CHAPTER SEVEN
Chemical Bonding and Molecular
Geometry
Ionic Bonding
Ions are atoms or molecules bearing an electrical charge.
A cation (a positive ion) forms when a neutral atom loses one or
more electrons from its valence shell, and
an anion (a negative ion) forms when a neutral atom gains one or
more electrons in its valence shell.
Compounds composed of ions are called ionic compounds (or
salts), and their constituent ions are held together by ionic bonds:
Ionic bonds: electrostatic forces of attraction between oppositely charged
cations and anions.
that are typically produced by the transfer of electrons between metallic
and nonmetallic atoms.
2
Cont…
Ionic solids
exhibit a crystalline structure and tend to be rigid and brittle;
they have high melting and boiling points, which suggests that
ionic bonds are very strong.
are also poor conductors of electricity in the solid state.
Once dissolved or melted, ionic compounds are excellent
conductors of electricity and heat because the ions can move
freely.
3
con.t.
Neutral atoms and their associated ions have very different physical and
chemical properties.
Figure : (a) Sodium is a soft metal that must be stored in mineral oil to
prevent reaction with air or water. (b) Chlorine is a pale yellow-green gas.
(c) When combined, they form white crystals of sodium chloride (table
4
salt).
The Formation of Ionic Compounds
Binary ionic compounds are composed of just two elements:
a metal (which forms the cations)and
a nonmetal (which forms the anions).
e.g. NaCl
Many metallic elements have relatively low ionization potentials
and lose electrons easily.
Nonmetal atoms have relatively high electron affinities and thus
readily gain electrons lost by metal atoms.
The formula for an ionic compound does not represent the physical
arrangement of its ions.
5
Cont.
The attractive forces between ions are isotropic-the same in all directions
(equally attracted to all of the nearby ions of opposite charge).
This results in three-dimensional lattice structure.
Figure: (a) maximize opposite charges interacting, in the expanded view (b)
each ion is “bonded” to all of the surrounding ions-six in this case
6
Electronic Structures of Cations and Anions
When forming a cation, an atom of a main group element tends to
lose all of its valence electrons,
Thus assuming the electronic structure of the noble gas that
precedes it in the periodic table.
the group numbers are equal to the numbers of valence shell
electrons and, consequently, to the charges of the cations
e.g., 20Ca is a group 2 element and its ground state electron
configuration is: 1s22s22p63s23p64s2.
Ca2+ (loses both of its valence electrons) = 1s22s22p63s23p6 = 18
electrons (Ar)
therefore isoelectronic with the noble gas Ar.
7
Cont.
For groups 13–17, the group numbers exceed the number of valence
electrons by 10.
Thus, the charge of a cation formed by the loss of all valence electrons
is equal to the group number minus 10.
e.g., Aluminum (in group 13) forms 3+ ions (Al3+ ).
Exceptions to the expected behavior involve elements toward the bottom of the
groups.
In addition to the expected ions Tl3+, Sn4+, Pb4+, and Bi5+, a partial
loss of these atoms’ valence shell electrons can also lead to the
formation of Tl+, Sn2+, Pb2+, and Bi3+ ions.
8
Cont…
Hg (group 12) forms a diatomic ion, Hg22+ and
forms monoatomic ion Hg2+.
Most transition metal cations have 2+ or 3+ charges
e.g., 26Fe (1s22s22p63s23p63d64s2)
forms Fe2+ = 1s22s22p63s23p63d6
Fe3+ = 1s22s22p63s23p63d5
When the inner transition metals form ions, they usually have a 3+ charge,
resulting from the loss of their outermost s electrons and a d or f electron.
Most monatomic anions form when a neutral nonmetal atom gains enough
electrons to completely fill its outer s and p orbitals,
for example, Oxygen has the electron configuration:
O= 1s 22s22p4,
8
whereas the O2- = 1s22s22p6.
9
Covalent Bonding
10
Formation of Covalent Bonds
Formed between nonmetal atoms by sharing of electron.
e.g., H2, contains a covalent bond between its two hydrogen atoms.
As the two atoms approach each other their valence orbitals (1s)
begin to overlap.
