Atoms, Molecules and Ions

Dalton’s Atomic Theory (1808)

1. Elements are composed of extremely small particles
called atoms.
2. All atoms of a given element are identical, having the
same size, mass and chemical properties. The atoms of
one element are different from the atoms of all other
elements.
3. Compounds are composed of atoms of more than one
element. In any compound, the ratio of the numbers of
atoms of any two of the elements present is either an
integer or a simple fraction.
4. A chemical reaction involves only the separation,
combination, or rearrangement of atoms; it does not
result in their creation or destruction. 2
Dalton’s Atomic Theory

Law of Multiple Proportions

3
16 X + 8Y 8 X2Y

Law of Conservation of Mass

4
Cathode Ray Tube

J.J. Thomson, measured mass/charge of e-

(1906 Nobel Prize in Physics) 5
Cathode Ray Tube

6
 Millikan’s Experiment

Measured mass of e-
(1923 Nobel Prize in Physics)

e- charge = -1.60 x 10-19 C

Thomson’s charge/mass of e- = -1.76 x 108 C/g
e- mass = 9.10 x 10-28 g 7
Types of Radioactivity

(uranium compound)
8
Thomson’s Model

9
 Rutherford’s Experiment
(1908 Nobel Prize in Chemistry)

 particle velocity ~ 1.4 x 107 m/s

(~5% speed of light)

1. atoms positive charge is concentrated in the nucleus

2. proton (p) has opposite (+) charge of electron (-)
3. mass of p is 1840 x mass of e- (1.67 x 10-24 g) 10
 Rutherford’s Model of
the Atom

atomic radius ~ 100 pm = 1 x 10-10 m

nuclear radius ~ 5 x 10-3 pm = 5 x 10-15 m

“If the atom is the Houston Astrodome,

then the nucleus is a marble on the 50-
yard line.”
11
 Chadwick’s Experiment (1932)
(1935 Noble Prize in Physics)

H atoms - 1 p; He atoms - 2 p
mass He/mass H should = 2
measured mass He/mass H = 4

 + 9Be 1
n + 12C + energy

neutron (n) is neutral (charge = 0)

n mass ~ p mass = 1.67 x 10-24 g
12
mass p ≈ mass n ≈ 1840 x mass e-

13
 Atomic number, Mass number and Isotopes
Atomic number (Z) = number of protons in nucleus
Mass number (A) = number of protons + number of neutrons
= atomic number (Z) + number of neutrons
Isotopes are atoms of the same element (X) with different
numbers of neutrons in their nuclei

Mass Number A
ZX
Element Symbol
Atomic Number

1 2 3
1H 1H (D) 1H (T)
235 238
92 U 92 U 14
The Isotopes of Hydrogen

15
Quantum Theory and the Electronic
Structure of Atoms

16
 Properties of Waves

Wavelength () is the distance between identical points on

successive waves.
Amplitude is the vertical distance from the midline of a
wave to the peak or trough.
Frequency () is the number of waves that pass through a
particular point in 1 second (Hz = 1 cycle/s).
The speed (u) of the wave =  x  17
Maxwell (1873), proposed that visible light consists of
electromagnetic waves.

Electromagnetic
radiation is the emission
and transmission of energy
in the form of
electromagnetic waves.

Speed of light (c) in vacuum = 3.00 x 108 m/s

All electromagnetic radiation

 x c 18
19
A photon has a frequency of 6.0 x 104 Hz. Convert this
frequency into wavelength (nm). Does this frequency fall in
the visible region?


x=c
 = c/ 
 = 3.00 x 108 m/s / 6.0 x 104 Hz
 = 5.0 x 103 m
 = 5.0 x 1012 nm

20
Mystery #1, “Heated Solids Problem”
Solved by Planck in 1900
When solids are heated, they emit electromagnetic radiation
over a wide range of wavelengths.

Radiant energy emitted by an object at a certain temperature

depends on its wavelength.

Energy (light) is emitted or

absorbed in discrete units
(quantum).

