules 8#ten 8bey Fhe 8ctet Rule

Share e
9
to gain octet

Hay #orm single& double

or tri$le bonds

Each atom has e

9

surrounding it
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!/ Covalent bonds can have $artial charges at o$$osite ends 6:
1ot 7ll 7toms Share Electrons ESually
1ot 7ll 7toms Share Electrons ESually

=hile electrons in a covalent bond are shared& the

electrons are not evenly distributed between the two
nuclei

Electronegativity is a measure o# the attractive #orce

that one atom in a covalent bond has #or the electrons o#
the bond
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!/ Covalent bonds can have $artial charges at o$$osite ends 62
Bond Ei$oles
Bond Ei$oles

7toms with di##erent electronegativity values will

share electrons uneSually

Electron density is uneven& with a higher charge

concentration around the more electronegative
atom

Bond dipoles indicate with delta )T- notation that

a $artial charge has arisen

Partial negative )T9- charge is assigned to the

more electronegative element

Such a bond is termed a polar bond

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!/ Covalent bonds can have $artial charges at o$$osite ends 6
Learning Chec*?
Learning Chec*?
'sing delta notation& indicate the bond $olarity #or
the #ollowing?

F9Cl

C98

C91

19Cl
T. T9
T. T9
T9 T.
T9 T.
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!/ Covalent bonds can have $artial charges at o$$osite ends 65
Mour FurnN
Mour FurnN
=hich o# the #ollowing is the correct assignment o#
the $artial charges in the bond 898>
7! 8)T.-98)T9-
B! 8)T9-98)T.-
C! 8)T9-98)T9-
E! 1one o# these
It is non9$olar
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!/ Covalent bonds can have $artial charges at o$$osite ends %4
Ei$ole Homent
Ei$ole Homent

UASVr

SA charge in coulombs& C

rA distance se$arating charges& m

" EA%!%/V"4
%4
C m
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!/ Covalent bonds can have $artial charges at o$$osite ends %"
Learning Chec*
Learning Chec*
Fhe C8 molecule has a di$ole moment o# 4!"" E and a bond
length o# ""% $m! =hat is the amount o# charge& in
electronic charge units& on either end o# the bond>
C
D
m C
- "4 ) 60 ! %
"
- "4 ) %/ ! %
m "4
$m
$m ""%
E 4!""
S
r
W
S rX S W
6"
%4
"6

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!0 Fhe reactivities o# metals and nonmetals can be related to their %6
8;idation 7nd Fhe Periodic Fable
8;idation 7nd Fhe Periodic Fable
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!: Erawing Lewis structures is a necessary s*ill %%
Lewis Structures For Covalent Structures
Lewis Structures For Covalent Structures

7rrange atoms around central atom

Sum valence electronsX divide by 6 to #ind $airs

Bond atoms to central atom with a single bond

bond $airs are shown as a lineX non9bonding e9 are

shown as dots

Com$lete the octet #or central atom

Eistribute e9 to com$lete the octet #or any attached

atoms

$lace e;tra electrons on central atom

#orm doubleBtri$le bonds i# necessary to com$lete octet

atoms andBor reduce #ormal charges
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!: Erawing Lewis structures is a necessary s*ill %/
E;ce$tions Fo 8ctet Rule
E;ce$tions Fo 8ctet Rule

H and He #ollow the duet rule

B usually has only : surrounding electrons

Be bonds with Yust / surrounding electrons

Elements in the %
rd
$eriod and higher contain PdQ
orbitals& so may accommodate more than ! Fhis
is not the most li*ely situation& but can occur!

Fhe result is an Pe;$anded octetQ

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!: Erawing Lewis structures is a necessary s*ill %0
Choosing 7 Central 7tom
Choosing 7 Central 7tom

Central atom is the uniSue atom

I# there is more than one element contributing only

one atom& the element #arther le#t on the $eriodic
table is the central atom

H is always terminal

Halogens are usually terminal

C is always central
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!: Erawing Lewis structures is a necessary s*ill %:
Eraw the Lewis Structure #or
Eraw the Lewis Structure #or
1F
1F
% %

=hich atom is the central atom>

How many valence e9 does 1F
%
have>

Bond 1 to F

Satis#y the 1 octet

How many e
9
remain> Eistribute them on F to
com$lete octet!

Eoes each atom have an octet> I# not& multi$le

bond!
N
F
:
:
..
5 + 3(7)=26 e
-
F
F
:
:
:
:
: :
:
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!: Erawing Lewis structures is a necessary s*ill %2
Learning Chec*?
Learning Chec*?
Eraw the Lewis Structure
Eraw the Lewis Structure
C8
6
HC1
N
C
H
O
C
O
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!: Erawing Lewis structures is a necessary s*ill %
Hulti$le Bonds 7nd Chains
Hulti$le Bonds 7nd Chains

7toms that o#ten #orm multi$le bonds are C& 8& 1&
P& and S

Because o# their #le;ibility in bonding ty$es& these

o#ten #orm the bac*bone o# large )more than 0
atoms- molecules
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!: Erawing Lewis structures is a necessary s*ill %5
E;$anded octet may occur #or atoms below the
E;$anded octet may occur #or atoms below the
6
6
nd nd
$eriod
$eriod
For e;am$le& SF
:

