Chapter 9: The Basics of Chemical Bonding

Chapter 9: The Basics
of Chemical Bonding
Chemical Bonds
 Attractive forces that hold atoms together
in complex substances
 Molecules and ionic compounds
Why study?
 Changes in these bonding forces are the
underlying basis of chemical reactivity
 During reaction:
 Break old bonds
 Form new bonds
Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Two Classes of Bonds
 Covalent bonding
 Occurs in molecules
 Sharing of e’s
 Ionic Bonding
 Occurs in ionic solid
 e’s transferred from 1 atom to another
 Simpler
 We will look at this first

Ionic Bonds
 Result from attractive forces between
oppositely charged particles
Na+ Cl –
 Metal - nonmetal bonds are ionic because:

 Metals have
 Low ionization energies
 Easily lose e– to be stable
 Non-metals have
 Very exothermic electron affinities
 Formation of lattice stabilizes ions
Ionic Compounds
 Formed from metal and nonmetal
Na + Cl Na+ + Cl NaCl(s)
e
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 Ionic Bond
 Attraction between + and – ions in ionic
compound.
 Why does this occur? Why is e
transferred?
 Why Na+ and not Na2+ or Na?
 Why Cl and not Cl2 or Cl+?
Ionic crystals:
 Exist in 3-dimensional array of
cations and anions = lattice
structure
Ionic chemical formulas:

 Always written as empirical
formula
 Smallest whole number ratio
of cation to anion
Energetics
 Must look at energy of system to answer
these questions
 For any stable compound to form from its
elements
 Potential Energy of system must be lowered.
 Net  in energy Hf° < 0 (negative)
 What are factors contributing to energy
lowering for ionic compound?
 Use Hess’s Law to determine
 Conservation of energy
 Envision two paths

Two Paths to Evaluate Energy
1. Na(s) + ½Cl2(g)  NaCl(s) Hf° = – 411.1 kJ/mol
2. Stepwise path
Na(s)  Na(g) Hf°(Na, g) = 107.8 kJ/mol
½Cl2(g)  Cl(g) Hf°(Cl, g) = 121.3 kJ/mol
Na(g)  Na+(g) + e– IE(Na) =495.4 kJ.mol
Cl(g) + e–  Cl–(g) EA(Cl) = – 348.8 kJ/mol
Na+(g) + Cl–(g)  NaCl(s) Hlattice = – 787 kJ/mol

Na(s) + ½Cl2 (g)  NaCl(s) Hf° = – 411 kJ/mol

Lattice Energy
 Amount that PE of system decreases when 1
mole of solid salt is formed from its gas
phase ions.
 Energy released when ionic lattice forms.

 Always HLattice= – = exothermic
 HLattice gets more exothermic (larger negative
value) as ions of opposite charge in crystal lattice
are brought closer together as they wish to be.
 Ions tightly packed with opposite charged ions next
to each other.
q q 
H Lattice 
d
 Any  in PE due to ionizing atoms is more than met
by  in PE from formation of crystal lattice. Even
for +2 and –2 ions
 overall exothermic to form ionic solids and they
are stable compounds.
Assuming that the separation between cations
and anions in the lattice is nearly identical,
which species would have the greatest lattice
energy?
A. Sodium chloride
B. Calcium chloride
C. Calcium nitride
D. Sodium oxide
E. Calcium oxide

Why do Metals form Cations and
Nonmetals form Anions?
Metal Nonmetal
 Left hand side of Periodic  Right hand side of
Table Periodic Table
 IE small and positive  IE large and positive
 Little energy required to  Difficult to remove e
remove e to give cations  EA large and negative
 EA small and negative  But easy to add e
or positive  Exothermic—large amount
 Not favorable to attract an of E given off
e to it.  PE of system 
 Least expensive, energy-  Least expensive, energy-
wise, to form cation wise, to form anion
Electron Configurations of Ions
 How e'ic structure affects types of ions formed
Ex.
Na 1s2 2s2 2p6 3s1 = [Ne] 3s1
Na+ 1s2 2s2 2p6 = [Ne]
IE1 = 496 kJ/mol small not too difficult
IE2 = 4563 kJ/mol large ~10 x larger very difficult
 Can remove 1st e, as doesn't cost too much
 Can’t remove 2nd e, as can't regain lost energy
from lattice
 doesn’t form.