E=hx
Planck’s constant (h)
h = 6.63 x 10-34 J•s 21
Mystery #2, “Photoelectric Effect”
Solved by Einstein in 1905 h

Light has both:

KE e-
1. wave nature
2. particle nature
Photon is a “particle” of light

h = KE + W
KE = h - W

where W is the work function and

depends how strongly electrons
are held in the metal 22
When copper is bombarded with high-energy electrons, X rays
are emitted. Calculate the energy (in joules) associated with
the photons if the wavelength of the X rays is 0.154 nm.

E=hx
E = h x c /
E = 6.63 x 10-34 (J•s) x 3.00 x 10 8 (m/s) / 0.154 x 10-9 (m)
E = 1.29 x 10 -15 J

23
Line Emission Spectrum of Hydrogen Atoms

24
25
 Bohr’s Model of
the Atom (1913)
1. e- can only have specific
(quantized) energy
values
2. light is emitted as e-
moves from one energy
level to a lower energy
level
1
En = -RH ( )
n2

n (principal quantum number) = 1,2,3,…

RH (Rydberg constant) = 2.18 x 10-18J
26
 E = h

E = h

27
 Ephoton = E = Ef - Ei
ni = 3 ni = 3 1
Ef = -RH ( 2 )
nf
ni = 2 1
Ei = -RH ( 2 )
nf = 2 ni
1 1
E = RH( 2 )
ni n2f

nnf f==11
28
29
Calculate the wavelength (in nm) of a photon emitted
by a hydrogen atom when its electron drops from the
n = 5 state to the n = 3 state.

1 1
Ephoton = E = RH( )
n2i n2f
Ephoton = 2.18 x 10-18 J x (1/25 - 1/9)
Ephoton = E = -1.55 x 10-19 J
Ephoton = h x c /
 = h x c / Ephoton
 = 6.63 x 10-34 (J•s) x 3.00 x 108 (m/s)/1.55 x 10-19J
 = 1280 nm
30
Why is e- energy quantized?

De Broglie (1924) reasoned

that e- is both particle and
wave.
h
2r = n  = mu

u = velocity of e-

m = mass of e-
31
What is the de Broglie wavelength (in nm) associated
with a 2.5 g Ping-Pong ball traveling at 15.6 m/s?

 = h/mu h in J•s m in kg u in (m/s)

 = 6.63 x 10-34 / (2.5 x 10-3 x 15.6)
 = 1.7 x 10-32 m = 1.7 x 10-23 nm

32
Chemistry in Action: Laser – The Splendid Light

Laser light is (1) intense, (2) monoenergetic, and (3) coherent

33
 Chemistry in Action: Electron Microscopy

e = 0.004 nm STM image of iron atoms

on copper surface
Electron micrograph of a normal
red blood cell and a sickled red
blood cell from the same person

34
 Schrodinger Wave Equation
In 1926 Schrodinger wrote an equation that
described both the particle and wave nature of the e -
Wave function () describes:
1. energy of e- with a given 
2. probability of finding e- in a volume of space
Schrodinger’s equation can only be solved exactly
for the hydrogen atom. Must approximate its
solution for multi-electron systems.

35
 Schrodinger Wave Equation
 is a function of four numbers called
quantum numbers (n, l, ml, ms)

principal quantum number n

n = 1, 2, 3, 4, ….

distance of e- from the nucleus

n=1 n=2 n=3

36
Where 90% of the
e- density is found
for the 1s orbital

37
 Schrodinger Wave Equation
quantum numbers: (n, l, ml, ms)

angular momentum quantum number l

for a given value of n, l = 0, 1, 2, 3, … n-1

l=0 s orbital
n = 1, l = 0
l=1 p orbital
n = 2, l = 0 or 1
l=2 d orbital
n = 3, l = 0, 1, or 2
l=3 f orbital
Shape of the “volume” of space that the e- occupies
38
l = 0 (s orbitals)

l = 1 (p orbitals)

39
l = 2 (d orbitals)

