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The Atomic Theory

Daltons atomic theory


Elements are composed of extremely small particles called as atoms.
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
Compounds are composed of atoms of more than one element.
A chemical rxtn involves only the separation, combination or
rearrangement of atoms. It doesnt result in their creation or destruction
Law of Conservation of Mass
Matter cannot be destroyed/created.

Component of Atom
Atom

as the basic unit of an element that can enters


into chemical combination

Atom is made up of smaller particles which are called


subatomic particles
Electron (-1)
Proton, (+1)
Neutron (0)

Atoms consist of a nucleus (+ve charge) and surrounded by an


electron cloud (-ve charge)
e
e

nucleus
e

electron

The protons and neutrons are packed


in an extremely small nucleus. Electron
are shown as clouds around the
nucleus

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


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

no. of proton = no of electron


4

An ion is an atom, or group of atoms, that has a net positive or


negative charge.
cation ion with a positive charge
If a neutral atom loses one or more electrons
it becomes a cation.
p>e
Na

11 protons
11 electrons

Na+

11 protons
10 electrons

anion ion with a negative charge


If a neutral atom gains one or more electrons
it becomes an anion.
e>p
Cl

17 protons
17 electrons

Cl-

17 protons
18 electrons
5

Atomic Number, (Z)


Atom No. (Z)

the number of proton in the nucleus of


each atom of an element

In neutral, proton = electron


Each elements is characterized by its proton number.
Each element has a differ proton number

E.g: atomic number N is 7


N has 7 proton & 7 electron = neutral atom
Therefore, atom with 7 protons is always nitrogen, N.

Mass Number, (A)


the total amount of neutrons & protons
present in the nucleus of an atom of an
element

Mass No. (A)

Mass number (A) = number of protons + number of neutrons


= atomic number (Z) + number of neutrons
Mass Number
Atomic Number

A
ZX

Element Symbol

Example:
How many protons, neutrons, and electrons are in

14
C?
6

6 protons, 8 (14 - 6) neutrons, 6 electrons

How many protons, neutrons, and electrons are in

11
6

C?

6 protons, 5 (11 - 6) neutrons, 6 electrons

Isotopes
Isotopes

atoms that have the same atomic number


but different mass number

Isotopes have the same number of electron - they have the


the identical chemical properties
They have different neutron number have different physical
properties (melting point, boling point, density)

The Isotopes of Hydrogen

hydrogen

deuterium

tritium

10

Electron Configuration
Show how e- are filled in the orbital
Its describe the arrangement of e- in an atom
number of electrons
in the orbital or subshell

1s1
principal quantum
number n

angular momentum
quantum number l

Orbital diagram

H
1s

The Pauli Exclusion Principle


Pauli Principle

State that no 2 e- in the same atom


can have the same 4 quantum
number (n, l, ml, ms)

an orbital can hold a max of 2 e- & they must has opposite


spins
If there are 3 e- in the same orbital;
e1: n = 1, l = 0, ml = 0, ms = + (permissible)
e2: n = 1, l = 0, ml = 0, ms = -

(permissible)

e3: n = 1, l = 0, ml = 0, ms = + (not permissible)

As Li (3 e-)

n = 1, l = 0, ml = 0, ms = +
1s

2s

n = 1, l = 0, ml = 0, ms = +
n = 1, l = 0, ml = 0, ms = -

Aufbau Principle
Aufbau German word means building up

Aufbau Principle

State that e- in an atom should be


filled in the orbitals in the order of
increasing energy level

e- should occupy the orbital with the lowest energy first


before it enters the one with higher energy

E.g: Li has 3 e The first 2 e- should be placed into 1s orbital (lowest


energy level)

1s

Follow by 3rd e- in the 2s orbital

1s

2s

Therefore, electron configuration of Li is = 1s2 2s1

Figure 2: Distribution of energy levels in an atom

Energy level
diagram

to follow the order of higher energy of the orbital, refer to


energy diagram

Figure 1: Order for fill


the e- in the orbital

1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s

Hunds Rule
State that e- will occupy all orbitals of
the same energy level singly with
parallel spin before they become paired

Hunds Rule

E.g: N (7 e-)

1s

2s

2p

Therefore, electron configuration of N is = 1s2 2s2 2p3

What is the electron configuration of Mg?


