Chapter 1

Structure Determines Properties

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1.1. Atomic Number and Mass Number

A
Z

12
6

16
8

Atomic number (Z) = number of protons in nucleus.

(this must also equal the number of electrons
in neutral atom)
Mass number (A) = sum of number of protons
+ neutrons in nucleus.
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Schrdinger Equation
Schrdinger combined the idea that an electron has
wave properties with classical equations of wave
motion to give a wave equation for the energy of an
electron in an atom.
Wave equation (Schrdinger equation) gives a
series of solutions called wave functions ().

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Wave Functions
Only certain values of are allowed.
Each corresponds to a certain energy.
The probability of finding an electron at a particular
point with respect to the nucleus is given by 2.
Heisenberg uncertainty principle: we can not tell
where an electron is; however, we can predict where it is
most likely to be.
Each energy state corresponds to an orbital.

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Boundary Surface
A boundary surface encloses the region
where the probability of finding an electron
is highon the order of 90-95%

Figure 1.2. Boundary surfaces of a 1s orbital and a 2s orbital.

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Quantum Numbers
Each orbital is characterized by a unique set of
quantum numbers.
The principal quantum number n is a whole number
(integer) that specifies the shell and is related to the
energy of the orbital.
The angular momentum quantum number l is usually
designated by a letter (s, p, d, f, etc) and describes the
shape of the orbital.

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Quantum Numbers
Each orbital is characterized by a unique
set of quantum numbers.
The magnetic quantum number ml describes the
orientation of the orbital in space.
The electron spin quantum number ms has a value
of +1/2 or -1/2.

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s Orbitals
s Orbitals are spherically symmetric.
The energy of an s orbital increases with the
number of nodal surfaces it has.
A nodal surface is a region where the probability of
finding an electron is zero.
A 1s orbital has no nodes; a 2s orbital has one;
a 3s orbital has two, etc.

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The Pauli Exclusion Principle

No two electrons in the same atom can have the
same set of four quantum numbers.
Two electrons can occupy the same orbital only
when they have opposite spins.
There is a maximum of two electrons per orbital.
Z

1s

2s

2p

C 6

Hunds rule: es fill orbital of equal energy first.

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node

z
x
px

s
Spherical

py

pz

Dumbbell- shaped along X, Y, Z axis

s: 1 orbital, 2 electrons
p: 3 orbitals, 6 electrons
d: 5 orbitals, 10 electrons
f: 7 orbitals, 14 electrons
Valence e-s

Li: 1s22s1

O: 1s22s22p4

11

Na: 1s22s22p63s1

n indicates the row the element is in.

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 Octet rule: Nobel or rare gases (helium, neon, and

argon) have 8 electrons in their valence shell.
Ionization energy is the energy required to remove
an e- from an atom.
Electron affinity is the energy change upon the
addition of an e- to an atom.
Energy absorbing reactions are called endothermic.
Energy releasing reactions are called exothermic.

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1.2. Ionic Bonding

An ionic bond is the force of electrostatic attraction
between oppositely charged ions.

Na+ (cation)
Cl (anion)

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Ionic Bonds
Ionic bond is a bond between atoms of opposite charges;
these atoms are called ions.
+ve ions are called cations; -ve ions are called anions.
Atoms lose/gain electrons to become ions that have the
same configuration as the nearest noble gas.
Na (g)

Na+

1s22s22p63s1
Sodium atom

1s22s22p6
Sodium ion

Cl (g)

e-

Cl-

e-

1s22s22p63s23p5

1s22s22p63s23p6

Chlorine atom

Chloride ion

Na+Cl-

Na (g) + Cl (g)

Ionic: electrostatic/coulombic
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1.3. Covalent Bonds

Gilbert Newton Lewis suggested Covalent Bonds- shared
e- pair.
H2

H
Hydrogen atom

.H
Hydrogen atom

H:H
Hydrogen molecule
Covalent bond
Lewis structures: e-s represented as dots
Bond dissociation energy: energy required to dissociate 2 Hs (435 kJ/mol)

F2

F F

Each fluorine has 8 e-s in its valence shell. What rule?

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Methane has 1 C and 4 Hs

H
H:C:H

: :

.
. C. .

+ 4 H

H
H
H

CH4

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1.4. Double Bonds and Triple Bonds

:

Ethylene

C::C

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H:C:::C:H

Acetylene

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1.5. Polar Covalent Bonds and Electronegativity

In a bond between two atoms, when one atom has larger
tendency to attract e-s, the e- distribution is polarized. Polar
Covalent Bond.

+HFDirect. of polar.