The strong attraction of each shared electron to both nuclei
stabilizes the system, and the potential energy decreases as the
bond distance decreases.
The bond length is determined by the distance at which the lowest
potential energy is achieved.
11
Figure : The potential energy of two separate H atoms (right) decreases as
they approach each other, and the single electrons on each atom are shared to
form a covalent bond.
12
Cont.
It is essential to remember that energy must be added to break
chemical bonds (an endothermic process),
whereas forming chemical bonds releases energy (an exothermic
process).
In the case of H2, a large amount of energy, 436 kJ, must be
added to break the bonds.
H2(g) → 2H(g) ΔH = 436KJ
Conversely, the same amount of energy is released when one
mole of H2 molecules forms from two moles of H atoms:
2H(g) → H2(g) ΔH = - 436KJ
13
Polarity of Covalent Bonds
If the atoms that form a covalent bond are identical (like, H2, Cl2
and other diatomic molecules) the electrons in the bond must be
shared equally.
We refer to this as a pure covalent bond (non-polar).
Electrons have an equal probability of being near each nucleus.
In the case of Cl2, each Cl shares one electron with the other,
forming one covalent bond:
+ →
The total number of nonbonding electrons are six, two electrons are
shared (i.e., bonding) and both have eight total electrons.
14
Cont.
When the atoms linked by a covalent bond are different, the
bonding electrons are shared, but no longer equally.
Instead, the bonding electrons are more attracted to one atom
than the other, giving rise to a shift of electron density
toward that atom.
This unequal distribution of electrons is known as a polar
covalent bond.
It is characterized by:
a partial negative charge(δ-) on the atom that attracts the electrons more
strongly and
a partial positive charge(δ+) on the atom that attracts the electrons less.
15
Cont.
e.g., the H–Cl, spend more time near the chlorine atom than near
the hydrogen atom.
Figure: (a) The distribution of electron density in the HCl molecule is
uneven.
The electron density is greater around the chlorine nucleus.
16
Lewis structures
We also use Lewis symbols to indicate the formation of
covalent bonds.
e.g., When two chlorine atoms form a chlorine molecule:
Each Cl atom has three pairs of electrons that are not used in
bonding (called lone pairs) and one shared pair of electrons.
A dash (or line) is sometimes used to indicate a shared pair of
electrons:
17
The Octet rule
The tendency of main group atoms to form enough bonds to obtain eight
valence electrons is known as the octet rule.
e.g., Group 4 (IV)element has four electrons in its outermost shell and
therefore requires four more electrons to reach an octet.
These four electrons can be gained by forming four covalent bonds,
e,.g.,CCl4 (carbon tetrachloride) and silicon in SiH4 (silane).
18
Cont.
Group 5 (V) elements such as nitrogen have five valence
electrons , one lone pair and three unpaired electrons.
form three covalent bonds, as in NH3.
Oxygen and other atoms in group 16 obtain an octet by
forming two covalent bonds:
19
Writing Lewis Structures with the Octet Rule
For simple molecules and molecular ions:
20
Cont.
For more complicated molecules and molecular ions there are some
steps:
1. Determine the total number of valence (outer shell) electrons
2. Draw a skeleton structure of the molecule or ion, arranging the
atoms around a central atom (the least electronegative element
should be placed in the center).
Connect each atom to the central atom
3. Distribute the remaining electrons as lone pairs on the terminal
atoms (except hydrogen), completing an octet around each atom.
4. Place all remaining electrons on the central atom.
5. Rearrange the electrons of the outer atoms to make multiple bonds
with the central atom in order to obtain octets wherever possible.
21
Cont.
Example: CHO2-
Step 1: total no. of valence electrons:
C = 4x1 = 4
H = 1x1 = 1
O = 6x2 = 12
+1
18 electrons
Distribute the remaining electrons as lone pairs:
Rearrange the electrons:
22
Exceptions to the Octet Rule
These molecules fall into three categories:
Odd-electron molecules have an odd number of valence
electrons, and therefore have an unpaired electron.
Electron-deficient molecules have a central atom that has
fewer electrons than needed for a noble gas configuration.
Hypervalent molecules have a central atom that has more
electrons than needed for a noble gas(octate) configuration.