Mg 12 electrons
1s < 2s < 2p < 3s < 3p < 4s
Electronic conf:

1s22s22p63s2

2 + 2 + 6 + 2 = 12 electrons

Abbreviated as [Ne]3s2
What are the possible quantum numbers for the last (outermost)
electron in Cl?
Cl 17 electrons
Electronic conf:

1s22s22p63s23p5

1s < 2s < 2p < 3s < 3p < 4s


2 + 2 + 6 + 2 + 5 = 17 electrons

Last electron added to 3p orbital


n=3

l=1

ml = -1, 0, or +1

ms = or -

Electron configuration for Cation and Anion


Na (11 e-) = 1s2 2s2 2p6 3s1
Ca (20 e-) = 1s2 2s2 2p6 3s2 3p6 4s2

Na+ = 1s2 2s2 2p6 or [Ne]


Ca2+ = 1s2 2s2 2p6 3s2 3p6 or [Ar]

F = 1s22s22p5

F- = 1s22s22p6 or [Ne]

H = 1s1

H- = 1s2 or [He]

Electron configuration of the transition


elements
Transition elements are the element with the half-filled d
orbitals.
These elements are found in the fourth row of periodic table
known as the d-block element.
The 3d orbitals are filled after 4s orbital is fully occupied by e-.
Example:

1s

2s

Titanium, Ti: (Z = 22)

2p

3s

3p

4s

3d

Electron conf: 1s2 2s2 2p6 3s2 3p6 4s2 3d2 or [Ar] 4s2 3d2

The Anomalous Electronic Configuration of


Chromium and Copper
Chromium , Cr and Copper, Cu = the element in d-block
It have irregularities for this element
Cr : 24 electrons
1s2 2s2 2p6 3s2 3p6 4s2 3d4

or

Expected to be based on the rules

BUT

[Ar] 4s2 3d4

To achieve the stability, one of the e- from the 4s orbital


occupies one of the 3d orbitals to have a half-filled orbital

the actual
Cr : 24 electrons
1s2 2s2 2p6 3s2 3p6 4s1 3d5

or

Cu : 29 electrons
1s2 2s2 2p6 3s2 3p6 4s2 3d9

[Ar] 4s1 3d5

Its said to have


fully-filled
orbital

turn as

1s2 2s2 2p6 3s2 3p6 4s1 3d10

or

[Ar] 4s1 3d10

24

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

25

Development of Periodic Table

CHAPTER 1.2
CHEMICAL BONDING

Content
Introduction
Ionic Bonding
Covalent Bond
Physical Properties Of Ionic Compound
Physical Properties Of Covalent Compound
Lewis Dot Structure
Resonance
Octet Rule
Exceptions To The Octet Rule

INTRODUCTION
Atoms are made up of smaller sub-particles:
electron, protons & neutrons
Proton + neutron are in small dense nucleus of
atom
Electron are arranged in orbitals outside the
nucleus according to Aufbau principle, Pauli
Exclusion principle & Hunds rule
An atom can gains or loses e- to become ion OR
share e- with other atom to become molecule

Atoms/ions are joined together by 2 main types of chemical


bonding
Ionic bond

Covalent bond
Why do atoms combine??
Combine to form a stable e- configuration similar to
the unreactive and chemically stable noble gas

The force that hold on the atoms/ions are called

CHEMICAL BOND

Chemical bonds form when


Attractive forces between the positive charged
nucleus & negative charged electron are countered
balance by repulsive forces among the nucleus and
electrons themselves.

21)types
chemical
bonds:bonds results of
Formation
Ionic of
bond
transfer of electron
2) Covalent bond

Formation of chemical bonds


as results of sharing of electron

When atoms interact to form a chemical bond,


only their outer region are in contact
Valence electrons
Lewis dot symbol is used to show how many valence

electron is belonged to an atom used in Lewis Structure


to demonstrate the formation of bond
Lewis dot
symbol

Consist of the symbol of an atom &


one dot for each valence electron in
an atom of the element

Valence electrons are the outer shell electrons of an atom.


