BONDING

CHAPTER 8
8.1 TYPES OF CHEMICAL BONDS
A. Ionic Bonding

1. Electrons are transferred

2. Metals react with nonmetals

3. Ions paired have lower energy (greater stability) than separated ions

B. Coulomb's Law

𝑄1𝑄2
𝐸 = 2.31 × 10−19 𝐽. 𝑛𝑚 ( )
𝑟
a. E = energy in joules

b. Q1 and Q2 are numerical ion charges

c. r = distance between ion center in nanometers

d. negative sign indicates an attractive force

C. Bond Length (covalent)

1. Distance at which the system energy is at a minimum

2. Forces at work

a. Attractive forces (proton - electron)

b. Repulsive forces (electron - electron, proton - proton)

3. Energy is given off (bond energy) when two atoms achieve greater stability
together than apart

D. Covalent Bonds

1. Electrons are shared by nuclei

 2. Pure covalent (non-polar covalent)

a. Electrons are shared evenly.

3. Polar covalent bonds a. Electrons are shared unequally b. Atoms end up with
fractional charges (1) δ+ or δ-.

8.2 ELECTRONEGATIVITY
A. Electronegativity

The ability of an atom in a molecule to attract shared electrons to itself

B. Electronegativity Trends

1. Electronegativity generally increases across a period

2. Electronegativity generally decrease within a family

C. Characterizing bonds

1. Greater electronegativity difference between two elements means less covalent

character and greater ionic character.

2. We will not use the subtraction of electronegativities to determine ionic character.

This text uses a practical definition to identify ionic compounds:

Any compound that conducts an electric current when melted is an

ionic compound.

8.3 BOND POLARITY AND DIPOLE MOMENTS

A. Dipolar Molecules

1. Molecules with a somewhat negative end and a somewhat positive end (a dipole
moment).

2. Molecules with preferential orientation in an electric field.

 3. All diatomic molecules with a polar covalent bond are dipolar.

B. Molecules with Polar Bonds but no Dipole Moment

1. Linear, radial or tetrahedral symmetry of charge distribution

a. CO2 - linear

b. CCl4 – tetrahedral

8.4 IONS: ELECTRON CONFIGURATIONS AND SIZES

A. Bonding and Noble Gas Electron Configurations

1. Ionic bonds

a. Electrons are transferred until each species attains a noble gas electron
configuration.

2. Covalent bonds

a. Electrons are shared in order to complete the valence configurations of both

atoms.

B. Predicting Formulas of Ionic Compounds

1. Placement of elements on the periodic table suggests how many electrons are lost
or gained to achieve a noble-gas configuration a. Group I loses one electron, Group II
loses two, Group VI gains two, Group VII gains one….

2. Formulas for compounds are balanced so that the total positive ionic charge is
equal to the total negative ionic charge.

C. Sizes of Ions

1. Anions are larger than the parent atom.

2. Cations are smaller than the parent atom.

3. Ion size increases within a family.

4. Isoelectronic ions

a. Ions with the same number of electrons.

b. Size decreases as the nuclear charge Z increases.

8.5 FORMATION OF BINARY IONIC COMPOUNDS
A. Lattice Energy

1. The change in energy that takes place when separated gaseous ions are packed
together to form an ionic solid.

𝑀+ (g) + 𝑋 − (g) → MX (s)

2. Energy change is exothermic (negative sign).

Formation of lithium

3. The formation of ionic compounds is endothermic until the formation of the lattice.

4. The lattice formed by alkali metals and halogens (1:1 ratio) is cubic except for cesium
salts.

B. Lattice Energy Calculations

𝑄1𝑄2
1. Lattice energy = 𝑘 ( )
𝑟

a. k = a proportionality constant dependent on the solid structure and the electron

configuration.

b. Q1 and Q2 are charges on the ions c. r = shortest distance between centers of the
cations and the anions.

2. Lattice energy increases as the ionic charge increases and the distance between
anions and cations decreases.
8.6 PARTIAL IONIC CHARACTER OF COVALENT BONDS
A. Calculating Percent Ionic Character
𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 𝑑𝑖𝑝𝑜𝑙𝑒 𝑚𝑜𝑚𝑒𝑛𝑡 𝑜𝑓 𝑋− 𝑌
Percent ionic character = (𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝑑𝑖𝑝𝑜𝑙𝑒 𝑚𝑜𝑚𝑒𝑛𝑡 𝑜𝑓 𝑋 +𝑌 − ) × 100%

B. Ionic vs. Covalent

1. Ionic compounds generally have greater than 50% ionic character.

2. Ionic compounds generally have electronegativity differences greater than 1.6.

3. Percent ionic character is difficult to calculate for compounds containing polyatomic

ions.