Ex. Ca [Ar] 4s2
Ca2+ [Ar]
IE1 small = 590 kJ/mol not too difficult
IE2 small = 1140 kJ/mol not too difficult
IE3 large = 4940 kJ/mol too difficult
 Can regain by lattice energy ~2000 kJ/mole if
+2, –2 charges.
 But 3rd e too hard to remove
 Can't recoup required energy through lattice
formation.
 doesn't happen
 Stability of Noble Gas Core below
valence e's effectively limits # e's that
metals lose.
 Ions formed have Noble gas e
configuration
 True for anions and cations
Ex. Cl 1s2 2s2 2p6 3s2 3p5 = [Ne]3s2 3p5
Cl 1s2 2s2 2p6 3s2 3p6 = [Ar]
 Adding another e
 requires putting it into next higher n shell
 Energy cost too high
Ex.
O 1s2 2s2 2p4
O 1s2 2s2 2p5 EA1 = 141 kJ/mol
O2 1s2 2s2 2p6 = [Ne] EA2 = +844 kJ/mol
EAnet = +703 kJ/mol endothermic
 Energy required more than made up for by 
in HLattice caused by higher 2 charge

Generalization:
 When ions form
 Atoms of most representative elements (s and p
block)
 Tend to gain or lose e's to obtain nearest Noble
gas e configuration
 Except He (2 e's), all noble gases have 8 e's in
highest n shell
Octet Rule
 Atoms tend to gain or lose e's until they
have achieved outer (valence) shell
containing octet (8 e's)
Octet Rule
 Works well with
 Group IA and IIA
metals
 Al
 Non-metals
 H and He can't obey
 Limited to 2 e's in n
= 1 shell
 Doesn't work with
 Transition metals
 Post transition metals
What is the correct electron configuration for Cs
and Cs+ ?
A. [Xe] 6s1 , [Xe]

B. [Xe] 6s2 , [Xe] 6s1
C. [Xe] 5s1 , [Xe]
D. [Xe] 6s1 , [Xe] 6s2
E. [Xe] 6p2 , [Xe] 6p1

Post Transition Metals
Ex.
Sn [Kr] 4d10 5s2 5p2
Sn2+ [Kr] 4d10 5s2
 Neither has Noble Gas e configuration
 Have emptied 5p subshell
Sn4+ [Kr] 4d10
 Does have empty n = 5

Transition Metals
 1st e's lost from ns orbital of outer shell
 Lose e's from highest n first, then highest ℓ
Ex. Fe [Ar] 3d6 4s2
Fe2+ [Ar] 3d6 loses 4s e's 1st
Fe3+ [Ar] 3d5 then loses 3d e
 Extra stability due to exactly half-filled d
subshell.
 Consequences
 TM2+ common oxidation state as remove 2 e's
from outer ns shell
 Ions of larger charge result from loss of d e's.
 Not easy to predict which ions form and
which are stable
 But ions with exactly filled or half-filled d
subshells are extra stable and tend to form.
 Mn2+ [Ar]3d5
 Fe3+ [Ar]3d5
 Zn2+ [Ar]3d10

What is the correct electronic configuration for
Cu and Cu2+ ?
A. [Ar] 3d 9 4s2, [Ar] 3d 9
B. [Ar] 3d 10 4s1, [Ar] 3d 8 4s1
C. [Ar] 3d 10 4s1, [Ar] 3d 9
D. [Ar] 3d 9 4s2, [Ar] 3d 10 4s1
E. [K] 3d 9 4s2, [Ar] 3d 9
 Filled and half-filled orbitals are particularly

stable.
Predicting Cation Configurations
Consider Bi, whose configuration is
[Xe]6s2 4f14 5d10 6p3. What ions are expected?
Rewrite config’n: [Xe]4f14 5d10 6s2 6p3

