LESSON 4.
1 a CHEMICAL BONDING and MOLECULAR GEOMETRY
• Whenever atoms or ions are strongly attached to one another, we say that there is a chemical bond
between them. There are three general types of chemical bonds: ionic, covalent (or molecular), and
metallic.
• The electrons involved in chemical bonding are the valence electrons (those residing in the incomplete
outer shell of an atom). The Lewis symbol (named after the chemist G. N. Lewis) for an element
consists of the chemical symbol for the element plus a dot for each valence electron. The number of
valence electrons of any representative element is the same as its group number in the periodic table.
• Atoms often gain, lose, or share electrons to achieve the same number of electrons as the noble gas
closest to them in the periodic table, because the noble gases have very stable electron arrangements
(that’s why they are generally unreactive). Because all noble gases (except He) have eight valence
electrons, many atoms tend to gain, lose, or share electrons until they are surrounded by eight valence
electrons (Octet Rule). An octet of electrons consists of full s and p subshells on an atom. There are
many exceptions to the octet rule (most importantly H, which follows the duet rule), but the octet rule
is still very useful.
• Ionic bond: refers to electrostatic forces that exist between ions of opposite charge. Ionic compounds
are generally combinations of metals and nonmetals (excluding the noble gases, Group 8A).
Na· + :Cl: à Na+ + [ Cl ]- (NaCl compound)
The arrow indicates the transfer of an electron from the Na atom to the Cl atom. Each ion has an octet
of electrons.
• Covalent (or molecular) bond: results from the sharing of electrons between two atoms. Molecular
compounds are generally composed of nonmetals only.
H· + ·H à H : H or H−H (H2 molecule)
:Cl· + ·Cl: à Cl : Cl or Cl−Cl (Cl2 molecule)
The sharing of a pair of electrons, like in the above examples, constitutes a single bond. When two
electron pairs are shared, two lines are drawn, representing a double bond. When three electron pairs
are shared, three lines are drawn, representing a triple bond.
:N· + ·N: à :N:::N: or :N º N: (N2 molecule)
Steps in writing Lewis Dot Structures for molecular compounds:
1. Find the total number of valence electrons.
2. Determine which atoms are the central atoms and which are the terminal atoms. The central atoms
are the least electronegative. The terminal atoms are the most electronegative.
3. Find the total number of electrons that will satisfy the octet and duet rule.
4. Determine the total number of bonds: (step 3 – step 1) ÷ 2
5. Distribute the remaining electrons starting from the terminal atoms towards the central atoms,
following the octet and duet rule.
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• Sometimes, molecules and ions cannot be adequately described by a single Lewis structure. Consider
the ozone molecule (O3). We could put the O=O double bond either on the left or on the right:
O=O−O : « :O−O=O
The two Lewis structures are equivalent except for the placement of electrons. Equivalent Lewis
structures of this sort are called resonance structures. To describe the structure of ozone properly, we
write both Lewis structures and use a double-headed arrow to indicate that the real molecule is a blend
of the two resonance structures (just like green paint is a blend of yellow paint and blue paint).
General exceptions to the octet rule include molecules that have an odd number of electrons and
molecules in which one or more atoms possess more or fewer than eight electrons. Molecules with an odd
number of electrons are relatively rare in the s and p blocks but rather common among the d- and f-block
elements. Compounds with more than an octet of electrons around an atom are called expanded-valence
molecules. One model to explain their existence uses one or more d orbitals in bonding in addition to the
valence ns and np orbitals. Such species are known for only atoms in period 3 or below, which
contain nd subshells in their valence shell.
Lewis dot structures provide a simple model for rationalizing the bonding in most known compounds.
However, there are three general exceptions to the octet rule:
1. Molecules, such as NO, with an odd number of electrons;
2. Molecules in which one or more atoms possess more than eight electrons, such as SF6; and
3. Molecules such as BCl3, in which one or more atoms possess less than eight electrons.
Exercises:
V. Identify the bonds between atoms of the following pairs of element as I for ionic or C for covalent
compound.