40
Schrodinger Wave Equation
quantum numbers: (n, l, ml, ms)

magnetic quantum number ml

for a given value of l

ml = -l, …., 0, …. +l

if l = 1 (p orbital), ml = -1, 0, or 1
if l = 2 (d orbital), ml = -2, -1, 0, 1, or 2

orientation of the orbital in space

41
ml = -1, 0, or 1 3 orientations is space

42
ml = -2, -1, 0, 1, or 2 5 orientations is space

43
 Schrodinger Wave Equation

(n, l, ml, ms)

spin quantum number ms
ms = +½ or -½

ms = +½ ms = -½

44
 Schrodinger Wave Equation
quantum numbers: (n, l, ml, ms)
Existence (and energy) of electron in atom is described
by its unique wave function .
Pauli exclusion principle - no two electrons in an atom
can have the same four quantum numbers.

Each seat is uniquely identified (E, R12, S8)

Each seat can hold only one individual at a
time
45
46
 Schrodinger Wave Equation
quantum numbers: (n, l, ml, ms)

Shell – electrons with the same value of n

Subshell – electrons with the same values of n and l

Orbital – electrons with the same values of n, l, and ml

How many electrons can an orbital hold?

If n, l, and ml are fixed, then ms = ½ or - ½

= (n, l, ml, ½) or= (n, l, ml, -½)

47
An orbital can hold 2 electrons
How many 2p orbitals are there in an atom?
n=2
If l = 1, then ml = -1, 0, or +1
2p
3 orbitals
l=1

How many electrons can be placed in the 3d subshell?

n=3 If l = 2, then ml = -2, -1, 0, +1, or +2

3d 5 orbitals which can hold a total of 10 e-

l=2 48
 Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

1
En = -RH ( )
n2

n=1

49
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l = 2

n=3 l = 1
n=3 l = 0

n=2 l = 1
n=2 l = 0

n=1 l = 0
50
“Fill up” electrons in lowest energy orbitals (Aufbau principle)

??

Be
Li
B5
C 3
64electrons
electrons
BBeLi1s1s
1s2s2s
2s2p
2 22 2 12 1

H
He12electron
electrons
He
H 1s
1s12 51
The most stable arrangement of electrons in
subshells is the one with the greatest number of
parallel spins (Hund’s rule).

F
O
C 97
N
Ne 6
810
electrons
electrons
electrons
Ne
C
N
O
F 1s 1s222s
2s2p2p3246
2 222 5

52
 Order of orbitals (filling) in multi-electron atom

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s
53
Electron configuration is how the electrons are
distributed among the various atomic orbitals in an
atom.
number of electrons
in the orbital or subshell
1s1
principal quantum angular momentum
number n quantum number l

Orbital diagram

H
1s1
54
What is the electron configuration of Mg?
Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s2 2 + 2 + 6 + 2 = 12 electrons
Abbreviated as [Ne]3s2 [Ne] 1s22s22p6

What are the possible quantum numbers for the last

(outermost) electron in Cl?
Cl 17 electrons 1s < 2s < 2p < 3s < 3p < 4s
1s22s22p63s23p5 2 + 2 + 6 + 2 + 5 = 17 electrons
Last electron added to 3p orbital
n=3 l=1 ml = -1, 0, or +1 ms = ½ or -½ 55
Outermost subshell being filled with electrons

56
57
 Paramagnetic Diamagnetic
unpaired electrons all electrons paired

2p 2p 58
Periodic Relationships Among
the Elements
When the Elements Were Discovered

60
 ns2np6
ns1 Ground State Electron Configurations of the Elements

ns2np1

ns2np2
ns2np3

ns2np4
ns2np5
ns2

d10
d1

d5

4f
5f
61
Classification of the Elements

62
 Electron Configurations of Cations and Anions
Of Representative Elements

Na [Ne]3s1 Na+ [Ne]

Atoms lose electrons so that
Ca [Ar]4s2 Ca2+ [Ar] cation has a noble-gas outer
electron configuration.
Al [Ne]3s23p1 Al3+ [Ne]

H 1s1 H- 1s2 or [He]

