CHM 211
CHM 211
ON
DEPARTMENT OF CHEMISTRY,
LECTURERS IN CHARGE
COURSE DESCRIPTION
Chemical bonding. Bonding theories; Valency bond theory; Molecular orbital theories.
IIIA (boron group), VA (Nitrogen group), noble gas. Introduction to first row
10,000 5000
Lyman Balmer Paschen
UV Visible
Pfund
Brackett
Lyman
K=1
L=2
M=3
N=4
O=5
P=6
Paschen
When the lines corresponding to a particular wavelength are examined, it is seen that
they all fit the equation:
1 1 1
R 2 2
nl nh
Where λ= wavelength of the particular line
R is Rydberg’s constant =1.097 x 107 m-1=1.097 x 105 cm-1 or 109,677cm-1,
nh = quantum number describing the higher energy state
nl = quantum number describing the lower energy state
(i.e. nl and nh are integers where nh is greater than nl)
1
-Wave number
1 1
R 2
2
nl nh
1. Lyman series
1 1
R 2
2 where nh 2,3,4,5
1 nh
2. Balmer series
1 1
R 2
2 where nh 3,4,5
2 nh
3. Paschen series
1 1
R 2
2 where nh 4,5,6
3 nh
4. Brackett series
1 1
R 2
2 where nh 5,6,7
4 nh
5
5. Pfund
1 1
R 2
2 where nh 6,7,8
5 nh
Bohr’s Theory of atomic spectrum of hydrogen
In 1911, Rutherford provided the idea of an atom consisting of a positively charged
nucleus surrounded by electrons and Bohr used this model of an atom to explain the
anomally of the discrete internal energy.
In the year 1913, Bohr made the following assumptions;
1. Electrons rotated around the nucleus of an atom in definite circular orbit and that a
definite orbit corresponded to a definite electronic energy
2. An electron in a circular orbit of a small radius would have a lower (that is more negative)
energy than an electron in an orbit of large radius.
3. Only certain orbits were possible for electrons [explanation=I can be shown from classical
mechanics(physics) that the energy of an electron in a circular orbit around a proton is
solely mainly determined by the radius of the orbit.
Bohr imposed one condition so that he could derive the Rydberg formular; He stated that
in each orbit, the angular momentum of the electron, mvr must be quantized that is, half a
value given by;
nh
mvr where m,v,r and h are mass, velocity of electron, radius of the orbit and Planck’s
2
constant respectively and n is called the quantum number of the orbit.
By using this assumption, it was determined that for each orbit, the energy and radius were
given by
hc
E h hc
Where ΔE= difference in energy in the two levels
By knowing the mass and the charge of electrons, Bohr calculated the radii of the possible
orbits for the hydrogen atom from this equation;
oh2n2
rn (this expression lies on the centrifugal force acting on the electron)
me e 2
Where o =permittivity of a vacuum=8.854 x 10-12Fm-1
h P or h mv
Thus λ canbe expressed in terms of electron energy rather than momentum. A kinetic
energy(½mv2) of an electron mass m and velocity v is given by
½mv2=E-V where E is total energy V= potential energy thus
E V h h
v 2 2 and
m mv E V
m 2
m
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BONDING THEORIES; VALENCE BOND THEORY, MOLECULAR BOND THEORIES.
Lewis Structure
Lewis proposed that a covalent bond is formed when two neighboring atoms share
one or more electron pair. Also, some molecules have non-bonding pairs of electrons on the
atom, which are called lone pair. These electrons contribute to the shape and reactivity of the
molecules (chemical properties) but do not directly bond the atoms together.
Octet Rule
For many light atoms following a lewis structure, a stable arrangement is attained
when the atom is surrounded by eight electrons (valence electrons corresponding to the s
and p electrons outside the noble gas core –ie s2p6 configuration).
Lewis explained the existence of some molecules by proposing the Octet Rule which
state that. ―Each atom shares electrons with neighboring atoms to achieve a total of eight
valence electrons (an octet)‖.This explains the observed valencies in a large number of
cases. The atoms continue to form bonds until they have made up an octet of electrons.
