8-1

1.0 Atomic Properties and Chemical Bonds 2.0 The Ionic Bonding Model

3.0 The Covalent Bonding Model

4.0 Electronegativity and Bond Polarity

5.0 An Introduction to Metallic Bonding

8-2

 Why atoms bond? Bonding lower the potential energy between positive and negative particles Whether the particles are oppositely charged ions or atomic nuclei and the electrons between them. The type and strength of chemical bonds determine the properties of the substance

8-3

8-4

Three Types of Chemical Bonding

1. Metal with nonmetal: electron transfer and ionic bonding 2. Nonmetal with nonmetal: electron sharing and covalent bonding

3. Metal with metal: electron pooling and metallic bonding

8-5

Ionic bonding between atoms with large differences in their tendencies to lose or gain eOccur between reactive metals (1A(1) or 2A(2) and nonmetals 7A (17) or top of group 6A (16) Metal atom (low IE) loses its one or two valence e- whereas the nonmetal atom (high negative IE) gain the e-(s) Electron transfer from metal to nonmetal occurs where each atoms forms an ion with noble gas e- configuration.

Electrostatic attraction between +ve and ve ions draws them into 3 dimensional array of ionic solid 8-6

When 2 atoms have small difference in their tendencies to lose or gain e- , we will observe electron sharing and covalent bonding.

Common in nonmetals atom (metals sometimes).

Each nonmetal atoms holds its own e- tightly (high IE) and tend to attract other e- .

The attraction of each nucleus for valence e- of the other draws the atoms together.
A shared electron pair is considered to be localized between the two atoms because it spends most of its time there linking in a covalent bond of certain length and strength.

8-7

In general, metal atoms are relatively large, and their few outer e- are well shielded by filled inner orbitals.

They tend to lose outer e- easily (low IE) but do not gain them easily.

These properties lead to metal atoms to share their valence electron but at a different way from covalent bonding. Simplest model for metallic bonding where all metal atoms pool their valence e- into evenly distributed sea of electrons that flows between and around the metal-ion cores and attracts and holds them together. The e- are said to be delocalized, moving 8-8freely throughout the piece of metal.

 Method of showing the valence electrons of interacting atoms For any main group elements
The A group number (1A to 8A) gives the number of valence electrons Place one dot per valence electron on each of the four sides of the element symbol. Pair the dots (electrons) until all of the valence electrons are used.

Example: Nitrogen, N, is in Group 5A and therefore has 5 valence electrons.

. :N . . . N. . . . N: . . . N. : :

8-9

Lewis generalized the bonding behaviour into the Octet Rule where the rules state when atoms are bond, they lose, gain or share electrons to attain a filled outer level of eight (or two) electrons
8-10

 The Lewis symbol provides information about element bonding behavior:

a. For metal: the total number of dots is the maximum number of electron an atom loses to form a cation. b. For nonmetal: the number of unpaired dots equals either the number of electrons an atom gains in becoming an anion or the number it shares in forming covalent bonds.

8-11

 Based on the transfer of electrons from metal atoms to nonmetal atoms to form ions that come together in a solid ionic compound

8-12

Li 1s22s1

F 1s22s22p5

Li+ 1s2

F- 1s22s22p6

Li 1s + F 1s 2s 2p 2s 2p

Li+

1s
+ F-

2s

2p

1s

2s

2p

Li .

. :F: :

Li+

: F: :

8-13

PROBLEM:

Use partial orbital diagrams and Lewis symbols to depict the formation of Na+ and O2- ions from the atoms, and determine the formula of the compound.

PLAN:

Draw orbital diagrams for the atoms and then move electrons to make filled outer levels. It can be seen that 2 sodiums are needed for each oxygen.

SOLUTION: O2Na 2s 3s Na 3s 3p 3p O 2s 2p Na Na . 2 Na+ . + : O: . . 2Na+ +: O : 2: 2p

8-14

Take the example of a piece of rock salt (NaCl) It is hard, rigid and brittle (cracks without deforming) These properties is due to the powerful attractive forces that holds the ions in specific positions throughout the crystals

Moving the ions out of position requires overcoming of the forces

If enough force is applied, ions of same charge are brought next to each other and repulsive forces crack the sample suddenly
8-15

Electrostatic forces

and the reason ionic compounds crack.