____1. H and Br ____6. K and Cl ____11. C and O ____16. Cl and F
____2. Li and O ____7. Br and Br ____12. Ca and O ____17. N and H
____3. P and F ____8. F and F ____13. H and F ____18. Ca and Br
____4. C and S ____9. Al and Br ____14. B and F ____19. N and N
____5. O and F ____10. N and I ____15. Cl and Cl ____20. Se and O
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VI. Show ionic bond formation between each of the following pairs of elements. Write the formulas of the
resulting ionic compound.
LEWIS STRUCTURE IONIC EMPIRICAL FORMULA
1. Be + S
2. Ba + Cl
3. Ca + O
4. Al + F
5. In + N
6. Sn + Cl
7. Ca + Br
6
8. Al + S
9. Rb + I
10. In + F
VII. Write Lewis structures for the following ions or molecules. Show the valence electron count for each.
1. CCl4 3. CH4
2. NH3 4. SO2
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5. CO2 8. SCl2
6. H2S 9. SO3
7. PH3 10. OF2
11. O3 (Ozone) -
12. CN (Cyanide)
8
-
13. NO2 (Nitrite Ion) 14. Draw the Lewis structure of the 7 Diatomic
molecules. (H2, O2, N2, Cl2, Br2, I2, F2)
Which is the double bond?
Which is the triple bond?
Exceptions to the Octet Rule
VIII. Write Lewis structures for the following ions or molecules that shows exceptions to the octet rule
1. PCl5 3. XeF4
2. BF3 4. AlH3
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3. NO2 6. ClO2
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MOLECULAR GEOMETRY
• We will discuss molecules that have a single atom bonded to two or more atoms of the same type.
(examples: CCl4, H2O, SO3, CO2) Such molecules conform to the general formula AXn in which the central
atom A is bonded to n X atoms. The shapes that AXn molecules can adopt depend on the value of n.
• An electron domain is a region in which it is most likely to find electrons. A bonding pair of electrons
defines an electron domain. A nonbonding pair (or lone pair) of electrons also defines an electron
domain.
• Imagine tying two balloons together at their ends. The balloons will try to get out of each other’s way.
They will naturally orient themselves to point away from each other. Electrons in molecules behave the
same way. Electron domains are negatively charged regions, so they repel one another. To minimize the
repulsions among them, the electron domains will arrange themselves like the balloons. This is called the
Valence-Shell Electron-Pair Repulsion (VSEPR) Model.
There are six basic shape types for molecules
1. Linear: In a linear model, atoms are connected in a straight line. The bond angles are set at 180°. A
bond angle is very simply the geometric angle between two adjacent bonds. For example, carbon
dioxide has a linear molecular shape.
2. Trigonal planar: Just from its name, it can easily be said that molecules with the trigonal planar shape
are somewhat triangular and in one plane (meaning a flat surface). Consequently, the bond angles are
set at 120°. An example of this is boron trifluoride.
3. Tetrahedral: Tetra- signifies four, and -hedral relates to a surface, so tetrahedral almost literally
means "four surfaces." This is when there are four bonds all on one central atom, with no extra
unshared electron pairs. In accordance with the VSEPR (valence-shell electron pair repulsion theory),
the bond angles between the electron bonds are 109.5°. An example of a tetrahedral molecule is
methane (CH4).
4. Octahedral: Octa- signifies eight, and -hedral relates to a surface, so octahedral almost literally means
"eight surfaces." The bond angle is 90°. An example is sulfur hexafluoride (SF6).
5. Pyramidal: Pyramidal-shaped molecules have pyramid-like shapes. Unlike the linear and trigonal planar
shapes but similar to the tetrahedral orientation, pyramidal shapes requires three dimensions in order
to fully separate the electrons. Here, there are only three pairs of bonded electrons, leaving one
unshared lone pair. Lone pair - bond pair repulsions change the angle from the tetrahedral angle to a
slightly lower value. An example is NH3 (ammonia).