Atoms gain electrons
so that anion has a F 1s22s22p5 F- 1s22s22p6 or [Ne]
noble-gas outer
O 1s22s22p4 O2- 1s22s22p6 or [Ne]
electron configuration.
N 1s22s22p3 N3- 1s22s22p6 or [Ne]
63
 Cations and Anions Of Representative Elements
+1
+2

+3

-2
-3

-1
64
Isoelectronic: have the same number of electrons, and
hence the same ground-state electron configuration

Na+: [Ne] Al3+: [Ne] F-: 1s22s22p6 or [Ne]

O2-: 1s22s22p6 or [Ne] N3-: 1s22s22p6 or [Ne]

Na+, Al3+, F-, O2-, and N3- are all isoelectronic with Ne

What neutral atom is isoelectronic with H- ?

H-: 1s2 same electron configuration as He

65
Electron Configurations of Cations of Transition Metals

When a cation is formed from an atom of a transition metal,

electrons are always removed first from the ns orbital and
then from the (n – 1)d orbitals.

Fe: [Ar]4s23d6 Mn: [Ar]4s23d5

Fe2+: [Ar]4s03d6 or [Ar]3d6 Mn2+: [Ar]4s03d5 or [Ar]3d5
Fe3+: [Ar]4s03d5 or [Ar]3d5

66
Effective nuclear charge (Zeff) is the “positive charge” felt by
an electron.

Zeff = Z -  0 <  < Z ( = shielding constant)

Zeff  Z – number of inner or core electrons

Z Core Zeff Radius (pm)

Na 11 10 1 186

Mg 12 10 2 160

Al 13 10 3 143

Si 14 10 4 132 67
 Effective Nuclear Charge (Zeff)

increasing Zeff
increasing Zeff

68
 Atomic Radii

metallic radius covalent radius

69
70
Trends in Atomic Radii

71
Comparison of Atomic Radii with Ionic Radii

72
Cation is always smaller than atom from
which it is formed.
Anion is always larger than atom from
which it is formed.
73
The Radii (in pm) of Ions of Familiar Elements

74
Chemistry in Action: The 3rd Liquid Element?

117 elements, 2 are liquids at 250C – Br2 and Hg

223
Fr, t1/2 = 21 minutes

Liquid?
75
Ionization energy is the minimum energy (kJ/mol) required
to remove an electron from a gaseous atom in its ground
state.

I1 + X (g) X+(g) + e- I1 first ionization energy

I2 + X+(g) X2+(g) + e- I2 second ionization energy

I3 + X2+(g) X3+(g) + e- I3 third ionization energy

I 1 < I 2 < I3

76
77
Variation of the First Ionization Energy with Atomic Number

Filled n=1 shell

Filled n=2 shell

Filled n=3 shell

Filled n=4 shell
Filled n=5 shell

78
 General Trends in First Ionization Energies

Increasing First Ionization Energy

Increasing First Ionization Energy

79
 Electron affinity is the negative of the energy change that
occurs when an electron is accepted by an atom in the
gaseous state to form an anion.

X (g) + e- X-(g)

F (g) + e- X-(g) H = -328 kJ/mol EA = +328 kJ/mol

O (g) + e- O-(g) H = -141 kJ/mol EA = +141 kJ/mol

80
81
Variation of Electron Affinity With Atomic Number (H – Ba)

82
Diagonal Relationships on the Periodic Table

83
 Group 1A Elements (ns1, n  2)

M M+1 + 1e-
2M(s) + 2H2O(l) 2MOH(aq) + H2(g)

4M(s) + O2(g) 2M2O(s)

Increasing reactivity

84
Group 1A Elements (ns1, n  2)

85
 Group 2A Elements (ns2, n  2)

M M+2 + 2e-
Be(s) + 2H2O(l) No Reaction
Mg(s) + 2H2O(g) Mg(OH)2(aq) + H2(g)
M(s) + 2H2O(l) M(OH)2(aq) + H2(g) M = Ca, Sr, or Ba
Increasing reactivity

86
Group 2A Elements (ns2, n  2)

87
 Group 3A Elements (ns2np1, n  2)

4Al(s) + 3O2(g) 2Al2O3(s)

