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Chemical Bonding I: Basic Concepts

Valence electrons are the outer shell electrons of an atom. The valence electrons are the electrons that particpate in chemical bonding.
$roup 1A 2A 3A A !A "A #A

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e& configuration ns1 ns2 ns2np1 ns2np2 ns2np3 ns2np ns2np!

% of valence e& 1 2 3

! " #
9.1

Lewis Dot Symbols for the Representative Elements & Noble Gases

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9.1

The Ionic Bond

'i ( ) 'i( ) &

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1s22s1 1s22s22p! 'i ) e (
&

1s2 1s22s22p" *+e, *-e, 'i( ( e& ) &

'i( (

) &

'i( ) &

9.2

0lectrostatic /'attice1 0nerg.

Lattice energy /01 is the energ. re=uired to completel. separate one mole of a solid ionic compound into gaseous ions.

0 8 ; Q(Qr

'attice energ. /01 increases as 2 increases and3or as r decreases.

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cmpd 4g)2 4g5 'i) 'iCl

Q( is the charge on the cation

Q& is the charge on the anion r is the distance bet<een the ions lattice energ. 29!# 28 (29&1 3936 28 (29&2 173" r )& : r Cl& 6!3

9.3

Born&+aber C.cle for >etermining 'attice 0nerg.

o +overall 8 +1o( +2o( +3o( + o( +! o

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9.3

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9.3

?odium Chloride

4ining ?alt

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Chemistry In Action:

?olar 0vaporation for ?alt

A covalent bond is a chemical bond in <hich t<o or more electrons are shared b. t<o atoms. @h. should t<o atoms share electronsA ) ( ) ) )

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#e& #e& 6e& 6e& 'e<is structure of )2
lone pairs

single covalent bond

lone pairs

lone pairs

) )

lone pairs

single covalent bond

9.

'e<is structure of <ater + ( 5 ( + + 5 + 2e&6e&2e&

single covalent bonds

or

Double bond B t<o atoms share t<o pairs of electrons 5 C 5 or 5 C 5

& 6e& 6e 6e& double bonds

Triple bond B t<o atoms share three pairs of electrons - & triple bond 6e&6e or -

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double bonds

triple bond 9.

'engths of Covalent Bonds

Triple bond : >ouble Bond : ?ingle Bond

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Bond 'engths
9.

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9.

Polar covalent bond or polar bond is a covalent bond <ith greater electron densit. around one of the t<o atoms

electron poor region

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electron rich region

e& poor

e& rich

+ (

) &

9.!

Electronegativity is the abilit. of an atom to attract to<ard itself the electrons in a chemical bond. 0lectron Affinit. & measurable9 Cl is highest
C /g) + eC&/g)

0lectronegativit. & relative9 ) is highest

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9.!

he Electrone!ativities of Common Elements

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9.!

"ariation of Electrone!ativity with Atomic N#mber

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9.!

Classification of bonds b. difference in electronegativit.

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7 2 7 : and :2 Dolar Covalent partial transfer of e&

>ifference

Bond T.pe Covalent

Ionic Dolar Covalent

Increasing difference in electronegativit. Ionic transfer e&

9.!

Covalent share e&

Classif. the follo<ing bonds as ionic9 polar covalent9 or covalent: The bond in CsClE the bond in +2?E and the -- bond in +2--+2. Cs B 7.# + B 2.1 - B 3.7

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Cl B 3.7 ? B 2.! 3.7 B 7.# 8 2.3 2.! B 2.1 8 7. 3.7 B 3.7 8 7 - B 3.7

Ionic Dolar Covalent Covalent

9.!

@riting 'e<is ?tructures

2. Count total number of valence e&. Add 1 for each negative charge. ?ubtract 1 for each positive charge. 3. Complete an octet for all atoms except h.drogen . If structure contains too man. electrons9 form double and triple bonds on central atom as needed.
9."

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1. >ra< s;eletal structure of compound sho<ing <hat atoms are bonded to each other. Dut least electronegative element in the center.

@rite the 'e<is structure of nitrogen trifluoride /-)31.

?tep 1 B - is less electronegative than )9 put - in center ?tep 2 B Count valence electrons - & ! /2s22p31 and ) & # /2s22p!1 ! ( /3 F #1 8 2" valence electrons ?tep 3 B >ra< single bonds bet<een - and ) atoms and complete octets on - and ) atoms. ?tep & Chec;9 are % of e& in structure e=ual to number of valence e& A 3 single bonds /3F21 ( 17 lone pairs /17F21 8 2" valence electrons

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)

9."

@rite the 'e<is structure of the carbonate ion /C532&1.

?tep 1 B C is less electronegative than 59 put C in center ?tep 2 B Count valence electrons C & &2 charge B 2e& /2s22p21 and 5 & " /2s22p 1

?tep 3 B >ra< single bonds bet<een C and 5 atoms and complete octet on C and 5 atoms. ?tep & Chec;9 are % of e& in structure e=ual to number of valence e& A 3 single bonds /3F21 ( 17 lone pairs /17F21 8 2" valence electrons ?tep ! & Too man. electrons9 form double bond and re&chec; % of e & 2 single bonds /2F21 8 1 double bond 8 6 lone pairs /6F21 8 1" Total 8 2 9."