6. Bent: The final basic shape of a molecule is the non-linear shape, also known as bent or angular. One of
the most unquestionably important molecules any chemist studies is water, or H2O. A water molecule
has a non-linear shape because it has two pairs of bonded electrons and two unshared lone pairs. Like
in the other arrangements, electrons must be spaced as far as possible. Lone pair - bond pair
repulsions push the angle from the tetrahedral angle down to around 106°.
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ELECTRON PAIR GEOMETRIES AND MOLECULAR SHAPES
Formula type Total Bonding Nonbonding Molecular Molecular
Example
(hybridization) electron domains domains Geometry shape
domains
CO2
AX2 2 2 0 linear
(sp)
BF3
AX3
trigonal
3 0
(sp2) planar
SO2
AX2E1
V – shaped
2 1
(sp2) (bent)
CH4
AX4 4 0 tetrahedral
3
(sp )
NH3
AX3E1
trigonal
4 3 1
(sp3) pyramidal
H 2O
AX2E2
V – shaped
2 2
(sp3) (bent)
PCl5
AX5
trigonal
5 5 0
(sp3d) bipyramidal
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SF4
3 4 1 seesaw
AX4E1 (sp d)
ClF3
3 2 T – shaped
AX3E2 (sp3d)
ICl2
2 3 linear
AX2E3 (sp3d)
SF6
AX6 6 0 octahedral
3 2
(sp d )
BrF5
6 square
5 1
AX5E1 (sp3d2) pyramidal
XeF4
AX4E2 (sp3d2) square
4 2
planar
HYBRIDIZATION
Hybridization is the combining of atomic orbitals to create new orbitals. The number of hybrid
orbitals depends on how many atomic orbitals one adds together.
1. sp Hybridization
The hybridization of one s orbital and one p orbital on a central atom gives rise to two sp orbitals.
Hybridization as sp gives two orbitals, which are in a linear arrangement, that is, 180o apart. An
example of sp hybridization is found in HgCl2 (mercury (II) chloride).
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2. sp2 Hybridization
The hybridization of one s orbital and two p orbitals on a central atom gives rise to three sp2
orbitals. Hybridization as sp2 gives three orbitals, which are planar and 120o apart. An example is
BCl3.
3. sp3 Hybridization
The hybridization of one s and all three p orbitals on a central atom gives rise to four sp3 orbitals.
Hybridization as sp3 gives four identical orbitals, which are aligned in a tetrahedral configuration and
so are 109.5o apart. This very common structure is found in CH4, NH3, NH4+, and CCl4; it is the usual
hybridization form of singly-bonded carbon atoms in organic compounds.
4. dsp2 Hybridization
Atoms of the transition metals and of other elements which have d atomic orbitals available to
them can use these d orbitals in hybridization. The hybridization of one s, two p, and one d orbital on
a central metal atom gives rise to four hybrid dsp2 orbitals. They are square planar in alignment and
90o apart, because the hybrid uses the dxy, s, px and py orbitals, all of which are in the xy plane. An
example of a square planar complex ion is Ni (CN)42-.
5. dsp3 Hybridization
Atoms which have d orbitals available to them can also use them to form other types of hybrid
orbitals. The hybridization of one s, one d, and three p orbitals on a central atom gives rise to five
dsp3 orbitals. Hybridization as dsp3 gives five orbitals, three equatorial and two axial, because this
hybridization uses the dz2, the s, and all three of the p orbitals; one of the p orbitals, pz, is
perpendicular to the xy plane. In effect, the trigonal bipyramidal geometry of this hybridization is the
trigonal plane of sp2 hybridization with the addition of the z axis component due to the pz and dz2
orbitals. An example of dsp3 hybridization is PCl5, whose geometry is that of a trigonal bipyramid.