23
Cont…
Odd-electron molecules
e.g. Nitric oxide NO:
N = 5 , O = 6, = 11
N __ O
- we distribute the electrons around both atoms (there is no
central atom)
- We give eight electrons to the more electronegative atom.
Rearrange the electrons to make multiple bonds
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Electron-deficient Molecules
The molecules central atoms that do not have a filled valence
shell.
e.g., BeH2 and BF3,
An atom like the boron atom in BF3, which does not have eight
electrons, is very reactive.
25
Cont...
Octet Rule Violations Xenon is a noble gas
What are the Lewis structures of XeF2 and XeF6?
Calculate the number of valence electrons:
XeF2: 8 + (2 × 7) = 22
XeF6: 8 + (6 × 7) = 50
Draw a skeleton joining the atoms by single bonds
Distribute the remaining electrons
26
Formal Charges and Resonances
Calculating Formal Charge
The formal charge of an atom in a molecule is the hypothetical charge the
atom would have if we could redistribute the electrons in the bonds evenly
between the atoms.
Formal charge = # valence shell electrons (free atm) −
#non-bonding electrons - 1/2# (bonding electrons)
Number of Valence
electron around the
atom in the molecule
The sum of the formal charges of all atoms in a molecule must be zero;
The sum of the formal charges in an ion should equal the charge of the
ion.
The formal charge calculated for an atom is not the actual charge of the
atom in the molecule.
27
28
Example:
Assign formal charges to each atom in the interhalogen ion ICl4−.
Step 1:We divide the bonding electron pairs equally for all I–Cl bonds:
Step 2:We assign lone pairs of electrons to their atoms.
Step 3: Subtract this number from the number of valence electrons for the neutral
atom
I: 7 – 8 = –1
Cl: 7 – 7 = 0
The sum of the formal charges of all the atoms equals –1,
Activity: Calculate the formal charge for each atom in the carbon
monoxide molecule: Formal charge of CO is zero.
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Predicting molecular structure using formal charge
The arrangement of atoms in a molecule or ion is called its molecular
structure.
1) A molecular structure in which all formal charges are zero is
preferable to one in which some formal charges are not zero.
2) If the Lewis structure must have nonzero formal charges, the
arrangement with the smallest nonzero formal charges is preferable.
3) Lewis structures are preferable when adjacent formal charges are zero
or of the opposite sign.
4) When we must choose among several Lewis structures with similar
distributions of formal charges, the structure with the negative formal
charges on the more electronegative atoms is preferable.
e.g,. CO2
30
Cont..
another example: the thiocyanate ion (NCS-)
have three different molecular structures: NCS–, CNS–, or CSN–
Note that: the sum of the formal charges in each case is equal to
the charge of the ion (–1).
The first arrangement of atoms is preferred (the lowest number
of atoms with nonzero formal charges)
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Example:
Which is the likely structure for nitrous oxide?
Solution
Determining formal charge yields the following:
The structure with a terminal oxygen atom best satisfies the criteria for
the most stable distribution of formal charge:
32
Resonance
If two or more Lewis structures with the same arrangement of atoms
can be written for a molecule or ion,
The actual distribution of electrons is an average of that shown by the
various Lewis structures
The more likely structure for the nitrite anion may actually be drawn in
two different ways, distinguished by the locations of the N-O and N=O
bonds:
A double bond between two atoms is shorter (and stronger) than a single
bond between the same two atoms.
Experiments show, however, that both N–O bonds in NO2−have the same
strength and length, and are identical in all other properties.
33
Cont..
It is not possible to write a single Lewis structure for NO2− in which
nitrogen has an octet and both bonds are equivalent.
Instead, we use the concept of resonance:
The actual electronic structure of the molecule (the average of the
resonance forms) is called a resonance hybrid of the individual resonance
forms.
A double-headed arrow between Lewis structures indicates that they
are resonance forms.
34
Cont…
The carbonate anion, CO32−, provides a second example of
resonance:
One oxygen atom must have a double bond to carbon to complete
the octet on the central atom.
All oxygen atoms, however, are equivalent, and the double bond
could form from any one of the three atoms.
