Chapter 1

Electronic
Structure
and
Bonding

Acids and Bases

Updated on 1/4/08
1
Orbital = 3D region around a nucleus in which there is a high
probability of finding an electron  shapes = s, p, d, f.

Electronic configuration of C atom…

Mass #
12 6 electrons total
2 2 2
6C
[1s 2s 2p ] 4 valence e's ->
involved in bonding
Atomic #

Atomic orbital energy diagram for C…

4 valence
2p electrons;
outer valence
E 2s shell

not involved
1s inner shell in chemical
properties

2
The Energies involved:
Electron (orbital) Potential Energy:

3d 4p
4s
ENERGY LEVEL

3p
3s

2p
2s

1s
Bond Angles

109.5
o 120
o

90o
180o
Types of chemical bonds and theories…

Octet rule = Atoms will gain, lose or share electrons to achieve

the electronic configuration of a group 8 element
(8 electrons in the outer shell = closed shell)

(1) Ionic Bonds: compounds have high m.p.'s, high H2O solubility

Na + Cl Na Cl

23 -1 e
Na (1s22s22p63s1) Na (1s22s22p6)
11
core
Ne
closed shell
electronic
valence shell configurations

Ar
35
Cl (1s22s22p63s23p5) +1 e
Cl (1s22s22p63s23p6)
17
core

Na  low ionization potential

Cl  high electron affinity
5
 H Lewis
4 H + C H C H electron dot
structure
H
Line represents an electron pair

H
Kekule or
H C H line bond structure
H
lone pair
or
nonbonding
H N H electrons

H
3 H + N _ another
H N H representation

H
6
 H 1s F 2p H-F
orbital orbital  bond
. + . . .

=
+ simple
picture
H H 0.74 Å  H-H appropriate
(1s) (1s)  bond for
VB theory
H atoms H2 molecule
H = -436 kJ/mol = -105 kcal/mol

7
 436 kJ/mol =

minimum E

8
(4) Molecular orbital atomic orbitals (AO’s) combine to form
theory: new molecular orbitals (MO’s)

nodal plane -
2 AO’s  H H
2 new MO’s (1s) (1s)

antibonding MO’s
are usually unfilled

(* orbital)

436
kJ/mol;
105
kcal/mol  bond

+
H H
(1s) (1s) 9
Formation of p MO’s from p-orbital overlap…

+ +
(p*)

- -

10
Hybridization…
CH4 is perfectly tetrahedral…

How can the structure of methane be explained based on bonds

formed from the one 2s and three 3p orbitals on C?

H
1.10 Å
109.5o (110 pm)
C
H H
H

1934, L. Pauling showed how s and p orbitals can be mathematically

combined to yield equivalent orbitals which form better bonds than
the original 2s and 2p AO‘s  better = stronger = lower energy = more stable

“New orbitals” -> hybrid orbitals

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 1s 2s 2px 2py 2pz sp3 sp3 sp3
Promotey sp3
Hybridize

109.5
o
z

Methane: Carbon
 Mix one s + three p’s -> 4 sp3 hybrid orbitals…
energy

+
C
-

- +

14
CH2O

120o
 1s 2s 2px 2py 2pz sp2 sp2
Promoted Hybridize
sp2
d

120o

Trigon
120o
al
Planar
2s + 2px +
Formaldehyde: 2p
Carbon z
 1s 2s 2px 2py 2pz sp2 sp2
Hybridize
sp2
Lone d
Pairs

120o

Trigon
120o
al
Planar
2s + 2px +
Formaldehyde: 2p
Oxygen z
 Formaldehy
de

2
p bond Sigma bond
Lone
Pairs
Mix one 2s + two 2p orbitals  three sp2 hybrid orbitals;
one 2p orbital “left over”  one p-bond…

133 pm

can form
p-bonds

19
Mix one 2s + one 2p orbitals  two sp hybrid orbitals;
two 2p orbitals “left over”  two p-bonds
energy

120 pm

20
 1s 2s 2px 2py 2pz sp
Promoted Hybridize
sp
d

Linear

2s + 2px

Hydrogen Cyanide:
Carbon
 1s 2s 2px 2py 2pz sp
Hybridize
sp
d

Linear

2s + 2px

Hydrogen Cyanide:
Nitrogen
p bond

p
bond
Hybrid orbitals used by atoms such as B, C, N, O, P, S
are described in the following table.

H H H
C C C H C C H
H H H H
H

# s 1 1 1
# orbitals
hybridized
# p 3 2 1
# hybrid
orbitals
4 sp3 3 sp2 2 sp

# of -bonds 4 3 2
# of p’s left 0 1 2
# of p-bonds 0 1 2
tetrahedral trigonal linear
shape ( 109.5º) planar ( 180º)
( 120º)

For example..in CH4 all four C-H bonds are identical…formed with
four equivalent sp3 hybrid orbitals of carbon.
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 Water: H2O Carbon dioxide:
Ammonia: NH3 CO2

Formaldehyde: Boron trifluoride:

H2CO BF3

Carbocation: CH3+
Carbanion: CH3:- Hydrogen Cyanide:
Radical: CH3. HCN

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 Hybridizations, bond lengths and energies

Bond Bond length Bond strength,

hydrid- (Å) E (kJ/mol)
ization
C-H C-C C-H C-C p
H
sp3 1.10 438
C H
longest & H H
weakest H H
H
C C sp3 1.10 1.54 420 376
H
H H
H H
C C sp2 1.076 1.33 444 611 235
H H
shortest &
strongest H C C H sp 1.06 1.20 552 835 224

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Electronegativity () differences ->
polar covalent bonds = bond dipole

= measure of
 = 2.5   3.0 ability of an
H  atom to attract
HH N e’s
C C H H
H Cs:  = 0.7
H HH  F:  = 4.0
  2.1
  2.1

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-
+
Cl Li

CH3 CH3
+ - 29
Polar bond has a dipole  molecules can have dipole moments ()
 = product of partial charges * separation distance

 = q * d  ’s can be measured experimentally

If q = +/- 1 e and d = 1 Å   = 4.8 D conversion factor…

4.8 D
=1
1e * 1Å
For H-Cl…
1.36 Å
4.8 D
 = 0.16 e * 1.36 Å * = 1.04 D H Cl
e*Å  = +0.16e -0.16e
q d

Does water have a dipole moment??