6. d2sp3 Hybridization
Atoms which have two or more d orbitals available to them can use more than one d orbital in
hybridization. The hybridization of two d orbitals, one s orbital, and three p orbitals on a central
atom gives rise to six hybrid d2sp3 orbitals. Hybridization as d2sp3 gives six orbitals which are
equivalent in energy and geometry. All adjacent orbitals are 90o apart, and all nonadjacent orbitals
are 180o apart. This form of hybridization has the geometric structure of an octahedron, with six
vertices and eight sides. The orbitals which contribute to the square planar geometry of the
equatorial plane of the octahedron are the s, px, py, and dxy atomic orbitals; the z axis component is
again due to the pz and the dz2 atomic orbitals. Molecules or ions which have this structure are said
to have octahedral structures or symmetry; sulfur hexafluoride and uranium hexafluoride are
examples of such molecules.
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POLARITY OF MOLECULAR COMPOUNDS
If the electrons are not distributed equally, the molecule is said to be polar. That is, the molecule has a
negative end and a positive end. It has two poles and is polar; it has a measurable dipole moment.
The electrons are not distributed evenly so the water molecule is polar. The negative end of the molecule is
the oxygen end. O is more electronegative than H and pulls the negative electrons toward itself. Also, there
are two lone pairs around oxygen.
You can write a formula denoting the negative and positive end of the molecule. The sigma (with a plus or
minus) above the symbol for the atom is the indicator for which end of the molecule is positive or negative.
INTERMOLECULAR FORCES OF ATTRACTION
•Physical properties forces
Intermolecular dependare
on the
these forces. forces
attractive The stronger the between
that exist forces between the particles,
molecules.
• (a) the higher
In gases, there the
is nomelting
strong point.
attractive force that is why the molecules can expand to fill their container.
(b)liquids,
In the higher the boiling point.
the intermolecular attractive forces are strong enough to hold molecules close together, but
(c)
not the lower
strong the vapor
enough pressure
to keep them (partial pressure
from moving pastofone
vapor in equilibrium
another. with liquids
That is why liquid or solid
can be in a closed
poured. In
container
solids, at a fixed temperature).
the intermolecular forces are strong enough not only to hold molecules together but also to lock
(d) the
them in higher
place. the viscosity (resistance to flow).
(e) the greaterforces:
1. Ion-dipole the surface
existtension
between(resistance to an
an ion and increase
a polar in surface
molecule. area).
Polar molecules are dipoles; they
have a positive end and a negative end. Positive ions are attracted to the negative end of a dipole,
and negative ions are attracted to the positive end.
2. Dipole-dipole forces: exist between neutral polar molecules. Polar molecules attract each other
when the positive end of one molecule is near the negative end of another. Dipole-dipole forces are
weaker than ion-dipole forces.
3. London dispersion forces: Nonpolar molecules can have instantaneous dipole moments. At all
times, electrons are moving around the nucleus. At one instant, the electrons of an atom could be
gathered on one side of the nucleus. The temporary dipole on one atom can induce a similar dipole
on an adjacent atom, causing the atoms to be attracted to each other. London dispersion forces
exist between all molecules.
4. Hydrogen bonding: exists between the hydrogen atom in a polar bond (particularly an H—F, H—O,
or H—N bond) and an unshared electron pair on a nearby small electronegative ion or atom (usually
an F, O, or N atom on another molecule).
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Exercises:
I. Predict the shape of the following:
General Molecular Molecular Geometry Polarity Hybridization
Compound
Lewis Structure Formula Shape
1. SeH2
2. InBr3
3. MgI2
4. SiBr4
5. ICl3
6. SeCl6
7. RnCl4
8. AsH3
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9. SnCl2
10. BeF2
11. SbCl5
12. XeF2
13. TeCl4
14. IF5
15. CO2
16. ICl2+
17
17. SiF62-
18. AsF2+
II. Specify the predominant intermolecular force involved for each substance in the space immediately
following the substance. Then in the last column, indicate which member of the pair you would expect to
have the higher boiling point.
Substance #1 Predominant Substance #2 Predominant Substance with
Intermolecular Intermolecular Higher Boiling Point
Force Force
(a) HCl(g) I2
(b) CH3F CH3OH
(c) H2O H 2S
(d) SiO2 SO2
(e) Fe Kr
(f) CH3OH CuO
(g) NH3 CH4
(h) HCl(g) NaCl
(i) Xe Cu
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