This gives rise to three resonance forms of the carbonate ion.
The actual arrangement of electrons in the carbonate ion is the
average of the three structures.
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Strengths of ionic and covalent bonds
A bond’s strength describes how strongly each atom is joined to
another atom, and
Therefore how much energy is required to break the bond between
the two atoms.
Ionic bond strength and lattice energy
An ionic compound is stable because of the electrostatic
attraction between its positive and negative ions.
The lattice energy of a compound is a measure of the strength of
this attraction.
The lattice energy (ΔHlattice) of an ionic compound is defined as the
energy required to separate one mole of the solid into its component
gaseous ions.
For the ionic solid MX, the lattice energy is the enthalpy change of
the process:
36
Cont…
For the ionic solid MX, the lattice energy is the enthalpy change of
the process:
MX(s) → Mn+(g) + Xn-(g) ∆Hlattice
lattice energies will be endothermic (positive values).
For sodium chloride, ΔHlattice= +769 kJ.
Thus, it requires 769 kJ to separate one mole of solid NaCl into
gaseous Na+ and Cl– ions.
When one mole each of gaseous Na+ and Cl– ions form solid NaCl,
769 kJ of heat is released.
37
Cont..
The lattice energy ΔHlattice of an ionic crystal can be expressed by the
following equation, (derived from Coulomb’s law, governing the
forces between electric charges):
In which :
C = is a constant that depends on the type of crystal
structure;
Z+ and Z– = are the charges on the ions; and
Ro = is the interionic distance (the sum of the radii of the
positive and negative ions).
Thus, the lattice energy of an ionic crystal increases rapidly as the charges of
the ions increase and the sizes of the ions decrease
For example, we can compare the lattice energy of MgF2 (2957 kJ/mol) to
38 that of MgI (2327 kJ/mol) to observe the effect of the ions.
2
Cont…
Doubling the charge of both the cation and anion quadruples the lattice
energy.
For example, the lattice energy of LiF (Z+ and Z– = 1) is 1023 kJ/mol,
whereas that of MgO (Z+ and Z– = 2) is 3900 kJ/mol (Ro is nearly the
same-about 200 pm for both compounds).
39
The Born-Haber Cycle
The Born-Haber cycle is an application of Hess’s law that breaks down
the formation of an ionic solid into a series of individual steps:
ΔH =ΔHof =ΔHos + ½ D + IE + (−EA) + (−ΔHlattice)
Where:
ΔHf0, the standard enthalpy of formation of the compound
IE, the ionization energy of the metal
EA, the electron affinity of the nonmetal
ΔHs0, the enthalpy of sublimation of the metal
D, the bond dissociation energy of the nonmetal
ΔHlattice, the lattice energy of the compound
40
Figure : The Born-Haber cycle shows the formation of solid cesium
fluoride from the necessary elements in their reference states.
The enthalpy change in this step is the negative of the lattice energy, so it
41 is also an exothermic quantity.
Cont..
Lattice energies calculated for ionic compounds are typically much
higher than bond dissociation energies measured for covalent bonds.
Whereas lattice energies typically fall in the range of 600– 4000
kJ/mol (some even higher),
covalent bond dissociation energies are typically between 150– 400
kJ/mol for single bonds.
For ionic compounds, lattice energies are associated with many
interactions, as cations and anions pack together in an extended
lattice.
For covalent bonds, the bond dissociation energy is associated with
the interaction of just two atoms.
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Bond strength of covalent bond
We measure the strength of a covalent bond by the energy required to
break it(separate the bonded atoms).
The stronger a bond, the greater the energy required to break it.
The energy required to break a specific covalent bond in one mole of
gaseous molecules is called the bond energy or the bond dissociation
energy.
The bond energy for a diatomic molecule, DX–Y , is defined as the standard enthalpy
change for the endothermicreaction:
XY(g) → X(g) + Y(g) DX-Y = ΔHO
e.g,. H-H bond: H2(g) → 2H(g) DH-H = ΔHO = 436kJ
The strength of a bond between two atoms increases as the number of electron pairs in
the bond increases.
Generally, as the bond strength increases, the bond length decreases.
the bond strength typically decreases as we move down the group.