Bi3+ and Bi5+
Consider Fe, whose configuration is: [Ar]4s2 3d6

What ions are expected?
Rewrite config’n: [Ar]3d6 4s2

Fe2+ and Fe3+
Predicting Anion Configurations
Non-metals gain electrons to become
isoelectronic with next larger noble gas
O: [He]2s22p4 + ? 2e– → ? O2– : [He]2s2 2p6
N: [He]2s22p3 + ? 3e– → ? N3– : [He]2s2 2p6

Lewis Symbols
 Electron bookkeeping method
 Way to keep track of e–’s
 Write chemical symbol surrounded by dots for each
e–
Group # IA IIA IIIA IVA
Valence e–'s 1 2 3 4
e– conf'n ns1 ns2 ns2np1 ns2np2
H He
Li Be B C
Na Mg Al Si
Group # VA VIA VIIA VIIIA
Valence e-'s 5 6 7 8
e- conf'n ns2np3 ns2np4 ns2np5 ns2np6
He
N O F Ne
P S Cl Ar
For the representative elements
Group # = # valence e–’s
 Can use to diagram e– transfer in ionic
bonding

Na + Cl Na+ + Cl
2+ 2
Mg + O Mg + O

Covalent Compounds
 Form individual separate molecules

 Atoms bound by sharing e–’s
 Do not conduct electricity
 Often low melting point
Covalent Bonds
 Shared pairs of e–’s between 2 atoms
 2 H atoms come together, Why?

Covalent Bond
 Attraction of valence e– of 1 atom by nucleus
of other atom
 Shifting of e– density
 As distance between nuclei ,  probability
of finding either e– near either nucleus
 Pulls nuclei closer together

 As nuclei get
close
 Begin to repel
each other
 Both have
high positive
charge
 Final internuclear distance between 2 atoms in bond

 Balance of attractive and repulsive forces
 Net attraction since bond forms

Electron Pair Bond
 e–’s come together in molecular bond

 In sense 1s orbital of each H is filled
 e–’s share same region of space  their
spins must be paired (1  and 1 )
 Refer to as e– pair bond
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Bond Dissociation Energy, D
 Energy needed to break one mole of bond
in covalent molecule in gas phase
 Symbolized D
 D varies with bond type
 Single, double, triple
 D varies with atoms involved
 D is always positive
 Formation of bonds stabilizes structure
energetically

Chemical Potential Energy
ΔH°rxn = {D (Bonds broken) }  {D (Bonds formed) }
Bond Energy Bon Bond Energy
Bond
(kJ mol−1) d (kJ mol−1)
C–C 348 C–Br 276
C═C 612 C–I 238
C≡C 960 H–H 436
C–H 412 H–F 565
C–N 305 H–Cl 431
C═N 613 H–Br 366
C≡N 890 H–I 299
C–O 360 H–N 388
C═O 743 H–O 463
C–F 484 H–S 338
C–Cl 338 H–Si 376
Covalent Bond
 2 quantities characterize this bond

Bond Length (bond distance)
 Distance between 2 nuclei = rA + rB
Bond Energy
 Also bond strength
 Amount of energy released when bond formed (
PE) or
 Amount of energy must put in to ―break‖ bond

Which species is most likely covalently bonded?
A. CsCl
B. NaF
C. CaF2
D. CO
E. MgBr2

Lewis Structures
 Molecular formula drawn with Lewis Symbols
 Method for diagramming electronic structure
of covalent bonds
 Uses dots to represent e–s
 Covalent bond
 Shared pair of e–s
 Each atom shares e–s so has complete octet
ns2np6
 Noble Gas e– configuration
 Except H which has complete shell with 2 e–s

Octet Rule:
When atoms form covalent bonds, tend to
share sufficient e–’s so as to achieve outer
shell having 8 e–’s
 Indicates how all atoms in molecule are attached
to one another
 Accounts for ALL valence e–’s in ALL atoms in
molecule
Let’s look at some examples
Noble Gases: 8 valence e–’s
 Full octet ns2 np6
 Stable monatomic gases
 Don’t form compounds
Diatomic Gases:
 H and Halogens
H2
 H· + ·H  H:H or HH
 Each H has 2 e–’s through sharing
 Can write shared pair of e–’s as line ()
 :=
 covalent bond