Example:
1. Chlorine: This atom has 7 electrons in its outer shell, so by sharing one electron with
another Cl atom both atoms attain an octet and form a chlorine molecule (Cl 2).
Cl Cl Cl Cl
2. CCl4:
Cl
C 4 Cl Cl C Cl
Cl
3. NH3:
N + 3[ H ] H N H
H
4. CO2:
C + 2[ O ] O C O
5. N2:
N + N N N
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From these, it can be seen that four electrons are shared between two atoms giving
rise to a double bond. 6 electrons shared gives rise to triple bonds.
Exceptions
Be + 2 [ F ] F Be F
F
B + 3[ F ] F B F
Be and B have less than 4 outer electrons and even if all the outer electrons are used
to form bonds, an octet cannot be attained.
3. When atoms have an extra energy level which is close in energy to the p level and may
not accept electrons and can be used for bonding. Eg PF 3 obeys octet rule but PF5
doesnot. [P=2,8,5]. This is because PF5 has 10 outer electrons: one 3s, three 3p and one
3d orbitals.
4. For molecules with odd numbers of electrons, octet rule doesnot apply eg NO=11
electrons, ClO2=19
5. Also compounds with more than four covalent bonds must break the octet rule. This
becomes more obvious after the first two periods of 8 elements.
Valence Theory.
This theory was proposed by Linus Pauling. This theory considers the interaction of
separate atoms as they are brought together to form a molecule. It is a way of expressing the
lewis theory in terms of wave concepts. In VB theory, a bond between atoms A and B is
formed when two atomic orbitals, one from each atom, merge with one another, and the
electrons they contain pair up (so that their spins are ↓↑). The merging of orbitals gives rise
to constructive interference—i.e., an enhancement of amplitude—between the wavefunctions
in the areas where they overlap, and hence an enhanced amplitude results in the
internuclear region. As a consequence of the formation of this region of heightened
amplitude, there is an increased probability of finding the electrons in the internuclear region
and, by implication, a lowering of the energy of the molecule.
In summary, a single bond in a Lewis structure corresponds to a σ bond of VB theory.
A double bond corresponds to a σ bond plus a π bond, and a triple bond corresponds to a σ
bond plus two π bonds.
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Illustration of Valence Bond theory
1. H2
Here, the VB wavefunction is formed by spin pairing of the electrons in the two
contributing atomic orbitals. This electron distribution is called a σ bond. This has a
cylindrical symmetry around the internuclear axis, and the electrons in it have zero orbital
angular momentum about that axis.
2. H2O
1s 2s 2p
2px 2py 2pz
Electronic structure of
oxygen atom-ground state
3. N2
1s 2s 2p
2px 2py 2pz
Electronic structure of
nitrogen atom-ground
state
4. HF
1s 2s 2p
2px 2py 2pz
Electronic structure of
fluorine atom-ground state
H has a singly occupied s orbital that overlaps with a singly filled 2p orbital on F
5. NH3
1s 2s 2p
2px 2py 2pz
Electronic structure of
nitrogen atom-ground
state
N has three singly filled 2p orbital each of which overlaps with a singly occupied s-orbital.
Promotion of electrons
Valence bond theory runs into an apparent difficulty with CH4. The valence-shell
electron configuration of carbon is 2s22px12py1, which suggests that it can form only two
bonds to hydrogen atoms, in which case carbon would have a valence of 2. The normal
valence of carbon is 4, however. This difficulty is resolved by noting that only the overall
energy of a molecule is important, and, as long as a process leads to a lowering of energy, it
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can contribute even if an initial investment of energy is required. In this case, VB theory
allows promotion to occur, in which an electron is elevated to a higher orbital. Thus, a carbon
atom is envisaged as undergoing promotion to the valence configuration 2s12px12py12pz1
as a CH4 molecule is formed. Although promotion requires energy, it enables the formation
of four bonds, and overall there is a lowering of energy. Carbon is particularly suited to this
promotion because the energy involved is not very great; hence the formation of tetravalent
carbon compounds is the rule rather than the exception.
