Inorganic chemistry (Chem.

2101)

UNIT 1
1. ATOMICSTRUCTURE ANDTHEPERIODICITY
1.1 Historical development of the atomic nature of substances

 Atomic theories and its structure will be discussed.

1.2. Dalton’satomic theory and the modern atomic theory
1.2.1 Postulates of Dalton’s Atomic Theory
Dalton's atomic theory was based directly on the ideas of
elements and compounds, and on the three laws of chemical
combination.
 The law of conservation of mass states that matter is neither
created nor destroyed. This law is also called the law of
indestructibility of matter. It means that the mass of the reactants
is exactly equal to the mass of the products in any chemical
reaction. A chemical reaction involves only the separation and
union of atoms.
The law of definite proportions states that a pure compound is always composed of the
same elements combined in a definite ratio by mass. For
example, water (HO) is
composed of hydrogen and oxygen only. These elements are always in the proportion of
11.19% hydrogen to 88.81% oxygen by mass and in the proportion 2 : 1 by volume.

The law of multiple proportions states that when two different compounds are formed
from the same elements, the masses of one of the elements in the two compounds,
compared to a given mass of the other element, is in a small whole-number ratio. For
example, carbon and oxygen form two compounds: carbon monoxide and carbon
dioxide. Carbon monoxide contains 1.3321 g of oxygen for each 1 g of carbon, whereas
carbon dioxide contains 2.6642 g of oxygen for each 1g of carbon. Hence, carbon
dioxide contains twice the mass of oxygen as does carbon monoxide.

An atom is the smallest fundamental particle of an element

 The basic postulates of Dalton’s Atomic Theory are
summarized as follows:

 All elements are made up of small particles called atoms.

 Atoms are indivisible and indestructible.
 All atoms of a given element are identical in mass and in all other
properties.
 Atoms are neither created nor destroyed in chemical reactions.
 Compounds are formed when atoms of more than one element
combine.
 In a given compound, the relative numbers and types of atoms are
constant.
 Example 1.1
1. A nitrogen oxygen compound is found to have an oxygen-to-
nitrogen mass ratio of 1.142 g oxygen for every 1.000 g of nitrogen.
Which of the following oxygen-to-nitrogen mass ratio(s)is/are
possible for different nitrogen-oxygen compound(s)?
a. 2.285 c. 0.571
b. 1.000 d. 2.500
2.Determine,which of the following oxygen-to nitrogen mass ratio(s)
is/are also possible for nitrogen-oxygen compound. (Refer
Example1.1 No.1 for required in formation)
a. 0.612 c. 1.713
b. 1.250 d. 2.856
Solution:
1. The given compound has 1.142 g of oxygen and 1.000 g of
nitrogen.
 Response (a) has 2.285 g of oxygen for the same 1.000 g of nitrogen.
The ratio of the masses of oxygen, 2.285:1.142, is almost exactly 2:1.
 Response (a) seems to be correct possibility, so is response (c).
Here the ratio is 0.571:1.142 = 0.500 = 1:2.
 Responses (b) and (d) are not possibilities. They yield ratios of
1.000:1.142 = 0.875 and 2.500: 1.142 = 2.189, respectively. Neither
of these can be expressed as a ratio of small whole numbers.
2. By the same method,
 a. 0.612:1.142 = 0.536:1 is not possible
 b. 1.250:1.142 = 1.095:1 is not possible
 c. 1.713:1.142 = 1.5:1 or 3:2, is possible
 d. 2.856:1.142 = 2.5:1 or 5:2 is possible
Exercises 1.1
1. A 15.20 g of nitrogen will react with 17.37 g, 34.74 g, or 43.43 g of
oxygen to form three different compounds.
a. Calculate the mass of oxygen per gram of nitrogen in each
compound.
b. How do the numbers in part (a) support the atomic theory
2. Hydrogen peroxide is composed of two elements: hydrogen and
oxygen. In an experiment, 1.250 g of hydrogen peroxide is fully
decomposed into its elements.
a. If 0.074 g of hydrogen are obtained in this experiment, how
many grams of oxygen must be obtained?
b. Which fundamental law does this experiment demonstrate?
c. How is this law explained by the atomic theory??
 1.1.1 Postulates of Modern Atomic Theory
 Modern atomic theory is generally said to begin with John
Dalton. Dalton’s work was mainly about the chemistry of atoms
– how they combine to form new compounds –rather than
about the internal structure of atoms. However, Dalton never
denied the possibility of atoms having a structure.
 Modern theories about the physical structure of atoms did not
begin until J.J. Thomson discovered the electron in 1897.
 In 1913, a Danish physicist, Niels Bohr, who had studied under
both Thomson and Rutherford, further modified the nuclear
model. He proposed that electrons move onlyin restricted,
successive shells and that the valence electrons determine the
chemical properties of different elements.
 In the 1920s, Bohr’s theory became the basis for quantum
mechanics, which explained in greater detail the complex
structure and behaviour of atoms.
The Modern Atomic Theory can be summarized as follows:

 Atoms are the smallest particles of all elements that can take
part in a chemical reaction.
 An atom is divisible. It can be subdivided into electrons,
protons, and neutrons. An atom is also indestructible i.e.,
atoms can neither be created nor destroyed during ordinary
chemical reactions.
 Atoms of the same element may not be identical in mass
because of the existence of isotopes.
 Atoms of the same elements have identical chemical properties.
 Atoms of different elements have different chemical properties.
 Atoms of two or more elements combine in simple whole-
number ratios to form compounds.
 How the Modern Theory Explains the Mass Laws?

 Chemical compounds are formed when atoms combine in

whole-number ratioslaw
( of multiple proportions). A given
compound always has the same relative number and types of
law( of constant composition).
atoms
 In a chemical reaction, the mass of the reactants (starting
materials) equals the mass of the reaction productslaw
( of
conservation of mass), provided no reactant remains.
 1.3.1 Discovery of the Electron

 J.J.Thomson (a British physicist and Nobel laureate) was

discovered the electron through his experiments on the stream
of particles (electrons) emitted by cathode rays.
 A theorist as well as an experimenter, in 1898, Thomson
advanced the "plum-pudding" theory of atomic structure,
holding that negative electrons were like plums embedded in a
pudding of positive matter. Thomson was knighted in 1908.
Cathode Rays
 In 1879, the English scientist William Crookes (1832-1919)
experimented with gas discharge tubes.
 When a very high electrical potential (~ 10,000 volts) is applied
across a gas taken in a discharge tube of a very low pressure (~
0.001 torr) some radiations are emitted from cathode
 These radiations are called cathode rays. Fig 1.1, shows
emission of cathode rays in a discharge tube.
 At this stage the glass walls of the discharge tube opposite to
the cathode starts glowing with a faint greenish light.
 It is now known that this greenish glow on the walls is due to
the bombardment of the glass wall with the cathode rays.
 Cathode rays normally travel in straight lines, but are deflected
when a magnet is brought nearby (Figure 1.1b).

Figure1.1 (a) Electric discharge in an (b)The cathode ray is bent

Evacuated tube. In the presence of a magnet.

 An English physicist Joseph John Thomson (1856-1940) in 1897
studied the behaviour of cathode rays in electric and magnetic
fields, Thomson established clearly that the rays consist of
negatively-charged particles.
 Moreover, his experiments showed that the particles were
identical, regardless of the materials from which the electrodes
were made or the type of gas in the tube.
 Thomson concluded that these negatively charged particles were
constituents of every kind of atom.
 We now call these particles electrons, a term that had been
coined by the Irish Physicist George Stoney in 1891 to describe
the smallest unit of electric charge. Cathode rays are beams of
electrons.
 Perhaps Thomson’s most significant experiment was the one
illustrated and described in Figure 1.1.
 By measuring the amount of deflection of a cathode ray beam in
electric and magnetic fields of known strengths, Thomson was
able to calculate the ratio of the mass of an electron to its charge.
 If we denote the mass of the electron as me and its electrical
charge as e, the mass-to-charge ration is me /e.
 This ratio has a value of – 5.686 × 10–12 kg C–1 (kilograms per
coulomb).
Figure 1.2 Thomson’s apparatus for determining the charge-to-mass ratio.
 In 1909, Robert A. Millikan, an American physicist, determined
the charge on the electron by observing the behaviour of
electrically-charged oil drops in an electric field.
• Based on careful experiments, Millikan established the charge
on an electron ase = –1.602 × 10 –19 C. From this value and the
value for me /e, we can calculate the mass of an electron. me =
me / e * e
= – 5.686 × 10 –12 kg C –1 × –1.602 × 10 –19 C = 9.109 × 10-31
kg
 In 1923, Millikan was awarded the Nobel Prize in physics for
his oil-drop experiment
 2.3.2 Radioactivity and Discovery of Nucleus
 Radioactivity is the spontaneous emission of radiation from the
unstable nuclei of certain isotopes. Isotopes that are radioactive are
called radioactive isotopes or radioisotopes. For example,
55 Cr, 226 Ra, 14 C, 238 U, 14 N
24 88 6 92 7

 are radioactive isotopes. Radioactive decay is defined as a nuclear

breakdown in which particles or (electromagnetic) radiation is
emitted.
 Shortly after the discovery of radioactivity, three types of rays were
identified in the emanations from radioactive substances.
 One type called alpha (α) particles which consist of particles that
have a mass that is about four times that of a hydrogen atom.
 They also have a charge twice the magnitude of an electron but
positive rather than negative.
 An alpha particle is now known to be a doubly-ionized
helium atom, that is, He2+
 A second type of radiation was shown to consist of negatively-
charged particles, identical to cathode rays. These particles are
called beta (β) particles, which are electrons, coming from
inside the nucleus.
 The third type of radiation, called gamma (γ) rays, is a form of
electromagnetic radiation much like the X-rays but of even
higher energy. Like X-rays, but unlike alpha and beta particles,
gamma rays are a form of energy and not a form of matter.
 Discovery of Nucleus

 In 1910, the New Zealand chemist and physicist, Ernest

Rutherford, who had studied with J.J. Thomson decided to use
α-particles to probe the structure of atoms.
 Together with his associate Hans Geiger, Rutherford carried out
a series of experiments using very thin foils of gold and other
metals as targets for α-particles from a radioactive source.

Figure 1.3 a Rutherford’s experimental design for measuring the scattering of α-particles by a
piece of gold foil.
b Magnified view of α-particles passing through and being deflected by the
nucleus.
 Discovery of Neutron
 Except for the lightest hydrogen isotope, protium (11 H), atoms
have more mass than is indicated by the numbers of their
protonsBefore
( the 1930’s, protons were considered as the sole
contributors to the mass of an atom).
 For example, a helium nucleus, with two protons has a mass
four times that of hydrogen.
 If all the mass came from the protons, a helium atom would
have only twice the mass of a hydrogen atom. The reason for
thisexcess”
“ mass puzzled scientists for several years.
 One hypothesis was that the atomic nucleus also contained
electrically neutral fundamental particles.
 In the 1920s and early 1930s, alpha particles were used as projectiles
to bombard a variety of materials.
 Bombardment of beryllium atoms produced a strange, highly
penetrating form of radiation.
 In 1932, James Chadwick (1891-1972) showed that this radiation was
best explained as a beam of neutral particles.
 These particles, called neutrons, were found to have about the same
mass as protons but no electric charge.
 This discovery finally provided an explanation for the mysterious
excess mass.
 A helium atom has two protons and two neutrons
 Because protons and neutrons have roughly the same mass (and
electrons have almost no mass) the helium atom should have about
four times the mass of the hydrogen atom.
 The mass of a neutron, mn = 1.67493 × 10 –27 kg, is about 1840 times
the mass of electron.
 1.4 MAKE UP OF THE NUCLEUS
1.4.1 Constituents of the Nucleus
 In 1914, Rutherford suggested that the smallest positive-ray particle was the
fundamental unit of positive charge in all nuclei. He called this particle,
which has a charge equal in magnitude but opposite in sign to that of an
electron, a proton.
 A proton has a mass of mp = 1.67262 × 10 –27 kg, which is about 1840 times
the mass of oppositely-charged electrons.
 Rutherford proposed that protons constitute the positively-charged matter in
the nuclei of all atoms.
Table 1.1 The three subatomic particles
 1.4.2 Atomic Mass and Isotopes
 Not all atoms of an element are identical in mass.
 All carbon atoms have six protons in the nucleus (Z = 6) but only 98.89
% of naturally occurring carbon atoms have six neutrons in the nucleus
A( = 12). A small percentage (1.11 %) have seven neutrons in the nucleus
A (= 13), and even fewer (less than 0.01 %) have eight (A = 14).
 Most elements found in nature are mixtures of isotopes.
 The average mass for the atoms in an element is called the atomic mass
of the element and can be obtained as averages over the relative masses
of the isotopes of each element, weighted by their observed fractional
abundances.
 If an element consists of n isotopes, of relative masses A1, A2…An and
fractional abundances of f1 , f2 …fn , then the average relative atomic mass A)
(
of the element is:

A = A1 f1 + A2 f2 + … + An fn .
 Example 1.2
1. There are two isotopes of lithium found on earth. Isotope 6Li
(6.01512mu ) accounts for 7.42% of the total, and isotope 7Li
mu ) accounts for the remaining 92.58%. What is the
(7.01600
average atomic mass of lithium?
Solution:
7.42/100 × 6.01512 mu + 92.58/ 100 × 7.01600 mu = 6.942 mu
2. Element X is toxic to humans in high concentration but essential to
life at low concentrations. Identify element X whose atoms contain 24
protons and write the symbol for the isotope with 28 neutrons.
3. Copper (Cu: atomic mass 63.546 mu) contains the isotopes 63Cu (mass = 62.9298
mu) and 65Cu (mass = 64.9278 mu). What percent of a Cu atom is 65Cu?
4. The element chlorine contains two isotopes: 35Cl, which has a mass of 34.97mu,
and 37Cl, which has a mass of 36.97 mu. Calculate the percentage of each chlorine
mu.
isotope. The average atomic mass of chlorine is 35.5
 1.5 ELECTROMAGNETIC RADIATION (EMR) AND ATOMIC
SPECTRA
1.5.1 Electromagnetic Radiation
 In 1873, James Clerk Maxwell proposed that light consists of
electromagnetic waves.
 According to his theory, an electromagnetic wave has an electric
field component and a magnetic field component.
 Further, his theory accurately describes how energy, in the form of
radiation, propagates through space as electric and magnetic fields.
Electromagnetic radiation is the emission and transmission of
energy in the form of electromagnetic waves.
 The wave properties of electromagnetic radiation are described by
two interdependent variables, frequency and wavelength.
Wavelength (λ, Greek lambda) is the distance between any point on
a wave and the corresponding point on the next wave; that is, the
distance the wave travels during one cycle.
 Figure 1.4 Electromagnetic waves

In Figure 1.4, two waves with different wave lengths (λ) and
thus different frequencies (ν) are shown.
Wavelength is commonly expressed in meters, but since
chemists often deal with very short wavelengths the nanometer,
picometer and the angstrom are also used.
Frequency (ν, Greek nu) is the number of cycles that pass a
given point in space per second, expressed in units of s–1 or hertz
(Hz).
 The speed of the electromagnetic wave (light), c (distance
travelled per unit time, in meters per second), is the product of its
frequency (cycles per second) and its wavelength (metres per cycle)
,
c0 = ν × λ ............................(1.1)
 In vacuum, light travels at a speed of 2.99792458 × 108 m s–1 (3.00
× 108 m s–1 to three segnificant figures).
 The speed of an electromagnetic wave depends on the nature of
the medium through which the wave is travelling.
 The speed of an electromagnetic wave in medium (c) is the
product of its wavelength and its frequency.
c = λ × ν ……………......(1.2)
 Another characteristic of a wave is its amplitude, the height of
the crest (or depth of the trough) of the wave.
 The amplitude of an electromagnetic wave is a measure of the
strength of its electric and magnetic fields.
 Thus, amplitude is related to the intensity of the radiation,
which we perceive as brightness in the case of visible light.

Figure 1.5 Amplitude (intensity) of waves.