Diatomic Gases:
F2
F + F FF F F
 Each F has complete octet
 Only need to form one bond to complete
octet
 Pairs of e–’s not included in covalent bond
are called Lone Pairs
 Same for rest of Halogens: Cl2, Br2, I2
Diatomic Gases:
HF
H + F HF H F
 Same for HCl, HBr, HI.
 Molecules are diatomics as need only 1e– to
complete octet
 Separate molecules
 Gas in most cases because very weak
intermolecular forces
How many electrons are required to complete
the octet around nitrogen, when it forms N2 ?
A. 2
B. 3
C. 1
D. 4
E. 6

 Many nonmetals form more than 1 covalent bond
C N O
Needs 4 e-’s Needs 3 e-’s Needs 2 e-’s
Forms 4 bonds Forms 3 bonds Forms 2 bonds
H
H N H O H
H C H
H H
H H
H C H H N H O H
H H H
methane ammonia water
Multiple Bonds
Single Bond
 Bond produced by sharing one pair of
e–’s between 2 atoms
 Many molecules share more than one pair

of e–’s between 2 atoms
 Multiple bonds

Double Bonds
 2 pairs of e–’s shared between 2 atoms
Ex. CO2
O C O O C O O C O
Triple bond
 3 pairs of e–’s shared between 2 atoms
Ex. N2
N N N N N N
Which species is most likely to have multiple
bonds ?
A. CO
B. H2O
C. PH3
D. BF3
E. CH4

Carbon Compounds
 Carbon-containing compounds
 Exist in large variety
 Mostly due to multiple ways in which C can form
bonds
 Functional groups
 Groups of atoms with similar bonding
 Commonly seen in C compounds
 Molecules may contain more than 1

functional group
Important Compounds of Carbon
Alkanes Ex.
 Hydrocarbons CH4 methane
 Only single bonds CH3CH3 ethane
CH3CH2CH3 propane
Isomers
 Same molecular formula H
 Different physical properties H C H
 Different connectivity H H
(structure) H C C C H
H H H H H H H
H C C C C H butane iso-butane
H H H H
Hydrocarbons
H C C H Ethylene
 Alkenes (ethene)
 Contain at least one
H H
double bond H H
H C C C C H
H H H H butene
H C C H acetylene
 Alkynes (ethyne)
 Contain at least one H H
triple bond H C C C C H butyne
H H
Oxygen Containing Organics
 Alcohols H H H
 Replace H with OH H C O H C C O
H H H H H
methanol ethanol
 Ketones H O H
 Replace CH2 with H C C C H
C=O
H H
 Carbonyl group
acetone
Carbonyl Group
 Carbon in hydrocarbon with double
bond to oxygen
 Aldehydes
 Ketones
 Carboxylic acids
 Amides

Oxygen Containing Organics
H O
 Aldehydes
 At least 1 atom H C C H
attached to C=O is H H
acetaldehyde
 Organic Acids H O
 Contains carboxyl
H C C O
group acetic acid
 COOH H H
 Esters H O
methyl acetate
 Alkyl group replaces H C C O (methylethanoate)
H on carboxylic acid H H C H
H
Nitrogen Containing Organics
 Amines
 derivatives of NH3 with H’s replaced by alkyl groups
H H H H H
H C N H H C N C H
H H H
methylamine dimethylamine
 Amides
 Contain -NH2 on carbon chain with carbonyl
H O
H C C N H
acetamide (ethanamide)
H H
How many isomers are there of butanol?
A. none
B. 2
C. 3
D. 6
E. 4

Electronegativity and Bond
Polarity
 2 atoms of same
element form bond
 Equal sharing of e’s
 2 atoms of different
elements form bond
 Unequal sharing of
e’s

Why?
 1 atom usually attracts es
more strongly than other
Result:
 Unbalanced distribution
of e density within bond
 e cloud tighter around Cl in HCl
 Slight + charge around H
 Slight – charge around Cl
 Not complete transfer of e from 1 atom to
another.

