GENERAL CHEMISTRY

General chemistry is a branch of chemistry which deals with behaviour and characteristics of
electrons. This topic deals with electron occupying space in an atom. The electron occurs in the
orbit/shell at the region called orbital. At the same time this topic deals with electron of an atom
which occurs in a compound. The general chemistry includes the following aspects or subtopics:-

 Atomic structure
 Atomic spectrum
 Wave mechanics
 Chemical bonding

Atomic structure
Atomic structure deals with structure and component of an atom. In the fifth century B.C. the
Greek philosopher Democritus expressed the belief that all matter consists of very small,
indivisible particles, which he named atom. Although Democritus’ idea was not accepted by
many of his contemporaries (notably Plato and Aristostle), somehow it endured. Experimental
evidence from early scientific investigations provided support for the notion of ‘atomism’ and
gradually gave rise to the modern definitions of elements and compounds.

But later, different scientists put forward atomic models. These atomic models account for
atomic structure. There are several atomic models which include the following:
i. Dalton’s atomic theory
ii. Thomson’s atomic theory
iii. Rutherford’s atomic model
iv. Bohr’s atomic model

Dalton’s atomic theory

The Dalton’s atomic theory includes the following main postulates;
i. Elements are composed of extremely small particles, called atoms.
ii. All atoms of a given elements are identical, having the same size, mass and chemical
properties
iii. Compounds are composed of atoms of more than one element. In any compound, the
ratio of the numbers of atoms of any two of the elements present is either an integer or
simple fraction.
iv. A chemical reaction involves only the separation, combination, or arrangement of atoms;
it does not result in their creation or destruction.
Dalton’s concept of an atom was far more detailed and specific than Democritus’.
The second hypothesis states that atoms of one element are different from atoms of
all other elements. Dalton made no attempt to describe the structure or composition
of atoms—he had no idea what an atom is really like. But he did realize that the different
properties shown by elements such as hydrogen and oxygen can be explained

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by assuming that hydrogen atoms are not the same as oxygen atoms.
The third hypothesis suggests that, to form a certain compound, we need not only
atoms of the right kinds of elements, but the specific numbers of these atoms as well.
This idea is an extension of a law published in 1799 by Joseph Proust, a French
chemist. Proust’s law of definite proportions states that different samples of the same
compound always contain its constituent elements in the same proportion by mass.
Thus, if we were to analyze samples of carbon dioxide gas obtained from different sources, we
would find in each sample the same ratio by mass of carbon to oxygen.
It stands to reason, then, that if the ratio of the masses of different elements in a given
compound is fixed, the ratio of the atoms of these elements in the compound also
must be constant.

Dalton’s third hypothesis also supports another important law, the law of multiple proportions.
According to this law, if two elements can combine to form more
than one compound, the masses of one element that combine with a fixed mass of
the other element are in ratios of small whole numbers.

For example, carbon forms two stable compounds

with oxygen, namely, carbon monoxide and carbon dioxide. Modern measurement
techniques indicate that one atom of carbon combines with one atom of oxygen in
carbon monoxide and that one atom of carbon combines with two oxygen atoms in
carbon dioxide. Thus, the ratio of oxygen in carbon monoxide to oxygen in carbon
dioxide is 1:2. This result is consistent with the law of multiple proportions because
the mass of an element in a compound is proportional to the number of atoms of the
element present in diagram above.
Dalton’s fourth hypothesis is another way of stating the law of conservation
of mass, which is that matter can be neither created nor destroyed. Because matter is made of
atoms that are unchanged in a chemical reaction, it follows that

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mass must be conserved as well. Dalton’s brilliant insight into the nature of matter was the main
stimulus for the rapid progress of chemistry during the nineteenth century.
The structure of an atom, according to Dalton’s atomic theory, we can define an atom as the
basic unit of an element that can enter into chemical reaction. Dalton imagined an atom that was
both extremely small and indivisible. However, a series of investigations that began in the 1850’s
and extended into the 20th C clearly demonstrated that atoms actually possess internal structure.

Isotopy
Isotopy: This could be defined as a situation where by atoms of an element has the same atomic
number but different mass numbers. The difference in the mass number is due to the difference
in the number of neutrons. ISOTOPES have the same chemical properties due to the same atomic
number which also determine their chemical reactivity and position of the element in the periodic
table. However, they have different physical properties.Examples of isotopes of hydrogen

Limitations of Dalton’s atomic theory

According to Dalton’s atomic theory, an atom is the ultimate, discrete and indivisible particle of
matter. Later researches proved that Dalton’s atomic theory was not wholly correct.
Dalton’s atomic theory suffered from the following drawbacks:
i) Atoms of the same or different types have a strong tendency to combine together to form a
new ‘group of atoms’. For example, hydrogen, nitrogen, oxygen gases exist in nature as ‘group
of two atoms’. This indicates that the smallest unit capable of independent existence is not an
atom, but a ‘group of atoms’.
ii) With the discovery of sub-atomic particles, e.g., electrons, neutrons and protons, the atom can
no longer be considered indivisible.
iii) Discovery of isotopes indicated that all atoms of the same element are not perfectly identical.
At least, they differ in their masses. Atoms of the same element having different masses are
called isotopes.
iv. Atoms can be created or destroyed by nuclear fusion or fission. Examples