Electronegativity is the tendency of an atom to attract e-s to

itself.
- Electronegative E- and electropositive E+ atoms.
E- increases across a row from left to right and decreases in
going down a column.
Fluorine has the highest E- value 4.0 (Linus Pauling Scale).
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Pauling Electronegativity Scale

Li

Be

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Na

Mg

Al

Si

Cl

0.9

1.2

1.5

1.8

2.1

2.5

3.0

Electronegativity increases from left to right in the

periodic table.
Electronegativity decreases going down a group.
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Generalization

The

greater

the

difference

in

electronegativity

between two bonded atoms; the more polar the bond.

..
: ..
F

HH

..
F:
..

:N

N:

Nonpolar bonds connect atoms of the same electronegativity.

..
F:
..

..

O H
..

:O C
..

:
O
..

Polar bonds connect atoms of different electronegativity.

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Electrostatic Potential Maps (EPM)

Electrostatic potential maps show the charge
distribution within a molecule.

..
F:
..

Solid
surface

Transparent
surface
Red is negative charge;
blue is positive.

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Dipole Moment ()
=exd
Charge on an electron 4.80 x 10-10 esu
Distances fall into 10-8 cm
debye, D = 10-18 esu cm

H-F = 1.710-18 esu.cm = 1.7 D

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1.6. Formal Charges

e- count (H)= (2) =1

e- count (O)= (4) + 4 =6

O:
+
H
N O :O :

e- count (N)= (8) =4

: :

e- count (O)= (4) + 4 =6

Formal charge = valence e-s

e- count (O)= (2) +6 =7

e- count

or
Formal charge = group # in
periodic table

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# of bonds

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# of unshared e-s
22

Constitutional Isomers
Isomers are different compounds that have the same
molecular formula.
Constitutional or structural isomers differ in the way their
atoms are bonded.

: :

Constitutional
isomers of CH3NO2

H
H C O N O
H

:
:
: :

H O
H C N+ _
H O
Nitromethane

Methyl nitrite

Constitutional
isomers of C3H6
1-Propene
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Cyclopropane
23

1.8. Resonance
Ozone:
O3

1.47
X

1 pm = 10-12 m
1 = 10-10 m

+
O

1.21
X

: :

:O

Both bonds were equal in length: 1.28

More than Lewis structure

:O

_:

: :

:O

+
O

+
O

Hybrid structure

+
O

: :

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-1/2

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Lewis structures: localized.

Resonance Structures: delocalized.

O -1/2
24

Table 1.6. Rules of Resonance

The positions of atoms stay the same, only the e-s positions are different.
+O
H3C N _
H3C O N O
O
nitromethane
methyl nitrite
Second row elements can not have more than 8 valence e-s (unstable).
O
H3C N
O
The more stable resonance structure is the one that has the smallest # of
_
opposite charges.
+
H3C O N O
H3C O N O

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: :

When one atom bears a formal charge, the most stable resonance
structure is the one where the charge resides on the more E- atom.
_
_
N C O
N C O
25

Table 1.6. Rules of Resonance (contd)

_

O
H3C N _
O

: :

: :

: :

O
H3C N + _
O

The resonance structures must have the same net charge.

The resonance structures must have the same # of unpaired e-s.

.O

: :

H3C N
.O

O
H3C N + _
O

e- delocalization stabilizes a molecule. The degree of stabilization

is greatest when resonance structures are of equal stability.
O
H3C N + _
O
H3C O N O
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O
H3C N +
O

_
+
H3C O N O
26

1.10. The Shapes of Some Simple

Molecules
Valence Shell Electron Pair
Repulsions (VSEPR)
The most stable arrangement of groups
attached to a central atom is the one that has the
maximum separation of electron pairs (bonded or
nonbonded).

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Table 1.7. Methane

Tetrahedral geometry
HCH angle = 109.5

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Table 1.7. Water

Bent geometry
HOH angle = 105

H
H
O

..
But notice the tetrahedral arrangement
of electron pairs.
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Table 1.7. Ammonia

Trigonal pyramidal geometry
HNH angle = 107

H
H

H
But notice the tetrahedral arrangement
of electron pairs.
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Table 1.7. Boron Trifluoride

FBF angle = 120
Trigonal planar geometry
allows for maximum separation
of three electron pairs.

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Multiple Bonds
Four-electron double bonds and six-electron
triple bonds are considered to be similar to a twoelectron single bond in terms of their spatial
requirements.

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Table 1.7. Formaldehyde

HCH and HCO
angles are close to 120
trigonal planar geometry

H
C

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Table 1.7. Carbon Dioxide

OCO angle = 180
linear geometry

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1.11. Molecular Dipole Moments

Molecular dipole moment is the result of all the
individual bond dipole moments of a substance.
O

Cl

=0D

Cl

Cl
Cl

=0D

C
Cl

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Cl

= 1.62 D

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1.13. Acids & Bases

Definitions
Arrhenius
An acid ionizes in water to give protons. A base
ionizes in water to give hydroxide ions.
Brnsted-Lowry
An acid is a proton donor. A base is a proton
acceptor.
Lewis
An acid is an electron pair acceptor. A base is
an electron pair donor.
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Arrhenius Acids and Bases

An acid is a substance that ionizes to give protons
when dissolved in water.

