Tufts University Chem 1 Lecture 22 Covalent Bonding Part I

Lewis Symbols
A Lewis symbol for an atom is a symbol for the element plus a dot for each valence electron.

Three Types of Chemical Bonds

Ionic [metal + non-metal(s)] Electrostatic attraction between ions Covalent [non-metals only] Sharing of electrons Metallic [metal or alloy] Metal atoms lose electrons to a common sea of electrons; resulting metal cations are cemented by the electron sea.
Chemical Bonding

Octet rule: Atoms tend to lose, gain, or share electrons until they Chemical are surrounded by eight valence Bonding electrons.

Covalent Bonds
In these bonds atoms share electrons. There are several electrostatic interactions in a covalent bond: Attractions between electrons and nuclei Repulsions between electrons Repulsions between nuclei The net effect is the attraction of two atoms.

Covalent Bonding
Non-metal atoms with unpaired electrons can share them and form a covalent bond.

Cl

Cl

H
Chemical Bonding

Cl

Cl
Chemical Bonding

There might be unshared (lone) electron pairs in molecules.

Lecture Problem
Covalent Bonding
Atoms can share one electron pair forming a single bond:

Explain the formation of covalent bonds between the following atoms using Lewis symbols:

Cl

Cl

a)

Br

or two electron pairs forming a double bond:

b)

Cl

or three electron pairs forming a triple bond:

Chemical Bonding

c)

Chemical Bonding

Polar Covalent Bonds

If a covalent bond is formed by different atoms, the sharing of bonding electrons will not be equal. In the HF molecule, fluorine pulls harder on the electrons it shares with hydrogen than hydrogen does. Therefore, the fluorine end of the molecule has more electron density than the hydrogen end.
Chemical Bonding

Electronegativity (, chi [kai])

The ability of an atom in a molecule to attract electrons to itself is measured on a scale from 0.7 for Cs to 4.0 for F No units for Not defined for noble gases (no stable molecules) On the periodic chart, electronegativity increases as you go from left to right across a row (with a local maximum on late transition metals). from the bottom to the top of a column.

Chemical Bonding

Dipole Moment
When two atoms share electrons unequally, a bond dipole results. The dipole moment, , produced by two equal but opposite charges separated by a distance, r, is calculated as:

Polar Covalent Bonds

= Qr

It is measured in Debyes (D): 1 D = 3.34 10-30 C m. [Charge Q is measured in Coulombs, C.]

Chemical Bonding

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

Chemical Bonding

Physical Properties of Covalent Compounds

Covalent bonds in molecules are strong, but interactions between molecules are usually weak. Weak intermolecular attractions mean that covalent molecular substances will usually appear as gases, liquids, or soft, low melting solids. Attraction between cations and anions in ionic compounds is strong, and such compounds are hard, high melting solids. HCl is a gas, it becomes liquid only below 85oC NaCl is a solid, it melts at +801oC and boils at +1490oC C20H42 is a waxy solid, melting point +37oC
Chemical Bonding

Covalent Bonds with Metalloids and d- and p-Metals

Metalloids and some d- and p-metals have relatively high electronegativity and may form covalent bonds and covalent (molecular) compounds. SiF4 and WF6 are gases: bonding in these molecules is covalent
F F Si F F

F F W F F F
Chemical Bonding

Acidic Oxides and Acids from Transition Metals

Covalent oxides are generally acidic. Thus, transition metals form acidic (covalent) oxides if the oxidation state is +5 or above. Example: CrO3, chromium trioxide or chromium(VI) oxide: - soft solid with relatively low melting point of +197oC; - an acidic oxide: CrO3(s) + H2O(l) H2CrO4(aq) Chromic acid, H2CrO4, is similar to sulfuric acid, H2SO4. Chromates (salts with the CrO42- anion) have the same solubility rules as sulfates: most chromates are soluble except those of Sr, Ba, Pb, Ag. Using Lewis structures, show how a molecule of CrO3 is formed from atoms CrO3

Chemical Bonding

Lewis Structures

Writing Lewis Structures

PCl3
Lewis structures are representations of molecules showing all electrons, bonding and nonbonding.
Chemical Bonding

1. Find the sum of valence electrons of all atoms in the polyatomic ion or molecule.
If it is an anion, add one electron for each negative charge. If it is a cation, subtract one electron for each positive charge.
Chemical Bonding

5 + 3(7) = 26

Writing Lewis Structures

2. The central atom usually is the least electronegative element that isnt hydrogen. Connect the outer atoms to it by single bonds. Keep track of the electrons: 26 6 = 20
Chemical Bonding

Writing Lewis Structures

3. Fill the octets of the outer atoms.

Keep track of the electrons: 26 6 = 20 18 = 2

Chemical Bonding

Writing Lewis Structures

4. Fill the octet of the central atom.

Writing Lewis Structures

5. If you run out of electrons before the central atom has an octet form multiple bonds until it does.

Keep track of the electrons: 26 6 = 20 18 = 2 2 = 0

Chemical Bonding Chemical Bonding

Lecture Problem. Draw an octet Lewis structure for each of the following: H2O NH4+ SCl2 O22- N2H2 C2H5OH

Formal Charges
Formal charge is the charge an atom would have in a molecule if all bonds were split in half To calculate formal charges:
For each atom, count the electrons in lone pairs and half the electrons it shares with other atoms. Subtract that from the number of valence electrons for that atom: The difference is its formal charge. Best Lewis structure has lowest (or no) formal charges.

Formal Charges vs Oxidation Numbers

Formal charges are different from oxidation numbers. Draw the best Lewis structure for CO2 and show formal charges on atoms. What are the oxidation numbers of the atoms?

Chemical Bonding

Chemical Bonding

Formal Charges
The best Lewis structure usually
is the one with the fewest charges. puts a negative charge on the most electronegative atom.

Determine the formal charges for the above Lewis structures. Which one is the best?

Chemical Bonding

Lewis Structures of Oxyacids and Oxyanions

Oxyacids and oxyanions have a central atom surrounded by the OH and O groups. There are no -O-O- (peroxy) fragments in their formulas.

Lecture Problem
Draw octet Lewis structures and determine formal charges for the following species: HNO3 BrO2- CH3COOH HPO42-

H2SO4
-1 O 2+ H O S O -1 O H H O O S O O H

no formal charges

real structure

unknown (unstable) isomer

Chemical Bonding

Chemical Bonding