Structure of a molecule with  = 0 D??

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Lewis e-dot structures  information about shape/hybridization…
E-dot structure may need formal charges to be complete

F. C. = charge on an atom assuming equal sharing of bonding e’s

F. C. = # valence e’s – ½ bonding e’s – nonbonding e’s

e’s “formally owned”

Nitric acid Lewis e-dot structure and FC example…

:
:

O: FC = 6-2-4 = 0 O:

: :
: :

O N FC = 5-4-0 = +1 O N

H :O: FC = 6-1-6 = -1 H :O:

:
:

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Resonance structures (delocalized e’s)…
Possible structures for a molecule for which 2 or more
e-dot structures can be written.

Rules..
(1) atoms never move & hybridization does not change
(2) just move p e’s
:

:
O: :O:
H3C N H3C N
:O: O:
:

:
What does nitromethane really look like? 

a 50:50 average (resonance hydrid) of the above two structures.

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 -0.5
O
+1
H3C N 1.5 bonds

O -0.5

33
Acids and bases
•Boyle (17th century)…
*Acids taste sour, corrosive to metals, change litmus (a dye extracted from
lichens) red, become less acidic when mixed with bases. Eg, vinegar.
*Bases feel slippery, change litmus blue, become less basic when mixed
with acids. Eg, alkali, ashes.
•Arrhenius (late 1800’s)…
H2SO4
*Acids dissolve in water to produce H+
*Bases produce OH- NaOH
•Bronsted-Lowry (1923)…
*Acid = H+ donor; base = H+ acceptor

H
+
NH3 + H-Cl N + Cl-
H H
H
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 Conjugate acid – H+  conj base
Conjugate base + H+  conj acid

conjugate - H+
conjugate
acid 2 base 2

NH3 + H2O NH4+ + HO-

conjugate conjugate
base 1 +H acid 1

O
formic O
acid C H + OH- + O
H O C H H
H O-

Write e-dot structures for conjugate acid and base of CH3NO2.

And possible structures for the conj acid of formic acid

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In water, acid strength is expressed by Keq or Ka or pKa …

Keq
H2O + HA H3O+ + A- Keq = equilibrium
constant
Keq = [H3O+][A-] / [H2O][HA]

[H3O+][A-] [H2O] is essentially

Ka = Keq [H2O] = constant
[HA]
pKa = -log(Ka)

O
Ka = 1.74 * 10-5
H3C C pKa = 4.76
OH
acetic acid - vinegar

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Equilibrium favors the side with the weaker acid…
Keq
HCO2H + OH - HCO2- + H2O
pKa = 3.75 pKa = 15.74

pKeq = 3.75 – 15.74 = -11.99

pKeq = -log(Keq)
Keq ~ 1012

Question: Is this a good way to make HC2-?

H C C H OH- H C C- H2O

Of the 2 acids…which is stronger?

Take-home question: Calculate Keq for this reaction.

What other info do you need?
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Organic acids and delocalized e’s…
Acid strength is determined primarily by stability of the conjugate base

species with
- charge

Which conjugate base

is more stable…
has lower energy?

38
Stability of the conjugate base is influenced by e-withdrawing substiutuents…

: H = 2.1 Br = 2.5 Cl = 3.0 F = 4.0

39
Effect of C hybridization on C-H acidity…

40
 Some acids & pKa’s…

H-I
-10
O-
H2SO4 HO S++ OH -4.8
O-
O
H3C C 4.76
OH

H2O 15.7 CH3-CH2-OH 16 NO2

OH 9.9 O2N OH 0.6

NO2
H3C CH3 H2C CH2 HC CH
~60 44 25

NH3 35

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 pH and structure…

When pH = pKa…
[HA] = [A-]

•pH < pKa of the acid, the compound will exist primarily in its acidic form
•pH > pKa of the acid, the compound will exist primarily in its basic form

O
 pH = 4.0, soln more acidic
pKa = 4.76 H3C C
OH
O
 pH = 6.0, soln more basic
H3 C C
O-
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Lewis acid/base definitions…
Lewis acid = e-pair acceptor
Lewis base = e-pair donor

Lewis acid examples…

H-Cl, CH3CO2H, CH3OH, Mg++, AlCl3, BF3, ZnCl2

Lewis base = anything with an unshared e-pair,

usually O, S, N, P

NH3 BF3 H3N BF3

43
 NH3 BF3 H3N BF3

What are the hybridizations of the N and B-containing species…shapes??

44
Question: identify the Lewis acids and bases…

AlCl3
O O
C + AlCl3 C
H H H H

45
Drawing chemical structures…

OH
H H H H
CH3CHCH2CH3 OH
H C C C C H
H O H H CH3CH(OH)CH2CH3
H
Kekule or condensed skeletal
line bond

O C
C C
Yuk!
C C
C

Question: What is the molecular formula for amantadine?

antiviral drug approved in

NH2 1976 for treatment of influenza A

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