2Al(s) + 6H+(aq) 2Al3+(aq) + 3H2(g)

88
Group 3A Elements (ns2np1, n  2)

89
 Group 4A Elements (ns2np2, n  2)

Sn(s) + 2H+(aq) Sn2+(aq) + H2 (g)

Pb(s) + 2H+(aq) Pb2+(aq) + H2 (g)

90
Group 4A Elements (ns2np2, n  2)

91
 Group 5A Elements (ns2np3, n  2)

N2O5(s) + H2O(l) 2HNO3(aq)

P4O10(s) + 6H2O(l) 4H3PO4(aq)

92
Group 5A Elements (ns2np3, n  2)

93
 Group 6A Elements (ns2np4, n  2)

SO3(g) + H2O(l) H2SO4(aq)

94
Group 6A Elements (ns2np4, n  2)

95
 Group 7A Elements (ns2np5, n  2)

X + 1e- X-1

X2(g) + H2(g) 2HX(g)

Increasing reactivity
96
Group 7A Elements (ns2np5, n  2)

97
 Group 8A Elements (ns2np6, n  2)

Completely filled ns and np subshells.

Highest ionization energy of all elements.
No tendency to accept extra electrons.

98
 Compounds of the Noble Gases

A number of xenon compounds XeF4, XeO3,

XeO4, XeOF4 exist.
A few krypton compounds (KrF2, for example)
have been prepared.
99
 Comparison of Group 1A and 1B

The metals in these two groups have similar outer

electron configurations, with one electron in the
outermost s orbital.
Chemical properties are quite different due to difference
in the ionization energy.

Lower I1, more reactive

100
 Properties of Oxides Across a Period

basic acidic

101
Chemistry in Action: Discovery of the Noble Gases

Sir William Ramsay

102
Chemical Bonding I:
Basic Concepts
Chapter 9

Copyright © The McGraw-Hill Companies, Inc.  Permission required for reproduction or display.
Valence electrons are the outer shell electrons of an
atom. The valence electrons are the electrons that
particpate in chemical bonding.
Group e- configuration # of valence e-
1A ns1 1
2A ns2 2
3A ns2np1 3
4A ns2np2 4
5A ns2np3 5
6A ns2np4 6
7A ns2np5 7
104
Lewis Dot Symbols for the Representative Elements &
Noble Gases

105
 The Ionic Bond
Ionic bond: the electrostatic force that holds ions together in an
ionic compound.
Li + F Li+ F -
1s22s11s22s22p5 [He]
1s
1s2[2Ne]
2s22p6

Li Li+ + e-

LiF F -
e- + F

Li+ + F - Li+ F -

106
 Electrostatic (Lattice) Energy
Lattice energy (U) is the energy required to completely separate
one mole of a solid ionic compound into gaseous ions.
E is the potential energy
Q+ is the charge on the cation
E = k Q + Q- Q- is the charge on the anion
r
r is the distance between the ions

Compound Lattice Energy

(kJ/mol)
Lattice energy increases MgF2 2957 Q: +2,-1
as Q increases and/or
MgO 3938 Q: +2,-2
as r decreases.

LiF 1036
r F- < r Cl-
LiCl 853 107
Born-Haber Cycle for Determining Lattice Energy

o
Hoverall = H1o+ H2o+ H3o+ H4o+ H5o 108
109
Chemistry In Action:
Sodium Chloride: A Common
and Important Compund

Mining Salt Solar Evaporation for Salt

110
A covalent bond is a chemical bond in which two or more
electrons are shared by two atoms.

Why should two atoms share electrons?