The valence electrons are the electrons that participate in
chemical bonding.
Group

e- configuration

# of valence e-

1A

ns1

2A

ns2

3A

ns2np1

4A

ns2np2

5A

ns2np3

6A

ns2np4

7A

ns2np5

7
33

To draw the Lewis dot symbol atomic symbol


is drawn with dots or crosses surrounding
Oxygen (Z= 8) - 1s2 2s2 2p4
E.g:
valence electron

Lewis dot symbol for Oxygen;

.O.
..
..

Lewis Dot Symbols for the Representative Elements & Noble


Gases

35

IONIC BOND
Define as = the electrostatic force that holds
ions together in an ionic compound
Ionic bond form when an atoms:

transferring (losing/gaining) e- from


atom to another atoms
Atom that donates its valence electron will be +ve

charged (CATION)
Atom that accept electron will be ve charged (ANION)

The opposite charged ions are held together by


strong electrostatic attraction
Atoms that donate their valence e are very

electropositive element metal of group 1A & 2A

Atoms that accept e- are very electronegative


elements nonmetals of group 6A & 7A
E.g: reaction between Li and F to form LiF

Li+ F -

Li + F

Li
LiF

e +

Li+ +

Li+ + e

Li+

38

Try This:

By using Lewis structures and curve arrows,


describe the transfer of electron(s) during the
formation of the following ionic compounds.
1. Na2O
2. CaF2

Physical Properties of Ionic Compound


Ionic compound are have high melting and boiling
point

The ions are stable ( have stable e- configuration) & the


ionic bonds are strong

Soluble in water but insoluble in organic solvents


as benzene
Can conduct electricity in liquid form or aqueous
form only
Because of the present of charged particles that can
move

COVALENT BOND
Means = is a chemical bond in which 2 or
more electrons are shared by 2 atoms
Covalent compound = compounds that contain
only covalent bond

In covalent bond,

A group of atoms are being held together


Electron in a shared pair is attracted to nuclei
of both atoms
Covalent bond usually formed by non-metal
atoms having the same or nearly same
electronegativity

Why should two atoms share electrons?


+

F
7e-

F F

7e-

8e- 8e-

Lewis structure of F2
single covalent bond

lone pairs

lone pairs

lone pairs

single covalent bond

lone pairs
43

Lone pair/unpaired electron


Pair of valence electron that are not involve in
covalent bond formation

The formation of these molecules illustrate the


OCTET RULE
An atom other than hydrogen tends to form bonds
until it is surrounded by 8 valence electrons
Atoms can form different types of covalent bonds:

Single bond

Double bond

Triple bond

Single bond

Two atoms are held together by one electron pair


H O H

or

Double bond

Is when 2 atoms share 2 pairs of electron(s)


Can found in molecules of CO2
O C

or

double bonds

Triple bond

Arise when 2 atoms share 3 pairs of electron(s),


example N2
N
N
triple bond

or

triple bond

Polar Covalent Bonds


Although atoms
often form
compounds by
sharing electrons,
HF
F
the electrons are not
always itshared
Fluorine pulls harder on the electrons
shares with
hydrogen than hydrogen does.equally.
2

Therefore, the fluorine end of the molecule has more

electron density than the hydrogen end.

Polar covalent bond or polar bond is a covalent bond


with greater electron density around one of the two
atoms
electron poor
region
H

electron rich
region
F

e- poor e- rich

H
d+

F
d-

49

Polar Covalent Bonds


When two atoms share

electrons unequally, a
bond dipole results.
The dipole moment,

m,produced by two equal


but opposite charges
separated by a distance, r.

Polar Covalent Bonds


The greater the
difference in
electronegativity,
the more polar is
the bond.

Physical Properties of Covalent Compound


covalent compound are have low melting and
boiling point
The weakness of intermolecular force of covalent bond

Can soluble in organic solvents as benzene but not


in water
Its not good as conductors of electricity in all form
Molecules that made up of particles are neutral not
charged

Hybridization of Atomic Orbitals

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

54

Valence Bond Theory and NH3


N 1s22s22p3

3 H 1s1
If the bonds form from overlap of 3 2p orbitals on nitrogen with the 1s orbital on each
hydrogen atom, what would the molecular geometry of NH3 be?

