Chemistry 100

Bettelheim, Brown, Campbell & Farrell

Ninth Edition

Introduction to General, Organic and Biochemistry Chapter 3

Chemical Bonds

Electronic Structure & Chemical Valence

An atom that loses one or more electrons becomes a positively charged ion called a cation.

Na 1s2, 2s2, 2p6, 3s1 Mg

1s2, 2s2, 2p6, 3s2
1 e-

Na+ +

1 e-

1s2, 2s2, 2p6 = [Ne]+ Mg 2+ + 2 e1s2, 2s2, 2p6 = [Ne]2+

F1s2, 2s2, 2p6 = [Ne]-

An atom that gains one or more electrons becomes a negatively charged ion called an anion.

1s2, 2s2, 2p5

The Octet Rule Some Limitations

The octet rule gives us a good way to understand why Group 1A-7A elements form the ions they do; but it is not perfect.
Ions of period 1 and 2 elements with charges greater than +2 are unstable. For example, boron does not lose its three valence electrons to become B3+, nor does carbon lose its four valence electrons to become C4+. Below period 2, +3 ions are stable, e.g. Al3+, Sc3+, Fe3+, etc. form. Ions of period 1 and 2 elements with charges greater than -3 are also unstable. For example, carbon does not gain four valence electrons to become C4-, and -3 ions only form in period 2 (N3-). The octet rule does not apply to Group 1B-7B (the transition elements), most of which form ions with two or more different positive charges.

Forming Chemical Bonds The Lewis Model

Ionic Bond - An atom may lose or gain enough electrons to acquire a filled valence shell and become an ion. When two ions of opposite charges are brought together an ionic bond results from the force of attraction between the cation and anion. Covalent Bond - An atom may share electrons with one or more other atoms so as to acquire a filled valence shell. A covalent bond is the result of the force of attraction between two atoms that share one or more pairs of electrons.

Electronegativity & Chemical Bonds

In forming an ionic compound the less electronegative element loses one or more electrons to the more electronegative element. The resulting Cations and Anions form the ionic bonds.

Li + F 1s 2, 2s 1 1s 2, 2s 2, 2p 5

Li + F [He] + [Ne] -

In forming a covalent compound the less electronegative element shares one or more electrons with the more electronegative element. The resulting molecule is polar because the more electronegative element gets more than an equal share.

H +

Naming Ionic Compounds

In any ionic compound the total number of positive charges must equal the total number of negative charges, the formula must be neutral! lithium ion and fluoride ion form LiF barium ion and bromide ion form BaBr2 aluminum ion and oxide ion form Al2O3 potassium ion and bicarbonate ion form KHCO3 sodium ion and phosphate ion form Na3PO4 The name does not indicate the number of each ion if the element forms only one kind of ion, e.g. aluminum oxide.

Naming Ionic Compounds

If a metal atom forms more than one cation we must indicate which one in the name: Iron (III) chloride is FeCl3 Iron(II) chloride is FeCl2 Manganese(IV) oxide is MnO2 Manganese(III) oxide is Mn2O3 Manganese(II) oxide is MnO Manganese(VII) oxide is Mn2O7 In every case the chemist must know the charges of ions which are constant.

Naming Ionic Compounds

For ionic compounds that contain polyatomic ions name the positive ion first followed by the name of the negative ion:
NH4NO3 is ammonium nitrate CaCO3 is calcium carbonate NaH2PO4 is sodium dihydrogen phosphate NaOH is sodium hydroxide CuCO3 is copper(II) carbonate Fe2(CO3)3 is iron(III) carbonate FeSO4 is iron(II) sulfate

Lewis Dot Electron Configurations

Lewis Dot Configurations as shown below are more useful in putting together covalently bonded compounds.

1A H

2A

3A

4A

5A

6A O

7A

8A He

Li Na

Be Mg

B Al

C Si

N P

O S

F Cl

Ne Ar

Drawing Lewis Dot Structures

To create a Lewis dot structure, choose the element nearest the center of the periodic chart: C in CH2F2. Pair one electron in the other atoms to the carbon to create the four single bonds.

F C F

F HCH F

Hydrogen and fluorine form only one bond each, they must always be on the outer perimeter of the molecule.

Drawing Lewis Dot Structures

Draw the Structure of methanol: CH3OH Carbon is nearest the center, Oxygen has two unpaired electrons, hydrogen has only one. Connect Carbon and Oxygen, then add hydrogens.