Thomson’s atomic model (plum pudding model)

Before discussing the Thomson’s atomic model (plum pudding model), let us discuss first the
discovery of electrons. Thomson was the first person to conduct the experiment to investigate if
air conducts electricity. The following circuit was used during the experiment:

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The emission tube has electrode at each end which is connected to the external circuit. The
emission tube is connected to the vacuum pump in order to maintain the low pressure in vacuum
tube. The cathode is the one that produces cathode rays known as electrons.
The circuit is switched on, which results into the following observations.
 The bulb (cathode) emitted light , which indicates the gas conducts electricity.
 There is glowing of emission tube or emission of light.
 There is fluorescence of emission tube.
 The stream of rays running from cathode to the anode. Through investigation of
properties of cathode rays by using magnetic field, electric field and gold leaf
electroscope results into discovery of electrons.
There is positive plate (+) say y and negative plate say x (-), when the plates conduct
electricity, electrons strike point C. When magnetic field is on, electrons strike point A.
when electric field and magnetic field off, electrons strike point B.

Explanation of Thomson’s experiment in terms of atomic structure

Ground state:-is the lowest energetic state of an atom. It is the state when an electron
filled in the lowest energy level available. This state makes an atom to be stable.
Excited state:-is the state of an atom when an electron filled in the highest energy level
before filling lowest energy level. If the electron excited jumps to the extent that the
nuclear attractive force acts upon it results pulling back of electron.
Convergent limit:-is a state of atom when an electron is removed completely from the
ground state to infinity. The convergent limit occurs if atom gains high energy which
results electrons to jump to the highest energy level where the nuclear force cannot act
upon it. This electron cannot return back to the ground state, but it left the atom positively
ionized.

Significant of convergent limit

These include the following:
i. It resulted into discovery of the ionization energy. This ionization energy is used
in inorganic section.
ii. It resulted into formation of ionic particles.

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 iii. It resulted into production of rays. These rays are known as atomic spectrum.

Thomson’s atomic theory

In Thomson's model, the atom is composed of electrons surrounded by a soup of positive charge
to balance the electrons' negative charges, like negatively charged "plums" surrounded by
positively charged "pudding".

Plum pudding model of the atom

Limitations of Thomson’s atomic model

a) It could not explain the result of the scattering experiment performed by Rutherford
b) It did not have any experimental evidence in its support.

Rutherford atomic model

Before discussing the Rutherford’s atomic model, let us first discuss his experiment conducted at
that time;
Rutherford Scattering experiment
Alpha particles from a radioactive source were allowed to strike a thin gold foil. Alpha particles
produce a tiny, but visible flash of light when they strike a fluorescent screen. Surprisingly, alpha
particles were found at large deflection angles and some were even found to be back-scattered.

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This experiment showed that the positive matter in atoms was concentrated in an incredibly
small volume and gave birth to the idea of the nuclear atom. In so doing, it represented one of the
great turning points in our understanding of nature.

If the gold foil were 1 micrometer thick, then using the diameter of the gold atom from the
periodic table suggests that the foil is about 2800 atoms thick.

From his experiment, he came to following conclusions:

 Most of the space in an atom is empty.
 The space occupied by the positive charges is very small.
 The positive charges and mass of the atom were concentrated in a very small volume within
an atom.
From these conclusions, he calculated that the radius of the nucleus is around 105 times less than
that of the atom.
Rutherford Atomic Model
Rutherford developed a nuclear model of atom on the basis of his experiment and observations.
The Rutherford atomic model has the following features:
 The centre of an atom is called nucleus. It is positively charged and almost all mass of the
atom resides in it.
 Electrons spin around the nucleus in a circular path.
 Comparatively, the size of the nucleus is smaller than the size of the atom.
 Electrons and the nucleus are held by coulombic/electrostatic force of attraction.

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 Limitation of Rutherford’s atomic model
According to Maxwell’s electromagnetic law, opposite charges cannot revolve around another
charge, i.e. electrons revolving in circular orbits will not be stable because during revolution,
they experience acceleration. Due to acceleration, they will lose energy in the form of radiation
arid fall into the nucleus. In such a case, the atom would be highly unstable and would collapse.

Bohr’s atomic model

To overcome the above defects of Rutherford’s model, Niels Bohr in 1913 gave a modification
based on Quantum theory of radiation. The important postulates are:

1. The electrons revolve around the nucleus only in certain selected circular paths called orbits.
These orbits are associated with definite energies and are called energy shells or energy levels or
quantum levels.

2. As long as an electron remains in a particular orbit, it does not radiate energy. This means that
energy of an electron in a particular path remains constant. Therefore, these orbits are also called
stationary states.

