Periodic Table

Nonmetals are on the right side of the periodic table (with the exception of H).

Nonmetals tend to gain electrons and act as Oxidizing Agents * greater affinity for electrons * high electronegativity * high ionization energy

Periodic Table

Metalloids border the stair-step line (with the exception of Al and Po).

Periodic Table

Metals are on the left side of the chart.

Metals tend to lose electrons and act as Reducing Agents * low affinity for electrons * low electronegativity * low ionization energy

CHEMICAL COMBINATION
-

Why do atoms combine to form a compound?

to form a stable

configuration

Noble gas configuration 8 valence electrons (ns + np) Octet Rule

2 Ways to Form a Stable Configuration

1) Electron transfer 2) Electron sharing

Electron Transfer

Na

Cl

Na+

Cl-

Cation

Anion

Ions

When atoms lose or gain electrons, they become ions.

Cations are positive and are formed by elements on the left side of the periodic chart (Metals). Anions are negative and are formed by elements on the right side of the periodic chart (Nonmetals).

Atomic versus Ionic Radius

isoelectronic = same number of electrons

Li+, Be2+, B3+, C4+ N3-, O2-, F1What happens to its ionic radius?

S4+ S3+ S2+ S1+ S S1- S2- S3- S4-

Pseudo-noble gas ion = completely-filled d subshell

Cu (Z = 29) : [18Ar] 4s1 3d10 Cu1+ [18Ar] 4s0 3d10 Zn (Z = 30) : [18Ar] 4s2 3d10 Zn2+ [18Ar] 4s0 3d10

Ionic Bonds
Ionic compounds (such as NaCl) are generally formed between metals and nonmetals metals and metalloids metalloids and nonmetals.
Ionic bond = electrostatic interaction

Writing A Chemical Formula

Because compounds are electrically neutral, one can determine the formula of a compound this way:
The charge on the cation becomes the subscript on the anion. The charge on the anion becomes the subscript on the cation. If these subscripts are not in the lowest whole-number ratio, divide them by the greatest common factor.

Common Cations

Common Anions

Electron Sharing

Electron Sharing
Covalent bonds = overlapping of atomic orbitals Formed by a nonmetal and a nonmetal or a nonmetal and a metalloid Covalency number = number of covalent bonds an atom can form = 8 number of valence electrons
F : CN = 8 7 = 1 C : CN = 8 4 = 4
H C H

FF HF
H H

Covalent bond formation

Head-on Overlap = Sigma () bond

Lateral / Side-on Overlap = Pi () bond

 Writing Lewis Structures

Atoms bond by using their valence electrons The number of valence electrons is equal to the group number of the atom
Carbon is in group 4A and has 4 valence electrons Hydrogen is in group 1A and has 1 valence electron Oxygen is in group 6A and has 6 valence electrons Nitrogen is in group 5A and has 5 valence electrons

To construct molecules the atoms are assembled with the correct number of valence electrons If the molecule is an ion, electrons are added or subtracted to give it the proper charge The structure is written to satisfy the octet rule for each atom and to give the correct charge If necessary, multiple bonds can be used to satisfy the octet rule for each atom

Example
Write the Lewis structure for the carbon dioxide (CO2)
The total number of electrons needed to satisfy the normal valence electrons of each atom (usually following Octet Rule) C : 1 C atom x 8 e- = 8 O : 2 O atoms x 8 e- = 16 ------24 electrons Calculate the valence electrons of each atom
C : 1 C atom x 4 e- = 4 O : 2 O atoms x 6 e- = 12 -------16 electrons Calculate the number of bonds 24 e- - 16 e- = 8 electrons/2 electrons per bond = 4 bonds

Example
Write the Lewis structure for the carbon dioxide (CO2)
Sketch the molecule Usually the atom with highest covalency number is positioned at the center Hydrogen and oxygen atoms are oftentimes found on the outer portion of the molecule C has 4 bonds, N has 3 bonds, O has 2 bonds, H and Halogens have 1 bond 24 e- - 16 e- = 8 electrons/2 electrons per bond = 4 bonds

Fill in electron pairs around the atoms up to the total electrons available, following the Octet Rule C : 1 C atom x 4 e- = 4 O : 2 O atoms x 6 e- = 12 -------16 electrons

 Example
Write the Lewis structure for the chlorate ion (ClO3-)
The total number of valence electrons including the electron for the negative charge is calculated

Three pairs of electrons are used to bond the chlorine to the oxygens

The remaining 20 electrons are added to give each atom an octet

 Exceptions to the Octet Rule

The octet rule applies only to atoms in the second row of the periodic table (C, O, N, F) which are limited to valence electrons in the 2s and 2p orbitals In second row elements fewer electrons are possible Example: BF3

In higher rows other orbitals are accessible and more than 8 electrons around an atom are possible Example: PCl5 and SF6

 Formal charge
A formal charge is a positive or negative charge on an individual atom The sum of formal charges on individual atoms is the total charge of the molecule or ion The formal charge is calculated by subtracting the assigned electrons on the atom in the molecule from the electrons in the neutral atom Electrons in bonds are evenly split between the two atoms; one to each atom Lone pair electrons belong to the atom itself

 Examples
Ammonium ion (NH4)+

Nitrate ion (NO3)-

Exercise:

Write the Lewis structure of the carbonate ion (CO32-) and bicarbonate ion (HCO3-).
O C O O
HO

2-

O C O

Carbonate ion

Bicarbonate ion

Write the formal charge of each atom in carbonate ion (CO32-) and bicarbonate ion (HCO3-).

*** Formal charges allow us to check whether a molecule or ion is a reasonable Lewis structure.
Additional rules in Formal Charges 1) Structures with zero or small formal charges are preferred than those with larger formal charges Nonzero formal charges on adjacent atoms are usually of opposite sign. Highly electronegative atoms should have negative rather than positive formal charges.

2) 3)

Consider the following molecules/ions:

CO2 CO32SO42ClO3-

 Resonance
Often a single Lewis structure does not accurately represent the true structure of a molecule The real carbonate ion is not represented by any of the structures 1,2 or 3

Experimentally carbonate is known not to have two carbon-oxygen single bonds and one double bond; all bonds are equal in length and the charge is spread equally over all three oxygens

 The real carbonate ion can be represented by a drawing in which partial double bonds to the oxygens are shown and partial negative charge exists on each oxygen The real structure is a resonance hybrid or mixture of all three Lewis structures Double headed arrows are used to show that the three Lewis structures are resonance contributors to the true structure

 One resonance contributor is converted to another by the use of curved arrows which show the movement of electrons
The use of these arrows serves as a bookkeeping device to assure all structures differ only in position of electrons

A calculated electrostatic potential map of carbonate clearly shows the electron density is spread equally among the three oxygens
Areas which are red are more negatively charged; areas of blue have relatively less electron density

Chapter 1

29

Resonance Structures
Consider the following molecules/ions: CO2 CO32

SO42ClO3NO3NO2

Uses a coordinate covalent bond

N O O O

N O

N O O

For a tutorial on Lewis Dot Structures, check out this link:

http://www.kentchemistry.com/links/bonding/lewisdotstruct.htm