Electronegativity and Bond
Polarity
 Leads to concept of
Partial charges
+ 
H——Cl
+ on H = +0.17
 on Cl = 0.17

Polar Covalent Bond
 Aka Polar bond
 Bond that carries partial + and – charges at
opposite ends
 Bond is dipole
 2 poles or 2 charges involved
Polar Molecule
 Molecule has partial + and – charges at
opposite ends due to a polar bond
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Dipole Moment
 Quantitative measure of extent to which bond is
polarized.
 Dipole moment = Charge on either end  distance
between them
 μ=q×r
 Units = debye (D)
 1D = 3.34 × 10–30 C·m (Coulombs·meter)
 The size of the dipole moment or the
degree of polarity in the bond depends
on the differences in abilities of bonded
atoms to attract e’s to themselves
Table 9.3 Dipole Moments and Bond
Lengths for Some Diatomic
Molecules

Electronegativity ()
 Relative attraction of atom for es in bond
 Ability of bonded atom to attract es to itself
 Quantitative basis
 Table of electronegativities - fig 8.5
 Difference in electronegativity
 = estimate of bond polarity
  = |1  2|
 Ex. N—H Si—F
 + + 

Electronegativity Table

Electronegativities
 Must know for 2nd row and H.
 (H) ~ 2.0
 (F) ~ 4.0
  by 0.5 for each element as go to left
H
 2
Li Be B C N O F
 1 1.5 2 2.5 3 3.5 4
P S Cl
2 2.5 3.0
 Calculate the bond polarity of the following
 HCl (H)~2 (Cl)~3  = 3 – 2 = 1
 CO (C)~2.5 (O)~3.5  = 3.5 – 2.5 = 1
 CH (C)~2.5 (H)~2  = 2.5 – 2 = 0.5
 LiF (Li)~1 (F)~4  = 4 – 1 = 3

 BeO (Be)~1.5 (O)~3.5  = 1.5 – 3.5 = 2

Which of the following species has the least
polar bond?
A. HCl
B. HF
C. HI
D. HBr

Trends in Electronegativity
  from left to right
 across period as Zeff 
  from top to bottom
 down group as n 
Ionic and Covalent Bonding
 2 extremes of bonding
 Actual is usually somewhere in between.

Using Electronegativities
 Difference in electronegativity
   A   B  Measure of ionic character of
bond

 Nonpolar Covalent Bond
 No difference in electronegativity
 Ionic Character of bond
 Degree to which bond is polar
 > 1.7 means mostly ionic
 >50% ionic
 More electronegative element almost completely
controls e
  < 0.5
 Means almost purely covalent
 Nonpolar; < 5% ionic
 0.5 <  < 1.7 polar covalent
Result
 Elements in same region of Periodic Table
 i.e., 2 nonmetals
 Have similar ’s
 Bonding more covalent
 Elements in different regions of Periodic

Table
 i.e., metal and nonmetal
 Have different ’s
 Bonding predominantly ionic
Reactivities of Elements Related
to Electronegativities
 Parallels between  and its reactivity
 Tendency to undergo redox reactions

Metals
 Low , means easy to oxidize (groups I and IIA)
 High , means hard to oxidize (Pt, Ir, Rh, Au, Pd)
 Reactivity  across row as  
Nonmetals
 Oxidizing power of nonmetal (how easily reduced)
parallels .
 Oxidizing power  across row as  
 Oxidizing power  down column as  

Drawing Lewis Structures
 Very useful
 Way of diagramming structure
 Used to describe structure of molecules
 Can be used to make reasonable accurate
predictions of shapes of molecules

 Not all molecules obey the Octet Rule.
 Holds rigorously for 2nd row elements like C,
N, O, and F
 B and Be sometimes have less than octet
BeCl2, BCl3
 2nd row can never have more than 8 e’s
 3rd row and below, atoms often exceed octet
 Why?
 n = 3 shell can have up to 18 e’s as now
have d orbitals in valence shell

Method for Drawing Lewis Structure
1. Decide how atoms are bonded

 Skeletal structure = arrangement of atoms.
 Central atom
 Usually given first
 Usually least electronegative
2. Count all valence es. (All atoms)
3. Place 2 es between each pair of atoms
 Draw in single bonds