 Light of a particular shade of red, for instance, always has the
same frequency and wavelength, but it can be dim (low
amplitude) or bright (high amplitude).
 Visible light occupies a small portion of the continuum of
radiant energy which is known as the electromagnetic spectrum
(Figure 1.6).
 The electromagnetic waves in the different spectral region
travel at the same speed but differ in frequency and wavelength.
 The long wavelength, low-frequency portion of the spectrum
comprises the microwave and radiowave regions.
 The infrared (IR) region overlaps the microwave region on one
end and the visible region on the other
 We perceive different wave lengths (or frequencies) of visible
light as different colours, from red (λ = 750 nm) to violet (λ =
400 nm).
 Light of a single wavelength is called monochromatic (Greek
“one colour”), whereas light of many wavelengths is
polychromatic (Greek “many colours”).
 White light is polychromatic.
 The region adjacent to visible light on the short-wavelength
end consists of ultraviolet (UV) radiation.
 Still shorter wavelengths (higher frequencies) make up the X-ray
and gamma ray (γ-ray) regions.
 Thus, a TV signal, Infrared (IR) light, and a gamma ray emitted
by a radioactive element differ principally in frequency and
wavelength.
Figure 1.6 Regions of the electromagnetic spectrum
 Example 1.3
1. The yellow light given off by a sodium lamp has a wavelength of 589
nm. What is the frequency of this radiation? Answer :
5.09 × 1014 s –1

2. A dental hygienist uses X-ray (λ = 1.00 Å) to take a series of dental

radiographs while the patient listens to an FM radio station (λ = 325
cm) and looks out the window at the blue
sky (λ = 473 nm). What is the frequency (in s ) of the
–1

electromagnetic radiation for each source?

Answer: 3.00 10 s ; 9.23 × 10 s 6.34 × 1014

18 –1 7 –1

s –1
Exercise 2.3
1. Some diamonds appear yellow because they contain nitrogenous
compounds that absorb purple light of frequency 7.23×1014 s–1.
Calculate the wavelength (in nm) of the absorbed light.
2. The FM station broadcasts traditional music at 102 MHz on
your radio. Units for FM frequencies are given in megahertz
(MHz). Find the wavelength of these radio waves in meters (m),
nanometers (nm), and angstrom (Å).
 1.5.2 The Quantum Theory and Photon
 Soon after Rutherford had proposed his nuclear model, a
major problem arose with it. A nucleus and an electron attract
each other, so if they are to remain apart, the energy of the
electron’s movement must balance the energy of attraction.
 However, the laws of physics had previously established that a
charged particle moving in a curved path must give off energy.
If this requirement is applied to an orbiting electron, why did
not the electron continuously lose energy and spiral into the
nucleus?
 Clearly, if electrons behaved the way as predicted in classical
physics, all atoms would have collapsed a long time ago!
• The breakthrough that soon followed forced a complete
rethinking of the classical picture of matter and energy.
• In the macroscopic world, the two are distinct: matter occurs
in pieces you can hold and weigh; you can change the amount
of matter in a sample piece by piece. Energy ismassless”;
“ its
amount can be changed in a continuous manner.
• Matter moves in specific paths, whereas light travels in diffuse
waves. As soon as 20th century scientists explored the
subatomic world, however, these clear distinctions between
particulate matter and wavelike energy began to fade.
• In the following sections, you will examine the theories and
experiments that led to the view of a quantized or particulate
nature of light.
  The quantum theory is concerned with the rules that govern the
gain or loss of energy from an object.
 In 1900, the German physicist Max Planck came to an entirely
new view of matter and energy.
 He proposed that a hot glowing object could emit (or absorb)
only certain amounts of energy. whereE is the energy of the
radiation, ν is the frequency, n is a positive integer n (= 1, 2, 3, ...)
called quantum number and h is proportionality constant now
called Planck’s constant. With energy in joules ( J) and
frequency in second (s –1), h has units of J s; (h = 6.626 × 10 –34 J
s)
E = nhν
 Planck’s contribution was to perceive that when we deal with the
gain or loss of energy from objects in the atomic size or
subatomic-size range, the rules “seem” to be different from those
that apply when we are dealing with the energy gain or loss from
objects of ordinary dimensions.
A Very Crude Analogy Might Best Illustrate What is Involved
 Imagine a large truck loaded with about 2 tons of fine-grained
sand. Let us assume that the amount of sand on the truck is
measured by a supersensitive scale that can measure the weight of
the 2-ton object to the nearest gram.
 With this scale as our measuring device, the gain or loss of a few
grains of sand from the truck would be too small to be measured.
A spade-ful of sand might be added or removed with no change
in the scale reading.
 Now imagine a tiny little truck operated by a driver of the size of
tiny ant.
 For this little truck, a full load of sand would consist of, perhaps,
a dozen grains of sand of the same size as those carried by the
large truck.
 In this microscopic world, the load on the truck can be added to
or decreased only by rolling on or off one or more grains of sand.
 On the scale that weighs this tiny truck, even one grain of sand
represents a substantial fraction of the load and is easily
measurable.
 In the given analogy, the sand represents energy. An object of ordinary or
macroscopic dimensions, like the large truck, contains energy in so many tiny
pieces that the gain or loss of individual pieces is completely unnoticed.

 On the other hand, an object of atomic dimensions, such as our imaginary

little truck, contains such a small amount of energy that the gain or loss of
even the smallest possible piece makes a substantial difference.

 The essence of Planck’s quantum theory is that there is such a thing as a

smallest allowable gain or loss of energy. Even though the amount of energy
gained or lost at one time may be very tiny, there is a limit to how small it
may be. Planck termed the smallest allowed increment of energy gained or
lost a quantum of energy.

 In the analogy, a single grain of sand represents a quantum of sand “energy”.

 It should be kept in mind that rules regarding the gain or loss of
energy are always the same, whether we are concerned with objects
on the size scale of our ordinary experience or with microscopic
objects.
 However, it is only when dealing with matter at the atomic level of
size that the impact of the quantum restriction is evident.
 Humans, being creatures of macroscopic dimensions, had no
reason to suppose that the quantum restriction existed until they
devised means of observing the behavior of matter at the atomic
level. The major tool for doing this at the time of Planck’s work was
the observation of the radiant energy absorbed or emitted by matter.
 An object can gain or lose energy by absorbing or emitting
radiant energy.
 Planck assumed that the amount of energy gained or lost at the
atomic level by the absorption or emission of radiation had to be
a whole-number multiple of a constant, times the frequency of
the radiant energy.
ΔE = hν, 2hν, 3hν, ...(1.3)
 where ΔE is the amount of energy gained or lost. The smallest
increment of energy at a given frequency,hν is the quantum of
energy.
 Example 1.4
1. Calculate the amount of energy (that is, the quantum
of energy) that an object can absorb from yellow light,
whose wavelength is 589 nm.
Solution:
 We obtain the magnitude of a quantum of energy absorbed
E = hν; h = 6.626 × 10–34 J s). The
from equation 1.3 (Δ
frequency, ν, is calculated from the given wavelength, ν co
= /λ
= 5.09 × 1014 s –1. Thus, we have: ΔE = hν = 6.626 × 10 –34 J s ×
5.09 × 1014 s –1 = 3.37 × 10–19 J
 The Photoelectric Effect
 Light shining on a clean metallic surface can cause the surface to
emit electrons. This phenomenon is known as the photoelectric
effect.
 For each metal, there is a minimum frequency of light (t hreshold
frequency) below which no electrons are emitted, regardless of
how intense the beam of light. In 1905, Albert Einstein
(1879–1955) used the quantum theory to explain the
photoelectric effect.
 He assumed that the radiant energy striking the metal surface is
a stream of tiny energy packets.
 Each energy packet, called a photon, is a quantum of energy, hν.
Eph = hν
 where Eph is the energy of a photon. Thus, radiant energy itself
is considered to be quantized. Photons of high-frequency
radiation have high energies, whereas photons of lower
frequency radiation have lower energy.
 When a photon is absorbed by the metal, its energy is
transferred to an electron in the metal. A certain amount of
energy is required for the electron to overcome the attractive
forces that hold it within the metal. Otherwise, it cannot
escape from the metal surface, even if the light beam is quite
intense.
 If a photon has sufficient energy, then an electron is emitted. If
a photon has more than the minimum energy required to free
an electron, the excess energy appears as the kinetic energy of
the emitted electron. This situation is summarized by the
equation
hv = Ek + Eb ………………;….(1.5)
• where Ek is the kinetic energy of the ejected electron, and Eb is
the binding energy of the electron in the metal. Rewriting
equation (1.5), using
Ek = ½ mev2 and Eb = hνo
Rusults in:
hν = hνo + ½ mev2
 where me is mass of an electron, and νo is the threshold frequency.
Equation (1.5) shows that the more energetic the photonhigh (
frequency), the higher the velocity of the ejected electron.
 Now consider two beams of light having the same frequency
which
( is greater than the threshold frequency) but different
intensities. The more intense beam of light consists of a larger
number of photons.
 Consequently, it ejects more electrons from the metal’s surface than the
weaker beam of light.
 Thus, the more intense the light the greater the number of electrons
emitted by the target metal.
 The higher the frequency of the light, the greater will be the kinetic
energy of the emitted electrons.
 Fortunately, we have equations to quantify these observations on the
nature of the photoelectric effect. Fore example,
ΔE = hν = hνo + ½ me v 2 …………....(1.6)
 where νo is the threshold frequency, me is the mass of the electron and v
is the velocity of the emitted electron.
 The energy (ΔE) of a quantum of radiation (hν) that goes into ejecting a
photoelectron out of the metal the
( work function hνo ) and the binding
mv 2). Equation 1.6 is one example
energy gives us the kinetic energy (½
of the first law of thermodynamics.
  To understand the photoelectric effect, consider the analogy of
a truck stuck in the mud.
 A stream of people can come by, and each of them
individually can give a push without getting the truck unstuck.
A small tractor also would have less than the threshold energy
necessary to dislodge the truck.
 A farm tractor on the other hand, would be able to overcome
the attractive forces of the mud and get the truck out. Larger
tractors also could do the job. Some could even exert more pull
than necessary thus giving the freed truck some kinetic energy.
 Example 2.5
 The maximum kinetic energy of the photoelectrons emitted
from a metal is 1.03 × 10–19 J when light that has a 656 nm
wavelength shines on the surface.
 Determine the threshold frequency, νo , for this metal. Given
quantities: h = 6.626 × 10 –34 J s, λ = 656 nm, kinetic energy of
photoelectron, Ek = 1.03 × 10 –19 J.

 Answer

3.02 × 1014 s–1 or Hz

 Exercise 2.4
1. The threshold frequency for metallic potassium is 5.46 × 1014
s–1. Calculate the maximum kinetic energy and velocity that the
emitted electron has when the wavelength of light shining on
the potassium surface is 350 nm. (The mass of an electron is
9.11 × 10–31 kg.)
4. A laser produces red light of wavelength 632.8 nm. Calculate the
energy, in kJ, of one mole of photons of this red light.
 1.5.3 Atomic Spectra
 Atomic or line spectra are produced from the emission of
photons of electromagnetic radiation (light).
 When an element is vaporized, and thermally or electrically
excited, it emits light with discrete frequencies.
 If dispersed by a prism, the light does not create a continuous
spectrum, or rainbow, as sunlight does. Rather, it produces a
line spectrum, a series of fine lines of individual colours
separated by colorlessblack)
( spaces.
 The wavelengths at which the colored lines occur are
characteristic of the element. (Figure 1.7). A line spectrum that
consists of only relatively few wavelengths that is produced
from light emitted by excited atoms is the unique feature of an
element, and can be used for identification purposes.
Figure 1.7 An experimental arrangement for studying the emission
spectra of atoms and molecules.
 1.5.4 The Bohr Model of the Hydrogen Atom
 In 1913, Niels Bohr, a Danish physicist, who had worked with
Rutherford, combined ideas from classical physics and the new
quantum theory to explain the structure of the hydrogen atom.
 He suggested a model for the hydrogen atom that predicted the
existence of line spectra.
 In doing so, he was able to explain the spectrum of radiation
emitted by hydrogen atoms in gas-discharge tubes.
 Based on the work of Planck and Einstein, Bohr made the
revolutionary assumption that certain properties of the electron
in a hydrogen atom – including energy, can have only certain
specific values.
 That is to say, these properties are quantized. Bohr proposed
the following three postulates for his model.
1. The hydrogen atom has only certain allowable energy levels,
called stationary states. Each of these states is associated with a
fixed circular orbit of the electron around the nucleus.
2. The atom does not radiate energy while in one of its stationary
states. That is, even though it violates the ideas of classical
physics, the atom does not change energy while the electron
moves within an orbit.
3. The electron moves to another stationary state (orbit) only by
absorbing or emitting a photon whose energy equals the
difference in the energy between the two states.
 Eph = Ef – Ei = hν .......................................(1.7)
The subscripts f and i represent the final and the initial
states, respectively. The Bohr radius, denoted by
ao (ao = 0.0529 nm) can be calculated using the
formula
ao =r/n 2………………………………………………. ...(1.8)
where n is a positive integer which is called quantum
number. r is the radius of the orbit and is given by:
.......................................(1.8)

Where εo is the vacuum dielectric constant (εo = 8.854 × 10–12 C V–1 m–1).
 A spectral line results from the emission of a photon of specific energy
and
( therefore, of specific frequency), when the electron moves from a
higher energy state to a lower one.
 An atomic spectrum appears as lines rather than as a continuum
because the atom’s energy has only certain discrete energy levels or
states.
 In Bohr’s model, the quantum number n (n = 1, 2, 3, ...) is associated
with the radius of the electron’s orbit, which is directly related to the
atom’s energy.
 The lower the quantum number, the smaller is the radius of the orbit
and the lower is the energy level of the atom. When the electron is in
the orbit closest to the nucleusn(= 1), the atom is in its lowest (first)
energy level, which is called the ground state.
 By absorbing a photon whose energy equals the difference between the
first and second energy levels, the electron can move to the next orbit.
 This second energy level (second stationary state) and all higher levels
are called excited states.
 The hydrogen atom in the second energy level (first excited state) can
return to the ground state by emitting a photon of a particular
frequency:
ΔE = Ee – Eg …………………………………………..(1.10)
 where Eg and Ee represent the ground and the excited energy states,
respectively.
 When a sample of atomic hydrogen absorbs energy, different hydrogen
atoms absorb different amounts. Even though each atom has only one
electron, so many atoms are present that all the allowable energy levels
(orbits) are populated by electrons.
 When an electron drops from orbits with n > 3 (second excited state),
the infrared series of spectral lines is producedi.e, Paschen Series.
The visible series arises from the photons emitted when an electron
drops to then = 2 orbit i.e, Balmer Series (first excited state), and the
ultraviolet series arises when these higher energy electrons drop to the
n = 1 orbit (ground state).
Figure 1.8 Representation of the observed spectral lines of the hydrogen atom.
  Since a larger orbit radius means a higher atomic energy level,
the farther the electron drops, the greater is the energy (higherv,
shorter λ) of the emitted photon.
 The spectral lines of hydrogen become closer and closer
together in the short wavelength high ( energy) region of each
series because the difference in energy associated with the jump
from initial stateni( ) to the final state (nf ) becomes smaller
and smaller as the distance from the nucleus increases.
 Having made this basic assumption, Bohr was then able to use
classical physics to calculate properties of the hydrogen atom.
 In particular, he derived an equation for the electron energy (En )
. Each specified energy value (E1 , E2 , E3 ,...) is called level of the
atom.
 A very useful result from Bohr’s work is an equation for
calculating the energy levels of an atom,En an energy.
 …………………………………………..(1.11)

where RH is the Rydberg constant, has a value of, RH = 2.18 ×

10 –18 J.
The number n is an integer called the principal quantum
number (n = 1, 2, 3, ...). Z is the charge of the nucleus. The
negative sign in the equation appears because it is defined as zero
energy when the electron is completely moved form the nucleus,
E n = 0 when n =∞, so, En < 0 for any smaller n. For the H
i.e.
atom, Z = 1, so we have
.......................................(1.12)
• Therefore, the energy of the ground state n = 1 is –2.18 × 10 –18
J. This equation is easily adapted to find the energy difference
between any two levels:
…...(1.13)