43
Cont..
We can use bond energies to calculate approximate enthalpy changes (ΔH).
This tell us whether a reaction is exothermic (when the bonds in the
products are stronger than the bonds in the reactants) or
endothermic (when the bonds in the products are weaker than those in the
reactants).
Where: D represents the bond energy in kilojoules per mole,
which is always a positive number
this calculation provides a rough estimate, not an exact value, for the
enthalpy of reaction.
44
Cont…
Consider the following reaction:
To form two moles of HCl, one mole of H–H bonds and one
mole of Cl–Cl bonds must be broken.
Because the bonds in the products are stronger than those in the
reactants, the reaction releases more energy than it consumes:
This excess energy is released as heat, so the reaction is
exothermic.
45
Example:
Using the bond energies in Table 6.3, calculate the approximate
enthalpy change, ΔH, for the reaction here:
CO(g) + H2(g) → CH3OH(g)
Solution
First, write the Lewis structures of the reactants and the products:
ΔH= ƩD bonds broken − ƩD bonds formed
We can compare this value to the value calculated based on
ΔH∘f data from Appendix G: (-90.5kJ)
This occurs because D values are the average of different bond
46
strengths
Cont..
It is important to be able to describe molecular bonds in terms of their
distances, angles, and relative arrangements in space.
A bond angle: is the angle between any two bonds that include a
common atom, usually measured in degrees.
A bond distance (or bond length): is the distance between the nuclei
of two bonded atoms along the straight line joining the nuclei.
Bond distances are measured in Ångstroms or picometers .
1 Å = 10–10 m
1 pm = 10–12 m, 100 pm = 1 Å).
e.g,. formaldehyde
molecule, H2CO.
47
Molecular structure and polarity
VSEPR Theory(Valence shell electron-pair repulsion theory
VSEPR theory enables us to predict:
the molecular structure, including approximate bond angles around a
central atom, of a molecule from an examination of the number of
bonds and lone pairs electrons in its Lewis structure.
predicts the arrangement of electron pairs around each central atom and,
usually, the correct arrangement of atoms in a molecule.
e.g,. gaseous BeF2 molecule =
shows only two electron pairs around the central beryllium atom and no
lone pairs of electrons on the central atom,
48
49
Electron-pair Geometry versus Molecular Structure
electron-pair geometry around a central atom is not the same thing
as its molecular structure.
The electron-pair geometries:
describe all regions where electrons are located, bonds as well as lone
pairs.
Is the same as the molecular structures when there are no lone electron
pairs around the central atom,
but they will be different when there are lone pairs present on the
central atom.
Molecular structure:
describes the location of the atoms, not the electrons.
It is the structure that includes only the placement of the atoms in the
molecule.
50
Cont…
e.g,. NH3,
has four electron pairs associated with the nitrogen atom,
a tetrahedral electron-pair geometry.
One of these regions, however, is a lone pair, which is not included in the
molecular structure, and
this lone pair influences the shape of the molecule.
The electron-pair geometry
51 NH3 is tetrahedral Trigonal pyramidal The actual bond angles
for
Cont…
The order of electron-pair repulsions from greatest to least
repulsion is:
Lone pair-lone pair>lone pair-bonding pair>bonding pair-bonding pair.
This order of repulsions determines the amount of space occupied by
different regions of electrons.
The order of sizes from largest to smallest is:
Lone pair > triple bond > double bond > single bond
52
Cont..
53
The molecular structures are identical to the electron-pair geometries
when there are no lone pairs present (first column).
For a particular number of electron pairs (row), the molecular structures
for one or more lone pairs are determined based on modifications of the
corresponding electron-pair geometry.
54
Cont…
an axial position (if we hold a model of a trigonal bipyramid by the two axial
positions, we have an axis around which we can rotate the model) and
an equatorial position (three positions form an equator around the middle of
the molecule).
the axial position is surrounded by bond angles of 90°,
whereas the equatorial position has more space available because of the 120°
bond angles
In a trigonal bipyramidal electron-pair geometry, lone pairs always occupy
equatorial positions.
because these more spacious positions can more easily accommodate the larger
lone pairs.