Promotion is the excitation of an electron to an orbital of higher energy in the course of
the bond formation. Promotion of electrons may occur if the outcome is to achieve more or
stronger bonds and a lower overall energy
1s 2s 2p
2px 2py 2pz
Electronic structure of
carbon atom-ground state
1s 2s 2p
Electronic structure of
carbon atom-excited state
Hybridization
Hybrid orbitals are formed when atomic orbitals on the same atom interfere.
The discussion is not yet complete, however. From physical and chemical evidence,
the 4 bonds in methane are equivalent. But form VB theory, 3 bonds are of one type (2p) and
the fourth bond is of distinctly different character (2s).)
Quantum mechanical considerations resolve this dilemma by invoking hybridization.
Hybridization is the mixing of atomic orbitals on the same atom or when atomic orbitals on
the same atom interfere, giving rise to hybrid orbitals. For effective mixing, the energy of the
orbitals must be the same.
sp3 hybridisation: Each is built from one 2s and three 2p orbitals. It is called an sp3 hybrid
orbital. Since each sp3 hybrid orbital has the same composition, all four bonds are identical
apart from their orientation in space. Here, the electron density distribution in the promoted
atom is equivalent to the electron density in which each electron occupies a hybrid orbital
formed by the interference between 2s and 2p orbitals. Each hybrid orbital contains an
unpaired electron and can form a σ bond by pairing with a 1s electron of a hydrogen atom.
Hence, the VB structure of methane is described as consisting of four equivalent σ bonds
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formed by overlap of the s orbitals of the hydrogen atoms with sp3 hybrid orbitals of the
carbon atom.
sp2 hybridisation: The structure of ethylene can be examined in VB terms to illustrate the use
of hybridization. To reproduce the Lewis structure given earlier, it is necessary to contrive a
double bond (i.e., a σ bond plus a π bond) between the two carbon atoms. Such a bonding
pattern can be achieved by selecting the carbon 2s orbital, from which an electron has been
promoted, and two of its 2p orbitals for hybridization, leaving one 2p orbital unhybridized and
ready for forming a π bond. When one 2s and two 2p orbitals are hybridized, they form sp2
hybrid orbitals, which have lobelike boundary surfaces that point to the corners of an
equilateral triangle; the unhybridized 2p orbital lies perpendicular to the plane of the triangle.
Each of the orbitals contains a single electron. Two of the hybrids can form σ bonds to two
hydrogen atoms, and one of the hybrids can form a σ bond to the other carbon atom (which
has undergone similar hybridization). The unhybridized 2p orbitals are now side-by-side and
can overlap to form a π bond. This description conforms to the Lewis description. It also
explains naturally why ethylene is a planar molecule, because twisting one end of the
molecule relative to the other reduces the overlap between the 2p orbitals and hence
weakens the π bond. All double bonds confer a torsional rigidity (a resistance to twisting) to
the parts of molecules where they lie. BF3 is another example:
1s 2s 2p
2px 2py 2pz
Electronic structure of
boron atom-ground state
1s 2s 2p
Electronic structure of
boron atom-excited state
sp hybridisation: This means one s atomic orbital and one p atomic orbital mixes to form a
set of 2 hybrid orbitals with different directional properties. Eg BeCl2 where be =[He]2s2
1s 2s 2p
2px 2py 2pz
Electronic structure of
beryllium atom-ground
state
1s 2s 2p
Electronic structure of
beryllium atom-excited
state
Mixing d orbtals:
3s 3p 3d
Electronic structure of
phosphorous atom-ground
state
Electronic structure of
Phosphorous atom-
excited state
However, d orbitals are in general too large and have high energy to mix completely
with s and p orbitals. The presence of electronegative atoms cause contraction of the d
orbitals and lower their energy, so mixing is possible. Also, the number of d orbitals occupied
by electrons affects the mixing, the more the number the shorter the distance. So d-orbitals
probably do participate in bonding in cases where d-orbital contraction occurs.
Number of Outer
Type of Hybridisation Arrangement
orbitals
2 sp linear
3 sp2 Trigonal planar
4 sp3 Tetrahedral
a.Trigonal bipyramid
5 a. sp3dz2 b. sp3d(x2-y2)
b. square based pyramid
6 sp3d2 Octahedron
7 sp3d3 Pentagonal bipyramid
[4 dsp2 Square planar
+ + . + .