1. Calculate the energies of the states of the hydrogen atom with n = 2

and n = 3, and calculate the wavelength of the photon emitted by the
atom when an electron makes a transition between these two states.
2. What is the wavelength of a photon emitted during a transition from
theni = 5 state to the nf = 2 state in the hydrogen atom?
3. How much energy, in kilojoules per mole, is released when an
electron makes a transition fromn = 5 to n = 2 in an hydrogen atom?
Is this energy sufficient to break the H–H bond (436 kJ / mol is needed
to break this bond)?
Hint : 1eV=(1eV =1.60217734×10-19 joule; 1.60217733×10-22)
×(6.0223×1023)= 96.49kj/mole.
5. Five lines in the H atom spectrum have wavelengths (in
Å):
a. 1212.7 b. 4340.5 c. 4861.3
d. 6562.8 e. 10938d
 Three lines result from transition to nf = 2 (visible series)
. The other two result from transitions in different
series-one with nf = 1, and the other with nf = 3.
Identify ni for each line.
 1.5.5 Limitations of the Bohr Theory
 The Bohr model of an atom was successful in accounting for
the spectral lines of H-atom which indicated that he was on the
right track.
 Despite its great success in accounting for the spectral lines of
the H atom, the Bohr model failed to predict the wavelengths
of spectral lines of atoms more complicated than hydrogen,
even that of helium, the next simplest element.
 It works beautifully for the hydrogen atom and for other one-
electron species such as He+ and Li2+.
 Bohr could not explain the further splitting of spectral lines in
the hydrogen spectra on application of magnetic field and
electric fields.
  In the years following Bohr’s development of a model for the
hydrogen atom, the dual nature of radiant energy had become a
familiar concept.
 Depending on the experimental circumstances, radiation might
appear to have either a wave-like or particle-like photon)
(
character.
Is it possible that under proper circumstances, matter can behave
as waves?
• Louis de Broglie made a rather bold intuitive extension of this
idea. Using Einstein’s equation and Planck’s equation for energy,
he proposed that a particle with a mass,m, moving at a speed,
v, has a wave nature consistent with a wavelength given by: λ
h/mν
= ………………………………...(1.14)
 where h is Planck’s constant. The quantity mν for any object is
called its momentum.
 The matter waves describe the wave characteristics of material
particles.
 Because de Broglie’s hypothesis is perfectly general, any object
of massm and velocity ν would give rise to a characteristic
matter wave.
 However, it is easy to see from Equation 1.14 that the
wavelength associated with an object of ordinary size, such as a
tennis ball is so tiny as to be completely out of the range of
any possible observation.
 This is not so for electrons, because their mass is very small.
 If de Broglie’s concept is correct and all particles travel in
waves, electrons should exhibit the typical wave-properties,
diffraction and interference.
 Electron particles with mass and charge create diffraction
patterns, just as electromagnetic waves do.
 Although electrons do not have orbits of fixed radius, de
Broglie thought that the energy levels of the atom are related to
the wave nature of the electron.
 The unsettling truth is that matter as well as energy show both
behaviors: each possesses both properties”.
“ In some
experiments, one property is observed, while in other
experiments, the other property is observed.
 The distinction between a particle and a wave is only
meaningful in the macroscopic world - it disappears at the
atomic level.
 The distinction is in the minds and the limiting definitions of
people, not in nature.
 This dual character of matter and energy is known as the wave-
particle duality.
 Example 1.6

1. Calculate the de Broglie wavelength of an electron that has a

velocity of 1.00 × 106 m/s. (electron mass, me = 9.11 × 10 –31 kg;
h = 6.626 × 10 –34 J s)
2. Calculate the frequency of the hydrogen line that corresponds
to the transition of the electron from then = 4 to the n = 2
state.
 Exercise 2.6

1. What is the characteristic wavelength of an electron

(in nm) that has a velocity of 5.97 × 106 m s–1 (me =
9.11 × 10 –31 kg)?
2. Calculate the energy required for the ionization of an
electron from the ground state of the hydrogen atom.
3. Calculate the wavelength (in nm) of a photon emitted
when a hydrogen atom undergoes a transition fromn =
5 to n = 2.
 1.6 THE QUANTUM MECHANICAL MODEL OF THE
ATOM
 Bohr’s model was very important because it introduced the
idea of quantized energy states for electrons in atoms.
 This feature is incorporated in our current model of the atom,
the quantum mechanical model of the atom.
 The sophisticated mathematical description of atomic structure
based on the wave properties of subatomic particles is called
wave mechanics or quantum mechanics.
 Principally, the Austrian physicist Erwin Scrödinger developed
a model of the hydrogen atom based on the wave nature of the
electron in the late 1920s.
 Mathematical equations describing the nature of electron waves
in atoms are fundamental to the modern picture of the atom.
 The wave equations that are acceptable solutions to the
Schrödinger equation are called wave functions.
 To obtain one of these acceptable solutions, we must assign
integral values called quantum numbers to three quantities in
the wave equation.
 This requirement is similar to the requirement for an integral
value ofn in the Bohr equation for the hydrogen atom.
 In contrast to the precise planetary orbits of the Bohr atom,
the wave mechanics picture of the hydrogen atom is less
certain.
 Instead of determining the exact location of the electron, we
can only speak of the probability of the electron being found
in certain regions of the atom. Or, if we adopt the view that
the electron is just a cloud of negative electric charge, we can
only speak of the charge densities in various parts of the atom.
 1.6.1 The Heisenberg's Principle
 Discovery of the wave properties of matter raised a new and
very interesting question.
 If a subatomic particle can exhibit the properties of a wave, is
it possible to say precisely where that particle is located? One
can hardly speak of the precise location of a wave. A wave, as a
whole, extends in space.
 Its location is therefore not defined precisely. To describe the
limitation (problem) of trying to locate a subatomic particle
that behaves like a wave, Heisenberg formulated what is known
as the Heisenberg uncertainty principle, which states that it is
impossible to know simultaneously both the momentum p (p
= mν) and the position of a particle with certainty.
 Mathematically, the Heisenberg's uncertainty principle is given
as
 where Δx and Δp are the uncertainties in measuring the
position and momentum, respectively.
The above equation says that if we measure the momentum of a
particle precisely
(i.e. if Δp is made very small), then the position will be
correspondingly less precise i.e, Δx will become larger). Similarly,
if the position of a particle is known more precisely, then its
momentum will be less precise.
The German physicist Werner Heisenberg in 1927 concluded
that there is a fundamental limitation to know both the
location and the momentum of a particle simultaneously, which
is due to dual behaviour of matter and radiation. Just as in the
case of quantum effects, the limitation becomes important only
when we deal with matter at the subatomic level, that is, with
mass as small as that of an electron.
 1.6.2 Quantum Numbers
 An atomic orbital is specified first by three quantum numbers that
are associated respectively, with the orbital's size energy),
( shape,
orientation and, later, independent of these three quantum
numbers, the electron spin.
 The first three sets of quantum numbers have a hierarchical
relationship: the size-related number limits the shape related
number, the shape-related number in turn limits the orientation-
related number.
 Three among the four quantum numbers characterize the orbitals
in the atom.
 That is, they describe the orbital or the space the electron is
supposed to occupy.
 The fourth quantum number is used to describe the spin of the
electrons that occupy the orbitals.
 The four quantum numbers are:
1. The principal quantum number n( ) is a positive integer
having values n = 1, 2, 3, ... . It gives the following
information:
(i) Relative size of the orbital or the relative distance of the
electron from the nucleus. Size of orbital increases with the
increase of principal quantum number n.
(ii) Energy of the orbital. Higher the n value, greater is the
energy. For example: when the electron occupies an orbital
withn = 1, the hydrogen atom is in its ground state and
has lower energy than when the electron occupies an
n = 2 (first excited state).
orbital with
(iii) Maximum number of electrons present in any shell (given
by the formula 2n 2).
 2. The azimuthal quantum number (l) is also known as angular
momentum or subsidiary quantum number. It is an integer having
values from 0 ton( – 1). For an orbital withn = 1, l can have a
value only of 0. For orbitals with n = 2, l can have a value of 0 or
1; for those with n = 3, l can be 0, 1 or 2; etc. So, the number of
l values equals the value of n. For a given value of n, the
possible
maximum possible value of l is (n – 1).
The azimuthal quantum number gives the following information:
(i). Number of sub-shell present within any shell.
(ii). It describes the shape of the orbital and is sometimes also
called the orbital-shape quantum number.
3. The magnetic quantum number (ml ) is also known as
the orbital-orientation quantum number.
 It is an integer having values from –l through 0 to +l.
The possible values of an orbital's magnetic quantum
number are set by its angular momentum quantum
numberthat( is, l determines ml ).
An orbital with l = 0 can have only ml = 0.
However an orbital with l = 1, can have ml value of
–1, 0, or + 1; thus there are three possible orbitals with
l = 1 each with its own spatial orientation.
 The number of possible ml values or orbitals for a
given l value is (2l + 1).
It prescribes the orientation of the orbital in the
three-dimensional space about the nucleus.
4. The electron spin quantum number (ms ) has only two
possible values, +½ represented
( by the arrow, ↑) and – ½
(represented by the arrow ↓). The name electron spin
quantum suggests that electrons have a spinning motion.
However, there is no way to attach a precise physical
reality to electron spin. The quantum numbers specify the
energy states of the atom.
• The atom's energy levels or shells are given by the n value.
• The atom's sublevels or subshells are given by the n and l
values. Each level contains sublevels that designate the
shape of the orbital.
• The atom's orbitals are specified by the n, l and ml values.
Thus, the three quantum numbers that describe an orbital
express its size (energy), shape and spatial orientation.
Each sublevel is designated by a letter:
l = 0, is an s sublevel
l = 1, is a p sublevel
l = 2, is a d sublevel
l = 3, is a f sublevel
 The letters s, p, d, and f are derived from the names of
spectroscopic lines: s, sharp; p, principal; d, diffuse; and f,
fundamental. Sublevels are named by joining the n value and
the letter designation.
 For example, the sublevel (subshell) with n = 2, l = 0 is called
the s2 sublevel; the only orbital in this sublevel has n = 2, l = 0
and ml = 0. A sublevel withn = 3, l = 1, is a 3p sublevel. It has
three possible orbitals: one with n = 3, l = 1 and ml = –1 ;
another with n = 3, l = 1 and ml = 0 and the third n = 3, l = 1,
and ml = +1.
  For a given principal quantum number, n, the total number of
orbitals is determined as: Number of orbitals =n 2 in a shell.
 Similarly, the number of orbitals in each subshell is determined
as: Number of orbitals in a subshell = l2+1.
Example 1.7
1. What values of the angular momentum quantum number (l) and
magnetic quantum number (ml ) are allowed for a principal quantum
number (n) of 3? How many orbitals are allowed for n = 3?
2. Give the name, magnetic quantum numbers, and numbers of
orbitals for each sublevel with the following quantum numbers:
a. n = 3, l = 2 c. n = 5, l = 1
b. n = 2, l = 0 d. n = 4, l = 3
 Exercise 2.7
1. Indicate whether each of the following is a permissible set of
quantum numbers. If the set is not permissible, state why it is not.
a. n = 3, l = 1, ml = +2 d. n = 0, l = 0, ml = 0
b. n = 4, l = 3, ml = –3 e. n = 3, l = 3, ml = –3
c. n = 3, l = 2, ml = –2
2. Consider the electronic configuration of an atom:
a. What are the n, l and ml quantum numbers corresponding to the
3s orbital?
b. List all the possible quantum number values for an orbital in the
5f sub shell.
c. In which specific subshell will an electron be present if the
quantum numbers n = 3, l = 1, and ml = –1?
3. Which of the quantum numbers relates to the electron only? Which
relate (s) to the orbital?
 1.6.3 Shapes of Atomic Orbitals

 The wave mechanical picture of an electron in an s-orbital looks

like a ball made of a raised soft hairy rug that
( is the orbital has
spherical symmetry).

1s 2s
Figure 1.9 a Geometric shape of 1s and 2s-orbitals.
dumb bell-shaped regions of p-orbitals

Figure 1.10 The three p -orbitals.

Double dumb bell-shaped regions of d-orbitals

Figure 1.11 The five d orbitals.

 1.7 ELECTRONIC CONFIGURATIONS AND
ORBITAL DIAGRAMS
 it is necessary to know the basic principles that govern the
distribution of electrons among atomic orbitals.
 The electron configuration for any atom follows the following
three principles:
 Aufbau Principle. In general, electrons occupy the lowest-
energy orbital available before entering the higher energy
orbital.

Figure: 1.12 Increasing order of filling orbitals.

 Hund’s Principle. Equal energy orbitals (degenerate orbitals) are
each occupied by a single electron before the second electrons of
opposite spin enters the orbital.
 In other words, each of the three 2p orbitals (2px, 2py and 2pz)
will hold a single electron before any of them receives a second
electron.
 Pauli’s Exclusion Principle. No two electrons can have the same
four quantum numbers.i.e. they must differ in at least one of the
four quantum numbers.
Note: aufbau is a German word, which mean building-up, while Pauli
and Hund are the names of scientists.
1.7.1 Ground State Electronic Configuration of the Elements
 The electronic configuration of an atom describes the
distribution of the electrons among atomic orbitals in the atom.
 Two general methods are used to denote electron configurations.
 The subshell (sublevel) notation uses numbers to designate
the principal energy levels or principal quantum number and
s, p, d and f to identify the sublevels or subshells.
the letters
 A superscript number following a letter indicates the number
of electrons in the designated subshell e).
( The designation
can be written as nl e.
 The electron configurations for hydrogen (H; Z = 1), helium
(He; Z = 2) and lithium (Li; Z = 3) are s11, 1s 2, 1s 2 2s 1
respectively.
 The other way to present this information is through an
orbital diagram, which consists of a box or( circle, or just a line)
for each orbital available in a given energy level, grouped by
sublevel, with an arrow indicating the electron’s presence and
its direction of spin.
 Traditionally ↑, ms = +½ and ↓, ms = –½, but these are
arbitrary, so it is necessary only to be consistent.
 The orbital diagrams for the first three elements are:
 In Li, the 2s orbital is only half-filled, so the fourth electron of
beryllium fills in with its spin paired:n = 2, l = 0, ml = 0, ms = +½.
 For beryllium, the 2s sublevel is filled, and the next lower energy
sublevel is the 2p.
 The three orbitals in the 2p sublevel have equal energy (same n and l
values), which means that the fifth electron of boron can go into any
one of thep2orbitals. Since a p sublevel has l = 1, the ml (orientation)
values can be –1, 0, or +1.
 For convenience, the boxes are lebelled from left to right, –1, 0, +1,
and assume it enters theml = –1 orbital: n = 2, l = 1, ml = –1, and ms
= +½.
 For our purposes here, the designation of ml = –1 for this boron
electron (and the box we chose to label –1, in which we placed the
arrow) is arbitrary.
 The 2p orbital’s have equal energy and differ only in their orientation.
 Exercise 1.8
1. Write the ground-state electron configuration for potassium, Z=19
2. Write the electron configuration of an element with atomic number 10.
3. Write the electron configuration of an element with (Z = 20 and A = 40 mu).
4. Draw the orbital diagrams for the valence electrons of the atoms: C, N, O, F
and Ne and determine the number of unpaired electrons for each atom.
Examine the electron configurations of chromium and copper. The
expected configuration, those based on the aufbau principle, is not the
ones observed through the emission spectra and magnetic properties of the
elements
Expected Observed
Cr (Z = 24) [Ar] 4s 23d 4 [Ar] 4s 13d 5
Cu (Z = 29) [Ar] 4s 23d 9 [Ar] 4s 13d 10
The reason for these exceptions to the aufbau principle are not completely
understood, but it seems that the half-filled 3d subshell of chromium (3d 5)
and the fully filled 3d subshell of copper (3d 10) lends a special stability to
the electron configurations. Apparently, having a half-filled 4s subshell and
a half-filled d3 subshell gives a lower energy state for a Cr atom than
having a filled 4s subshell.
 Because there is little difference between the 4s and 3d
orbital energies, expected and observed electron
configurations are quite close in energy.
 At higher principal quantum numbers, the energy
difference between certain subshell is even smaller than
that between thed 3and 4s subshells.
As a result, there are still more exceptions to the Aufabu
principle among the heavier transition elements.
 Exercise 1.9

1. Write the electron configuration for the Co3+,

Cl– , Al+, Cr, As–, and Cu.
2. Write the electron configuration and the orbital
diagram of the first excited state of sodium. (Hint:
The outermost electron is excited).
3. What is the electron capacity of the nth energy
level? What is the capacity of the fourth energy
level?
 1.8 ELECTRONIC CONFIGURATIONS AND THE PERIODIC
TABLE OF THE ELEMENTS
1.8.1 The Modern Periodic Table
1.8.2 Classification of the Elemen
Elements are placed in the periodic table in accordance to valence electron entering
the orbital of lowest energy. There are 18 groups and 7 periods in the modern
periodic table.
Representative or main group elements: These consist of all s- and p-block elements.
The chemical properties of the representative elements are determined by the number
of valence electrons in their atoms.
Transition elements: These are d-block elements. There are four series of transitional
elements, 3d, 4d, 5d and 6d depending on the energy levels of d-orbitals.
Inner transition elements: These are the f-block elements. There are two series of
f-block elements, 4f and 5f series called lanthanides and actinides, respectively. The
periodic table is unable to include the inner transition elements in its main frame. They
have been allotted the same single place in the periodic table though their electronic
configurations are not identical. Besides, the variation in their properties is not much.
Figure 1.13 Classification of elements according to the type of subshells being filled.
 1.8.3 Periodic Properties

 Some physical properties, such as thermal and

electrical conductivity, density, and hardness are
displayed only by bulk matter, that is, by large
aggregations of atoms.
 In this section you will examine some periodic
atomic properties like atomic radii, ionization
energies, electron affinities, electronegativity, and
metallic character.
 Atomic Size (Atomic Radii)
 Exact size of an isolated atom cannot be measured because its
outermost electrons have a chance of being found at relatively
large distances from the nucleus.
 What can be measured is the distance between the nuclei of two
adjacent atoms, and can derive a property called the atomic
radius from this distance.
 One of the most common methods to determine atomic radius
is to assume that atoms are spheres that touch each other when
they are bonded together (Figure 1.14).