4. Complete octets of terminal atoms
(atoms attached to central atom) by
adding es in pairs
5. Place any remaining e’s on central atom
in pairs
6. If central atom does not have octet
 Form double bonds
 If necessary, form triple bonds

Ex. N2F2
2 N = 2  5e = 10 e Skeletal Structure
2F = 2  7e = 14 e
Total = 24 e
F N N F
single bonds  6 e Complete terminal
atom octets
18 e
F lone pairs  12 e F N N F
6 e
N electrons  6 e Put remaining es on
central atom
0 e
F N N F
 Not enough electrons to complete N octets
 Must form double bond between N’s to
satisfy both octets.
F N N F F N N F

Ex. SiF4 Skeletal Structure
F
1 Si = 1  4e= 4 e
4F = 4  7e = 28 e F Si F
Total = 32 e
single bonds  8 e F
Complete terminal
24 e
atom octets
F lone pairs  24 e
0 e F
F Si F
F
Ex. H2CO3
 CO32 oxoanion, so C central, and O’s
around, H+ attached to two O’s
1 C = 1  4e = 4 e O
3 O = 3  6e = 18 e H O C O H
2 H = 2  1e = 2 e
Total = 24 e O
single bonds  10 e
H O C O H
14 e
O lone pairs  14 e
 But C only has 6 e
0 e
 Too few e O
 Must convert 1 of H O C O H
lone pairs on O to
2nd bond to C
 Form double bond
between C and O O
H O C O H

Ex. PCl5
1 P = 1  5 e = 5 e Cl
5 Cl = 5  7e = 35 e Cl Cl
P
Total = 40 e
Cl Cl
30 e
Cl
Cl lone pairs  30 e
0 e
Cl Cl
P
 P has 10 e Cl Cl
 OK as 3rd row element
 Can expand its shell
Ex. BBr3
Br
1 B = 1  3 e = 3 e
3 Br = 3  7e = 21 e B
Total = 24 e Br Br
18 e
Br lone pairs  18 e Br
0 e
 B has only 6 e B
 Does not form double bond Br Br
 Has incomplete octet
Ex. CO2
1 C = 1  4e = 4 e O C O
2 O = 2  6e = 12 e
O C O
Total = 16 e 
single bonds  4 e O C O O C O
12 e
O lone pairs  12 e
O C O O O O
0e 
 C only has 4 e O C O O C O
 Must form 2 double
bonds to O to complete  Which of these is correct?
C’s octet  Need another criteria
 3 ways you can do this  Come back to this
Lewis Structures—Theory
 Lewis Structures meant to describe how
atoms share es in chemical bonds
 Theory
What experimental observations back up
this theory?
 Look at properties related to number of e
pairs shared between 2 atoms

What is wrong with the following structure?
A. Too few total electrons

B. Too many total electrons
C. Lack of octet around nitrogen
D. Too many electrons around the N atom
E. Structure is correct as written

Review of Covalent Bond
Properties
Bond Length
 Distance between nuclei of bonded atoms
Bond Energy
 Energy required to separate bonded atoms
into neutral particles
Bond Order
 Number of pairs of es shared between 2
atoms
 Measure of amount of e density in bond
Bond Order, Bond Length and Bond
Energy
Greater Bond Order = Greater e density
 Nuclei held together more tightly
 Larger bond energy, D
 Larger D means
 Nuclei drawn closer together
 Shorter bond length
 As bond order , bond length , and
bond energy 
 Assumes comparing bonds between same 2
elements
Ex. H2SO4 O
1 S = 1  6e = 6 e H O S O H
4 O = 4  6e = 24 e O
2 H = 2  1e = 2 e O
Total = 32 e
single bonds  12 e H O S O H
20 e O
O lone pairs  20 e O
0 e
H O S O H
• n=3, has empty d orbitals
• Could expand it's octet O
• Could write structure with double bonds.
How Do We Know Which is Accurate?
Experimental evidence
 In this case bond lengths from X-ray data
 S—O bonds (no H attached) are shorter 142 pm
 S—O—H, S—O longer 157 pm
 Indicates that 2 bonds are shorter than other 2
 Structure with S=O for 2 O’s without H’s is more
accurate
 Preferred Lewis Structure
 Even though it seems to violate octet rule
unnecessarily