𝑛ℎ
3. The electronic motions are those which their angular momentum is integral of where n=1, 2,
2𝜋
𝑛ℎ
3…..mvr=2𝜋 where n is Plank’s constant which is 6.626×10-34Js
4. If an electron jumps from one stationary state to another, it will absorb or emit radiation of a
definite frequency giving a spectral line of that frequency which depends upon the initial and
final levels. When an electron jumps back to the lower energy level, it radiates same amount of
energy in the form of radiation.∆𝐸 = 𝐸2 − 𝐸1

Shortcomings of Bohr’s atomic model

i. The Bohr’s model did not account for electrons which were found in a chemical bonding
ii. The Bohr’s did not explain spectral lines of multi –electron atoms but accounted for uni-
electron hydrogen atom
iii. Bohr viewed an electron as being placed at a certain distance from the nucleus. However
it was proved by Weaver Heisenberg’s uncertainty principle that it is impossible at any
time to predict the exact position and velocity of an electron in an atom.
Qns
State the three postulates of Dalton’s atomic theory and give two drawbacks of his theory

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 Mass spectrometer
Is an instrument which is used to determine the relative atomic masse of an element. Mass
spectrometers have an ability to determine the relative molecular mass of a compound and
formula of a compound in a spectrographic plate.
Mass spectrograph is a plate of mass spectrometer which detects and records the atomic mass of
an element. The spectrographic plate is a detector and recorder.

How mass spectrometer works?

1. Place the vapourized sample in a vacuum chamber inside the machine.
2. The vapourized sample is introduced in the ionization chamber. The sample is bombarded
with a beam of electrons so the atoms or molecules it contains are turned into ions.
3. The ions are accelerated by two plates of negative charges toward the magnetic field. These
two plates are connected to negative potential which accelerate ions as a beam of light
toward the magnetic field.
4. The beam of ions are deflected in the magnetic field. The extent deflection depends on the
mass charge ratio m/e. the light particle deflected more than the heavy particles more than the
heavy particles.
5. The deflected ions strike on the detector. The ions at the same mass charge ratio strike on the
same spot. Once the ions strike the detector in the collector that converts the intensity of the
ions into electric signals which is amplified into large electric current.
6. The current is used to operate a pen that moves on a paper tracing the peaks of the isotopes
of the ion are recorded in terms of atomic mass and relative abundance.

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 The following includes the example of mass spectrum

Calculation of relative atomic masses

Relative atomic mass of an element is the average value of all the known isotope atomic weight
relative to the proportional abundances.
For example, isotopic element X contained y% of azX and w% of bzX; the relative atomic mass of
an element is determined as given below:-

𝑦 𝑤
R.A.M of X=[100 × 𝑎]+[100 × 𝑏]
Since y+w=100
The length of peaks of each isotopic atom applied to find the relative atomic mass. Each atom
has peak due to different mass charge ratio m/e.

Mass spectrum

(𝑦×5)+(𝑥×10)+(𝑧×15)
R.A.M of Q=
𝑦+𝑥+𝑧

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 Examples
1. The element silicon has three stable isotopes. Mass spectrographic measurement indicate
the following isotopic masses, 27.9769, 28.9765 and 29.9738 a.m.u. The relative
abundances of the three isotopes are 92. 20%, 4.07% and 3.09% respectively. Calculate
average atomic mass of silicon.
Solution
Isotopic masses=27.9769, 28.9765 and 29.9738 a.m.u
Relative abundances=92. 20%, 4.07% and 3.09%
R.A.M=?
(27.9769×92.20)+(28.9765×4.07)+(29.9738×3.09)
R.A.M of Si= 92.20+4.07+3.09
∴ 𝑇ℎ𝑒 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑆𝑖𝑙𝑖𝑐𝑜𝑛 𝑖𝑠 29.0799 𝑎. 𝑚. 𝑢
2. Element Z occurs naturally as a mixture of 69Z and 71Z.
i. Briefly explain the significance of the number 69 and 71 and give a term which
describes these two components in the natural element.
ii. If 69Z and 71Z have relative atomic mass of 69.8, find the percentage of 69Z and
71
Z in a sample.
solution
i. The significance of these numbers enables us to determine the relative atomic
mass of an element and the term used is isotope.
ii. Isotopic masses= 69 and 71
Let percentage of 69Z be x
Percentage of 71Z be (100-x)
(𝑥×69)+((100−𝑥)×71)
R.A,M of Z= but R.A.M of Z is 69.8
100
69𝑥+7100−71𝑥
69.8= 100
6980=69𝑥 + 7100 − 71𝑥
6980 − 7100 = 69𝑥 − 71𝑥
𝑥 = 40%
∴The percentage of 69Z is 40% and 71Z is (100-40) that is 60%.
3. Consider the mass spectrum of magnesium

Calculate the relative atomic mass of magnesium from the mass spectrum

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 Solution

∴ 𝑡ℎ𝑒 𝑟𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑎𝑔𝑛𝑒𝑠𝑖𝑢𝑚 𝑖𝑠 24.3

Questions

Atomic spectrum
The atomic spectrum is the electromagnetic radiation which has definite colour
because it has intermediate wavelength which can be detected by human eye.
These spectra have no harmful effect on human. Atomic spectrum produced once the atom gain
energy which cause the electron to be excited and jump from lowest energy level. This results
into an atom being unstable in order to maintain the stability this electron returns back to its
ground state which accompanied with release of energy in form of radiation. These radiations
have wavelength which detected by human eye of definite colour, definite wave and definite.