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5

( /3 F "1 ( 2 8 2 valence electrons

T<o possible s;eletal structures of formaldeh.de /C+251 + C 5 + + + C 5

An atomGs formal charge is the difference bet<een the number of valence electrons in an isolated atom and the number of electrons assigned to that atom in a 'e<is structure.
formal charge on an atom in a 'e<is structure

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total number of valence electrons in the free atom total number of nonbonding electrons

&

&

1 2

total number of bonding electrons

The sum of the formal charges of the atoms in a molecule or ion must e=ual the charge on the molecule or ion.
9.#

&1 + C

(1 5 +

formal charge on an atom in a 'e<is structure

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total number of valence electrons in the free atom total number of nonbonding electrons

C B e& 5 B " e& 2+ B 2F1 e& 12 e&

2 single bonds /2F21 8 1 double bond 8 2 lone pairs /2F21 8 Total 8 12

&

&

1 2

total number of bonding electrons

formal charge on C formal charge on 5

&2 & H F " 8 &1

8 " &2 & H F " 8 (1

9.#

+ +

7 C

7 5

formal charge on an atom in a 'e<is structure

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total number of valence electrons in the free atom total number of nonbonding electrons

C B e& 5 B " e& 2+ B 2F1 e& 12 e&

2 single bonds /2F21 8 1 double bond 8 2 lone pairs /2F21 8 Total 8 12

&

&

1 2

total number of bonding electrons

formal charge on C

& 7 &H F 6 8 7 87

formal charge on 5

8 " & &H F

9.#

)ormal Charge and 'e<is ?tructures

1. )or neutral molecules9 a 'e<is structure in <hich there are no formal charges is preferable to one in <hich formal charges are present. 2. 'e<is structures <ith large formal charges are less plausible than those <ith small formal charges. 3. Among 'e<is structures having similar distributions of formal charges9 the most plausible structure is the one in <hich negative formal charges are placed on the more electronegative atoms. @hich is the most li;el. 'e<is structure for C+25A &1 + (1 5 + 7 C 7 5
9.#

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C + +

A resonance structure is one of t<o or more 'e<is structures for a single molecule that cannot be represented accuratel. b. onl. one 'e<is structure.

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5 ( 5 & & 5 ( 5 & 5 C 5 &

@hat are the resonance structures of the carbonate /C532&1 ionA

&

C 5

&

C 5 &

&

9.6

0Fceptions to the 5ctet Iule

The Incomplete 5ctet

Be+2

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Be B 2e& 2+ B 2F1e& e& + ) B ) )

Be

B)3

B B 3e& 3) B 3F#e& 2 e&

3 single bonds /3F21 8 " 9 lone pairs /9F21 8 16 Total 8 2

9.9

0Fceptions to the 5ctet Iule

5dd&0lectron 4olecules

-5

The 0Fpanded 5ctet /central atom <ith principal =uantum number n J 21 )

?)"

? B "e& ") B 2e& 6e&

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- B !e& 5 B "e& 11e& 5 ) ) ? ) ) )

" single bonds /"F21 8 12 16 lone pairs /16F21 8 3" Total 8 6

9.9

Chemistry In Action: Kust ?a. -5

-52& /aq1 ( )e2( /aq1 ( 2+( /aq1

-5 /g1 ( )e3( /aq1 ( +25 /l1

-2 /g1 ( 52 /g1

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2-5 /g1

The enthalp. change re=uired to brea; a particular bond in one mole of gaseous molecules is the bond energy. +2 /g1 Cl2 /g1 +Cl /g1 52 / g 1 -2 /g1

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+ /g1 ( + /g1 Cl /g1 ( Cl /g1 +7 8 2 2.# ;K + /g1 ( Cl /g1 +7 8 31.9 ;K 5 /g1 ( 5 /g1 +7 8 96.# ;K - /g1 ( - /g1 +7 8 9 1. ;K Bond 0nergies

$on% Ener!y +7 8 3". ;K

5 -

5 -

?ingle bond : >ouble bond : Triple bond

9.17

Average bond energy in pol.atomic molecules +25 /g1 5+ /g1 + /g1 ( 5+ /g1 +7 8 !72 ;K + /g1 ( 5 /g1 +7 8 2# ;K

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!72 ( 2# 8 " ;K Average 5+ bond energ. 8 2

9.17

Bond 0nergies /B01 and 0nthalp. changes in reactions

Imagine reaction proceeding b. brea;ing all bonds in the reactants and then using the gaseous atoms to form all the bonds in the products.

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+7 8 total energ. input B total energ. released 8 B0/reactants1 B B0/products1

9.17

+2 /g1 ( Cl2 /g1

2+Cl /g1

2+2 /g1 ( 52 /g1

2+25 /g1

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9.17

Lse bond energies to calculate the enthalp. change for: +2 /g1 ( )2 /g1 2+) /g1

T.pe of bonds bro;en

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-umber of bonds bro;en Bond energ. /;K3mol1

+7 8 B0/reactants1 B B0/products1
0nerg. change /;K1

+ )

+ )

1 1

3". 1!".9

3". 1!".9
0nerg. change /;K1

T.pe of bonds formed

-umber of bonds formed

Bond energ. /;K3mol1

!"6.2

113".

+7 8 3". ( 1!".9 B 2 F !"6.2 8 &! 3.1 ;K

9.17