Figure 1.14 Atomic radius for a diatomic molecule.

 Figure 1.14 depicts a way to define the radius of an atom
using the distanced between the nuclei of two atoms on
an element in a molecule.
 It is assumed that the atom is a hard sphere with a radius
equal to half the bond distance, 1/2d.
 For example, the distance between iodine atoms in an
iodine molecule I2, (I—I) is 2.66 Å, so we can define the
radius of an iodine atom to be half this distance: 1.33 Å:
similarly, the distance between iron atoms (Fe) in iron
metal is 2.48Å.
 Therefore, each iron atom in the metal has a radius of
1.24Å.
 Within a vertical group of the periodic table, each succeeding
member has one more principal shell occupied by electrons,
thus, atomic radii increases from top to bottom within a group
of the periodic table.
 To describe how atomic radii vary within a period of the
periodic table, it is helpful to employ a new concept.
 The effective nuclear charge (Zeff ) acting on an electron is the
actual nuclear charge less the screening effect of other electrons
in the atom.
 For example, consider a sodium atom. If the 3s valence
electron were at all times completely outside the region in
which the ten electrons of the neon core s(12 2s 2 2p 6) are
found, the 3s electron would be perfectly screened or shield
from the positively charged nucleus; it would experience an
attraction to a net positive charge of only +11 – 10 = +1.
  The corresponding situation for magnesium
atom would be that of the two 3s electrons
outside the neon core and a net positive charge
s 3
of +12 – 10 = +2 acting on each of the
electrons.
 Similarly it is found that the net positive
charge acting on the valence electrons would
progressively increase across the third period.
 The effective nuclear charge increases from left to right in a
period of representative elements in the periodic table.
 Because the effective nuclear charge increases, valence electrons
are pulled in toward the nucleus and held more tightly.
 Atomic radii of the A-group elements (main group element)
tend to decrease from left to right in a period of the periodic
table.
 The restriction to A-group elements is an important one.
 In a series of B-group elements (t ransition elements), electrons
enter an inner electron shell, not the valence shell.
 In this process, the effective nuclear charge remains essentially
constant instead of increasing.
 For example, compare the effective nuclear charges, Zeff , of iron,
cobalt, and nickel.
Because the effective nuclear charges are almost the same, we
conclude that the radii should also be almost the same. The actual
values are 124, 124, and 125 pm, respectively, for Fe, Co and Ni.
Exercise 1.10
1. Arrange the following atoms in order of increasing atomic radius: F, P, S, As.
2. The atoms and ions Na, Mg+, Al2+ and Si3+ all have the same number of
electrons. For which of these will the effective nuclear charge acting on the
outer most electron be the smallest? For which will it be greatest? Explain
 Ionization Energy (IE)
 The ionization energy (IE) is the amount of energy required to
remove the outermost electron in an isolated gaseous atom or ion.
 Multi-electron atoms can lose more than one electron, so the
ionization energies required to remove each electron are numbered
in sequence from the ground-state atom. Consider for example the
boron atom, which has five electrons, two in
an inner core (1s 2) and three valence electrons (2s 22p 1).
 The five ionization steps and their ionization energies, IE1
through IE5, are:
The first ionization energy (IE1) is the energy needed to remove
an electron from the highest occupied sublevel of the gaseous
atom. Atom(g) → Ion+(g) + e– ΔE = IE1 > 0

The second ionization energy (IE2) removes the second electron.

Since the electron is being pulled away from a positively charged
ion, IE2 is always larger than IE1:

Ion+ (g) → Ion2+ (g) + e– ΔE = IE2 (always > IE1 )

 The first ionization energy is a key factor in an elements
chemical reactivity because, atoms with a low IE1 tend to form
cations during reactions, whereas those with a high IE1except
,(
the noble gases) often form anions.
 The elements exhibit a periodic change in first ionization energy.
There is a roughly inverse relationship between IE1 and atomic
size.
 The only significant deviations from this pattern occur in Group
IIIA.
 Although IE1 decreases as expected from boron (B) to
aluminium (Al), no decrease occurs for the rest of the group.
 As with the atomic size trends, filling the d sublevels of the
intervening transition elements in period 4, 5 and 6 causes a
greater than expected Zeff , which holds the outer electrons
tightly in this larger IIIA members.
 As we move across a period, Zeff generally increases so atomic
radii become smaller.
 As a result, the attraction between the nucleus and the outer
electrons increases, so an electron becomes more difficult to
remove.
 In general, ionization energy increases across a period; it is easier
to remove an electron from an alkali metal than from a noble gas.
 There are two exceptions in the otherwise smooth increase in
ionization energy trend, which occur at Groups IIIA and VIA in
period 2 (at B and at O) and in period 3 (at Al and at S).
 The first deviation occurs because the np sublevel is higher in
energy than the ns sublevel.
 The second deviation occurs because the np 4 electron occupies
the same orbital as another np electron, the first such pairing,
so electron repulsions raise the orbital energy.

 Removing this electron relieves the repulsions and leaves a

stable, half-filled np sublevel; thus the fourth p electron is
pulled off more easily.

 For the representative elements, removing a core electron

requires much more energy compared to removing a valence
electron.
Figure 1.15 A graph of first ionization energy versus atomic number.
 Example 1.8
Explain the irregularities in the trends across periods.
1. Boron, with Z = 5 and the electron configuration 1s 22s 22p 1, has
smaller first ionization energy (801 kJ mol–1) than does
beryllium (Z = 4), which has the electron configuration 1s 22s 2
and IE1 = 900 kJ mol –1.

Solution: The 2p electron of boron is at a higher energy than the

2s electron of beryllium and is therefore easier to remove. This
kind of discontinuity occurs generally in proceeding from a
Group IIA or Group IIB elements to a Group IIIA element.
2. IE1 values for nitrogen ([He]2s 22px p1 y p1 z 1) is higher than
oxygen ([He]2s 22px 2py 1pz 1).

Solution: The observed IE1 values are 1314 kJ/mol for oxygen and

1402 kJ/mol for nitrogen.

In 2p orbitals, the repulsion between the paired electrons in
the 2px orbital of oxygen makes the removal of one of those
electrons easier to accomplish than the removal of an unpaired
electron from the half-occupied p2 orbital of nitrogen.
 Exercise 1.11
1. Use the third period of the periodic table as an example
to illustrate change in the first ionization energies of the elements as we move
from left to right. Explain the trend.
2. Ionization energy measurements are usually carried out with atoms in the gaseous
state. Why?
3. The first and second ionization energies of K are 419 kJ
mol and 3052 kJ mol and those of Ca are 590 kJ
–1 –1

mol and 1145 kJ mol, respectively, compare their

–1 –1

value and comment on the differences.

4. Why does potassium have a lower first ionization than lithium?
5. Based on their positions in the periodic table, predict which atom of the
following pairs will have larger first ionization energy:
a. Ga, Ge b. Br, Sb c. K, Cr, d. Mg, Sr e. O, Ne
 Electron Affinity (EA)
 Ionization energy refers to the process of forming a gaseous
positive ion from a gaseous atom.
 The corresponding atomic property for the formation of
gaseous negative ion is electron affinity, the energy change that
occurs when an electron is added to a gaseous atom or ion.
 An electron approaching a neutral atom experiences an
attraction for the positively charged nucleus.
 Repulsion of the incoming electron by electrons already present
in the atom tends to offset this attraction. Still, in many cases
the incoming electron is absorbed by the atom and energy is
evolved as in the process:
F (g) + e– → F– (g); EA = –328 kJ mol–1
 When a fluorine atom gains an electron, energy is given off.
 The process is exothermic and the electron affinity is therefore a
negative quantity.
The given information suggest a rough correlation
between electron affinity and atomic size. Smaller an
atom, more negative is its electron affinity.
The smaller the atom the closer an added electron can
approach the atomic nucleus and the more strongly it is
attracted to the nucleus.
This certainly seems to be the case for the Group IA
elements, for Group VIA from S to Po and for Group
VIIA from Cl to At.
The first row elements present some problems.
The electron affinity of O is not as negative as that of S,
nor i that of F as negative as that of Cl.
Here it may be that electron repulsions in the small
compact atoms keep the added electron from being
tightly bound as we might expect.
  In most cases, the added electron goes into an energy sublevel
that is already partly filled.
 For the Group IIA and VIIIA atoms, however, the added
electron would be required to enter a significantly higher
np level for the Group IIA atoms and thes
energy level, the
level for the next principal level for the Group VIIIA atoms.
In these cases a stable anion does not form.
 As the stepwise loss of multiple electrons in the formation of
positive ions has been described, in the same manner, the
stepwise addition of electrons in anion formation can be
described, and we can write a separate electron affinity for each
step. For oxygen atom, it can be written as:
 Electronegativity
 Atoms of the elements in the upper right of the periodic table
(small, non-metal atoms) attract bonding electrons most
strongly. Therefore, they have the greatest electro negativities.
 Atoms of the elements to the left side of the table (large, metal
atoms) have a weaker hold on electrons.
 They have the smallest electro negativities. On an electro
negativity scale devised by Linus Pauling, the most non-metallic
and hence most electronegative element, fluorine, is assigned a
value of 4.0.
 Typical active metals have electro negativities of about 1.0 or
less.
 Within a period of the periodic table, elements become more
electronegative from left to right. In the second period, the
trend is regular.
That is, it increases by about 0.5 per element as we move from
lithium at the far left to fluorine at the far right. In other periods
the trend is in the same direction but less regular;
 Within a group, electro negativity decreases from top to
bottom. Chlorine is less electronegative than fluorine and
sulphur is less electronegative than oxygen.
 A comparison of electro negativities is not quite straight
forward when considering two elements that are neither in the
same period nor in the same group.
 Metallic Character

 Metallic character refers to the chemical properties associated

with elements classified as metals.
 These properties arise from the elements ability to lose
electrons.
 As one moves across a period from left to right in the periodic
table, the metallic character decreases, as atoms are more likely
to gain electrons to fill their valance shell rather than to lose
them to remove the shell.
 Down a group, the metallic character increases, due to the
lesser attraction from the nucleus to the valence electrons.
 1.8.4 Advantages of Periodic Classification of the Elements
Some of the advantages of periodic classification of elements are:
1. The classification of elements is based on the atomic number,
which is a fundamental property of an element.
2. The reason for placing isotopes at one place is justified as the
classification is on the basis of atomic number.
3. It explains the periodicity of the properties of the elements and
relates them to their electronic configurations.
4. The position of the elements that were misfits on the basis of
mass number (anomalous pairs like argon and potassium) could
be justified on the basis of atomic number.
5. The lanthanides and actinides are placed separately at the
bottom of the periodic table.
6. The table is simple, systematic and easy way for remembering
the properties of various elements as it is based on the
electronic configuration.
 2. Chemical Bonding and Structure
1.1 INTRODUCTION
Form a group and discuss the following questions:
1. Why do atoms readily combine to form molecules?
2. Why molecules are more stable than free atoms?
3. What keeps the atoms together in a molecule?
4. Why do elements combine in certain fixed ratio?
5. The following diagram shows how energy varies as two H atoms
approach each other to form H2. Interpret the diagram to show
the decrease in potential energy favouring bonding.
Figure 1.1 Energy diagram for hydrogen molecule.
 1.1.1 Octet Rule
 You have studied in your earlier classes that noble gases have
very stable electron arrangements such as 2; 2, 8; 2, 8, 8 and
their outer shells are fully saturated.
 The first three are shown in Figure 1.2 and explains why noble
gases are so reluctant to form compounds with other elements.

Figure 1.2 First three noble gases.

 The noble gases have very stable electron configuration, as
reflected by their high ionization energies, low electron affinity
and general lack of reactivity.
 Because all noble gases (except He) have eight valence
electrons, many atoms undergoing reaction also attain eight
valence electrons.
 The ns 2np 6 electron configuration of the valence shell of all
noble gas (except Helium) atoms, is commonly called an octet
of electrons.
 The octet rule, a useful generalization that applies to all types
of bonding which states that when atoms bond, they lose, gain
ns 2np 6
or share electrons to attain the electronic configuration
of the nearest noble gas.
 Nearly every main-group monoatomic ion has a filled outer
level of electrons either
( two or eight), the same number as in
the nearest noble gas.
 Compounds such as CH4 and NH3 obey octet rule, whereas
others like BeCl2, BF3, SF6, PCl3 and PCl5 though stable, but do
not obey octet rule.
 Such compounds are exceptions to the octet rule.
 In such compounds the central atom is either short of
electrons or has excess of electrons as compared to the octet.
 These are discussed later in this unit. Though there are certain
exceptions to the octet rule, yet it provides us a useful
framework for introducing many important concepts of
bonding.
Note! Octet rule states that during the formation of a chemical
compound, each atom
 has an octet (8) electrons in its highest occupied energy level
by gaining, losing, or sharing electrons.
 1.1.2 Types of Chemical Bonding
 Ionic Bonding is formed by electron transfer from a
metal to a non-metal with different electro negativity
values.
 Covalent Bonding is formed as a result of electron
sharing between two non-metals. If the electro
negativity values are very similar then it is non-polar
covalent bonding but if the electro negativity values
are much different, then it is a polar covalent bonding.
 Metallic Bonding refers to the interaction between the
delocalised electrons and the metal nuclei.
 1.2 IONIC BONDING

 You are familiar with how sodium metal reacts with

chlorine gas, Cl2, to form sodium chloride, NaCl, a
substance composed of Na+ and Cl– ions.
2Na(s) + Cl2(g) → 2NaCl(s)

 Let us look at the electronic configurations of sodium

and chlorine atoms for a possible interpretation of the
reaction between them. A sodium atom, Na, by losing
an electron, forms a sodium ion, Na+, which has the
same electron configuration as the noble gas neon.
A chlorine atom, Cl, by gaining an electron, forms a chloride ion,
Cl–, which has the same electron configuration as the noble gas
argon.
 When particles have opposite electric charges, a force
of attraction exists between them; known as
electrostatic force of attraction.
 In sodium chloride, the sodium ions and the chloride
ions are held together by electrostatic force of
attraction, thus forming an ionic bond or electrovalent
bond.
Note! Ionic compounds are usually formed when
metal cations bond with non-metal anions.The only
common exception is ammonium ion which is not a
metal, but it forms ionic compounds.
 1.2.1 Lewis Electron-Dot Symbols
 The American Chemist Gilbert N. Lewis (1875–1946) created a
simple shorthand system for depicting the electrons involved
in bonding and the sequence of atoms in a molecule.
 In a Lewis electron-dot symbol of an atom, the element symbol
represents the nucleus and inner electrons, (core electrons),
and it is surrounded by a number of dots equal to the number
of valence electrons. You can write the Lewis symbol of any
main group element from its group number (IA to VIIIA),
which gives the number of valence electrons.
 These are placed one at a time on the four sides of the element
symbol and then paired up until all are used.
 For example, the Lewis electron-dot symbol for phosphorus
can be written as:
 The Lewis electron-dot symbols for elements of period 2 may
be written as:

Exercise 2.2
1. Use Lewis electron-dot symbols to depict the formation of
sodium and bromide ions from the atoms and determine the
formula of the compound.
2. Use Lewis electron-dot symbols to show the transfer of electrons
from magnesium atoms to nitrogen atoms to form ions with noble
gas electron configurations. What is the formula and name of the
product?
3. Use Lewis electron-dot symbol to show the transfer of electron
from aluminium to oxygen atoms to form ions with noble gas
electron configurations. What is the formula and name of the
product?
 1.2.2 Formation of Ionic Bonding
 The formation of ionic compounds is not merely the result of
low ionization energies and high affinities for electrons, although
these factors are very important.
 It is always an exothermic process; the compound is formed
because it is more stable (lower in energy) than its elements.
 Much of the stability of ionic compounds result from the
packing of the oppositely charged positive and negative ions
together. A measure of just how much stabilization results from
this packing is given by the lattice energy (U).
 This quantity is the energy change occurring when gaseous ions
come together to form one mole of a solid ionic compound, or
the enthalpy change required for one mole of the solid ionic
substance to be separated completely into ions far removed from
one another.
 The lattice energy is an important indication of the
strength of ionic interactions and is a major factor
influencing melting points, hardness, and solubility of
ionic compounds.
 The lattice energy plays a crucial role in ionic
compound formation, but it is difficult to measure it
directly.
 Nevertheless, the lattice energies of many compounds
have been determined using Hess's law of heat
summation, which states that an overall reaction's
enthalpy change is the sum of the enthalpy changes for
the individual reactions that make it up:
Lattice energies can be calculated through a Born-Haber cycle, in
which a series of steps from elements to ionic compounds for
which all the change in enthalpies are known except the lattice
energy.
This general approach to describing the energetics of ionic
compound formation is applied to sodium fluoride in the steps
outlined below and illustrated in Figure 2.3. Consider the Born-
Haber cycle for the formation of sodium fluoride.
We choose steps that we can measure to depict the energy
components of ionic compound formation, from which we
calculate the lattice energy.
Figure 2.3 The Born-Haber cycle for NaF(s).
 Consider the Born-Haber cycle for the formation of sodium
fluoride. We choose steps that we can measure to depict the
energy components of ionic compound formation, from
which we calculate the lattice energy.
 We begin with the elements in their standard states, metallic
sodium and gaseous diatomic fluorine.
 There are two routes to follow: either the direct combination
reaction (Route A) or the multi-step cycle (Route B), one step
of which is the unknown lattice energy.
 From Hess's law, it is known that both routes involve the same
overall enthalpy change.
 The formation of NaF(s) from its elements is shown as
happening either in one overall reaction (Route A) or in five
steps, each with its own enthalpy change (Route B).
 The overall enthalpy change for the process (ΔfH°) is
calculated as the sum of the enthalpy changes ΔH° step1 ,

through ΔH°step4. Therefore, ΔH°step5, the lattice energy (UNaF),

can be calculated. ΔfH° of NaF(s) (Route A) = sum of ΔH°
for steps in cycle (Route B).
The formation of NaF(s) from its elements is shown as

happening either in one overall reaction (Route A) or in five
steps, each with its own enthalpy change (Route B).
 To preview Route B, the elements are converted to individual
gaseous atoms (Step 1 and Step 2), the electron transfer steps
form gaseous ions (Step 3 and Step 4), and the ions form a solid
(Step 5). We identify each ΔH° by its step number:
Step 1: Converting solid sodium to separate gaseous sodium atoms
involves breaking the metallic bonds that hold atoms in the
sample, so it requires energy:

(This process is called atomization, and the enthalpy change is ΔatH°.)

