CHEMISTRY

The Central Science 9th Edition

Chemical Bonds, Lewis Symbols, and the Octet Rule

Chemical bond: attractive force holding two or more atoms together. Covalent bond results from sharing electrons between the atoms. Usually found between nonmetals. Ionic bond results from the transfer of electrons from a metal to a nonmetal. Metallic bond: attractive force holding pure metals together. (electron sea)

Chapter 8 Basic Concepts of Chemical Bonding

Cindy Fuhrer Huntley High School

Lewis Symbols

As a pictorial understanding of where the electrons are in an atom, we represent the electrons as dots around the symbol for the element. The number of electrons available for bonding are indicated by unpaired dots. These symbols are called Lewis symbols. We generally place the electrons on four sides of a square around the element symbol.

The Octet Rule

Ionic Bonding
Consider the reaction between sodium and chlorine: Na(s) + Cl2(g) NaCl(s) Hf = -410.9 kJ

All noble gases except He have an s2p6 configuration. Octet rule: atoms tend to gain, lose, or share electrons until they are surrounded by 8 valence electrons (4 electron pairs). Caution: there are many exceptions to the octet rule.

The reaction is violently exothermic. We infer that the NaCl is more stable than its elements. Why? Na has lost an electron to become Na+ and chlorine has gained the electron to become Cl. Note: Na+ has an Ne electron configuration and Cl has an Ar configuration. That is, both Na+ and Cl have an octet of electrons surrounding the central ion.

NaCl forms a very regular structure in which each Na+ ion is surrounded by 6 Cl ions. Similarly, each Cl ion is surrounded by six Na+ ions. There is a regular arrangement of Na+ and Cl in 3D. Note that the ions are packed as closely as possible. Note that it is not easy to find a molecular formula to describe the ionic lattice.

 Lattice energy: the energy required to completely separate an ionic solid into its gaseous ions. Lattice energy depends on the charges on the ions and the sizes of the ions: Q1Q2

El =

is a constant (8.99 x 10 Q1 and Q2 are the charges on the ions, and d is the distance between ions. Lattice energy increases as The charges on the ions increase The distance between the ions decreases.
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Jm/C2),

Electrostatic (Lattice) Energy

Q is the charge on the cation Q+Q- Q+ is the charge on the anion E =k r -

r is the distance between the ions

Lattice energy (E) increases as Q increases and/or as r decreases.

cmpd lattice energy MgF2 2957 Q= +2,-1 MgO 3938 Q= +2,-2 LiF LiCl
1036 r F < r Cl 853
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 Examples Which in each pair would have the greatest lattice energy?
1. LiF or LiCl 2. NaCl or MgCl2 3. KBr or KI 4. MgCl2 or MgO 5. CaO or NaF

Examples Which in each pair would have the greatest lattice energy?
1. LiF or LiCl 2. NaCl or MgCl2 3. KBr or KI 4. MgCl2 or MgO 5. CaO or NaF

Born-Haber Cycle Application of Hesss Law

1. Vaporize the metal (enthalpy of vaporization)
Na (s) Na (g)

Born-Haber Cycle Application of Hesss Law

4. Add electron(s) to nonmetal (electron affinity)
Cl (g) + eCl- (g)

2. Break diatomic nonmetal molecules (if applicable) (bond enthalpy)

Cl 2 (g) Cl-

5. Put ions together to form compound (lattice energy)

Na+ + ClNaCl (s)

3. Remove electron(s) from metal (ionization energy)

Na (g) Na+ (g) + e-

 Overall Reaction: Na (s) + Cl 2 (g)

Step
NaCl (s)
1 2

Heat of Vap Bond Enthalpy Ionization Energy Electron Affinity Lattice Energy

This is useful because all quantities are directly measurable except lattice energy. The BornHaber cycle can be used to calculate lattice energy from the other values.