Types of spectrum that can be produced by the atoms

i. Continuous spectrum
-Is the spectrum which contains all possible frequency over wide range of energy .
continuous spectra are colourless and have no definite lines because they contain very
short wavelength which are not detected by an eye.
ii. Line spectrum
- Is a spectrum which consists of scattered definite lines. These spectra have very
long wavelength.

iii. Band spectrum

- Is the spectrum which consists of a group of definite line in a small bands.

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 BOHR- ATOMIC THEORY
HYDROGEN SPECTRUM
-Is a definite line and colour resulted when electric discharge is passed through hydrogen gas in
the emission tube under very high pressure.
The H-spectrum recorded in the spectrographic plate. The following is a horizontal diagram of
H-spectrum.

The explanation of horizontal diagram in terms of atomic structure

First band:- is a colourless band or invisible band. These are spectra produced by electrons whish
are excited from the first shell. The electrons from the first shell experience stronger aattractive
force which use the highest energy level. When these electrons return back release high amount
of energy which have shorter wavelength. These wavelengths are not detected by human eye.
The radiations formed are continuous spectrum such as x-rays, sun rays e.t.c.

Second band:- is a visible band which has definite line and colour. These spectral lines produced
by electron which excited from the second shell. The electron in the second shell needs moderate
energy in order to jump towards the highest energy level when returns back release a normal
energy which its wavelength detected by a human eye.

Third band:- is invisible band. These spectra are colourless and have no definite line. The
electron which produces these spectra causes the scattered spectra which appear as a colourless
band. This is due to the lowest energy level and highest wavelength.

The following includes vertical diagram of H-spectrum

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Lyman series:- is a series of spectrum which resulted by electron which excited from the first
shell (n=1). These series corresponds to the invisible band or colourless band.

Balmer series:-is a series of spectrum which resulted by electron which excited from the second
shell (n=2). This corresponds with visible or violet band.

Paschen series:- is a series of spectrum which resulted by electron which excited from the third
shell (n=3).

Bracket series:- is a series of spectrum which resulted by electron which excited from the fourth
shell (n=4).
Pfund series:- is a series of spectrum which resulted by electron which excited from the fifth
shell (n=5).

Quantum theory
Planck’s quantum theory
Planck put forward the quantum theory. This theory has three main postulates which include the
following:-
i. Any radiation should be associated with energy.
ii. The energy is released in form of radiation, occur in small packets called quanta.
iii. The energy is directly proportional to the frequency.
∆𝐸 ∝ 𝑓
∆𝐸 = ℎ𝑓
Since h=planck’s constant (6.63× 10 Js)
-34

Since f=𝑐⁄𝜆
∆𝐸 = ℎ 𝑐⁄𝜆 but c=3×108ms-1

Examples
1. Calculate the energy of a photo of radiations whose wavelength is 5.89× 10-7 cm emitted
from the sodium atoms when heated.
Soln
𝜆 = 5.89 × 10-7cm→ 5.89 × 10-9m
∆𝐸=?
From
𝑐
∆𝐸 = ℎ
𝜆
But c=3×108ms-1 and h=6.63× 10-34 Js
∆𝐸 =(6.63× 10-34 × 3 × 108)/5.89× 10-9
∴The energy of a photo of radiation is 3.377× 10-17Joules.

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 Rydberg’s equation
Rydberg put forward a principle which applied to find wavelength of spectrum. The wavelength
of H-spectrum determined is applied to find frequency and energy of H-spectrum. The wave
number is inversely proportional to the square of energy level differences.
⊽∝1/∆𝑛2

1
But ⊽=𝜆
1 1
=RH( 12 − )
𝜆 𝑛1 𝑛22
Where 𝝺-wavelength
n1 and n2-energy levels
RH-Rydberg constant 1.097× 107m-1

Transition energy
Transition energy is the energy which is required to shift electron from one shell to another. The
energy required to shift electron from one shell to another should be equal to the energy
difference between those two shells. The energy difference between lowest energy level E1 and
highest energy level E2 is obtained by using the following expression:-
∆𝐸 = 𝐸2 − 𝐸1
The trend of transition of electrons include the following,
∆𝐸 = 𝐸2 − 𝐸1 , transition takes place from 𝐸1 to 𝐸2 exactly
∆𝐸 > 𝐸2 − 𝐸1 , transition takes place from 𝐸1 toward above 𝐸2
∆𝐸 < 𝐸2 − 𝐸1 , transition takes place from 𝐸1 and hang between 𝐸1 and 𝐸2

But if electron gains enough energy which is equal to ionization energy results the electron to
jump completely from the ground state to infinite. This electron cannot return back instead
leaves the atom positively ionized completely.
The following expression is used to find the energy associated by electrons or energy of that
shell.
1 1
From 𝜆=RH( 12 − )
𝑛1 𝑛22
Let 𝑛1 =n
𝑛2 =∞
1 1 1
So =RH( 2 − 2)
𝜆 𝑛 ∞
1 1 1
= RH( 2 ) since 2 ≈ 0
𝜆 𝑛 ∞
1 𝑅𝐻
=
𝜆 𝑛2
ℎ𝑐
But ∆𝐸 = 𝜆

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∆𝐸 1
=
ℎ𝑐 𝜆
ℎ𝑐𝑅𝐻
∆𝐸 = 2
𝑛
But h=6.63× 10-34Js, c=3×108ms-1 and RH=1.097× 107m-1
6.63×10−34 3×108 ×1.097×107
So ∆𝐸 = 𝑛2
2.1819×10−18
∆𝐸 = J
𝑛2
But 1eV= 1.6× 10-19J
13.6𝑒𝑉
∴ ∆𝐸 =
𝑛2

But it discovered that the energy increase from the nucleus towards the high energy level. Energy
increases from the first shell toward seventh shell. From the seventh shell the energy is zero or
the energy at infinite is zero. Then the energy from infinite which is zero towards the lowest shell
tends to decrease and results to be negative value of energy.