Step 2: Converting fluorine molecule to fluorine atoms involves
breaking the covalent bond in F2, so it requires energy. One
mole of F atoms are needed to form one mole of NaF, so start
with ½ mol F2:

Step 3: Removing the 3s electron from Na to form Na+ requires

energy:

Step 4: Adding an electron to F to form F– releases energy:

Step 5: Forming the crystalline ionic solid from the gaseous ions
is the step whose enthalpy changes (the lattice energy) is
unknown:

We know the enthalpy change of the formation reaction (Route A),

Therefore, we calculate the lattice energy using Hess's Law: Solving

for UNaF gives
 Exercise 2.3
1. Write the formulas and names of the compounds formed
from the following ionic interactions: (use periodic table)
a. The 2+ ion and 1– ion are both isoelectronic with the
atoms of a chemically unreactive period 4 element.
b. The 2+ ion and the 2– ion are both isoelectronic with the
period 3 noble gas.
c. The ions formed are the largest and smallest ionizable
atoms in period 2.
2. In each of the following ionic compounds identify the
main group to which X belongs:
3. For lithium, the enthalpy of sublimation is +161 kJ mol–1, and
the first ionization energy is +520 kJ mol–1. The dissociation
energy of fluorine is +154 kJ mol–1, and the electron affinity of
fluorine is –328 kJ mol–1. The lattice energy of LiF is –1047 kJ
mol–1. Calculate the overall enthalpy change for the reaction?

4. Using the following data: Enthalpy of sublimation of Ca =

+178.2 kJ mol–1 Enthalpy of dissociation of Cl2 = +243.4 kJ mol–1
Enthalpy of formation of CaCl2 = –795.8 kJ mol–1 First and second
Ionization energies for Ca are +590 kJ mol–1 and +1145 kJ mol–1
respectively. The electron affinity of Cl = –348.7 kJ mol–1
Determine the lattice energy of CaCl2
 Factors Affecting Formation of Ionic Bonding
 The formation of ionic bonding is influenced by various
factors. Some of the major factors are presented below.
 Ionization energy (IE): Elements having low IE have a more
favourable chance to form a cation, thereby having a greater
tendency to form ionic bonds.
 Thus, low ionization energy of metallic elements favours the
formation of an ionic bond. That is why alkali and alkaline
earth metals form ionic compounds.
 Electron affinity (EA): The other atom participating in the
formation of an ionic compound must form an anion by
gaining electron(s) and losing energy. Higher electron affinity
favours the formation of an anion.
 Generally, the elements having higher electron affinity favour the
formation of an ionic bond. Halogens have high electron affinities,
and therefore halogens generally form ionic compounds when they
react with metals.
 Lattice energy: When a cation and an anion come closer, they get
attracted to each other due to the electrostatic (coulombic) force
of attraction.
 The electrostatic force of attraction between oppositely-charged
ions release a certain amount of energy and an ionic bond is
formed.
 If the coulombic attraction forces are stronger, then more energy
gets released and a more stable or a stronger ionic bond is formed.
 Larger lattice energy would favour the formation of an ionic bond.
Lattice energy thus is a measure of coulombic attractive force
between the combining ions.
 The lattice energy (U) of an ionic compound depends directly
on the product of the ionic charges (q1 × q2), and inversely on
the distance (r) between them.

where q1 and q2 are the charges on +ve and –ve ions

respectively, and r is the distance between the charges q1 and
q2 .
Thus, small ions having higher ionic charge shall have
larger lattice energy.
If the total energy released is more than that which is
absorbed, then the formation of ionic compound is favoured.
2.2.3 Exceptions to Octet Rule in Ionic Compounds

 As you have studied in grade 9, the octet rule works

well for the representative metals (Group IA, IIA) and
the nonmetals, but not for the transition elements and
post-transiton elements.

 This is because they have d and f subshell orbitals.

 There are certain exceptions to octet rule. We will

discuss it here in context with the ionic compounds
 Ions of some elements which are near to helium in the periodic
table do not obey the octet rule.
 The tendency of these atoms (H, Li, Be and B) is to attain an
arrangement of two electrons like the noble gas He (duplet
configuration), which is also a stable configuration.
 Hydride ion (H–), lithium ion (Li+), beryllium ion (Be2+ ) and
boron ion (B3+ ) are isoelectronic with He.
 Therefore, compounds like LiH, BeCl2 and BF3 are stable in spite
of short of electrons around the central atom than the octet.
 In these cases the number of electrons around Li, Be and B is 2, 4
and 6 respectively.
 Although atoms with less than an octet may be stable, they will
usually attempt to form a fourth bond to get eight electrons. BF3 is
stable, but it will form BF4 when possible.
 More than Octet (18-Electron Rule):
 The ions of some transition elements and post-transition
elements do not usually obey the octet rule.
 For transition metals, the 18-electron rule replaces the octet
rule, due to the involvement of d orbitals of these atoms.
 The atoms of these elements would have to lose a large
number of electrons to achieve the noble-gas configurations.
 This will require enormous amount of ionization energy,
which cannot be available easily.
 Nevertheless, these elements also form positive ions.
 But these ions do not have the usual noble gas valance shell
electron configurations of ns2np6 and are not isoelectronic
with any of the noble gases.
 It is important to note that when these atoms form
positive ions, electrons are always lost first from the
shells with the highest value of the principal quantum
number (n).
 Consider the electron configurations of the ions of the
transition elements iron and zinc and the post-
transition elements gallium and tin. Electron
Configurations of Iron:
 Electron configurations of zinc:

Electron configurations of gallium:

The post-transition element gallium (Ga) loses electrons first from
the 4p orbital and then from the 4s orbital to from a Ga3+ ion as

On closely examining the electron configurations of Zn2+ and

Ga3+, we will realize that ions have completely-filled outer
subshells and a noble gas core. Their valance electron
configuration can be generally represented as ns2np6nd10.
 Electron configurations of tin:
The heavier post-transition elements like Pb and Sn lose the p
electrons or both the p and s electrons from the valence shell.

Generally, these properties are exhibited by ions of elements from i)

Group IB and Group IIB (transition elements) and ii) Group IIIA
and Group IVA (heavier post-transition elements) Neither of these
configurations are noble gas configurations.
 2.3 COVALENT BONDING AND MOLECULAR GEOMETRY

 define covalent bonding;

explain the formation of covalent bonding;
give examples of covalent molecules;
draw Lewis structures or electron dot formulas of some
covalent molecules;
 illustrate the formation of coordinate covalent bonding using
examples;
define resonance structures;
draw resonance structures of some covalent molecules and
polyatomic ions;
discuss the exceptions to the octet rule in covalent bonding;
distinguish between polar and non polar covalent molecules;
describe the properties of covalent molecules;
carryout an activity to investigate the effects of heat, electricity
and some solvents on covalent compounds (naphthalene,
graphite, iodine and ethanol);
 describe the valence shell electron pair repulsion theory
(VSEPR);
 distinguish between the bonding pairs and non bonding
pairs of electrons
 describe how electron pair arrangements and shapes of
molecules can be predicted from the number of electron
pairs;
 explain why double bonds and lone pairs cause
deviations from ideal bond angles;
 explain the term dipole moment with the help of a
diagram;
 describe the relationship between dipole moment and
molecular geometry;
 describe how bond polarities and molecular shapes
combine to give molecular polarity;
 predict the geometrical shapes of some simple molecules;
 construct models to represent shapes of some simple molecules;
 define intermolecular forces;
 name the different types of intermolecular forces;
 explain dipole dipole interactions;
 give examples of dipole dipole interaction;
 define hydrogen bonding;
 explain the effect of hydrogen bond on the properties of
substances;
 give reason why H bonding is stronger than ordinary dipole
dipole interaction;
 explain dispersion (London) forces; give examples of dispersion
forces; and
 predict the strength of intermolecular forces for a given pair of
molecules;
 Formation of Covalent Bonding
 Consider the formation of hydrogen molecule (H2). When two
hydrogen atoms are far apart, each behaves as though the other
were not present.
 As they approach each other and the distance between the two
nuclei decreases, each nucleus starts to attract the other atom's
electron, which lowers the potential energy of the system.
Attractions continue to draw the atoms closer, and the system
becomes progressively lower in energy.
 As attractions increase, repulsions between the nuclei and the
electrons will also increase.
 At some internuclear distance, maximum attraction is achieved
in the face of the increasing repulsion, as the system has its
minimum energy. Any shorter distance would increase
repulsions and cause a rise in potential energy (see Figure 2.1).
 Thus, a covalent bond, such as the one that holds the hydrogen
atoms together, arises from the balance between nucleus-electron
attractions and electron electron and nucleus-nucleus repulsions.
 Therefore, a covalent bond is formed when a pair of electrons is
shared between two atoms.
 Some examples of covalent molecules are HCl, H2S, C2H4, N2,
CCl4, BCl3, H2O, NH3, SO2, PCl5, O3, etc. Generally,
substances that contain covalent bonds are called molecules.
Note: Ionization energy of hydrogen (IE1 = 1312 kJ mol –1) is very
high making it difficult to lose electron.
 Representation of Covalent Bond (Drawing
Lewis Structures)

 The representation of covalent bonding through Lewis symbols

and share electron pairs is called a Lewis structure. Lewis
structure for hydrogen molecule formed from hydrogen atoms
is

If we ‘‘double count’’ the shared electrons each H atom appear

to have two electrons in its valence shell analogous to the electron
configuration of helium.
Similarly, consider fluorine, which also exists in the diatomic
form, F2. Fluorine atoms are also joined by a covalent bond.
 Each fluorine atom in the fluorine molecule has eight valence
electrons, an arrangement is similar to that of the noble gas
neon.
 The fluorine atoms obey the octet rule.
 The shared pairs of electrons in a molecule are called bonding
pairs.
 The other electron pairs that stay with on atom and are not
shared are called non-bonding pairs or lone pairs.
 We can write the Lewis formula for a convalent compound of
known geometry by using the following rules.
 1. Determine the total number of valence electrons. It is this
number of electrons that must appear in the final Lewis
structure.
 The total number of electrons for a molecule is the sum of
the valence electrons for each atom. For a polyatomic anion,
which has one or more extra electrons, add one electron for
each unit of negative charge.
 For a polyatomic cation, which is missing one or more
electrons, subtract one electron for each unit of positive
charge.
Exercise 2.4
Determine the total number of valence electrons for the following
species:
a. CO2 c. NH+4
b. SO2–4 d. N2O4
2. Write the skeletal structure. The most electropositive atom
usually occupies the central position. Connect bonded
atoms with an electron-pair bond (a dash). Hydrogen is an
exception; it is always a terminal atom, even when bonded
to a more electronegative atom.
3. Place electron pairs around terminal atoms so that each
(except hydrogen) has an octet.
4. Assign any remaining electrons as lone-pairs around the
central atom.
5. If at this stage, a central atom has fewer than eight
electrons, a multiple bond(s) is likely. Move one or more
lone-pair of electrons from a terminal atom(s) to a region
between it and the central atom to form a double or a
triple bond.
 Exercise 2.5

1. Write a plausible Lewis structure of:

a. nitrogen trichloride, NCl3 b. chlorate ion, ClO3-

c. phosphonium ion, PH4+ d phosgene, COCl2

2. Draw a Lewis structure for CO32–, SF4 and HCOOH
(formic acid).
3. Which of the following atoms cannot serve as a central atom
in a Lewis structure O, He, F, H, P? Explain.
4. Write a plausible Lewis structure for carbonyl sulphide, COS.
 Coordinate-Covalent Bonding
 Covalent bonds are formed through the contribution of one
electron each by atoms involved in an electron-pair bond
 There is another possibility in which one atom can “donate”
two of its electrons to provide the shared pair between itself
and an “acceptor” atom. When one atom provides both the
electrons for a shared pair, the bond is called a coordinate-
covalent bond.
 Some examples of molecules which contain coordinate-
covalent bond include O3, NH3BF3 and POCl3.
 Resonance Structures
 For some molecules, there is no best choice between a number
of equally acceptable Lewis structures.
 Consider the simple example of ozone, O3, in which the
arrangement of nuclei is O–O–O. This molecule has 6 × 3 = 18
valence electrons, and it is possible to draw two possible
structures for O3:

Both the structures satisfy octet rule. The two structures for O3
suggest that the bond between O1 and O2 differs from that
between O2 and O3 one single bond and one double bond.
Therefore, in each of the two structures one bond should be a
single bond while the other a double bond.
 Since both the bonds are identical which one is a double bond?

The Lewis structure is equivalent except for the placement of the

electrons (i.e., the location of the double bond). In such a situation,
the correct way to describe ozone molecule as Lewis structures
would be:
 This indicates that the ozone molecule is described by an
average of two Lewis structures (i.e. the resonance forms).
 The bond-lengths between the oxygens are intermediate
between characteristic single and double bond-lengths between
a pair of oxygen.
 This description of O3 is called resonance, a circumstance in
which two or more possible Lewis structures can be written
and the true structure is a composite or hybrid of them.
 The different structures used to represent the molecule or ion
are called contributing structures or resonance structures, and
we write them linked by double-headed arrows.
 The actual species that exists is called a resonance hybrid.
 The resonance structures differ only in the distribution of
electrons.
 In molecules such as CH4, H2S, NF3, PF5, SF6 etc in which
resonance is not involved, bonding electron pairs can be
described as existing in fairly well-defined regions between the
two atoms.
 These electrons are localized. In O3, to produce O-to-O bonds
that are intermediate between single and double bonds, we
need to think of some of the electrons in the resonance hybrid
as being delocalized.

 Delocalized electrons are bonding electrons that are spread

over several atoms.
 Exercise 2.6

1. Write three equivalent structures for the SO3 molecule that

obey the octet rule.

2. Draw Lewis structures of all the important resonance forms of

each of the following:

a. NO2F(N central) b. HNO3 c. NO2–

 Exceptions to the Octet rule in Covalent Bonding
 It has been noticed that there are three groups of molecules
that are exceptions to the octet rule.
Less than octet (central atom is deficient of electrons):
Molecules whose central atoms have fewer than eight
electrons (Below octet).
This group consists of molecules containing central atoms
from Group IIA and IIIA. BeCl2, BF3 and AlCl3, whose Lewis
formula are shown below, are typical examples:
 More than octet (central atom has excess of electrons):
 Molecules whose central atoms have more than eight
electrons (Expanded octet).
 This group consists of molecules containing central
atoms from periods 3, 4, 5, and 6. PF5, SF6 and XeF4
are typical examples of this type;
 Molecules containing an odd number of electrons:
 Even if stable molecules of this kind are rare, they do exist.
Some examples are ClO2, NO and NO2 having 19, 11 and 17
valence electrons respectively.
 The best way to suggest the Lewis-like structure for these
molecules is:
 Exercise 2.7
1. Suggest the Lewis-like structure for NO and NO2

molecules.