8-16

 Ionic compounds do not conduct electricity in the solid state

But when its melted or dissolved in water, it can conduct electricity

Based on ionic bonding model, the solid consists of immobilized ions

When it melts or dissolves, the ions are free to move and carry an electric current

8-17

8-18

Solid ionic compound

Molten ionic compound

Ionic compound dissolved in water

This also explains the high temp. needed to melt or boil an ionic compound
Because freeing the ions from their positions requires large amounts of energy The inter ionic attraction is so strong that the vapour will consists of ion pairs, gaseous ionic molecules rather than individual ions.
8-19

Compound CsBr NaI MgCl2 KBr CaCl2 NaCl LiF KF MgO

8-20

mp (0C) 636 661 714 734 782 801 845 858 2852

bp (0C) 1300 1304 1412 1435 >1600 1413 1676 1505 3600

 Molecules bond together by covalent bonds range from diatomic hydrogen to biological and synthetic macromolecules
Based on sharing electrons

Formation of Covalent bond in H2

Point 1 : Atoms are far apart Point 2 : Distance between nuclei decreases, each nucleus starts to attract the other atoms electron which lower the potential energy of the system

8-21

 Formation of Covalent bond in H2 Point 3: The attractions increase with some repulsions between nuclei and the electrons.
At some internuclear distance, max. attraction is achieved in the face of increasing repulsion.

System has its min. energy

Point 4 : With shorter distance, repulsion will increase with the rise in potential energy.

8-22

8-23

 Therefore, a covalent bond is the bond that holds atoms together in H2 molecule
Arise from balance between nucleus-electron attractions and electron-electron and nucleus-nucleus repulsion

Formation of bond results in greater electron density between nuclei

8-24

Each atom achieves full outer valence level of electrons

Each atom in covalent counts the shared electrons as belonging entirely to itself

In H2 , two electrons are shared electron pair and this fills the outer level of both H atom
The shared pair represented by H:H or H-H

The outer level electron that is not involved in bonding are called lone pairs
In HF, the bonding pair fills the outer level of H atoms, together with 3 lone pairs and fills the outer level of F atom as well
8-25

The bond order is the no. of electron pairs being shared by any pair of bonded atoms. Covalent bond in H2 , HF or F2 is single bond which consist of a single bonding pair of electron
Bond order is 1 (most common type of bond)

Double bond consist of two bonding electron pairs

Where 4 electrons are shared between 2 atoms Bond order is 2 C2H4 contain C-C double bond & 4 C-H single bond

A triple bond consists of 3 bonding pairs

Where 2 atoms share 6 electrons (Eg: N2) Bond order is 3
8-26

In covalent substances, we need to distinguish 2 different sets of forces 1. The strong covalent bonding forces holding the atoms together within the molecule 2. The weak intermolecular forces holding the molecules near each other in macroscopic sample.

Example: Pentane (C5 H12 ) boils

The weak interactions between pentane molecules are affected but not the strong C-C and C-H covalent bonds with each molecule
8-27

Strong covalent bonding forces within molecules

Weak intermolecular forces between molecules

8-28

Network covalent solids

Molecules that are held together by covalent bonds that extend to 3 dimensions throughout the sample.
Examples: Quartz and diamond

Quartz (SiO2) melts at 1550oC

Composed of silicon and oxygen atoms connected by covalent bonds that extend throughout sample

Diamond melts around 3550oC

Covalent bonds connecting each of its carbon atom to four others throughout the sample Hardest natural substance
8-29

8-30

Most important concepts in chemical bonding is

Electronegativity (EN)
The relative ability of a bonded atom to attract the shared electron Not the same as electron affinity It refers to a separate atom in the gas phase gaining an electron from a gaseous anion.