∆𝐸 = 𝐸2 − 𝐸1
=𝐸∞ − 𝐸𝑛
But 𝐸∞ = 0
13.6𝑒𝑉
=0− 𝑛2
13.6𝑒𝑉
∆𝐸 = −
𝑛2

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The negative sign value occurs because the energy of infinite is zero. Since energy increases
from nucleus towards highest energy level results the energy of each shell be negative value.
This formula is used to determine energy of electron at each shell.

Examples
1. (i) Find the first ionization energy of potassium.
(ii) Find the wavelength, frequency and energy of third of Balmer series.
(iii) If the wavelength of the first number of Balmer’s series is 6563 Å. Calculate Rydberg’s
constant and wavelength of the first member of the Lyman series.
(iv) Find the energy associated with electrons in quantum number 2
2. (a) The U.V light has a wavelength 2950 Å. Calculate its frequency and energy
(b) Given 𝐸4 = −1.36 × 10−19 J
𝐸2 = −5.44 × 10−19 J
If the electron dropped from 𝐸4 to 𝐸2 . Find the frequency wavelength and energy released.
3. Given line spectrum

2030Å 4059Å 7010Å 8092Å

(i) Which line has highest frequency and energy?

(ii) Which line has the lowest frequency and energy?
(iii) Find the energy and frequency of each line in (i) and (ii)
4. State either or not the transition of electrons would occur if energy supplied is
i. Greater than 𝐸4 − 𝐸2
ii. Equal to 𝐸4 −𝐸2
iii. Less than 𝐸4 −𝐸2
iv. Greater than 𝐸3 − 𝐸2 but less than 𝐸4 −𝐸2
Solution for qn 1
i. The electronic configuration of Potassium, K=2:8:8:1
Now n=4
−13.6𝑒𝑉
From ∆𝐸 = 𝑛2
−13.6𝑒𝑉
∆𝐸 = =-0.85 eV
42
𝑏𝑢𝑡 1𝑒𝑉 = 1.6 × 10−19
So ∆𝐸 =-1.36× 10−19J
The ionization energy= 𝐸∞ − 𝐸4 i.e. 𝐸𝑖𝑜𝑛 = 0 − −1.36 × 10−19J=1.36× 10−19 J,

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 ii. Balmer series, 𝑛1 = 2
Third line, 𝑛2 = 2 + 3 = 5
𝝺=?
f=?
∆𝐸 =?
1 1 1
From = 𝑅𝐻 ( − )
𝜆 𝑛12 𝑛22
But 𝑅𝐻 = 1.097 × 107 m-1
1 1 1
Now 𝜆 = 1.097 × 107(22 − 52 ) =2.3037× 106 m-1
1
=2.3037× 106 m-1
𝜆
∴ λ = 4.34 × 10-7m

Now let us find f

𝑐
From f= 𝜆 but c=3× 108ms-1
3×108
So f=4.34×10−7=6.912× 1014 Hz

Energy
From ∆𝐸 = ℎ𝑓 but h=6.63× 10−34Js
So ∆𝐸 =6.63× 10−34 × 6.912 × 1014 = 4.583 × 10−19 J
iii. 𝝺= 6563Å = 6563 × 10−10m
Balmer series, 𝑛1 = 2
1st line of Balmer series= 2 + 1 = 3
𝑅𝐻 =?
1 1 1
From = 𝑅𝐻 ( − )
𝜆 𝑛12 𝑛22
1 1 1
= 𝑅𝐻 (22 − 32 )
6563×10−10
1
= 0.13889𝑅𝐻
6563×10−10
𝑠𝑜 𝑅𝐻 = 1.097 × 107 m-1
Now let us find wavelength of the first member of the Lyman series
Lyman series, 𝑛1 = 1
1st line of Lyman series, 𝑛2 = 1 + 1 = 2
𝝺=?
1 1 1
From = 𝑅𝐻 ( − )
𝜆 𝑛12 𝑛22
1 1 1
= 1.097 × 107 ( 2 − 2 )
𝜆 1 2
1
= 8.2275 × 106 m-1
𝜆
∴𝝺= 1.215 × 10−7 m

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 iv. 𝑛=2
∆𝐸 =?
−13.6𝑒𝑉
From ∆𝐸 = 𝑛2
−13.6𝑒𝑉
Now ∆𝐸 = = −3.4𝑒𝑉
22
But 1eV=1.6× 10−19 J
∴ ∆𝐸 = −5.44 × 10−19 J