2. The following species do not obey the octet rule. Draw a

Lewis structure for each one and state the type of octet rule

exception:

a. BH 3 b. AsF 4
- c. SeCl
4 d. PF 6
-

e. ClO 3 f. BrF 3 g. BeF 2 h. XeF 2

 Polar and Non-Polar Covalent Molecules
 When bonding electron-pairs in a covalent bond are shared
equally, the result is a nonpolar covalent bond.
 When the atoms are alike in a covalent bond, the two atoms with
equal electronegativities will exhibit equal sharing of an electron
pair, and the electrons are not drawn closer to one atom than to
the other.
 The H–H and Cl–Cl bonds are nonpolar. In a covalent bond
between atoms of different electronegativities, there is an unequal
sharing of an electron pair and the electrons spend more of their
time around the more electronegative atom. Such a bond is said
to be polar covalent bond. The H–Cl bond is a polar bond.
 This is because chlorine is more electronegative than the hydrogen
atom and represented as to indicate the polar nature of a bond

Hδ + – Clδ–
 In the representation the δ+ and δ– (read “delta plus” and
“delta minus”) signify that one end (H) is partially positive and
the other end (Cl) is partially negative.
 The term partial charge signifies something less than the full
charges of the ions that would result from complete electron
transfer.
 For a diatomic molecule having a polar covalent bond, such as
HCl, we can describe a quantity called the dipole moment,
which is a vector sum of the bond moments in a molecule.
Bond moment is a measure of polarity of a diatomic covalent
bond.
 The dipole moment (μ) is defined as the product of the
magnitude of the charge (δ) at either end of the dipole
multiplied by the distanced)( that separates the charge.
μ=δ×d
 The SI-unit of dipole moment is coulomb-metre (C.m).
 Dipole moments are often expressed in the non-SI unit debye
(D), where 1D = 3.33564 × 10–30 Cm.
Note! For a diatomic molecule, the bond moment is the dipole
moment.
 The dipole moment of a polyatomic molecule (three or more
atoms) depends on the geometry of the molecule.
 If the bond moments are equal in magnitude but opposite in
direction, then they will cancel each other and the resultant dipole
moment will be zero, provided that the vector sum of the bond
moments is zero.
 Exercise 2.8
 Both CO2 and BCl3 have zero dipole moments, but the C = O
and B – Cl bond moments are not zero. Explain.
Properties of Covalent Compounds
Unlike any ionic compound, many of the covalent compounds
are found in gaseous state at room temperature.
Consider methane (CH4), the simplest compound between
carbon and hydrogen, which have comparable, intermediate
electronegativities.
It is a gas at room temperature. Cooling methane to a low
temperature condenses it first to a liquid and then to a solid.
Unlike melted ionic compounds, liquid covalent compounds do
not conduct electricity.
Therefore, liquid methane does not conduct electricity.
Covalent compounds are molecular substances.
They have low melting and boiling points. Most covalent
compounds are soluble in non-polar solvents. Generally,
 Covalent compounds exist as separate molecules
because electrically neutral atoms form them and the
forces of attraction between these molecules are
relatively weak.
 • Due to weak intermolecular forces, many covalent
molecules or covalent compounds are liquids or gases
at room temperature. However, some covalent
molecules like iodine are solids at room temperature.
 Covalent compounds are volatile.

 Generally they have low melting points and boiling

points.

 Covalent compounds are generally insoluble in water.

 Most covalent compounds are soluble in nonpolar

solvents.

 Nonpolar covalent compounds are non-electrolytes

because they do not conduct electricity.
 2.3.1 Molecular Geometry
Valence Shell Electron Pair Repulsion (VSEPR) Theory
A molecule is an independent, minute architecture extending
in three dimensions throughout its tiny volume of space. Let us
discuss the shapes of molecules and their effect on the
properties of a molecule.
We start by describing the Valence Shell Electron Pair
Repulsion (VSEPR) model, which allows us to convert two-
dimensional
Lewis structure into three-dimensional (3D) geometry.
The basic principle of VSEPR theory is that the pair of valence
shell electrons around the central atom stays as far apart from
each other as possible to minimize repulsion among them.
For simplicity, a set of electrons is defined as any number of
electron pairs that occupies a localized region around a central
atom.
• This set may consists of a single bond (–), a double
bond (=), a triple bond (≡), lone-pair(s) or in some
cases even a lone (single) electron. Each of these is a
separate set of electrons that repels the other groups
and occupies as much space as possible around the
central atom - one set of electrons repels the other sets
to maximize the angles between them.

• The three-dimensional arrangement of these sets gives

rise to the shape of the molecule.
 Electron Pair Arrangement and Molecular Shape
 The electron pair arrangement is defined by the sets of
electrons, both bonding and nonbonding (lone-pair), around
the central atom.
 On the other hand the molecular shape is defined by the
relative positions of the atomic nuclei.
 Molecular shapes that occur when all the surrounding electron
sets are bonding sets differ from molecular shapes when some
of the electron sets are non-bonding sets.
 Thus, the same electron set arrangement can give rise to
different molecular shapes.
 To classify molecular shapes, the AXm En designation is assigned,
where A is the central atom, X is the atom,E is lone-pair
(nonbonding) electron sets, m and n are positive integers.
 The arrangements that best minimize repulsions naturally
depend on the number of electron sets.
 Repulsive forces among valence pairs diminish in the following
order: Lone pair vs lone pair > lone pair vs bonding pair >
bonding pair vs bonding pair.
 In this section, you will see electrons set ranging from two to
six around the central atom.
 Two electron sets locate themselves on opposite sides of the
atom in a linear arrangement, three sets form a trigonal planar
structure, four sets arrange themselves at the corners of a
tetrahedron, five sets define a trigonal bipyramid, and six sets
form an octahedron.
 In the case of multiple (double or triple) bonds the
counting is not different, because you are already
informed that a double bond is considered as one set
and a triple bond as another set of electrons.

 For example, in the case of CO2, O=C=O, there are

two sets of electrons around the central atom,
acetylene, C2H2, H–C≡C–H, two sets of electrons
around each of the central atoms.
 Guidelines for Applying VSEPR Model
 The VSEPR model is an approach of using the number of
electrons surrounding a central atom to study the molecular
structures, based on the theory that the structure around a
given atom is determined principally by minimizing electron-
pair repulsion.
 Here are some guidelines for applying the VSEPR model:
1. First, write the Lewis structure of the molecule, in this
model, consider only the electron sets (pairs) of the
central atom.
2. Count the total number of electron sets around the
central atom, including both the bonding pairs and lone pairs.
Usually a lone pair, a single unpaired electron and any bond:
single, double or triple, each count as one area of electron
density. For species with more than one central atom, treat
each central atom separately.
3. Use the VSEPR geometry to predict the shape of
the molecule.
4. In predicting bond angles, bear in mind that the
repulsion of the lone pairs is stronger than between
those of the bonding pairs. VSEPR theory is best
used as a tool to explain why a given structure is
distorted rather than as a predictive tool.
In explaining why the distortion occurs you need to
balance three competing influences:
 lone pairs take up more space than bonding pairs.
Repulsions between electrons in a lone-pair and the
other electrons (in either bonds or other lone pairs)
may cause distortions in the structure.
 triple bonds are fatter than double bonds, which are
fatter than single bonds. The amount of electron-
electron repulsion experienced between a bond and lone
pairs or other bonding pairs decreases in the order:
triple > double > single. Therefore, we expect that a
triple bond may cause more distortions in the structure
than either a double or single bond and that a double
bond will cause more distortion when compared to a
single bond.
 bonds which involve a significant difference in electro-
negativity between the atoms in the bond will have the
electrons in the bond distorted toward the more
electronegative atom. This will decrease electron density
near the central atom and lessen the repulsion between
this bonding-pair and other electron pairs in the
molecule.
 Molecular Shape and Molecular Polarity

 Many aspects of molecule’s chemical behaviour can be

understood if one knows the geometryshape)
( of a
substance.
Molecular shape affects many properties of the molecule
like molecular polarity, which in turn influence melting
and boiling points, solubility, and even reactivity.
 Molecular polarity is created by molecules with a net
imbalance of charge.
 In molecules with more than two atoms, both shape and
bond polarity determines the molecular polarity.
 Bond Polarity and Dipole Moment
 Polar bonds do not necessarily lead to polar molecules.
 For example, the large electro-negativity difference between C
and oxygen makes each C-O bond quite polar.
 However, because carbon dioxide (CO2) is a AX2 type molecule
with two sets of electrons around the central atom, and its
shape is linear, and its bonds are directed 180° from each other,
so there is no net dipole moment (μ); μ = 0 D
 Another molecule with identical atoms bonded to the central
atom is water. Unlike carbon dioxide, water has a significant
dipole moment (μ = 1.87 D). Both water and carbon dioxide
are triatomic molecules and you may expect them to exhibit
similar shape and polarity.
 Due to the effect of the lone pairs of electrons on its shape,
water is a polar molecule.
 In each O–H bond, electron density is pulled toward the more
electronegative O atom, but the bond polarities do not
counterbalance each other, because the water molecule is V-shaped.
 Instead, the bond polarities partially reinforce each other, and the
oxygen end of the molecule is considerably more negative than the
other end.
 Carbon dioxide and water demonstrate how molecular shape
influences polarity.
 When two or more different molecules have the same shape, the
nature of the atoms surrounding the central atom can have a major
effect on the polarity of a molecule.
 Consider tetrachloromethane (CCl4) and trichloromethane (CHCl3),
two AX4 type molecules - tetrahedral shape with different polarities.
 In CCl4, the surrounding atoms are all Cl atoms. Although each C–Cl
bond is polar, the molecule is nonpolar because the individual bond
polarities counterbalance each other.
 In CHCl3, an H atom substitutes for one of the Cl atoms, disturbing
the balance and giving chloroform a significant dipole moment.
 If you consider the two constitutional isomers of
dichloroethane (C2H2Cl2), they have the same molecular
formula. However, they have different physical and chemical
properties.
 VSEPR theory predicts that all the nuclei lie in the same plane
with a trigonal planar molecular shape around each carbon
atom.
 The trans isomer has no dipole moment (μ = 0 D) because the
C – Cl bond polarities balance each other.
 In contrast, the cis-isomer is polar (μ = 1.90 D) because the
bond dipoles partially reinforce each other, with the molecular
dipole pointing between the Cl atoms.

Bond Angle
Bond angle is the angle formed by two surrounding atoms with
the central atom at the vertex.
Ideal bond angles are observed when all the bonds around a
central atom are identical and connected to the same type of
atom.
When this is not the case, such as when lone pairs, multiple
bonds, or different surrounding atoms are present, the bond
angles deviate from the ideal angles.
 Predicting the Shapes of Molecules

Figure: The basic electron-pair geometries predicted by VSEPR theory maximize the space
around any region of electron density (bonds or lone pairs).
 There are two types of electrostatic forces at work in any
sample of matter.
 These are: intramolecular and intermolecular forces.
Intramolecular force which is a chemical bond (ionic,
covalent or metallic) is a force that exists within a particle
(molecule or polyatomic ion) and affects the chemical
property of the species. Whereas, intermolecular forces exist
between particles and influence physical properties of the
species Intermolecular forces are due to the attraction
between ions and molecules.
 Intermolecular forces are relatively weak as compared to
intramolecular forces, because they typically involve lower
charges that are farther apart.
 The charges that give rise to intermolecular forces are farther
apart because they exist between nonbonded atoms in
adjacent molecules.
 Though there are several important types of intermolecular
forces, only dipole-dipole, hydrogen bonding, and, London
(Dispersion) forces, will be discussed.
Dipole-Dipole forces
When polar molecules are brought near one another, their partial charges
act as tiny electric fields that orient them and give rise to dipole-dipole
forces; the partially positive end of one molecule attracts the partially
negative end of another.
For compounds of approximately the same mass and size, greater is the
dipole moment, greater is the dipole-dipole forces between their molecules,
so greater is the energy required to separate their particles.
These can be manifested in several of its physical properties.
For instance, both methyl chloride (CH3Cl) and ethanal (CH3CHO) have
comparable mass and size, but CH3Cl has a smaller dipole moment
than CH3CHO; therefore less energy is needed to overcome the dipole-
dipole forces between its molecules and it boils at a lower temperature.
Dipole-dipole forces give polar cis-1,2-dichloroethene a higher boiling point
than nonpolar trans-1, 2- dichloroethene.
 Hydrogen Bonding
 Hydrogen bonding is a special type of dipole-dipole forces that
arise between molecules that have a hydrogen atom bound to a
smaller sized, most electronegative atoms.
 These atoms are: Fluorine, Oxygen and Nitrogen. The bond
formed between hydrogen and such an atom is highly polar.
 The partially positive (δ+) H of one molecule is attracted to
the partially negative (δ–) lone pair on the F, O or N of the
same or another molecule. As a result a hydrogen bond result.
 The atom sequence that leads to an H bond (dotted line) is
indicated below.
 The following three examples illustrate the sequence.
 Hydrogen bonds hold water molecules in a rigid but open
structure. When ice melts, some of the hydrogen bonds break.
 Water molecules move into the holes that are in the ice
structures.
 The molecules are therefore closer together in liquid water
than in ice. This means that liquid water at 0°C is denser than
ice. Water is most unusual in this regard.
 When water on the surface of lakes and other areas freezes, the
ice floats on the liquid water.
 If the solid were denser than the liquid as is true for nearly
every other substance, the surface of the lake would freeze and
sink until the entire lake was solid; aquatic plants and animals
would be endangered.
 Dispersion or London Forces
 Intermolecular forces in which non-polar atoms or molecules
interact by inducing dipoles in each other are known as
dispersion or London Forces.
 These classes of intermolecular forces cause substances like
CO2, Cl2, noble gases, etc, to condense and solidify.
 An attractive force must be acting between these non-polar
molecules and atoms, or they would remain gaseous under any
conditions.
 In fact, bond dipoles exert some weak attraction but the
intermolecular forces are mainly responsible for the condensed
state of non-polar substance. These forces are known as
London forces or dispersion forces, named after Fritz London,
the physicist who explained the quantum mechanical basis of
the attractive forces.
 Dispersion forces are very weak and are caused by a sudden shift of
electron density to one side of the nucleus than the other. So the
molecule has an instantaneous dipole.
 These instantaneous dipole will induce the neighbouring non-polar
molecule. As a result, an induced-dipole is created. This process occurs
throughout the sample and keeps the particles together.
 These dipoles are collectively known as dispersion forces or London
forces. They are present between all particles (atoms, ions, and
molecules.)
 For substance with the same molar masses, the strength of the
dispersion forces is often influenced by molecular geometry shape).
(
Shapes that allow more points of contact have more area over which
electron clouds can be distorted, so stronger attractions result.
 This is probably the reason why n-pentane (CH3CH2CH2CH2CH3)
exhibits higher boiling point than its isomer 2,2-dimethyl propane.
 Exercise 2.11
1. In which of the following substances do
hydrogen bonds occur? Explain with the help
of diagrams.

2. Identify the dominant intermolecular force that is present in

each of the following substance and select the substance with the
higher boiling point in each pair:
a. CH3OH or CH3CH2OH c. MgCl2 or PCl3
b. Hexane or cyclohexane d. CH3NH2 or CH3F
3. Which type of intermolecular force is dominant in

the following substances?

a. ICl b. H2O

c. F2 d. HBr

4. Compare intermolecular forces with that of

intramolecular bonding.
 2.4 METALLIC BONDING

In simple terms, metallic bonding is referred to as bonding in metal

atoms. It is also defined as interaction between metal nuclei and the
delocalized electrons.
Delocalized electrons are also called as conduction electrons. Metals
nuclei are the positive ions and so metallic bonding can be imagined
as sea of electrons in which positive metal ions are embedded.
Positive metal ions are called Kernels. Thus metallic bonding can be
summarized as: The force of attraction which binds together the
positive metal ions or Kernels with the electrons within its sphere of
influence.
Is a metal made up of atoms or ions?
The strength of the metallic bond depends on the:
1. number of electrons in the delocalised 'sea' of electrons. (More
delocalised electrons results in a stronger bond and a higher melting
point.)
2. packing arrangement of the metal atoms.(The more closely packed
the atoms are the stronger the bond is and the higher the melting
point.)
 2.4.2 Electron-Sea Model
 The electron-sea model of metallic bonding proposes that all
the metal atoms in the sample contribute their valence
electrons to fromsea"
" of electrons, which is not localized for a
particular atom.
 The metal ions (t he nuclei with their core electrons) are
submerged within this electron sea in an orderly array. See
Figure 2.10.