55
Cont…
Theoretically, we can come up with three possible arrangements for the
three bonds and two lone pairs for the ClF3 molecule.
Figure: (a) In a trigonal bipyramid, the two axial positions are located
directly across from one another, whereas the three equatorial positions are
located in a triangular arrangement. (b–d)
The two lone pairs (red lines) in ClF3 have several possible arrangements,
but the T-shaped molecular structure (b) is the one actually observed,
consistent with the larger lone pairs both occupying equatorial positions.
56
Predicting Electron Pair Geometry and Molecular Structure
1) Write the Lewis structure of the molecule or polyatomic ion.
2) Count the number of regions of electron density (lone pairs and
bonds) around the central atom. A single, double, or triple bond
counts as one region of electron density.
3) Identify the electron-pair geometry based on the number of
regions of electron density: linear, trigonal planar, tetrahedral,
trigonal bipyramidal, or octahedral (Figure 6.10, first column).
4) Use the number of lone pairs to determine the molecular
structure. If more than one arrangement of lone pairs and chemical
57
bonds is possible, choose the one that will minimize repulsions,
Molecular structure and dipole moment
polar covalent bonds connect two atoms with differing electronegativities, leaving
one atom with a δ+ and the other atom with a δ–, as the electrons are pulled
toward the more electronegative atom.
This separation of charge gives rise to a bond dipole moment.
The magnitude of a bond dipole moment is represented by the Greek letter mu
(μ) and is given by the formula shown here:
μ = Qr
Where: Q = is the magnitude of the partial charges
(determined by the electronegativity difference) and
r = is the distance between the charges:
This bond moment can be represented as a vector.
58
Cont…
Dipole vectors are shown as arrows pointing along the bond from the
less electronegative atom toward the more electronegative atom.
A small plus sign is drawn on the less electronegative end to indicate
the partially positive end of the bond.
The length of the arrow is proportional to the magnitude of the
electronegativity difference between the two atoms.
Figure: (a) There is a small difference in electronegativity between C
and H.
(b) The electronegativity difference between B and F is much
59 larger.
Cont…
In a molecule if charge separation is exists, the molecule is said to be a
polar molecule (or dipole);
otherwise the molecule is said to be nonpolar.
The dipole moment measures the extent of net charge separation in the
molecule as a whole
Homonuclear diatomic molecules such as Br2 and N2 have no
difference in electronegativity, so their dipole moment is zero.
For heteronuclear molecules such as CO, there is a small dipole
moment.
For HF, there is a larger dipole moment because there is a larger
difference in electronegativity.
60
Cont…
When a molecule contains more than one bond, the geometry must be
taken into account.
If the bonds in a molecule are arranged such that their bond moments
cancel (vector sum equals zero), then the molecule is nonpolar.
1) e.g., CO2
we determine that the CO2 molecule is linear with polar C=O bonds on
opposite sides.
The bond moments cancel because they are pointed in opposite directions.
2) H2O = there are two bonds to a central atom, and the electronegativity
difference again shows that each of these bonds
has a nonzero bond moment.
the molecular structure is bent because of the lone pairs on O, and the two
bond moments do not cancel.
Therefore, water does have a net dipole moment and is a polar molecule
61 (dipole).
Cont…
Chloromethane, CH3Cl, is a tetrahedral molecule with three slightly
polar C-H bonds and a more non polar C-Cl bond.
The relative electro negativities of the bonded atoms is H < C < Cl
62
Cont…
To summarize, to be polar, a molecule must:
1) Contain at least one polar covalent bond.
2) Have a molecular structure such that the sum of the vectors of each
bond dipole moment does not cancel.
Properties of Polar Molecules
when placed in an electric field with the positive end of the molecule
oriented toward the negative plate and the negative end toward the
positive plate
We can use an electrically charged object to attract polar molecules,
but nonpolar molecules are not attracted.
polar solvents are better at dissolving polar substances, and nonpolar
solvents are better at dissolving nonpolar substances.
63
Figure 6.15: (a) Molecules are always randomly distributed in the liquid state in the absence of
an electric field. (b) When an electric field is applied, polar molecules like HF will align to the
dipoles with the field direction.
64