If use the
3 2p orbitals
predict 90o

Actual H-N-H
bond angle is
107.3o
55

Hybridization mixing of two or more atomic


orbitals to form a new set of hybrid orbitals.
1. Mix at least 2 nonequivalent atomic orbitals (e.g. s
and p). Hybrid orbitals have very different shape
from original atomic orbitals.
2. Number of hybrid orbitals is equal to number of
pure atomic orbitals used in the hybridization
process.
3. Covalent bonds are formed by:

a. Overlap of hybrid orbitals with atomic orbitals


b. Overlap of hybrid orbitals with other hybrid
orbitals

56

Formation of sp3 Hybrid Orbitals

57

Formation of Covalent Bonds in CH4

58

sp3-Hybridized N Atom in NH3

Predict correct
bond angle

59

Formation of sp Hybrid Orbitals

60

Formation of sp2 Hybrid Orbitals

61

How do I predict the hybridization of the central atom?


1.

Draw the Lewis structure of the molecule.

2.

Count the number of lone pairs AND the number of atoms bonded to
the central atom

# of Lone Pairs
+
# of Bonded Atoms

Hybridization

Examples

sp

BeCl2

sp2

BF3

sp3

sp3d

PCl5

sp3d2

SF6

CH4, NH3, H2O

62

63

sp2 Hybridization of Carbon

64

Unhybridized 2pz orbital (gray), which is perpendicular to the plane of the


hybrid (green) orbitals.

65

Bonding in Ethylene, C2H4

Sigma bond (s) electron density between the 2 atoms


Pi bond (p) electron density above and below plane of nuclei
bonding atoms

of the
66

Another View of p Bonding in Ethylene, C2H4

67

sp Hybridization of Carbon

68

Bonding in Acetylene, C2H2

69

Another View of the Bonding in Ethylene, C2H4

70

Describe the bonding in CH2O.


H
C

C 3 bonded atoms, 0 lone pairs


C sp2

71

Sigma (s) and Pi Bonds (p)


1 sigma bond

Single bond
Double bond

1 sigma bond and 1 pi bond

Triple bond

1 sigma bond and 2 pi bonds

How many s and p bonds are in the acetic acid (vinegar) molecule CH3COOH?

s bonds = 6
H

+1=7

p bonds = 1

H
72

Experiments show O2 is paramagnetic

No unpaired eShould be diamagnetic

Molecular orbital theory bonds are formed from


interaction of atomic orbitals to form molecular
orbitals.
73

Energy levels of bonding and antibonding molecular


orbitals in hydrogen (H2).

A bonding molecular orbital has lower energy and greater stability than the
atomic orbitals from which it was formed.
An antibonding molecular orbital has higher energy and lower stability than the
atomic orbitals from which it was formed.
74

Constructive and Destructive Interference

75

Two Possible Interactions Between Two Equivalent p Orbitals

76

General molecular orbital energy level diagram for the second-period homonuclear
diatomic molecules Li2, Be2, B2, C2, and N2.

77

Molecular Orbital (MO) Configurations


1.

The number of molecular orbitals (MOs) formed is always equal to the number
of atomic orbitals combined.

2.

The more stable the bonding MO, the less stable the corresponding
antibonding MO.

3.

The filling of MOs proceeds from low to high energies.

4.

Each MO can accommodate up to two electrons.

5.

Use Hunds rule when adding electrons to MOs of the same energy.

6.

The number of electrons in the MOs is equal to the sum of all the electrons on
the bonding atoms.

78

1
bond order =

bond order

Number of
electrons in
bonding MOs

Number of
electrons in
antibonding
MOs

0
79

80

Delocalized molecular orbitals are not confined between two adjacent


bonding atoms, but actually extend over three or more atoms.

Example: Benzene, C6H6

Delocalized p orbitals

81

Electron density above and below the plane of the benzene molecule.

82

Bonding in the Carbonate Ion, CO32-

83

Chemistry In Action: Buckyball Anyone?

84

Intermolecular Forces

Three States of Matter

1.5

Factors in Determining State of Matter


I.

Kinetic Energy

II.

Intermolecular Forces; Attractive Forces


between different molecules

neglible in gases
important in solids, liquids

GAS-Effect of Kinetic Energy


Overwhelms Attractive Force

Liquid Molecules have Enough Kinetic


Energy to Slide Past One Another.