H C H

O H

H HC O H H

Always connect the higher valence elements before adding monovalent elements.

Drawing Lewis Dot Structures

Draw the structure of formaldehyde: H2CO Connect the Carbon and Oxygen, since there are only two hydrogens, connect a second pair of C & O electrons.

H C

H HC O
a double bond

When two atoms share two pairs of electrons a double bond is formed. Always connect the higher valent elements so that the remaining unpaired electrons match the number of monovalent elements.

Drawing Lewis Dot Structures

Draw the structure of hydrogen cyanide: HCN Connect the Carbon and Nitrogen so the remaining unpaired electrons match the number of hydrogens.

HC N
a triple bond

Draw the structure of acetylene: H2C2 Connect the two Carbons so the remaining unpaired electrons match the number of hydrogens.

H C CH
a triple bond

Drawing Lewis Dot Structures

Elements beyond the second period can violate the octet rule and expand their octet. Write the structure of Phosphorus(V) Fluoride: PF5

F F

F P F F

F F F P F F

We split the pair on phosphorus and bond fluorine atoms to each unpaired electron. The result is a compound with 10 electron pairs around phosphorus.

Drawing Lewis Dot Structures

Draw the structure of sulfuric acid: H2SO4 Connect the oxygen atoms to sulfur by using two models of oxygen from the table of electron configurations.

O H O H S O O

O HOSO O H

Note that sulfur has twelve electrons in its valence shell if the two red oxygens are viewed as double bonds. These sulfur-oxygen bonds are called dative bonds.

Naming Molecular Compounds

A molecular compound is a compound in which all bonds are covalent. When naming binary molecular compounds the less electronegative element is named first (it is generally written first in the formula). The prefixes mono-, di-, tri-, tetr-, etc. are used to show the number of atoms of each element; mono- is commonly omitted when it refers to the first atom, and is rarely used with the second atom: CO is carbon monoxide; SF2 is sulfur difluoride, NO is nitrogen oxide N2O is dinitrogen oxide

N2O4 is dinitrogen tetroxide, NO2 is nitrogen dioxide

The Geometric Structures of Molecules

Valence-Shell Electron-Pair (VSEPR) Model Valence electrons of an atom may be involved in forming single, double, or triple bonds, or they may be unshared. Each involvement creates a negatively charged region of electron density around the nucleus. Because like charges repel each other, the various regions of electron density around an atom spread so that each is as far away from the others as possible while remaining connected to the atomic core. The shape of a molecule reflects this distribution of electron density about each atom.

The Geometric Structures of Molecules

Predicting the shape of a molecule of CH2F2 : Count the regions of electron density about the element(s) nearest the center of the Periodic Chart. Then apply the following criteria: 2 = linear, angles 180E 3 = trigonal, angles 120E 4 = tetrahedral, angles 109.5E 5 = trigonal bipyramid, angles 120E and 90E 6 = octahedral, angles 90E

The Geometric Structures of Molecules

Predicting the shape of a molecule of CH2F2 : Count the regions of electron density about the element nearest the center of the Periodic Chart. 4 = tetrahedral, angles 109.5E

F F HCH F 4 H C H F

The Geometric Structures of Molecules

Predicting the shape of a molecule of CH3OH

H H C H O H

H HC O H H

4 +4

Predicting the shape of a molecule of H2O

HO H

O H

The Geometric Structures of Molecules

Predicting the shape of a molecule of formaldehyde: H2CO

H HC O

3 H
a double bond

H C

Predicting the shape of a molecule of acetylene: H2C2

H C CH

2+2
a triple bond

H C C H

The Geometric Structures of Molecules

Predicting the shape of a molecule of PF5

F F F F

F F F P F F 5

Predicting the shape of a molecule of SF6

F F F S F F

F F F S F F F 6

Geometry and Polarity of Molecules

Molecules are polar if their bonds are polar and the geometry of molecules doesnt cancel out the effect. Polarity in covalent bonds is caused when the EN is between 0.5 and 1.9 Pauling units. This polarity creates a dipole in which one end is negative the other is positive. This is depicted by:

When the effect of all the arrows along bonds are added vectorally the result is a dipole moment. This means the molecule is polar. In some molecules the bond dipoles cancel and the molecule is non-polar.

Geometry and Polarity of Molecules

Water is polar: Carbon dioxide is not polar:

O H

O C O zero dipole moment

CH2F2 is polar:

F H C H F

But CF4 is not polar!