3 4 5

Born-Haber Cycle for Determining Lattice Energy, page

Step
1 Enthalpy of Vaporization 2 Bond Enthalpy 3 Ionization Energy 4 Electron Affinity 5 Lattice Energy

H
endothermic endothermic endothermic Exothermic Exothermic (highly)
o Hoverall = Ho + Ho + Ho + Ho + Ho 1 2 3 4 5 9.3

Covalent Bonding
When two similar atoms bond, none of them wants to lose or gain an electron to form an octet. When similar atoms bond, they share pairs of electrons to each obtain an octet. Each pair of shared electrons constitutes one chemical bond. Example: H + H H2 has electrons on a line connecting the two H nuclei.

Covalent Bonding

Lewis Structures Covalent bonds can be represented by the Lewis symbols of the elements:
Cl + Cl Cl Cl In Lewis structures, each pair of electrons in a bond is represented by a single line:

Multiple Bonds It is possible for more than one pair of electrons to be shared between two atoms (multiple bonds):
One shared pair of electrons = single bond (e.g. H2); Two shared pairs of electrons = double bond (e.g. O2); Three shared pairs of electrons = triple bond (e.g. N2).

Cl Cl

H F

H O H

H N H H

H H C H H

H H O O N N Generally, bond distances decrease as we move from single through double to triple bonds.

Bond Polarity and Electronegativity

In a covalent bond, electrons are shared. Sharing of electrons to form a covalent bond does not imply equal sharing of those electrons. There are some covalent bonds in which the electrons are located closer to one atom than the other. Unequal sharing of electrons results in polar bonds.

Electronegativity Electronegativity: The ability of one atom in a molecule to attract electrons to itself. Pauling set electronegativities on a scale from 0.7 (Cs) to 4.0 (F). Electronegativity increases
across a period and up a group.

Electronegativity and Bond Polarity Difference in electronegativity is a gauge of bond polarity or location of the atoms on the periodic table:
Nonpolar Covalent Bond - equal or almost equal sharing of electrons, electronegativity difference of 0 -0.3 or both nonmetals Polar Covalent Bond- unequal sharing of electrons, electronegativity differences 0.4-1.6 Ionic Bond - transfer of electrons, electronegativity difference greater than 1.7, metal to nonmetal especially group 1 or 2 to 16 or 17

Electronegativity and Bond Polarity There is no sharp distinction between bonding types. The positive end (or pole) in a polar bond is represented + and the negative pole -.

Dipole Moments Consider HF:

The difference in electronegativity leads to a polar bond. There is more electron density on F than on H. Since there are two different ends of the molecule, we call HF a dipole.

Dipole moment, , is the magnitude of the dipole: = Qr where Q is the magnitude of the charges. Dipole moments are measured in debyes, D.

Drawing Lewis Structures

1. Add the valence electrons. 2. Write symbols for the atoms and show which atoms are connected to which. 3. Complete the octet for the central atom, then complete the octets of the other atoms. 4. Place leftover electrons on the central atom. 5. If there are not enough electrons to give the central atom an octet, try multiple bonds.

Examples Draw Lewis Structures for each: 1. H2O 2. CO2 3. NCl3 4. SO2 5. SO3

Formal Charge It is possible to draw more than one Lewis structure with the octet rule obeyed for all the atoms. To determine which structure is most reasonable, we use formal charge. Formal charge is the charge on an atom that it would have if all the atoms had the same electronegativity.

To calculate formal charge: All nonbonding electrons are assigned to the atom on which they are found. Half the bonding electrons are assigned to each atom in a bond. Formal charge is: valence electrons - number of bonds - lone pair electrons

Formal Charge Consider:

Formal Charge Consider: For N:

C N
For C:
There are 4 valence electrons (from periodic table). In the Lewis structure there are 2 nonbonding electrons and 3 from the triple bond. There are 5 electrons from the Lewis structure. Formal charge: 4 - 5 = -1.

C N

There are 5 valence electrons. In the Lewis structure there are 2 nonbonding electrons and 3 from the triple bond. There are 5 electrons from the Lewis structure. Formal charge = 5 - 5 = 0.

We write:

C N

Examples Determine the formal charge on each atom for each: 1.H2O 2.CO2 3.NCl3 4.SO2 5.SO3

Formal Charge The most stable structure has:

the lowest formal charge on each atom, the most negative formal charge on the most electronegative atoms.