.. A
+
+
H

A base is a substance that ionizes to give hydroxide

ions when dissolved in water.

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..
OH
..

. ..
M+ + . OH
..
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Arrhenius Acids and Bases

Strong acids dissociate completely in water.
Weak acids dissociate only partially.

.
H + + . A

Strong bases dissociate completely in water.

Weak bases dissociate only partially.

M
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..
OH
..

. ..
M+ + . OH
..
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Acid Strength is Measured by pKa

H

Ka =

.
H + + . A
[H+][A]
[HA]

pKa = log10Ka

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1.14. Acids and Bases:

The Brnsted-Lowry View
Brnsted-Lowry definition:
An acid is a proton donor
A base is a proton acceptor

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A Brnsted Acid-Base Reaction

A proton is transferred from the acid to the
base.
+
B

B .. + H A
base

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acid

.
.
H + A

conjugate
acid

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conjugate
base

41

Proton Transfer from HBr to Water

H
.. O+

H
..
.. O .. + H Br ..
..
H

base

acid

..
..
H + .. Br
..

conjugate conjugate
acid
base
H3O+: hydronium ion

With Brnsted-Lowry View : Acid does not dissociate

in H2O: it transfers a proton to water. Therefore, water
acts as a base.
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Water as a Brnsted Acid

H
.. N

H
..

.. N ..
+ H OH
..
H

base

Chem 207

acid

..
H + .. OH
..

conjugate conjugate
acid
base

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Dissociation Constants (pKa) of Acids

Stronger
acid

Acid
HI

-10.4

Conj. base

-5.8

Br

H2SO4

-4.8

HSO4

HCl

-3.9

Cl

-1.7

H2O

HBr

Weaker
acid

pKa

H3O

Strong acids are stronger than hydronium ion.

The stronger the acid, the weaker the conjugate base.
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Dissociation Constants (pKa) of Acids

Acid
+

H3O
HF

CH3CO2H
NH4

H2O

pKa
1.7

Conj. base
H2O

3.5

4.6

CH3CO2

9.2

NH3

15.7

HO

Weak acids are weaker than hydronium ion.

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Dissociation Constants (pKa) of Acids

Acid

pKa

Conj. base

CH3OH

15.2

CH3O

H2O

15.7

HO

CH3CH2OH
(CH3)2CHOH
(CH3)3COH

~16

CH3CH2O

~17

(CH3)2CHO

~18

(CH3)3CO

Alcohols resemble water in acidity; their conjugate

bases are comparable to hydroxide ion in basicity.
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Dissociation Constants (pKa) of Acids

Acid
NH3
(CH3)2NH

pKa
~36
~36

Conj. base

NH2

(CH3)2N

Ammonia and amines are very weak acids;

their conjugate bases are very strong bases.

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Dissociation Constants (pKa) of Acids

pKa

Acid
HC
H

CH
H

26

H2C

43

H
CH2

CH3CH3

HC

H
H

Conj. base
H

H
45
62

H2C

CH

CH3CH2

Most hydrocarbons are extremely weak acids.

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1.15. What Happened to pKb?

A separate basicity constant Kb is not necessary.
Because of the conjugate relationships in the
Brnsted-Lowry approach, we can examine acidbase reactions by relying exclusively on pKa values.

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Example

H
H
N
H

Which is the stronger base, ammonia (left) or

pyridine (right)?
Recall that the stronger the acid, the weaker the
conjugate base. Therefore, the stronger base is the
conjugate of the weaker acid.
Look up the pKa values of the conjugate acids of
ammonia and pyridine in Table 1.8.
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Example
H
H N H
H

N
H

Chem 207

pKa = 9.3

weaker acid

pKa = 5.2

stronger acid

Therefore, ammonia is a
stronger base than pyridine.
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1.16. How Structure Affects Acid Strength

The strength of the bond to the atom from which
the proton is lost.
The electronegativity of the atom from which the
proton is lost.
Changes in electron delocalization on ionization.

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Bond Strength
Bond strength is controlling factor when comparing
acidity of hydrogen halides.

pKa

HF
3.1

HCl
-3.9

weakest acid

HI
-10.4

strongest acid

strongest HX bond
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HBr
-5.8

weakest HX bond
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Bond Strength
Recall that bond strength decreases in a group in
going down the periodic table.
Generalization:

Bond strength is most important

factor when considering acidity of protons bonded to

atoms in same group of periodic table (as in HF, HCl,
HBr, and HI).
Another example: H2S (pKa = 7.0) is a stronger acid
than H2O (pKa = 15.7).