8.7 THE COVALENT CHEMICAL BOND: A MODEL

A. Strengths of the Bond Model

1. Associates quantities of energy with the formation of bonds between elements.

2. Allows the drawing of structures showing the spatial relationship between atoms in
a molecule.

3. Provides a visual tool to understanding chemical structure.

B. Weaknesses of the Bond Model

1. Bonds are not actual physical structures

2. Bonds cannot adequately explain some phenomena

a. resonance

8.8 COVALENT BOND ENERGIES AND CHEMICAL REACTIONS

A. Average Bond Energies
B. Multiple Bonds

1. Single bonds - 1 pair of shared electrons

2. Double bonds - 2 pairs of shared electrons

3. Triple bonds - 3 pairs of shared electrons

4. As the number of shared electrons increases, the bond length shortens.

C. Bond Energy and Enthalpy

1. ∆H = sum of the energies required to break old bonds(endothermic) +

sum of the energies released in forming new bonds (exothermic)

2. ∆H = ∑ D (Bonds broken) - ∑ D (Bonds formed)

a. D always has a positive sign

8.9 THE LOCALIZED ELECTRON BONDING MODEL

A. Lone electron pairs

1. Electrons localized on an atom (unshared).

B. Bonding electron pairs

1. Electrons found in the space between atoms (shared pairs).

C. Localized Electron Model

1. A molecule is composed of atoms that are bound together by sharing pairs of

electrons using the atomic orbitals of the bound atoms.
D. Derivations of the Localized Model

1. Valence electron arrangement using Lewis structures

2. Prediction of molecular geometry using VSEPR (valence shell electron pair

repulsion)

3. Description of the type of atomic orbitals used to share or hold lone pairs.

8.10 LEWIS STRUCTURES

A. Electrons and Stability

1. The most important requirement for the formation of a stable compound is that the
atoms achieve noble gas configurations.

2. Duet rule a. Hydrogen, lithium, beryllium, and boron form stable molecules when
they share two electrons (helium configuration).

3. Octet Rule a. Elements carbon and beyond form stable molecules when they are
surrounded by eight electrons.

B. Writing Lewis Structures

1. Rules

a. Add up the TOTAL number of valence electrons from all atoms.

b. Use a pair of electrons to form a bond between each pair of bound atoms. Lines
instead of dots are used to indicate each pair of bonding electrons.

c. Arrange the remaining atoms to satisfy the duet rule for hydrogen and the octet rule
for the second-row elements.

8.11 EXCEPTIONS TO THE OCTET RULE

A. Boron Trifluoride

1. Note that boron only has six electrons around it.

2. BF3 is electron deficient and acts as a Lewis acid (electron pair acceptor).

3. Boron often forms molecules that obey the octet rule.

B. Sulfur Hexafluoride

1. Note that sulfur has 12 electrons around it, exceeding the octet rule.

2. Sulfur hexafluoride is very stable.

3. SF6 fills the 3s and 3p orbitals with 8 of the valence electrons, and places the other
4 in the higher energy 3d orbital.

C. More About the Octet Rule

1. Second row elements C, N, O and F should always obey the octet rule.

2. B and Be (second row) often have fewer than eight electrons around them, and
form electron deficient, highly reactive molecules.

3. Second row elements never exceed the octet rule.

4. Third row and heavier elements often satisfy (or exceed) the octet rule.

5. Satisfy the octet rule first. If extra electrons remain, place them on elements having
available d orbitals a. When necessary to exceed the octet rule for one of several third-
row elements, assume that the extra electrons be placed on the central atom.

8.12 RESONANCE
A. Nitrate ion

1. Experiments show that all N-O bonds are equal.

2. A single Lewis structure cannot represent the nitrate ion.

3. A resonance structure is drawn by writing the three variant structures, connected

by a double-headed arrow.

B. Resonance

1. When more than one valid Lewis structure can be written for a particular molecule.

2. The actual structure is an average of the depicted resonance structures.

C. Odd Electron Molecules

1. Molecules in which there is not an even number of electrons

2. Does not fit localized electron model.

D. Formal Charge

1. Number of valence electrons on the free atom minus Number of valence electrons
assigned to the atom in the molecule

a. Lone pair (unshared) electrons belong completely to the atom in question

b. Shared electrons are divided equally between the sharing atoms.

2. The sum of the formal charges of all atoms in a given molecule or ion must equal
the overall charge on that species.

a. If the charge on an ion is -2, the sum of the formal charges must be -2.

E. Using Formal Charge to Evaluate Lewis Structures

1. If nonequivalent Lewis structures exist for a species, those with the formal charges
closest to zero, and with negative formal charges on the most electronegative atoms are
considered the best candidates.