. .
Bonding molecular orbitals(σ1s)
+ -
. . + . . -
Antibonding molecular orbitals(σ*1s)
A bonding molecular orbitals is of lower energy than two separate atomic orbitals,
while, antibonding molecular orbitals has a higher energy than the two separate atomic
orbitals. Also, two electrons with opposite spins can occupy each molecular orbital-Pauli
exclusion principle.
Hence for the hydrogen molecule, both electrons occupy the bonding molecular
orbital, a chemical bond being established because this bonding molecular orbital is of lower
energy than two singly atomic orbital of the H atoms.
+ . . -
The σ*1s unoccupied
Increasing energy
+ +
. .
σ*1s2
+. .-
He .+. He
2
1s
1s2
σ1s2
The lower energy of the bonding molecular orbital is effectively cancelled out by the
higher energy of antibonding molecular orbital so no chemical bond is established, hence no
He2 molecule is formed.
He diatomic ion.
σ*1s1
Increasing Energy
+. .-
He .+. He
2
1s
1s1
σ1s2
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He2+ contains 3 electrons and 2 are in a bonding molecular orbital while the third
occupy the antibonding molecular orbital. There is some overall bonding and this specie can
exist. It can be obtained by subjecting He gas at a low pressure to a high energy discharge.
Application of Molecular orbital Theory For p atomic orbitals
P atomic orbitals can overlap in two distinct ways:
1. Two 2px can overlap along x-axis and give rise to σ bonding and antibonding
molecular orbital.
2. Two 2px can also overlap laterally and again give rise to π bonding and antibonding
molecular orbital.
1. Example . the Molecular orbital diagram for fluorine molecule (9F).
σ *2Px
π*2Py2 π*2Pz2
π2Py2
π2Pz2
σ2Px2
σ*2S2
2S 2S
σ2S2
F2= 1s 1s 2 s 2 s 2 p
*
2 2 2
*
2 2
x
2 p 2y
2 pz2
*2 p 2y
2 pz2
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Chemistry of Group IIIA (Boron Group)
This group marks the beginning of the p-block elements. Members Include: Boron
(105B), Aluminium (2713Al), Gallium (7031Ga), Indium (11549In), Thallium (20481Tl). Boron is the
only non-metallic in the group and the group is also electron deficient. This calls for its
separate studies.
Boron (105B): [He] 3s2 3p1
Aluminium (2713Al): [Ne] 3s2 3p1
Gallium (7031Ga): [Ar] 3d10 4s2 4p1
Indium (11549In): [Kr] 4d10 5s2 5p1
Thallium (20481Tl): [Xe] 4f14 5d10 6s2 6p1
Elemental boron has properties that places it on the borderline between metal and non
metals. It is a semiconductor, not a metallic conductor and chemically it must be classed as a
non metal. In general, B chemistry resembles that of Si more closely than that of Al, Ga, In
and Tl.
Isolation of the Element
Boron is not an abundant element, but it occurs in some concentrated deposits in arid
parts of California, and elsewhere, as borax Na2B4O5(OH)4.8H2O and kernite,
Na2B4O5(OH)4.2H2O.
Compounds of Group IIIA Elements
1) Oxygen compounds of boron
(i) Boron oxides
(ii) Boric acid
(iii) Borates
Aluminum is the commonest metallic element in the earth’s crust and occurs in rocks such
as feldspars and micas. More accessible deposits are hydrous oxides such as bauxite,
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Al2O3.nH2O and cryolite, Na3AlF6. Gallium and indium occur only in traces in aluminum and
zinc ores.
Compounds of aluminum includes alumina Al2O3(α and γ) , Al(OH)3 thallium oxide (Tl2O)
as well as binary compounds: Al4C3.
Nitrogen hydrides
(i) NH3 (ii) NH4+ salts (iii) N2H4
Oxides of Nitrogen
(i) N2O (ii) NO (iii) NO2 (iv) N2O4 (v) N2O5