Liquid Molecules have Enough Kinetic


Energy to Slide Past One Another.

Solid Molecules Kinetic Energy is


NOT Strong Enough to Allow
Molecules to Slide Past One Another

Intermolecular Forces
(Attractive Forces, van der Waal
Forces)
Part II

Intermolecular Forces
Intermolecular forces; attractive forces between diff. Molecules
which bring the molecules in contac with eac other
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular

41 kJ to vaporize 1 mole of water (inter)

930 kJ to break all O-H bonds in 1 mole of water (intra)

Measure of intermolecular force

Generally,
intermolecular forces
are much weaker
than intramolecular
forces.

boiling point
melting point

DHvap
DHfus
DHsub

11.2

Types of Intermolecular Forces


1. Dipole/ Dipole Forces (Polar Molecules)

Hydrogen Bonds

2. London/ Dispersion Forces (NonPolar


Molecules)

Intermolecular Forces
I. Dipole-Dipole Forces
Attractive forces between polar molecules

Orientation of Polar Molecules in a Solid

11.2

Intermolecular Forces

II. Dispersion Forces


Attractive forces that arise as a result of temporary dipoles induced in
atoms or nonpolar molecules

11.2

Polarizability
Ease at which the electron distribution in an
atom or molecule can be distorted and a
temporary dipole induced
More electrons (greater Molar Mass) leads to
greater polarizability.

Formation of Temporary Dipoles

1. Random movement of electrons

2. ion-induced dipole interaction

3. dipole-induced dipole interaction

What type(s) of intermolecular forces exist between each of the following


molecules?

HBr
HBr is a polar molecule: dipole-dipole forces. There are also dispersion forces
between HBr molecules.

CH4
CH4 is nonpolar: dispersion forces.
S

SO2
SO2 is a polar molecule: dipole-dipole forces. There are also dispersion forces
between SO2 molecules.

11.2

Boiling Point- Temperature at which


there is enough Kinetic Energy to
Overcome Intermolecular Forces
Liquid

Gas

Has Intermolecular Forces

No Intermolecular Forces

Boiling Point Increases with..


1. Stronger Intermolecular Force

2. If same Intermolecular Force;

increasing Molar Mass, higher boiling point

Explain why the Higher Molar Mass


Compound, CF4, has a Lower Boiling
Point than H2Se

CF4
Boiling Point; -150.0C
Molar Mass ~ 88 g/mole
Intermolecular Force;
Dispersion Force

H2Se
Boiling Point; -42.0 C
Molar Mass ~ 81 g/mole
Intermolecular Force; DipoleDipole Force

Boiling Points of
Polar Hydrogen Compounds
Boiling Point;
C

H2O

Approximate
Molar Mass;
g/mole
18

H2S

34

-60

H2Se

81

-42

H2Te

130

-2

+ 100

Hydrogen Bond
Strong Type of DipoleDipole Force. This
Type of Intermolecular
Force Happens When
H is directly bonded to
O, N, or F.

High Strength of H- bond


1. Large electronegativity difference between H
and N, O, or F.
2. Small size of H atom allows it to get close to
another molecule

Hydrogen Bond

O-H Covalent Bond that Makes H-bonding Possible

Which of the Two Polar Molecules Has


a Higher Boiling Point ?
diethyl ether
H
H
H

C
H

ethanol
H
H

Importance of H-Bonds in H2O


1. Very high boiling point for water (H2O(l)) for
its Molar Mass.

2. The solid form of the material is less dense


than liquid form

Ice Floats on liquid water.


Water expands as it freezes

Ice Cubes float on water (Left)


Solid benzene sinks to the bottom of liquid
benzene (right)

Importance of H-Bonds in H2O


1. Very high boiling point for water
(H2O(l)) for its Molar Mass.
2. Ice floats on liquid water.

The solid form of the material is less


dense than liquid form
Water expands as it freezes

3. High specific heat of Water

Determining Type of Intermolecular


Force
Polar Molecules ?
YES

NO

H Directly Bonded
to O, N, or F ?
NO

Dispersion/
London Forces

Dipole/Dipole Force

YES

Hydrogen Bonding

Increasing Strength of Intermolecular Force