Solution for qn 2
−10
a) 𝝺=2950Å= 2850 × 10 m
f=?
∆𝐸 =?
𝑐
From f= but c=3× 108 m/s
𝜆
3×108
Now f=2950×10−10 = 1.0169 × 1015 Hz
But ∆𝐸 = ℎ𝑓
So ∆𝐸 = 6.63 × 10−34 × 1.0169 × 1015 = 6.742 × 10−19 J

b) 𝐸4 = −1.36 × 10−19 J
𝐸2 = −5.44 × 10−19 J
𝑓 =?
𝞴 =?
∆𝐸=?
From ∆𝐸 = 𝐸4 − 𝐸2
∆𝐸 = (−1.36 − −5.44) × 10−19=4.08× 10−19 J
∴Energy released is 4.08× 10−19J

Again from ∆𝐸 = ℎ𝑓 but h=6.63× 10−34 Js

∆𝐸 4.08×10−19
𝑓= = 6.63×10−34=6.1538× 1014 Hz
ℎ
∴Frequency is 6.1538× 1014 Hz

For wavelength, 𝝺
𝑐
𝑓=𝜆=
𝑐 3×108
Now 𝜆 = 𝑓=6.1538×1014=4.875× 10−7m
∴wavelength is 4.875× 10−7 m

Solution for qn3

Do it for your own, but remember frequency is inversely proportional to the
wavelength.

18 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Solution for qn 4
i. Results transition of electron from 𝐸2 and above 𝐸4 .
ii. Transition takes place from 𝐸2 to 𝐸4
iii. Results of transition from 𝐸2 but cannot reach instead hangs between 𝐸2 to 𝐸4
iv. Results to transition of electron from 𝐸2 and 𝐸4 but cannot reach 𝐸4

Note
1Å= 10−10 m
1nm= 10−9m
Wave-particle duality nature of matter
States that, matter has particle nature as well as wave nature. This means that
matter has dual properties or two properties that is particle nature and wave
nature. The wave-particle duality nature of matter was put forward by De-Broglie
scientist. De-Broglie derived an expression which applied to find the De-Broglie’s
wavelength.

De- Broglie’s wavelength is in terms of energy and momentum.

Hence from Einstein’s equation
∆𝐸 = 𝑚𝑐 2 ………………(i)
From planck’s equation
ℎ𝑐
∆𝐸 = …………………(ii)
𝜆
Comparing eqn (i) and (ii)
ℎ𝑐
𝑚𝑐 2 =
𝜆
ℎ
𝝺= 𝑚𝑐 but mc=p (momentum)
ℎ
So 𝝺= 𝑝
De-Broglie’s wavelength in terms of energy
ℎ 1
𝝺= 𝑚𝑐 (multiply by 𝑐 both sides)
𝜆 ℎ
= but mc2= ∆𝐸
𝑐 𝑚𝑐 2
𝒉𝒄
∴𝞴=
∆𝑬

Examples
a) Alpha particles emitted from radium have energy of 4.4 MeV. What is the De-
Broglie’s wavelength?
b) The mass of moving particles is 9.01× 10−19kg. what is the De-Broglie’s
wavelength?
c) The momentum of particle is 2.0× 10−10gms-1. What is the De-Broglie;s
wavelength? (Ans. 3.315× 10−21 m)

19 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Solution for (a)
6
∆𝐸 = 4.4 𝑀𝑒𝑉 = 4.4 × 10 eV
𝑏𝑢𝑡 1𝑒𝑉 = 1.6 × 10−19 J
𝑡ℎ𝑒𝑛 ∆𝐸 = 7.04 × 10−13 J
𝞴 =?
𝒉𝒄
From 𝞴 = ∆𝑬 but h=6.63× 10−34 Js, c=3× 108 m/s
6.63×10−34 ×3×108
So 𝝺= = 2.825 × 10−13 m
7.04×10−13
∴ 𝐷𝑒 − 𝐵𝑟𝑜𝑔𝑙𝑖𝑒 𝑠 𝑤𝑎𝑣𝑒𝑙𝑒𝑛𝑔𝑡ℎ 𝑖𝑠 2.825 × 10−13m
′

Solution for (b)

−19
m=9.01× 10 kg
𝝺=?
ℎ
From 𝝺= 𝑚𝑐
6.63×10−34
Now 𝝺=3×108 ×9.01×10−19=2.453× 10−24 m
∴ 𝞴 = 𝟐. 𝟒𝟓𝟑 × 𝟏𝟎−𝟐𝟒 m

Question (c) test yourself

Heisenberg’s uncertainty principle
Heisenberg’s uncertainty principle states that, it is impossible to determine
position and momentum of electrons simultaneously with greater accuracy.
It is impossible to determine position and momentum of electrons because:-
i. The size of electron is very small and as such radiation of high energy
extremely small wavelength are required to detect it.
ii. Impact of these high energetic photons changes the direction and speed
of the electron. Thus situation disturbs the position of electron.
The uncertainties in determination of these two quantities vary inversely. If one
is determined fairly accurately, the other must be corresponding less accurately.
Heisenberg put forward an expression which is used to determine uncertainty
position and momentum of electrons.
Where p= 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚
∆𝑥 = 𝑢𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛
1
𝑠𝑜 𝑝 ∝
∆𝑥
ℎ
∴𝑝=
4𝜋∆𝑥

Example
i. The uncertainty in the momentum of particles is 3.3× 10−19kgms-1.
Find accuracy with which its position can be determined.