F + F F F
7e- 7e- 8e- 8e-

Lewis structure of F2

single covalent bond lone pairs F F lone pairs

single covalent bond

lone pairs F F lone pairs

111
Lewis structure of water single covalent bonds

H + O + H H O H or H O H
2e-8e-2e-

Double bond – two atoms share two pairs of electrons

O C O or O C O
8e- 8ebonds
double -
8e- double bonds

Triple bond – two atoms share three pairs of electrons

N N or N N
8e-8e
triple -
bond
triple bond
112
 Lengths of Covalent Bonds

Bond Lengths
113
Triple bond < Double Bond < Single Bond
114
Polar covalent bond or polar bond is a covalent bond
with greater electron density around one of the two
atoms

electron rich
electron poor
region
region e- poor e- rich

H F H F
+ -

115
Electronegativity is the ability of an atom to attract
toward itself the electrons in a chemical bond.

Electron Affinity - measurable, Cl is highest

X (g) + e- X-(g)

Electronegativity - relative, F is highest

116
The Electronegativities of Common Elements

117
Variation of Electronegativity with Atomic Number

118
Classification of bonds by difference in electronegativity

Difference Bond Type

0 Covalent
2 Ionic
0 < and <2 Polar Covalent

Increasing difference in electronegativity

Covalent Polar Covalent Ionic

share e- partial transfer of e- transfer e-

119
Classify the following bonds as ionic, polar covalent, or
covalent: The bond in CsCl; the bond in H2S; and the NN bond
in H2NNH2.

Cs – 0.7 Cl – 3.0 3.0 – 0.7 = 2.3 Ionic

H – 2.1 S – 2.5 2.5 – 2.1 = 0.4 Polar Covalent

N – 3.0 N – 3.0 3.0 – 3.0 = 0 Covalent

120
 Writing Lewis Structures

1. Draw skeletal structure of compound showing

what atoms are bonded to each other. Put least
electronegative element in the center.
2. Count total number of valence e-. Add 1 for
each negative charge. Subtract 1 for each
positive charge.
3. Complete an octet for all atoms except
hydrogen
4. If structure contains too many electrons, form
double and triple bonds on central atom as
needed. 121
Write the Lewis structure of nitrogen trifluoride (NF3).
Step 1 – N is less electronegative than F, put N in center
Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 – Draw single bonds between N and F atoms and complete
octets on N and F atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?

3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

F N F

F
122
Write the Lewis structure of the carbonate ion (CO32-).
Step 1 – C is less electronegative than O, put C in center
Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4)
-2 charge – 2e-
4 + (3 x 6) + 2 = 24 valence electrons
Step 3 – Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e-

2 single bonds (2x2) = 4

1 double bond = 4
O C O 8 lone pairs (8x2) = 16
Total = 24
O 123
 Two possible skeletal structures of formaldehyde (CH2O)

H
H C O H C O
H

An atom’s formal charge is the difference between the

number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
formal charge total number
total number total number
( )
on an atom in of valence 1
electrons in - -
a Lewis
= of nonbonding of bonding
electrons 2 electrons
structure the free atom

The sum of the formal charges of the atoms in a molecule

or ion must equal the charge on the molecule or ion.
124
 -1 +1 C – 4 e- 2 single bonds (2x2) = 4
H C O H O – 6 e- 1 double bond = 4
2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12

formal charge total number

total number total number
( )
on an atom in of valence 1
electrons in - -
a Lewis
= of nonbonding of bonding
electrons 2 electrons
structure the free atom

formal charge
on C
= 4 -2 - ½ x 6 = -1

formal charge
on O
= 6 -2 - ½ x 6 = +1

125
 H 0 0 C – 4 e- 2 single bonds (2x2) = 4
C O O – 6 e- 1 double bond = 4
H 2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12

formal charge total number

total number total number
( )
on an atom in of valence 1
electrons in - -
a Lewis
= of nonbonding of bonding
electrons 2 electrons
structure the free atom

formal charge
on C
= 4 - 0 -½ x 8 = 0

formal charge
on O
= 6 -4 - ½ x 4 = 0

126
 Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.
Which is the most likely Lewis structure for CH2O?

-1 +1 H 0 0
H C O H C O
H
127
A resonance structure is one of two or more Lewis structures
for a single molecule that cannot be represented accurately by
only one Lewis structure.

+ - - +
O O O O O O

What are the resonance structures of the

carbonate (CO32-) ion?