2. Only experimental evidence can conclusively determine the correct bonding

situation in a molecule.

8.13 MOLECULAR STRUCTURE: THE VSEPR MODEL

A. Valence Shell Electron Pair Repulsion (VSEPR)

1. The structure around a given atom is determined principally by minimizing

electron-pair repulsions.

2. Non-bonding and bonding electron pairs will be as far apart as possible.

B. Effect of Unshared Electron Pairs

1. The ideal tetrahedral angle is 109.5°.

2. Lone (unshared) electron pairs require more room than bonding pairs (they have
greater repulsive forces) and tend to compress the angles between bonding pairs.

3. Lone pairs do not cause distortion when bond angles are 120° or greater.

C. VSEPR and Multiple Bonds

1. For the VSEPR model, multiple bonds count as one effective electron pair.
 2. When a molecule exhibits resonance, ANY of the resonance structures can be
used to predict the molecular structure using the VSEPR model.

D. Molecules Containing No Single Central Atom

1. Apply the principal of distancing shared and unshared electron pairs.

2. Look at real 3-dimensional, rotatable models to develop predictive skills.

 QUESTIONS
1. Choose the statement that best describes the PbCl4 molecule in the gas phase.
A) The bond angles are all about 109°.
B) The molecule is polar.
C) The molecule has a dipole moment.
D) The bonds are nonpolar.
E) More than one of the above.
Answer: Pb atom has 4 valence electrons at the last level. Since the compound Pb𝐶𝑙4
has 1 Pb and 4 Cl, this indicates that the 4 valence electrons of the lead (Pb) will react
with each of the chlorine (Cl). So, the geometry is tetrahedral, with a linkage angle of
109.5.
2. Which of the following has a zero-dipole moment?
A) NH3
B) NO2
C) PF5
D) SO2
E) HCN
Answer: PF5 has a zero-dipole moment because of its symmetrical geometry (trigonal
bipyramidal). Although the P-F bond is polar, the entire PF5 molecule is nonpolar because
the dipole of P-F bond gets canceled out by each other resulting in the zero net dipole
moment.
3. Of the following, which molecule has the largest bond angle?
A) O3
B) OF2
C) HCN
D) H2O
E) More than one of the above have equally large bond angles.
Answer: HCN is linear and the bond angle is 180. So, it is the largest bond angle.

4. The bond angles about the carbon atom in the formaldehyde molecule, H2C=O, are
about:
a) 120°
b) 60°
c) 109°
d) 180°
e) 90°
Answer: In formaldehyde. The central atom has 3 electron clouds emanating from it. The
carbon atom has 2 single bonds to hydrogen and a double bond to oxygen. For these
clouds to be as far as possible from one another, they will form a plane containing the
central atom. The bonds will emanate from the central atom at angles of about 120 to
each other.

5. Which of the following bonds would be the most polar without being considered ionic?
a) Mg-O
b) C-O
c) O-O
d) Si-O
e) N-O
Answer: Si-O is the most polar because it has the largest electronegativity difference.
Mg-O removed from the answers because the bond between Mg and O is ionic.

6. Which of the following bonds would be the least polar, yet still be considered polar
covalent?
a) Mg-O
b) C-O
c) O-O
d) Si-O
e) N-O
Answer: Because the electronegativity difference between N-O is 3.44-3.04=0.4
7. Choose the compound with the most ionic bond.
a) LiCl
b) KF
c) NaCl
d) LiF
e) KCl
Answer: Because the most ionic bond means the one which has the highest difference
in electronegativities between the ions. The differences in electronegativities are:
- LiCl (3.16-0.98 = 2.18)
- KF (3.98-0.82 = 3.16)
- NaCl (3.16-0.93 = 2.23)
- LiF (3.98-0.98 = 3.00)
- KCl (3.16-0.82 = 2.34)
KF has the largest number, so it has the strongest attraction between the ions and is the
most ionic.
8. Which of the following bonds is least polar?
a) C—O
b) H—C
c) S—Cl
d) Br—Br
e) They are all nonpolar
Answer: (Br—Br) bond is the least polar because the electronegativity between Br and
Br is the least.

9. In the gaseous phase, which of the following diatomic molecules would be the most
polar?
a) CsF
b) CsCl
c) NaCl
d) NaF
e) LiF
Answer: Because the electronegativity difference between Cs and F is the largest
(3.98-0.79 = 3.19), so it is the most polar.

10. Based on electronegativities, which of the following would you expect to be most
ionic?
a) N2
b) CaF2
c) CO2
d) CH4
e) CF4
Answer: Because the electronegativity difference between Ca and F is the largest
(3.98-1 = 2.98), so it the most ionic.