Resonance Structures Some molecules are not well described by Lewis Structures. Typically, structures with multiple bonds can have similar structures with the multiple bonds between different pairs of atoms

Resonance Structures Example: experimentally, ozone has two identical bonds whereas the Lewis Structure requires one single (longer) and one double bond (shorter).

O O

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Resonance Structures Resonance structures are attempts to represent a real structure that is a mix between several extreme possibilities.

Resonance Structures Example: in ozone the extreme possibilities have one double and one single bond. The resonance structure has two identical bonds of intermediate character.

O O

O
O3, NO3-,

O
SO42-,

O O

Common examples:

NO2, and benzene.

Examples Draw Lewis Structures for each, and include all relevant resonance structures:
1. NO32. CO323. NO2

Resonance in Benzene Benzene consists of 6 carbon atoms in a hexagon. Each C atom is attached to two other C atoms and one hydrogen atom. There are alternating double and single bonds between the C atoms.

Experimentally, the C-C bonds in benzene are all the same length. Experimentally, benzene is planar.

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 We write resonance structures for benzene in which there are single bonds between each pair of C atoms and the 6 additional electrons are delocalized over the entire ring:
or

Exceptions to the Octet Rule

There are three classes of exceptions to the octet rule:
Molecules with an odd number of electrons; Molecules in which one atom has less than an octet; Molecules in which one atom has more than an octet.

Benzene belongs to a category of organic molecules called aromatic compounds (due to their odor).

Odd Number of Electrons Few examples. Generally molecules such as ClO2, NO, and NO2 have an odd number of electrons. N O N O

Less than an Octet Relatively rare. Molecules with less than an octet are typical for compounds of Group 13. Most typical example is BF3. Formal charges indicate that the Lewis structure with an incomplete octet is more important than the ones with double bonds.

More than an Octet This is the largest class of exceptions. Atoms from the 3rd period onwards can accommodate more than an octet. Beyond the third period, the d-orbitals are low enough in energy to participate in bonding and accept the extra electron density.

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Examples Draw Lewis Structures for Each 1. PCl5 2. SF6 3. BeCl2 4. BF3 5. XeF4

Strengths of Covalent Bonds

The energy required to break a covalent bond is called the bond dissociation enthalpy, D. That is, for the Cl2 molecule, D(Cl-Cl) is given by H for the reaction: Cl2(g) 2Cl(g). When more than one bond is broken: CH4(g) C(g) + 4H(g) H = 1660 kJ the bond enthalpy is a fraction of H for the atomization reaction: D(C-H) = H = (1660 kJ) = 415 kJ. Bond enthalpies can either be positive or negative.

Bond Enthalpies and the Enthalpies of Reactions We can use bond enthalpies to calculate the enthalpy for a chemical reaction. We recognize that in any chemical reaction bonds need to be broken and then new bonds get formed. The enthalpy of the reaction is given by the sum of bond enthalpies for bonds broken less the sum of bond enthalpies for bonds formed.

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 Mathematically, if Hrxn is the enthalpy for a reaction, then H rxn = D(bonds broken ) D(bonds formed ) We illustrate the concept with the reaction between methane, CH4, and chlorine: CH4(g) + Cl2(g) CH3Cl(g) + HCl(g) Hrxn = ?

In this reaction one C-H bond and one Cl-Cl bond gets broken while one C-Cl bond and one H-Cl bond gets formed. H rxn = {[D(C - H ) + D(Cl - Cl )] [D(C - Cl ) + D(H - Cl )]}
= 104 kJ The overall reaction is exothermic which means than the bonds formed are stronger than the bonds broken. The above result is consistent with Hesss law.

Example Use bond energies from table 8.4 to calculate H for the following reaction:
H H C H C H C H H H H C Cl H C H H

Cl

C H

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Bond Enthalpy and Bond Length We know that multiple bonds are shorter than single bonds. We can show that multiple bonds are stronger than single bonds. As the number of bonds between atoms increases, the atoms are held closer and more tightly together. NOTE: A double bond between two atoms is not twice as strong as a single bond between the same two atoms.

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