20 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Solution
p= 3.3 × 10−19 kgms-1
∆𝑥 =?
ℎ
From 𝑝 = 4𝜋∆𝑥 but h= 6.63 × 10−34Js
ℎ
So ∆𝑥 = 4𝜋𝑝
6.63×10−34
Now ∆𝑥 = =1.599× 10−16 m
4×3.14×3.3×10−19
∴ 𝑡ℎ𝑒 𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 𝑡ℎ𝑎𝑡 𝑐𝑎𝑛 𝑏𝑒 𝑑𝑒𝑡𝑒𝑟𝑚𝑖𝑛𝑒𝑑 𝑖𝑠 1.599× 10−16 m.

Wave mechanics
Wave mechanics deals with electron occupying space. The electrons
revolve the nucleus through orbit and occur in the orbital.
Orbital is the region within an atom that can be occupied by maximum of
two electrons that have opposite spin. Any orbital can accommodate a
maximum of two electrons.
The energy level of atoms is a specific region around the nucleus
electrons can occupy in atoms. A shell is a complete group of orbitals
possessing the same quantum number.
Quantum number
Quantum number is a number which describes the characteristics of
electrons. The quantum number is a number which describes main
energy level, orientation of orbitals and spinning of electrons.
There are four types of quantum numbers which include the following:-
1. Principal Quantum Number (n): n = 1, 2, 3, …, 8 .
Principal quantum number is a number which specifies the location and
the energy of electron. This number describes the energy level of
electrons. The principal quantum number called shell/orbit (main energy
level) and stationary state. The principal quantum number has specific
name from the nucleus K, L, M, N e.t.c.
2. . Angular Momentum (Secondary, Azimunthal) Quantum Number (l): l =
0, ..., n-1.
Specifies the shape of an orbital with a particular principal quantum
number. The secondary quantum number divides the shells into smaller
groups of orbitals called subshells (sublevels). Usually, a letter code is
used to identify l to avoid confusion with n:

The subshell with n=2 and l=1 is the 2p subshell; if n=3 and l=0, it is the
3s subshell, and so on. The value of l also has a slight effect on the energy
of the subshell; the energy of the subshell increases with l (s < p < d < f).

21 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 3. Magnetic Quantum Number (ml): ml = -l, ..., 0, ..., +l.
Specifies the orientation in space of an orbital of a given energy (n) and
shape (l). This number divides the subshell into individual orbitals which
hold the electrons; there are 2l+1 orbitals in each subshell. Thus the s subshell
has only one orbital, the p subshell has three orbitals, and so on.
4. Spin Quantum Number(ms): ms = +½ or -½.
Specifies the orientation of the spin axis of an electron. An electron can spin
in only one of two directions (sometimes called up and down).

Application of quantum number

Quantum number is applied to find the number of sub-shell (l), number of orbitals (ml) and total
number of electron(s) of the given number (n).

Examples
1. Find the total number electrons in the principal quantum number 3.
(Ans. 18 electrons)
2. Find the total number of orbitals in the principal quantum 2.
(Ans. 4 orbitals)
Other questions
1. The modern theory of electron behaviour is based on two assumptions. State them
Answer
i. An electron has a dual nature
ii. It is practically impossible to determine both position and momentum of an
electron exactly.

Questions
Explain the meaning of the following terms
a) Quantization of energy and radiation

22 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 b) Wave-particle duality of matter
c) Quantum number

Rules for filling electrons in the orbitals of an atom

The orbitals of an atom can be filled with electrons by applying the following rules:-
i. Aufbau principle (Building up principle)
It states that, the electrons in an atom are so arranged that they occupy orbitals in the
order of increasing energy.
Thus, the orbital with the lowest energy will be filled first, then the next higher and so on.
Follow this order:-

ii. Pauli’s exclusion principle

It states that, no two electrons in the same atom can have identical values for all four of
their quantum number.
This means that, no more than one electron can occupy the same orbital, and that two
electrons in the same orbital must have opposite spins.
For example, in 1s-orbital of Helium there are two electrons. According to the concept of
quantum number and Pauli’s rule, their quantum numbers are:-
Electron n L ml ms
Electron 1 1 0 0 1
+
2
Electron 2 1 0 0 1
−
2

Applications of Pauli’s exclusion principle

Pauli’s exclusion principle leads to the following conclusions:-
i. An orbital cannot have more than two electrons.
ii. In any main level (shell), the maximum number of electrons is twice the number of
orbitals, or is equal to 2n2, where n is the principal quantum number.