Figure 2.10 Schematic illustrations of electron-sea model for the electronic structure of
metals.
 In contrast to ionic bonding, the metal ions are not held in
place as rigidly as in ionic solid. In contrast to covalent
bonding, no particular pair of metal atoms is bonded through
any localized pair of electrons. Rather, the valence electrons
are shared among all the atoms in the substance, which is held
together by the mutual attraction of the metal cations for the
mobile, highly delocalized electrons.
 An electron-pair in a covalent resonance hybrid is delocalized
over only a few atoms, but the extent of delocalization in
metal is much greater. The bonding-electrons are free to move
throughout the three dimensional structure.
2.4.3 Properties of Metals Related to the Concept of Bonding
 The general properties of metals include malleability and
ductility and most are strong and durable.
 They are good conductors of heat and electricity. Their
strength indicates that the atoms are difficult to separate, but
malleability and ductility suggest that the atoms are relatively
easy to move in various directions.
 These properties suggest the nature of the metallic bonding
between atoms.
 Metallic bonds show typical metallic properties such as high
electrical conductivity, lustre, and high heat conductivity.
 Metals are good conductors of electricity and heat because
of their mobile electrons. They are strong and opaque in
nature.
 Most metals are malleable, which means that they can be
hammered into thin sheets, and ductile, which means that
they can be drawn into wires.
 These properties indicate that the atoms of the metallic
lattice are capable of slipping with respect to one another.
When a piece of metal is struck by a hammer, the metal
ions move to a new lattice positions, sliding past each
other through intervening electrons.
 Most metals are solids with high melting and much higher
boiling points; because the atoms of metals have strong
attractive forces between them and much energy is
required to overcome this force. For instance, the increase
in melting point between
 the alkali metals [Group IA] and the alkaline earth metals
[Group IIA] can be explained by the IIA metals having
two valence electrons, available for metallic bonding,
whereas the IA metals have only one
 The greater attraction between the M2+ ions and twice
the number of mobile electrons mean that higher
temperatures are needed to melt such solid.
 The metals have a wide range of melting points, (from
39°C (mercury) to 3410°C (tungsten).
 The properties of metals suggest that their atoms
possess strong bonds, yet the ease of conduction of
heat and electricity suggest that electrons can move
freely in all directions in a metal.
 The general observations give rise to a picture of "
positive ions in a sea of electrons" to describe metallic
bonding.
 2.5 CHEMICAL BONDING THEORIES
At the end of this section, you should be able to:
 name two chemical bond theories;
 explain the valence bond theory;
 distinguish the Lewis model and the valence bond model;
 discuss the overlapping of orbitals in covalent bond formation;
 explain hybridization;
 show the process of hybridization involved in some covalent molecules;
 draw hybridization diagram for the formation of sp, sp2, sp3, sp3d and
sp3d2 hybrids;
 suggest the kind of hybrid orbitals on the basis of the electron
structure of the central atom;
 predict the geometrical shapes of some simple molecules on the basis
of hybridization and the nature of electron pairs.
 discuss the hybridization involved in compounds
containing multiple bonds;
 explain bond length and bond strength;
 explain molecular orbital theory;
 describe molecular orbital-using atomic orbitals;
 describe bonding and anti bonding molecular orbitals;
 draw molecular orbital energy level diagrams for
homonuclear diatomic molecules;
 write the electron configuration of simple molecules using
the molecular orbital model;
 define bond order and determine the bond order of some
simple molecules and molecule-ions;
 determine the stability of a molecule or an ion using its
bond order; and predict magnetic properties of molecules.
 2.5.1 Valence Bond Theory (VBT)
 Lewis theory provides a simple, qualitative way to describe
covalent bonding, and VSEPR theory allows us to carry the
description further.
 Probable molecular shapes were predicted by VSEPR theory.
Now consider a quantum mechanical approach to covalent
bonding that confirms much of what is described through
VSEPR theory, but which allows extending that description still
further.
 The valence-bond approach is the most useful approach to
answer questions like: what is a covalent bond? And how can
we explain molecular shapes from the interaction of atomic
orbitals?
 The basic principle of valence bond theory is that a covalent
bond forms when orbitals of two atoms overlap and the
overlap region, which is between the nuclei, is occupied by a
pair of electrons.
 For instance, form an image in your mind of two hydrogen
atoms approaching one another.
 The moment they get closer, their electron-charge clouds begin
to combine into a whole.
 This intermingling is described as the overlap of the 1s orbitals
of the two atoms.
 The overlap results in an increased electron charge-density in
the region between the atomic nuclei. The increased density of
negative charge serves to hold the positively-charged atomic
nuclei together.
 In the valence bond (VB) method, a covalent bond is a region
of high electron charge-density that results from the overlap of
atomic orbitals between two atoms.
 The strength of the bond between any two atoms generally
depends on the extent of the overlap between the two orbitals.
 As the two atoms are brought more closely together, however,
the repulsion of the atomic nuclei becomes more important
than the electron-nucleus attraction and the bond become
unstable.
 For each bond, then, there is a condition of optimal orbital
overlap that leads to a maximum bond strength (bond energy) at
a particular internuclear distancebond
( length).
 The valence bond method attempt to find the best
approximation to this condition for all the bonds in a molecule.
 The bonding of two hydrogen atoms into a hydrogen molecule
through the overlap of their 1s orbitals is pictured in Figure 2.11.

Figure 2.11 Atomic orbital overlap and bonding in H2 .

 Note! The s orbital is spherical, but p and d orbitals have
particular orientations -
 more electron density in one direction than in another - so a
bond involvingp or d orbitals will tend to be oriented in the
direction that maximizes overlap.

Figure 2.12 Oribital and spin pairing in three diatomic molecules.

  In the HCl bond, for example, the 1s orbital of hydrogen
overlaps the half-filled 3p orbital of Cl along the axis of that
orbital. In Figure 2.11B any other direction would result in less
overlap and, thus, a weaker bond. Similarly, in the Cl–Cl bond
of Cl2, the two p orbitals
3 interact end-to-end, that is along the
orbital axes, to attain maximum overlap (Figure 2.11C).
 VSEPR theory predicts a tetrahedral bond angle (109.5°) in H2S.
However, if we take in to account the strong repulsions
between the lone pairs of electrons on the S atom and the
bond pairs, bonds are expected to be forced into a smaller
angle.
 The measured bond angle in the H2S molecule is 92.1°,
suggesting that the valence bond method describes the covalent
bonding in H2S better than the VSEPR theory does (see Figure
2.12).
 There are not many cases, however, where the VB method
produces superior results.
 A combination of VSEPR theory and the VB method are used
in describing the shape of the molecules.

Figure 2.13 Atomic oribital overlap and bonding in H2S.

 Overlap of Atomic Orbitals (Sigma and Pi Bonds)
 To see the detailed makeup of covalent bonds, it is essential to
focus on the mode by which orbitals overlap because orbital
overlap is necessary for sharing of electrons and bond
formation.
 Various type of atomic orbital overlap leads to covalent bond
formation.
 Three simple basic ones are s-s , s-p and p-p shown in Figure
2.13.
1. s-s overlap in which half filled s orbitals overlap,
2. s-p overlap where half filled s orbital of one atom overlaps with
one of the p orbital having one electron only and
3. p-p overlap in which two half filled p orbitals overlap.
 Figure 2.14 Atomic orbital overlap.
(A) s-s overlap, (B) s-p overlap, (C) p-p overlap along the orbital
axis and
(D) p-p sideways overlap.
  Because of the directional nature of p orbital, the overlap may
take place in two ways: (i) the half filled p orbitals along the
line joining the two nuclei. This is called as head on, end-to-
p orbitals
end, end on or linear overlap and (ii) the half filled
overlap along the line perpendicular to the nuclear axis.
 This overlapping of p orbitals is parallel to each other, hence is
called lateral or sideways overlapping.
 These two modes give rise to the two types of covalent bonds,
namely, sigma (σ) and pi (π) bond respectively. Valence bond
theory is used to describe the two types here, but they are
s - s and s
essential features of molecular orbital theory as well.
- p will always overlap along the nuclear axis, hence results
only in sigma bonds.
 Sigma bond has its highest electron density along the bond
axis (an imaginary line joining the nuclei) in between the
bonded nuclei. All single bonds have their electron density
concentrated along the bond axis, and thus are sigma bonds.
 A side - to - side or parallel overlap forms another
type of covalent bond called a pi (π) bond. It has
two regions of electron density.
 One above and one below the sigma bond axis.
One π-bond holds two electrons that occupy both
regions of the bond.
 A double-bond always consists of one σ and one π
bond. The double-bond increases electron density
between the nuclei.
 A triple bond consists of one σ and two π bonds.
Now it can be seen clearly why a double and triple
bonds were considered as one electron set in the
discussion of VSEPR.
 The reason is that each electron pair occupies a
distinct orbital, a specific region of electron density,
so repulsions are reduced.
 The extent of overlap influences bond strength,
however, many factors, such as lon-pair repulsions,
bond polarities, and other electrostatic contributions
affect overlap and the relative strength of σ and π
bonds between other pairs of atoms.

 Thus as a rough approximation, a double bond is

about twice as strong as a single bond, and a triple
bond is about three times as strong.
 Hybridization of Orbitals
 Valence bond theory employs the concept of
hybridization.
 It is the overlap or blending of s, p and d orbitals to
explain bond formation.
 In applying the valence bond method to the ground
state electron configuration of carbon you can assume
that the filleds 1orbital will not be involved in the
bonding and focus your attention on the valence-shell
orbitals.
 Ground State C:

From its ground state configuration, two unpaired electrons in the 2p

subshell are observed.
One can predict the simplest hydrocarbon molecule to be CH2, by
overlapping the two unpaired electrons from two H atoms with the two
unpaired electrons of carbon.
However, you might question the existence of this molecule because it
does not follow the octet rule. In fact, experiment shows that CH2 is not a
stable molecule.
The simplest stable hydrocarbon is methane, CH4.
To account for this, you need an orbital diagram that shows four unpaired
electrons in the valence shell of carbon, requiring four bonds (and therefore
four atoms of hydrogen).
To get such a diagram imagine that one of the 2s electrons is promoted to
the empty 2p orbital.
To excite the 2s electron to a higher energy sublevel, energy must be
absorbed.
  The resulting electron configuration is that of an
excited state having energy greater than the
configuration in the ground state.

Valence bond theory proposes that the one 2s and all three 2p
orbitals of the carbon atom 'mix' to produce four new orbitals that
are equivalent to each other in energy and in shape and pointing in
different directions with equal H–C–H bond angles.
This blending is called hybridization and the resultant orbital as
hybrid orbitals.
 It is a hypothetical process (not an observed one) that can be
carried out as a quantum mechanical calculation.
 The symbols used for hybrid orbitals identify the kinds and
numbers of atomic orbitals used to form the hybrids.
 In hybridization scheme, the number of new hybrid orbitals is
equal to the total number of atomic orbitals that are combined.
 Hybridization provides a useful and convenient method of
predicting the shapes of molecules.
 It must be noted that though it is valuable in predicting and
describing the shape, it does not explain the reason for the shape.
 Exercise 2.12
1. How do carbon and silicon differ with regard to the
types of orbitals available for hybridization? Explain
2. Are these statements true or false? Correct any that is
false.
a. Two σ bonds comprise a double bond.
b. A triple-bond consists of one π bond and two σ bonds.
c. Bonds formed from atomic s orbitals are always σ bonds.
d. A π-bond consists of two pairs of electrons
e. End-to-end overlap results in a bond with electron
density above and below the bond axis.
 sp hybrid orbitals
 When two electron sets surround the central atom, you
observe a linear molecular shape. VB theory explains this by
proposing that mixing two non-equivalent orbitals of a central
atom one s and one p, gives rise to two equivalent sp hybrid
orbitals that lie 180° apart.
 Combination (mixing) of one s and one p orbital is called sp
hybridization and the resultant orbitals are calledsp hybrid
orbitals.
 For instance, the beryllium atom has two electrons and four
orbitals in its valence shell.
 In the triatomic molecule BeCl2, which is present in gaseous
BeCl2 at high temperatures, the s2and one of the 2p orbitals
of the Be atom are hybridized into sp hybrid orbitals.
 The remaining two 2p orbitals are left unhybridized and
unoccupied in the orbital diagram.
  Since there are no unpaired electrons this atom cannot form
any covalent bonds.
 It follows that in BeCl2, the Be atom is not in the ground state
but it is in the excited state, with sufficient extra energy to
unpair as 2electron.

As shown in Figure 2.15 the two sp hybrid orbitals are directed along a
straight line, +366666 180° apart. It is predicted that the BeCl2 molecule
should be linear, and this prediction is confirmed by experimental
evidence. Most examples ofsp hybridization are found in organic
molecules, especially those with triple bonds.
Figure 2. 15 The sp-hybridization scheme illustrated.
 sp2 hybrid orbitals
 Now turn your attention to boron, a Group IIIA element.
 The boron atom has four orbitals but only three electrons in
its valence shell. In most boron compounds the hybridization
scheme combines ones2and two 2p orbitals into three sp2
hybrid orbitals.
 Using orbital diagrams to represent this hybridization, we have
sp 2 hybrization for B
 The atom in its ground state has only one unpaired electron,
so that it can form only one covalent bond, but in the excited
state there are three unpaired electrons, hence three bonds can
be formed.

Figure 2.16 The sp2 hybridization scheme illustrated.

 As shown in Figure 2.15 the sp 2 hybrid orbitals are
distributed geometrically within a plane at 120° angles.
 The valence bond method predicts that BCl3 is a
trigonal planar molecule with 120° Cl–B–Cl bond angle.
 This indeed is what is observed experimentally.
 By far the most common examples of sp 2
hybridization are found in organic molecules with
double bonds.
 sp3 hybridization
 Carbon, the central atom in a molecule of methane CH4 has only two
unpaired electrons in the ground state.
 The two electrons in the 2p level are not paired, i.e., put into the same box,
in accordance with Hund's rule. Carbon in its excited state can form four
bonds.
 The one 2s and three 2p-orbitals of carbon are mixed to produce four new
orbitals that are equivalent to each other in energy and in shape, but pointing
in different directions, as shown in Figure 2.17. sp3 hybridization for carbon

The four sp3 hybrid orbitals point to the corners of a regular

tetrahedron, and make bond angle of 109.50° in CH4 (Figure 2.17).
Figure 2.18sp 3 Hybrid orbitals and bonding in methane scheme illustrated.
 We might also expect to use sp3 hybridization not only for
structures of the type AX4 type (as in CH4), but also for AX3E
type (as in NH3) and AX2E2 type (as in H2O).
 Nitrogen has three unpaired electrons in its ground state,
sufficient to form three bonds; so it is not necessary to excite
the atom. sp3 hybridization of the central atom N in NH3

accounts for the formation of three N–H bonds and a lone-pair of electrons on
the N atom (Figure 3.19). The predicted H–N–H bond angles of 109.5° are close
to the experimentally observed angles of 107°.
 Figure 3.19 sp3 hybrid orbitals and bonding in NH3 .
A similar scheme for H2O accounts for the formation of two O–
H bonds and two lone-pairs of electrons on the oxygen atom.

The predicted H–O–H bond angle of 109.5° is also reasonably close to

the observed angle of 104.5°. As in our discussion of the VSEPR theory,
we can explain somewhat smaller than tetrahedral bond angles in NH3
and H2O in terms of repulsions involving lone-pair electrons.
 sp3d hybridization
 A maximum of eight valence electrons can be accommodated
by any hybridization scheme involving only s and p orbitals.
 Hybridization schemes for structures involving expanded
octets must include additional orbitals and these extra orbitals
can come from a d-subshell.
 For example, we need five hybrid orbitals to describe bonding
in PCl5.
 In a gaseous molecule of phosphorus pentachloride, PCl5, the
central atom phosphorus has only three unpaired electrons in
its ground state
 Electrons must be unpaired to provide the correct number of
unpaired electrons for bond formation.
Five orbitals are being used and sp3d hybridization occurs, giving a
trigonal bipyramidal structure. The sp3d hybrid orbital and their
trigonal bipyramidal structure is shown in Figure 2.20.
Figure 2.20 The sp3d hybrid orbitals in the molecule of PCl5 .
Like other hybrid orbitals we have considered, the five sp3d hybrid orbitals are
arranged in a symmetrical fashion, but unlike the other case, the five sp3d
orbitals are not all equivalent.
Three of the orbitals are directed in the plane of the central atom at 120° angles
with one another; the remaining two are perpendicular to the plane of the other
three. The three positions in the central plane are called the equatorial positions
and the two positions perpendicular to the plane are called axial positions.
Hybridization may take place only between orbitals of roughly the same energy.
It follows that it is not possible to hybridize the 2s or 2p levels with the 3s, or the
3s or 3p level with the 4s. The d levels are intermediate in energy, and may in
certain circumstance be used with the energy levels either below or above, that is 3s
with 3d, and 3d with 4s are both possible.
 sp 3d 2 Hybridization
 Another structure featuring an expanded octet is SF6. Here, six
hybrid orbitals are required in order to describe bonding.
 These are obtained through the hybridization scheme sp3d2,
represented by the orbital diagrams.