Need Criteria to Predict When This
Occurs
 Covalent bond = shared e pair
 If es shared equally
 Each atom ―owns‖ ½ of e pair or 1 e
 When ―break‖ bond
 ½ of these es going to each atom in bond
 So for S
 have 4 bonds
 Have 4 es
 2 es less than 6 es, S has as atom
 In bookkeeping sense
 S has 2+ charge if it obeys octet rule
Formal Charge (FC)
 Apparent charge on atom
 Bookkeeping method
 Does not represent real charges
FC = # valence e  # lone pair e  ½ (#
bonding e)
FC = # valence e  [# bonds to an atom + #
unshared e ]
 Indicate Formal charges by placing them in
circles around atoms

FC = #valence e  [#bonds to atom
+ # unshared e ]
-1 Structure 1
O FCS = 6  (4 + 0) = 2
+2 FCH = 1  (1 + 0) = 0
H O S O H FCO(s) = 6  (1 + 6) =  1
O -1 FCO(d) = 6  (2 + 4) = 0
O Structure 2
FCS = 6  (6 + 0) = 0
H O S O H FCH = 1  (1 + 0) = 0
FCO(s) = 6  (2 + 4) = 0
O
FCO(d) = 6  (2 + 4) = 0
H2SO4
 No formal charges on any atom in Structure 2
Conclusion:
 When several Lewis Structures are possible
 Those with smallest formal charges
 Most stable
 Preferred
Most Stable Lewis Structure
1. Least number of FC's best
2. All FC  1
3. Any negative FC on most electronegative element
Can Use FC to Explain B Chemistry
 BCl3
 Why doesn’t a double bond form here?
 FCB = 3 – 0 – 3 = 0
 FCCl = 7 – 6 – 1 = 0
 All FC's = 0 so stable, doesn't need to form
double bond

CO2 Which Structure is Best
 Use FC to determine +1 1
which structure is best
O C O
FCC = 4  (4 + 0) = 0
FCO(s) = 6  (1 + 6) = 1
FCO(d) = 6  (2 + 4) = 0
O C O
FCO(t) = 6 – (3 + 2) = +1
-1 +1
 Central structure Best O C O
 All FC’s = 0
What is the formal charge on Xe for the
following ?
A. +2, +4
B. +2, +3
C. +4, 0
D. +4, +2
Resonance: When Single Lewis
Structure Fails

O
N = 3 O = 3.5
N
1N=1 5e= 5 e
3 O = 3  6e = 18 e
O O
1 charge = 1 e

Total = 24 e O
18 e N
O lone pairs 18 e O O
0 e
Ex. NO3 
O
 Lewis structure predicts
1 bond shorter than N
other 2 O O
Experimental observation:
 All 3 N—O bond lengths are same
 All shorter than N—O single bonds
 Have to modify Lewis Structure
 e can't distinguish O atoms
 Can write 2 or more possible structures
simply by moving where e are
 Changing placement of e
What are Resonance Structures?
 Multiple Lewis Structures for single molecule
 No single Lewis structure is correct
 Structure not accurately represented by any 1 Lewis
Structure
 Actual structure = "average" of all possible structures
 Double headed arrow between resonance structures
used to denote resonance
 1  1 
O O O
+1
+1
N N+1 N
O O O O O O
1
1 1 1
Resonance Structures
 Lewis structures assume e is localized
between 2 atoms
 In cases where need resonance structures,
e are delocalized
 Smeared out over all atoms
 Can move around entire molecule to give
equivalent bond distances

Resonance Hybrid O
 Way to depict
N
resonance delocalization
O O
Ex. CO32 O

C = 2.5 O = 3.5 C
1 N = 1  5e = 5 e O O
3 O = 3  6e = 18 e 
O
1 charge = 1 e
Total = 24 e C
single bonds  6 e O O
18 e
O 
O lone pairs 18 e
0 e C
C only has 6 e so form O O
double bond
Three Equivalent Resonance
Structures
1
O  O
1
 O 
C C C
O O O O O 1 O
1 1 1
 All have same net formal charges on C and O’s
 FC = 1 on singly bonded O’s
 FC = O on doubly bond O and C