S
F
F
F
F
F
F
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!: Erawing Lewis structures is a necessary s*ill /4
Carbon Hates Lone PairsN
Carbon Hates Lone PairsN

7#ter you have drawn your structure& chec* to see i#

carbon has any lone )unshared- e9 $airs

i# it does& chec* to see i# there is any other arrangement

Fwo common s$ecies e;ist with lone $airs on C? C1

9
&
and C8! =hat are their Lewis structures>
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!: Erawing Lewis structures is a necessary s*ill /"
=rite Electron Eot Structures For
=rite Electron Eot Structures For
Le8F
/
SbCl
0
HC8
%
9
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!: Erawing Lewis structures is a necessary s*ill /6
Mour FurnN
Mour FurnN
Eraw the Lewis structure #or LeF
:
! How many
bonding $airs are there>
7! :
B!
C! 60
E! 1one o# these
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!: Erawing Lewis structures is a necessary s*ill /%
Bond Length 7nd Bond 8rder
Bond Length 7nd Bond 8rder

Bond length is the distance between the nuclei o# the

two atoms in a bond

Bond order is the number o# electron $airs shared

between the atoms

7s bond order increases& the bond length decreases and

the bond energy increases& $rovided we are com$aring
bonds between the same elements
Bond Bond Length )$m- Bond Energy )*+Bmol-
CGC "0/ %/
CZC "%/ :"0
CRC "64 "6
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!: Erawing Lewis structures is a necessary s*ill //
Formal Charges
Formal Charges
FC A J[ Oalence e
9
K GJ [ bonds . [ unshared e
9
K

Sum o# FC A charge on $article

Calculated #or all atoms in the structure

7 good structure should have ?

small #ormal charge values )4 is best-

#ew atoms with a non9Cero #ormal charge

most electronegative element is 4 or negative

no adYacent $ositive or negative #ormal charges

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!: Erawing Lewis structures is a necessary s*ill /0
Learning Chec*N?
Learning Chec*N?
:
[
[
+
Calculate Fhe Formal Charges 8n
Each 7tom
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!: Erawing Lewis structures is a necessary s*ill /:
Mour FurnN
Mour FurnN
=hat is the #ormal charge on 1 in 1H
/
.
>
7! 4
B! ."
C! 9"
E! .6
E! 1one o# these
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!: Erawing Lewis structures is a necessary s*ill /2
Coordinate Covalent Bonds
Coordinate Covalent Bonds

In most covalent bonds& each atom su$$lied one o#

the e
9
in the bond $air

=hen the same atom su$$lies both e

9
& bond is
called a coordinate covalent bond.
Com$are 1 to 1 in 1H
/
! Its lone $air site is now
occu$ied by a bond? the bond is coordinate!
e;! 1 vs 1 in 1H
/
1
H
H H 1
H
.
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!2 Resonance a$$lies when a single Lewis structure #ails /
Isomerism and Resonance? Oariations on a
Isomerism and Resonance? Oariations on a
Fheme
Fheme

Structures with the same #ormula in which the

atoms are in di##erent arrangement are termed
isomers

I# the atoms are in the same geometric

con#iguration but the electrons are arranged
di##erently& the structures are termed
resonance structures

How do you *now i# your structure is

reasonable> Chec* the formal chargesN
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!2 Resonance a$$lies when a single Lewis structure #ails /5
Learning Chec*?
Learning Chec*?
=hich is better>
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!2 Resonance a$$lies when a single Lewis structure #ails 04
Evidence o# Resonance? Carbonate& C8
Evidence o# Resonance? Carbonate& C8
% %
69 69
C :O
..
:O:
..
O:
..
C :O
..
..
:O:
..
O:
C :O
..
..
:O:
..
O:
..
..
69
69
69
.. 0
0
0
0
0
0
-1
-1
-1
-1
-1
-1

Fhree $ossible ways o# writing the Lewis structure

Structures have eSually good #ormal charge

distribution

E;$erimental bond lengths are the same

7ctual molecule must be a blend

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!2 Resonance a$$lies when a single Lewis structure #ails 0"
Resonance Structures? Fhe 1itrate Ion& 18
Resonance Structures? Fhe 1itrate Ion& 18
% %
9 9
N
O
O
O
0
-1
+ 1
-1
N
O
O
O
-1
-1
0
+ 1
O
N
O
O
0
-1
-1
+ 1
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!2 Resonance a$$lies when a single Lewis structure #ails 06
Learning Chec*?
Learning Chec*?
Eraw three structures #or 1
6
8! Identi#y the best!

Eraw three resonance structures #or the $hos$hate

ion& P8
/
%9
! Identi#y the best!
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!2 Resonance a$$lies when a single Lewis structure #ails 0%
Mour FurnN
Mour FurnN
=hich is the best structure #or the sul#ate ion>
7! B! C! E!
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