The sp3d2 hybrid orbitals and their octahedral orientation are shown in Figure 2.21.
 Figure 2.21 The sp3d2 hybrid orbitals SF6.

In hybridization schemes, one hybrid orbital is produced for

every single atomic orbital involved. In a molecule, each of the
hybrid orbitals of the central atom acquires an electron pair,
either a bond-pair or a lone-pair. And the hybrid orbitals have
the same orientation as the electron-set arrangement predicted
by VSEPR theory.
 When one describes the probable hybridization scheme for a
structure, he/she must choose a scheme that conforms to
experimental evidence.
 This can be done by mixing the VSEPR and valence bond
approaches. The procedure is outlined in the following four
steps and illustrated in Example 2.4.
1. Write a reasonable Lewis structure for the species
2. Use VSEPR theory to predict the electron-set arrangement of
the central atom
3. Select the hybridization scheme that correspond to the VSEPR
prediction
4. Describe the orbital overlap
The resulting molecular shape is that of a square pyramid with bond
angles of approximately 90°.
Exercise 2.13
1. Name the three types of hybrid orbitals that may be formed by
an atom with only s and p orbitals in its valence shell. Draw the
shapes of the hybrid orbitals so produced.
2. Describe a hybridization scheme for the central atom and
molecular geometry of the triiodide ion, I3–.
 The use of VSEPR theory to predict geometric structures of
molecules and polyatomic ions with double and triple covalent
bonds has already been described.
 When you combine this knowledge with the valence bond
method, you gain additional insight.
 For example, the Lewis structure of ethene (ethylene) is
depicted as

With VSEPR theory you predicted that the electron set geometry
around each carbon atom is trigonal planar (AX3 type). This
corresponds to H–C–H bond angles of 120°. To account for
these bond angles in the valence bond method, you assume that
the 2s and two of the 2p orbitals of the valence shell combine to
produce sp2 hybridization of the two carbon atoms.
All the C–H bonds in C2H4 are formed by the overlap of sp2
hybrid orbitals of the C atoms with 1s orbitals of the H atom,
with these orbitals directed along hypothetical lines joining the
nuclei of the bonded atoms.
A double covalent bond consists of one σ and one π bond.
The features of a double bond described here are illustrated in
Figure 2.22.
Figure 2.22 Bonding in ethylene, C2H4.
 VSEPR theory describes H2C = CH2 as consisting of two
planar CH2 groups, each with a 120° H–C–H bond angle. But
it does not tell us how the two groups are oriented with
respect to one another
 Are they both in the same plane? Is one perpendicular to the
other? The valence bond description of a double-bond gives
the answer.The maximum sidewise overlap between the
unhybridizedp 2orbitals to form a π bond occurs when both
CH2 groups lie in the same plane.
 Ethene is a planar molecule. If one CH2 group is twisted out
of the plane of the other, the extent of overlap of the p2
orbitals is reduced, the π bond is weakened, and the molecule=
becomes less stable.
 Aside from the restriction in rotation about a double bond just
described, electron pairs in π bonds do not fix the positions of
bonded atoms to one another.
 These positions are established by the σ bonds, the so-called
sigma-bond frame-work, and there is only one σ bond framework
because all the electrons in a multiple covalent bond constitute a
single electron set.
 We can describe a triple covalent bond in a manner similar to that
just used for a double bond. Consider the Ethyne (acetylene)
molecule, C2H2. Its Lewis structure is
H — C ≡≡≡ C — H
 The molecule is linear, with 180° H–C–C bond angles, as
predicted by VSEPR theory and confirmed by experiment. To
account for these bond angles with the valence bond method, we
assume sp hybridization of the valence shell orbitals of the two C
atoms.
In the C ≡≡≡ C bond in C2H2, as in all triple bonds, one bond
is a σ-bond and two are π- bonds. The bonding scheme in
acetylene is illustrated in Figure 2.23.

Figure 2.23 Bonding in acetylene, C2H2.

 Exercise 2.14
1. Describe a hybridization scheme for the central atom S
and the molecule geometry of
a. SO3 and b. SO2

2. Describe a hybridization scheme for the central atom

and the molecular geometry of CO2.

3. Discuss the bonding in nitrate ion, predict the ideal

bond angles, bond length, shape of the ion, the number
of sigma and pi bonds.
 2.5.2 Molecular Orbital Theory (MOT)
 Molecular orbital theory is a method of accounting for
covalent bonds that depends on quantum theory and
mathematical principles.
 This theory is based on the fact that electrons are not
the substantive little dots as we portray in Lewis
structures.
 We can speak only about energy levels/spatial
probabilities when reckoning with them.
 We do this reckoning by thinking of quantized
electron distribution as atomic orbitals (AOs ) spdf].
[
 Combination of Atomic Orbitals
 Atomic orbitals are capable of combining or overlapping, to produce
new electron distributions called molecular orbitals (MOs) – one MO
for every AO.
 The quantum mechanical treatment of electrons in atoms as matter
waves yields atomic orbitals (AOs). A similar treatment applied to
electrons in molecules yields molecular orbitals (MOs), which are
mathematical descriptions of regions of high electron charge density
in a molecule.
 It is easy to understand molecular orbital theory in principle; we seek
an arrangement of appropriately placed atomic nuclei and electrons to
produce an energetically favourable, stable molecule.
 The difficulty comes in practice, in trying to construct a wave
equation for a system of several particles. The usual approach is to
write approximate wave equations by relating them to atomic orbitals.
 Bonding and Anti-Bonding Molecular Orbitals
 Bonding molecular orbitals have a region of high electron
density between the nuclei. Anti-bonding molecular orbitals
have region of zero electron density (a node) between the
nuclei.
 Typical results are like those shown for H2 molecule in Figure
2.23. In place of atomic orbitals of the separated atoms, the
molecular orbitals for the united atoms are obtained, and these
are of two types.
 One type, a bonding molecular orbital, places a high electron
charge density in between the two nuclei and the other type,
an anti-bonding molecular orbital, places a high electron
charge density away from the region between the two nuclei.
 Electrons in bonding orbitals contribute to bond formation
and electrons in anti-bonding orbitals detract from bond
formation.
 When two atomic orbitals overlap end-to-end, they
form two sigma-molecular orbitals (MOs).
 Consider the H2 molecule, which has two H atoms
and therefore two s1 AOs.
 The two 1s atomic orbitals combine (see Figure 2.23)
to produce two σ MOs, which differ in energy and
location.
 One of the σ MOs is a bonding orbital, denoted σ1s,
the other is an anti-bonding orbital denoted σ ∗ s1.
 The relative energy levels of these two MOs are
different.
 The σ1s MO has a lower energy than the original 1s
AOs, while the σ * 1s MO has a higher energy.
 Electron Configuration of Diatomic Molecules
 After applying two principles of filling orbitals
The aufbau principle and
The Pauli exclusion principle
 we can predict that both electrons in H2 will go into
the lower energy orbital denoted by (σ1s) 2. A
molecular-orbital diagram shows the relative energy and
number of electrons in each MO, as well as the atomic
orbitals from which they form.Figure 2.24 is
the molecular orbital diagram for H2.
Figure 2.24 Molecular orbital diagram and bonding in the H2 molecule.
There are no more electrons in H2 so the σ1s * orbital remains
empty in the ground state.
Note! The number of molecular orbitals formed must equal the
number of atomic orbitals available for combination. Unfilled
molecular orbitals are considered to be there, even when there
are no electrons in them.
 Exercise 2.15
1.Draw a molecular orbital energy diagrams for
a. C2- b. C2 c. C2+
 The order of energy of molecular orbitals has been
determined mainly from spectroscopic data.
a. In simple homonuclear diatomic molecules (total
electrons = 14 or less) the order is:

b. For simple homonuclear diatomic molecules (total electrons

greater than 14) the 2 py 2 pz π = π comes after σ2px
and the order is:
 Note that the 2py atomic orbital give π bonding and π
antibonding (π*) MOs of the same energy as those produced from
2pzorbitals.
 The π2py and πpz2 orbitals are said to be double degenerate, and
similarly πpy∗2 and πpz∗2 are double degenerate.
 A similar arrangement of MOs exists from σs3 to σ ∗3px , but the
energies are known with less certainty.
 The Aufbau principle is used to derive the electronic structure of
some simple diatomic molcules or molecule ions.
 The total number of electrons from the two atoms which make
the molecule are filled into molecular orbitals.
 The MOs of lowest energy are filled first, each MO holds two
electrons of opposite spins and when orbitals are degenerate,
Hund’s rule applies and electrons are not paired.
 Example 2.4
1. Use the molecular orbital theory to derive the
electron configuration of

a. H b. Li c. Hed. O.
Which of these molecules or molecules ions exist?

Solution:

a. H molecule ion. This may be considered as

a combination of H atom and a H ion,
giving one electron to be accommodated in a MO;

b. Li molecule. Each Li atom has two electrons

in its inner shell, and one in its outer shell, making a total of six electrons
arranged:

(σ) (σ*) (σ)

C. He2+ Molecule ion. If this is considered as a He atom
and a He+ ion there arethree electrons, which are
arranged. The filled bonding orbital gives stabilization
whilst the half-filled gives destabilization. Overall, there is
some stabilization, so the helium molecule ion should
exist, and it has been observed spectroscopically.
(σ1s)2 (σ* s1) 2
d. O2 molecule. Each oxygen has eight electrons, making a
total of sixteen for the molecule. These are arranged:
The anti bonding (π*2py ) and (π* 2pz ) orbitals are

singly occupied in accordance with Hund's rule. As

in previous examples, the inner shell does not
participate in bonding and the bonding and
s orbitals
antibonding 2 cancel each other. A σ
bond results form the filling of (σpx2 ) 2. Two half π
bonds arise form π2pz and π2py bonding and
antibonding. Therefore, bonds are
formed.
 Exercise 2.16
 Use the molecular orbital theory and derive the
electron configuration of the following molecules.
Identify those which exist and do not exist.
a. He2 b. Be2 c. B2 d. C2 e. N2
Bond Order
The term bond order is used to indicate whether a covalent bond
is single (bond order = 1), double (bond order = 2) or triple (bond
order = 3). For example, in a molecular orbital treatment of
(σ)22. Since
oxygen, a sigma bond results from the filling of px
(π ∗ is half-filled therefore cancels half the effect of (π ) 2, half
)1
py 2 2py
a pi bond pz π2
results. Similarly another half pi bond arise from
and , π ∗
giving a total of The bond order is said to be
pz 2
2, and it can be calculated in the above manner, or by calculating
the number of electrons occupying bonding orbitals minus the
number of electrons in antibonding orbitals, all divided by two.
 Magnetic Properties
A species with unpaired electrons exhibits paramagnetic property.
The species is attracted by an external magnetic field. A species in which all the
electrons are paired, exhibits diamagnetism. Such species are not attracted (and, in
fact, are slightly repelled) by a magnetic field.
The antibonding π∗p2y and π ∗ p2z orbitals for O2 are singly occupied in
accordance with Hund's rule. Unpaired electrons give rise to paramagnetsim.
Since there are two unpaired electrons with parallel spins, this explains why
oxygen is paramagnetic.
This was the first success of the MO theory in successfully predicting the
paramagnetisim of O2, a fact not even thought of with VB representation of the
oxygen molecule (O == O).
 Exercise 2.17
1. What is the bond order for CN–, CN and CN+?
2. Which homonuclear diatomic molecules of the second period
elements, besides O2, should be paramagnetic?
2.6 TYPES OF CRYSTALS
At the end of this section, you should be able to:
• define a crystal;
• name the four types of crystalline solids and give examples;
• mention the types of attractive forces that exist within each
type of crystalline solids;
• describe the properties of each type of crystalline solids; and
• build a model of sodium chloride crystal structure.
 A crystal is a piece of a solid substance that has plane
surface, sharp edges, and a regular geometric shape.
 The fundamental units-atoms, ions or molecules are
assembled in a regular, repeating manner extending in
three dimensions throughout the crystal.
 An essential feature of a crystal is that its entire structure
can be figured from a tiny portion of it.
 Some solids, like glass, lack this long-range order and are
said to be amorphous.
 The structural units of an amorphous solid, whether they
are atoms, molecules or ions occur at random positions.
As in liquids, there is no ordered pattern to the
arrangement of an amorphous solid.
 A structural unit of a crystalline solid has a characteristic
repetitive pattern.
 The crystal types and their basic units are
(i) ionic (electrostatic attraction of ions),
(ii) Molecular (electrostatic attraction of dipoles in molecules)
(a) Polar (dipole-dipole and Hbonding) and
(b) Non-polar (London forces)
(iii) Network (covalently bonded atoms); and
(iv) metallic (positive nuclei in electron sea).
 There are four important classes of crystalline solids.
 Ionic Crystals
 The fundamental units of an ionic solids are positive and
negative ions.
 As a result, the inter-particle forces (ionic bonds) are much
stronger than the van der Waals forces in molecular solids.
 To maximize attractions, cations are surrounded by as many
anions as possible, and vice versa.
 The properties of ionic solids are direct consequences of the
strong inter-ionic forces, which create a high lattice energy.
 Crystalline ionic solids are usually, brittle, and non conductors
of electricity, although molten crystals may be good conductors.
 They usually have high melting points. Some of the more
familiar ionic solids are table salt (NaCl), saltpeter (KNO3),
washing soda (Na2CO3.10H2O), and black board chalk (CaCO3).
Figure: 2. 25 Crystal model of sodium chloride.
 Molecular Crystals
 Various combinations of dipole-dipole, dispersion and hydrogen-bonding
forces are operative in molecular solids, which accounts for their wide range of
physical properties.
 Dispersion forces are the principal forces acting in non-polar substances, so
melting points generally increase with molar mass.
 Among polar molecules, dipoledipole forces and where ever possible,
hydrogen-bonding dominate.
 Nevertheless, intermolecular forces are still relatively weak, so the melting
points are much lower than ionic, metallic and network covalent solids.
 The fundamental unit of a molecular solid is the molecule. Such solids are
common among organic compounds and simple inorganic compounds.
 Molecular crystals are usually transparent, brittle, and break easily when
stressed.
 They are usually non conductors of heat and electricity and usually have low
melting points. Familiar molecular crystalline solids include sugar, dry ice
(solid carbon dioxide), glucose and aspirin.
 Covalent Network Crystals
 In this type of crystalline solids, separate particles are not present.
 Instead, strong covalent bonds link the atoms together throughout
the network of covalent solid.
 As a consequence of the strong bonding, all these substances have
extremely high melting and boiling points, but their conductivity and
hardness depend on the nature of their bonding.
 The two common crystalline forms of elemental carbon are examples
of network covalent solids.
 Although graphite and diamond have the same composition, their
properties are strikingly different, graphite occurs as stacked flat sheets
of hexagonal carbon rings with a strong sigma-bond framework and
delocalized pielectrons over the entire sheet.
 These mobile electrons allow graphite to conduct electricity. Common
impurities, such as O2 makes graphite soft.
 In diamond, each carbon atom is bonded to four other carbon atoms
tetrahedrally in a giant structure.
 The carbons are joined by single bonds. Strong single bonds
throughout the crystal make diamond among the hardest
substance known.
 Because of its localized bonding electrons, diamond (like most
network covalent solids) is unable to conduct electricity.
 The most important network covalent solids are the silicates.
 In a covalent network solid, the whole crystal is one giant
molecule.
 The fundamental units are atoms covalently bonded to their
neighbours.
 These crystals are usually hard, non conductors of heat and
electricity, and have high melting points.
 Examples of covalent network solids include quartz (SiO2) and
diamond.
 Metallic Crystals
 The strong metallic bonding forces hold individual atoms
together in metallic solids.
 The properties of metals, such as high electrical and thermal
conductivity, luster and malleability result from the presence of
delocalized electrons, the essential feature of metallic bonding
(introduced in Section 2.4).
 Metals have a wide range of melting points and hardness, which
are related to the packing efficiency of the crystal structure and
the number of valence electrons available for bonding.
 For example, Group IIA metals are harder and higher melting than
Group IA metals, because the IIA metals have closer packed
structures and twice as many delocalized valence electrons.
 The fundamental units of pure metallic solids are identical metal
atoms
 Metallic crystals are opaque with reflective surfaces.
 They are ductile and malleable, good conductor of heat and
electricity, and they usually have high melting points. Copper,
silver, gold, iron and aluminium are familiar examples of
metals.

Figure 2.26 Model of metallic crystal

Table 2.2 Comparison of the four types of crystals