11. What is the correct order of the following bonds in terms of decreasing polarity?
a) N-Cl, P-Cl, As-Cl
b) P-Cl, N-Cl, As-Cl
c) As-Cl, N-Cl, P-Cl
d) P-Cl, As-Cl, N-Cl
e) As-Cl, P-Cl, N-Cl
Answer: The electronegativity differences are:
N-Cl (3.16-3.04 = 0.12), P-Cl (3.16-2.19 = 0.97), As-Cl (3.16-2.18 = 0.98)
12. In which of the following compounds does the bond between the central atom and
bromine have the greatest ionic character?
a) LiBr
b) KBr
c) SeBr2
d) AsBr3
e) CaBr2
Answer: Because the electronegativity difference between K and Br is the largest (2.96-
0.82 = 2.14)

13. Which of the following arrangements is in order of increasing size?

a) Ga3+ > Ca2+ > K + > Cl− > S 2−
b) S 2− > Cl− > K + > Ca2+ > Ga3+ 4 | P a g e
c) Ga3+ > S 2− > Ca2+ > Cl− > K +
d) Ga3+ > Ca2+ > S 2− > Cl− > K +
e) Ga3+ > Ca2+ > S 2− > K + > Cl−
Answer: Because with increasing the positive charge of the ion, the radius decreases.
With increasing the negative charge of the ion, the radius increases. So, (𝐺𝑎3+) has the
smallest size and (𝑆 2−) has the largest size.

14. Which of the following ionic compounds has the largest lattice energy (i.e., the
lattice energy most favorable to a stable lattice)?
a) BaO
b) BeO
c) CsI
d) NaBr
e) BaS
Answer: Because BeO has the highest charges on the ions, plus the smaller radii,
directly resulting in a greater lattice.

15. Which of the following ionic compounds has the smallest lattice energy (i.e., the
lattice energy least favorable to a stable lattice)?
a) LiF
b) CsI
c) NaCl
d) BaO
e) MgO
Answer: CsI has the smallest lattice energy because the total charge equal 1 and size
of Cs and I is very large as the lattice energy is inversely proportional with the size and
direct with the charge.
16. The first electron affinity value for oxygen is _______ and the second electron
affinity value is ________.
a) unfavorable (endothermic), favorable (exothermic)
b) unfavorable (endothermic), unfavorable (endothermic)
c) favorable (exothermic), favorable (exothermic)
d) favorable (exothermic), unfavorable (endothermic)
e) More information is needed.
Answer: When oxygen gains the first electron, energy releases. That’s why the first
electron affinity is negative. But after the first electron affinity, oxygen becomes an
anion. So, it has a negative charge now. Now if the oxygen wants to gain another
electron, a repulsion will occur, because oxygen has a negative charge (as it is anion)
and electron gained has a negative charge. In this case we have to serve an extra
amount of energy, so, the second electron affinity is positive.

17. As indicated by Lewis structures, which of the following would probably not exist as
a stable molecule?
a) CH3OH
b) CH2O
c) CH3O
d) C2H2
e) C3H4
Answer: CH₃O would not exist as a stable molecule because, in this compound oxygen
is not stable. In order to stable the oxygen carbon should form the double bond with
oxygen. While the valency of carbon is four and it already forms three bonds with three
hydrogen atoms in this compound. There is one electron left to form the bond with
oxygen. So, there are not enough electrons which could bonded with oxygen and form
stable compound.

18. Consider the following molecules.

I. BF3
II. CHBr3 (C is the central atom)
III. Br2
IV. XeCl2
V. CO
VI. SF4
Select the molecule(s) that fit the given statement. (These molecules have a zero
net dipole moment.)
A) III, V
B) I, III, IV
C) III, IV, V
D) I, III, IV, VI
E) none of them
 Answer: BF3 has zero dipole moment (each B-F bond is polar/ forms a dipole
because there is electronegativity difference between B and F. but, the shape of the
molecule is trigonal planar which is symmetrical, so the dipoles cancel each other.)
Br2 has zero dipole moment because the electronegativity difference between Br
and Br equal zero. XeCl2 has zero dipole moment (the two Xe-Cl bonds are equal in
magnitude and opposite in direction, so they cancel each other)

19. How many of the following molecules possess dipole moments?

BH3 , CH4 , PCl5 , H2O, HF, H2
A) 1
B) 2
C) 3
D) 4
E) 5
Answer: HF and H2O have dipole moments.

20. Which of the following molecules has a dipole moment?

A) BH3
B) SiF4
C) PF3
D) O2
E) none of these
Answer: PF3 has a dipole moment. Phosphorus and fluorine have different
electronegativity and the PF3 molecule also contains a lone pair.