Resonance Structures Not Always
Equivalent
 2 or more Lewis Structures for same compound
may or may not represent e distributions of equal
energy
How Do We Determine Which are Good
Contributors?
1. All Octets are satisfied
2. All atoms have as many bonds as possible
3a. FC  1
3b. Any negative charges are on electronegative
atoms.
4. As little charge separation as possible.
Drawing Good Resonance Structures
1. All must be valid Lewis Structures
2. Only e are shifted
 Usually double or triple bond and lone pair
 Nuclei can't be moved
 Bond angles must remain the same
3. Number of unpaired electrons, if any, must remain
the same
4. Major contributors are the ones with lowest E (see
above)
5. Resonance stabilization is most important when
serves to delocalize charge onto 2 or more atoms

N = 3 C = 2.5 O = 3.5 N C O
1 C = 1  4e = 4 e 
1 N = 1  5e = 5 e
N C O
1 O = 1  6e = 6 e 
1 charge = 1 e N C O
Total = 16 e
single bonds  4 e 
N C O
12 e
O lone pairs 12 e
0 e 
N C O
1
FCN = 5 – 2 – 3 = 0 
FCC = 4 – 0 – 4 = 0 N C O
FCO = 6 – 6 – 1 = –1 Best
1
FCN = 5 – 4 – 2 = –1
FCC = 4 – 0 – 4 = 0 
N C O
FCO = 6 – 4 – 2 = 0 OK
FCN = 5 – 6 – 1 = –2 2 +1
FCC = 4 – 0 – 4 = 0 
Not
FCO = 6 – 2 – 3 = N C O Accept-
+1 able
Resonance Stabilization
 Actual structure is more stable than either

single resonance structure
 For Benzene
 The extra stability is ~146 kJ/mol
 Resonance Energy
 Extra stabilization energy from resonance
Which of the structures below exhibit
resonance?
A. NO2
B. H2O
C. N3-
D. N2O (nitrogen is central atom)
E. CH3CH2CH

Coordinate Covalent Bonds
Ammonia
 Normal covalent bonds
 One electron from each atom shared
between the two
H
3H + N N
H H

Ammonium Ion
 H+ has no electrons
 N has lone pair
 Can still get 2es shared between them
H H +
N + H+ H N H
H H
H
 Both electrons of shared pair come from just
one of two atoms
 Once bond formed, acts like any other
covalent bond
 Can't tell where electrons came from after
bond is formed
 Useful in understanding chemical reactions

 Especially boron (electron deficient
molecule) reacts with nitrogen compounds
that contain lone pair of electrons
H Cl H Cl
N + B H N B Cl
H H Cl Cl
H Cl

Ex. What is the best Lewis Structure for
HClO4?
XeF4
I3–
BrF5

Chapter 9: The Basics of Chemical Bonding

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Chapter 9: The Basics of Chemical Bonding

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Chapter 9: The Basics

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Metal - nonmetal bonds are ionic because:

Ionic chemical formulas:

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

A. [Xe] 6s1 , [Xe]

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Filled and half-filled orbitals are particularly

Rewrite config’n: [Xe]4f14 5d10 6s2 6p3

Consider Fe, whose configuration is: [Ar]4s2 3d6

Rewrite config’n: [Ar]3d6 4s2

O: [He]2s22p4 + ? 2e– → ? O2– : [He]2s2 2p6

N: [He]2s22p3 + ? 3e– → ? N3– : [He]2s2 2p6

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Form individual separate molecules

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Final internuclear distance between 2 atoms in bond

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 e–’s come together in molecular bond

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 2 quantities characterize this bond

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Many molecules share more than one pair

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Molecules may contain more than 1

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 CO (C)~2.5 (O)~3.5  = 3.5 – 2.5 = 1

 CH (C)~2.5 (H)~2  = 2.5 – 2 = 0.5

 LiF (Li)~1 (F)~4  = 4 – 1 = 3

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

 Elements in different regions of Periodic

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

Jespersen/Brady/Hyslop Chemistry: The Molecular Nature of Matter, 6E

1. Decide how atoms are bonded