- - - -
O C O O C O O C O

O O O
- - 128
 Exceptions to the Octet Rule

The Incomplete Octet

Be – 2e-
BeH2 2H – 2x1e- H Be H
4e-

B – 3e- 3 single bonds (3x2) = 6

3F – 3x7e- F B F
BF3 9 lone pairs (9x2) = 18
24e- Total = 24
F

129
 Exceptions to the Octet Rule

Odd-Electron Molecules

N – 5e-
NO O – 6e- N O
11e-

The Expanded Octet (central atom with principal quantum number n > 2)

F
F F
S – 6e- 6 single bonds (6x2) = 12
SF6 6F – 42e- S 18 lone pairs (18x2) = 36
48e- Total = 48
F F
F
130
 Chemistry In Action: Just Say NO

NO2- (aq) + Fe2+ (aq) + 2H+ (aq)

NO (g) + Fe3+ (aq) + H2O (l)

N2 (g) + O2 (g) 2NO (g)

131
The enthalpy change required to break a particular bond in one
mole of gaseous molecules is the bond enthalpy.

Bond Enthalpy
H2 (g) H (g) + H (g) H0 = 436.4 kJ
Cl2 (g) Cl (g) + Cl (g) H0 = 242.7 kJ
HCl (g) H (g) + Cl (g) H0 = 431.9 kJ
O2 (g) O (g) + O (g) H0 = 498.7 kJ O O
N2 (g) N (g) + N (g) H0 = 941.4 kJ N N

Bond Enthalpies
Single bond < Double bond < Triple bond
132
Average bond enthapy in polyatomic molecules

H2O (g) H (g) + OH (g) H0 = 502 kJ

OH (g) H (g) + O (g) H0 = 427 kJ

502 + 427
Average OH bond enthalpy = = 464 kJ
2

133
Bond Enthalpies (BE) and Enthalpy changes in reactions
Imagine reaction proceeding by breaking all bonds in the reactants and
then using the gaseous atoms to form all the bonds in the products.

H0 = total energy input – total energy released

= BE(reactants) – BE(products)

endothermic exothermic 134

H2 (g) + Cl2 (g) 2HCl (g) 2H2 (g) + O2 (g) 2H2O (g)

135
Use bond enthalpies to calculate the enthalpy change for:
H2 (g) + F2 (g) 2HF (g)

H0 = BE(reactants) – BE(products)

Type of Number of Bond enthalpy Enthalpy

bonds broken bonds broken (kJ/mol) change (kJ/mol)
H H 1 436.4 436.4
F F 1 156.9 156.9
Type of Number of Bond enthalpy Enthalpy change
bonds formed bonds formed (kJ/mol) (kJ/mol)
H F 2 568.2 1136.4

H0 = 436.4 + 156.9 – 2 x 568.2 = -543.1 kJ/mol

136
 Mass Relationships in
Chemical Reactions

Copyright © The McGraw-Hill Companies, Inc.  Permission required for reproduction or display.
 Micro World Macro World
atoms & molecules grams

Atomic mass is the mass of an atom in

atomic mass units (amu)

By definition:
1 atom 12C “weighs” 12 amu

On this scale
1
H = 1.008 amu
16
O = 16.00 amu 138
The average atomic mass is the weighted
average of all of the naturally occurring
isotopes of the element.

139
Chem 141 Ms. Angelica A. Macalalad
 Naturally occurring lithium is:
7.42% 6Li (6.015 amu)
92.58% 7Li (7.016 amu)

Average atomic mass of lithium:

7.42 x 6.015 + 92.58 x 7.016

= 6.941 amu
100

140
Average atomic mass (6.941)

141
The Mole (mol): A unit to count numbers of particles

Dozen = 12

Pair = 2

The mole (mol) is the amount of a substance that

contains as many elementary entities as there
are atoms in exactly 12.00 grams of 12C
1 mol = NA = 6.0221367 x 1023
Avogadro’s number (NA) 142
 eggs
Molar mass is the mass of 1 mole of shoes in grams
marbles
atoms
1 mole 12C atoms = 6.022 x 1023 atoms = 12.00 g
1 12C atom = 12.00 amu

1 mole 12C atoms = 12.00 g 12C

1 mole lithium atoms = 6.941 g of Li

For any element

atomic mass (amu) = molar mass (grams)
143
 One Mole of:

C S

Hg

Cu Fe
144
1 12C atom 12.00 g 1.66 x 10-24 g
x =
12.00 amu 6.022 x 10 23 12
C atoms 1 amu

1 amu = 1.66 x 10-24 g or 1 g = 6.022 x 1023 amu

M = molar mass in g/mol

NA = Avogadro’s number
145
How many atoms are in 0.551 g of potassium (K) ?