Linus Pauling, American chemist developed the common scale of relative EN value for elements
8-31

Discussion based on HF bond (Pauling approach)

Where expected bond energy of HF is 296 kJ/mol;
to be average of energies between H-H (432 kJ/mol) and F-F bond (159 kJ/mol)

But actual is 565 kJ/mol (higher) This is due to an electrostatic (charge) contribution to H-F bond energy
If F attracts the shared e- pair more strongly than H F is more electronegative than H Electrons will spend more time closer to F Unequal sharing makes F end of the bond is partially ve and H end is partially +ve Attraction between these partial charges increases the energy required to break the bond.
8-32

Nucleus of smaller atom is closer to the shared pair compared a larger atom. It attracts bonding electrons more strongly Therefore, electronegativity is inversely related to atomic size In general,
EN increases up a group and across period Nonmetals are more electronegative than metals

Most electronegative element is fluorine and followed by oxygen. The least electronegative element (also as the most electropositive) is francium.
8-33

8-34

8-35

 Important use of electronegativity is in determining an atoms oxidation number 1. The more electronegative atom in a bond is assigned all the shared electrons while the less electronegative atom is assigned with none 2. Each atom in a bond is assigned all of its unshared electrons 3. The oxidation number is

8-36

 Example: In HCl,
Cl is more electronegative than H Has 7 valence e- but is assigned 8 (2 shared + 6 unshared) Oxidation number is 7-8 = -1 H has 1 valence e is assigned none Oxidation number is 1-0 = +1
8-37

 In HF, atoms has different electronegativities forming a bond Bonding pair is shared unequally Unequal distribution of electron density
Bonds has partially negative and positive poles

Polar covalent bond is depicted by a polar arrow ( ) pointing toward the negative pole or by + and - symbols representing partial charge
8-38

8-39

3.0

2.0

DEN

0.0

8-40

 Occurs among large numbers of metal atoms interact.

The electron-sea model of metallic bonding proposes that:

All the metal atoms in sample contribute their valence e- to form an electron sea that is delocalized throughout the sample. The metal ions (the nuclei with their core electrons) are submerged within this electron sea in an orderly array.
8-41

 Difference with ionic bonding

The metal ions are not held in place as rigidly as in ionic solid

Difference with covalent bonding

No particular pair of metal atoms is bonded through a localized pair of electrons

The valence electrons are shared among all the atoms in the sample.
A piece of metal is held together by the mutual attraction of the metal cations for the mobile, highly delocalized valence electrons
8-42

 Physical properties of metals vary over a wide range

Most are solids with moderate to high melting points, typically bent/dent rather than crack or shatter.
Unlike typical ionic and covalent substance, metals conduct heat and electricity well in both the solid and liquid states.

Two features of electron-sea model that accounts for these properties are regularity of the metal-ion array and the mobility of the valence e8-43

 Melting points and boiling points of metals are related to the energy of metallic bonding
Melting point are only moderately high because of the attractions between moveable cations and electrons need not be broken during melting Boiling requires each cation and its electron(s) to break away from the others Example: Gallium can melt in hand (mp 29.8C) but doesnt boil until over 2400C Boiling are quite high
8-44

Element
Lithium (Li) Tin (Sn) Aluminum (Al)

mp(0C)
180 232 660

bp(0C)
1347 2623 2467

Barium (Ba)
Silver (Ag) Copper (Cu) Uranium (U)

727
961 1083 1130

1850
2155 2570 3930

8-45

 Periodic trends are consistent with the electron-sea model Alkaline earth metals (2A(2)) have higher melting points than alkali metals (1A(1))

The 2A metal atoms have 2 valence e- and form 2+ cations

Greater attraction between these cations and twice as many valence e- means stronger metallic bonding than 1A metal atoms,
Higher temperature needed to melt 2A solids
8-46

8-47

 Mechanical and conducting properties can also be explained When a piece of metal is deformed by hammer The metal ions slide past each other through the electron sea and end up in new positions Thus, metal-ion cores does not repels each other

8-48

metal is deformed

8-49