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Electronegativity
Electronegativity is controlling factor when
comparing acidity of protons bonded to atoms in
the same row of the periodic table.

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Electronegativity

pKa

CH4

NH3

H2O

HF

60

36

15.7

3.1

weakest acid

strongest acid

least electronegative

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most electronegative

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Electronegativity
R
.. O .. + H A

..O+ H

.
.
+ A

The equilibrium becomes more favorable as A

becomes better able to bear a negative charge.
Another way of looking at it is that H becomes more
positive as the atom to which it is attached becomes
more electronegative.
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Bond Strength Versus Electronegativity

Bond strength is more important when comparing
acids in which the proton that is lost is bonded to
atoms in the same group of the periodic table.
Electronegativity is more important when comparing
acids in which the proton that is lost is bonded to
atoms in the same row of the periodic table.

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Acidity of Alcohols
In many acids the
acidic proton is
bonded to
oxygen.

Alcohols (ROH)
resemble water
(HOH) in their
acidity.

Chem 207

pKa
HOH

15.7

CH3OH

15.2

CH3CH2OH

16

(CH3)2CHOH

17

(CH3)3COH

18

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Acidity of Alcohols
Electronegative substituents can increase the acidity
of alcohols by drawing electrons away from the OH
group.

pKa
Chem 207

CH3CH2OH

CF3CH2OH

16
weaker

11.3
stronger
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Inductive Effect
F
F

The greater acidity of CF3CH2OH compared to

CH3CH2OH is an example of an inductive effect.
Inductive effects arise by polarization of the
electron distribution in the bonds between atoms.
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Electrostatic Potential Maps

The greater positive character of the proton of the
OH group of CF3CH2OH compared to CH3CH2OH is
apparent in the more blue color in its electrostatic
potential map.

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CH3CH2OH

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CF3CH2OH

62

Another example of the inductive effect

CH3C O H
pKa

Chem 207

4.7
weaker

CF3C

O H

0.50
stronger

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Electron Delocalization
R
.. O .. + H A

R
.. +

.
.
H
+ A
O

Ionization becomes more favorable if electron

delocalization increases in going from left to right in
the equation.
Resonance is a convenient way to show electron
delocalization.
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Nitric Acid

O
O + H

N+

H
pKa = -1.4

H
O+ H +

O
N+

O

Nitrate ion is stabilized

by electron delocalization.
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Nitric Acid
Nitrate ion is stabilized by
electron delocalization.

N+

Negative charge is shared

equally by all three oxygens.

O
O

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N+

O

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O
N+

O

66

Acetic Acid

O
O + H

H
pKa = 4.7

CH3

H
O+ H +

H
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O
C
CH3
67

Acetic Acid
Acetate ion is stabilized by electron delocalization.
Negative charge is shared equally by both oxygens.

O
O

CH3

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O
C
CH3

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1.17. Acid-Base Equilibria

Generalization
The equilibrium in an acid-base reaction is favorable
if the stronger acid is on the left and the weaker acid is
on the right.
Stronger acid + Stronger base

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Weaker acid + Weaker base

69

Example of a strong acid

H
..
.. O .. + H Br ..
..
H

H
.. .
.. O+ H + .. Br
.. .
H

pKa = -5.8
stronger acid

pKa = -1.7
weaker acid

The equilibrium lies to the side of the weaker acid

(to the right).
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Example of a weak acid

O + HOCCH
3

H
pKa = 4.7
weaker acid

+
OH + OCCH

H
pKa = -1.7
stronger acid

The equilibrium lies to the side of the weaker acid

(to the left).
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1.18. Lewis Acids and Lewis Bases

Definitions
Arrhenius
- An acid ionizes in water to give protons. A base
ionizes in water to give hydroxide ions.
Brnsted-Lowry
- An acid is a proton donor. A base is a proton
acceptor.
Lewis
- An acid is an electron pair acceptor. A base is an
electron pair donor.
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Lewis Acid-Lewis Base Reactions

The Lewis acid and the Lewis base can be either
a neutral molecule or an ion.
Lewis acid

Chem 207

+ Lewis base

A+

AB

AB

A+

AB +

AB +

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Example: Two Neutral Molecules

CH2CH3
F3B

CH2CH3
Boron trifluoride

Lewis acid

F3B

CH2CH3

+
O

CH2CH3

Lewis base

Product is a stable substance. It is a liquid with a boiling

point of 126 C. Of the two reactants, BF3 is a gas and
CH3CH2OCH2CH3 is a liquid with a boiling point of 34 C.
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