1 mol K = 39.10 g K
1 mol K = 6.022 x 1023 atoms K

1 mol K 6.022 x 1023 atoms K

0.551 g K x x =
39.10 g K 1 mol K

8.49 x 1021 atoms K

146
Molecular mass (or molecular weight) is the sum of
the atomic masses (in amu) in a molecule.

1S 32.07 amu
2O + 2 x 16.00 amu
SO2 SO2 64.07 amu

For any molecule

molecular mass (amu) = molar mass (grams)

1 molecule SO2 = 64.07 amu

1 mole SO2 = 64.07 g SO2 147
How many H atoms are in 72.5 g of C3H8O ?

1 mol C3H8O = (3 x 12) + (8 x 1) + 16 = 60 g C3H8O

1 mol C3H8O molecules = 8 mol H atoms
1 mol H = 6.022 x 1023 atoms H

1 mol C3H8O 8 mol H atoms 6.022 x 1023 H atoms

72.5 g C3H8O x x x =
60 g C3H8O 1 mol C3H8O 1 mol H atoms

5.82 x 1024 atoms H

148
Formula mass is the sum of the atomic masses
(in amu) in a formula unit of an ionic compound.

1Na 22.99 amu

NaCl 1Cl + 35.45 amu
NaCl 58.44 amu

For any ionic compound

formula mass (amu) = molar mass (grams)

1 formula unit NaCl = 58.44 amu

1 mole NaCl = 58.44 g NaCl 149
What is the formula mass of Ca3(PO4)2 ?

1 formula unit of Ca3(PO4)2

3 Ca 3 x 40.08
2P 2 x 30.97
8O + 8 x 16.00
310.18 amu

150
Mass Spectrometer

Heavy
Light
Light

Heavy
Mass Spectrum of Ne

151
Percent composition of an element in a compound =
n x molar mass of element
x 100%
molar mass of compound
n is the number of moles of the element in 1 mole
of the compound
2 x (12.01 g)
%C = x 100% = 52.14%
46.07 g
6 x (1.008 g)
%H = x 100% = 13.13%
46.07 g
1 x (16.00 g)
%O = x 100% = 34.73%
46.07 g
C2H6O 52.14% + 13.13% + 34.73% = 100.0%
152
Percent Composition and Empirical Formulas
Determine the empirical formula of a
compound that has the following
percent composition by mass:
K 24.75, Mn 34.77, O 40.51 percent.

1 mol K
nK = 24.75 g K x = 0.6330 mol K
39.10 g K
1 mol Mn
nMn = 34.77 g Mn x = 0.6329 mol Mn
54.94 g Mn
1 mol O
nO = 40.51 g O x = 2.532 mol O
16.00 g O

153
Percent Composition and Empirical Formulas

nK = 0.6330, nMn = 0.6329, nO = 2.532

0.6330 ~
K: ~ 1.0
0.6329
0.6329
Mn : = 1.0
0.6329
2.532
O: ~ 4.0
~
0.6329

KMnO4

154
Exercise #1

Phosphoric acid (H PO ) is a colorless, syrupy liquid used in

3 4

detergents, fertilizers, toothpastes, and in carbonated beverages for a

“tangy” flavor. Calculate the percent composition by mass of H, P,
and O in this compound.

155
Exercise #2

Ascorbic acid (vitamin C) cures scurvy. It is composed of

40.92 percent carbon (C), 4.58 percent hydrogen (H), and
54.50 percent oxygen (O) by mass. Determine its empirical
formula.

156
157