23 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 iii. Hund’s rule of maximum multiplicity
It states that, when electrons are placed in a set of orbitals of equal energy, they are
spread out as much as possible to give as few paired electrons as possible.
Explanation
Two electrons with parallel spins, tend to be as far apart as possible to minimize the
electrostatic repulsion. Therefore, the electrons prefer to occupy the orbital singly as far
as possible.
NB
In writing the electronic configuration the atoms or orbital of the same value are usually
written together irrespective of their relation energy level. To save time and space noble
gases are often utilized. Examples
Soudium, Na= [𝑁𝑒]4𝑠1
Iron, 𝐹𝑒 = [𝑁𝑒]3𝑑6 4𝑠 2

Qn
1. Briefly explain why the following sets of quantum number are NOT allowed.
i. n= 1, 𝑙 = 1, 𝑚𝑙 = 0
ii. 𝑛 = 1, 𝑙 = 0, 𝑚𝑙 = 2
iii. 𝑛 = 4, 𝑙 = 3, 𝑚𝑙 = 4
iv. 𝑛 = 0, 𝑙 = 0, 𝑚𝑙 = 0
v. 𝑛 = 2, 𝑙 = −1, 𝑚𝑙 = 1
Solution
i. 𝑙 −value must be smaller than 𝑛 −value since 𝑙 = 𝑛 − 1
ii. When 𝑙 = 0, 𝑚𝑙 −value is only 0
iii. For 𝑙 = 3, 𝑚𝑙 can range from -3 to +3, thus 𝑚𝑙 =4 is not allowed
iv. 𝑛 −value cannot be equal to zero
v. 𝑙 −value cannot be a negative number

Note
In filling electrons different ways can be used to represent:-
i. Orbital diagram
ii. Noble gas structure
iii. Sub energy level

Examples
1) By using 3 different ways for each of the following atoms, write their electronic
configuration
i. C
ii. N
iii. Zn
2) Write the electronic configuration of Na+ and F- then show the element whose electronic
configuration resembles these ions. Show that electronic configuration of Cu and Cr is
unusually written. Give reason
24 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Solution for qn 1
2 2 2
i. 6C=1𝑠 2𝑠 2𝑝

ii. 7N=
iii. 30Zn=[Ar]3𝑑10 4𝑠 2
Solution for qn 2
The electronic configuration of Na+
Na+=[Ne]3𝑠 0
The electronic configuration of F-
F-=[Ne]
∴The element that resembles these ions is Ne

The electronic configuration for Cu and Cr

1 10
29Cu=[Ar]4𝑠 3𝑑
1 5
24Cr=[Ar]4𝑠 3𝑑
Full filled and half filled d-orbitals are very stable electronic configuration. The stability gained
is the cause of 4s to be unpaired and make 3d-orbitals either full-filled or half filled.

Questions
1. Write the electronic configuration of the following elements/ions
i. 8O
ii. 19K
iii. 28Ni
iv. Cu+ (atomic number of Cu=29)
v. Cl- (atomic number of Cl=17)
vi. Fe3+ (atomic number of Fe=26)
2. Why is the electronic configuration 1𝑠 2 2𝑠 2 2𝑝𝑥2 2𝑝𝑦0 2𝑝𝑧0 not correct for the ground state of
nitrogen?

CHEMICALBONDING
Chemical bonding is a process whereby atoms combine to form a molecule or
compound.
Chemical bond is the chemical force/force of attraction which keeps the atoms in any
molecule or compound together.

Types of the chemical bond

i. Ionic/electrovalent bond
ii. Covalent bond
iii. Coordinate/dative bond
I. Ionic/Electrovalent bond
An ionic or electrovalent bond formed by complete transfer of one or more electrons
from the atom of the metal to that of a non-metal.

25 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Note
As a result of electron transfer the following changes occur in the reacting atoms:-
a) Both the atoms acquire stable noble gas configurations.
b) The atom that loses electrons becomes positively charged ion called cation, the
atom which gains these electrons becomes negatively charged ion called anion.
c) The two oppositely charged ions i.e. the cation and the anion are then held
together by the coulombic/electrostatic force of attraction to form an ionic bond.
During the formation of ionic bond, a certain amount of energy is released
Example, Na + Cl Na+Cl-
This ionic bond may be defined as the electrostatic force of attraction which holds the oppositely
charged ions together.
Electrovalency
Electrovalency is the number of electrons lost or gained by an atom. The element which gives up
electron(s) to form positive charge or ion is said to have positive valency while the element
which accepts electrons to form negative ion is said to exhibit negative valency.

Properties of ionic/Electrovalent Bond

An ionic bond has the following properties:-
i. An ionic bond is formed due to electrostatic attraction between the positively and
negatively charged ions.
ii. An ionic bond is non-directional, the strength of interaction between two ions depend
upon distance but not direction
iii. An ionic bond gets broken when the substance is dissolved in polar solvent such as water
or alcohol or when the substance is melted.
Typical example of ionic bond
1
a) Na + Cl2 NaCl
2
b) Na loss of e Na+ + e
c) Cl + e gain of e Cl-
Na+ + Cl- NaCl

Factors influencing the formation of ionic bond

The main steps involved in the formation of an electrovalent bond are:-
a) Removal of electrons from an atom, in this stage energy equal to the ionization energy is
absorbed.
b) Gaining of electrons by the other atoms. In this energy equal to the electron affinity is
released.
c) Combination of cation and anion. The ions are held together by electrostatic force of
attraction. In this step, energy equal to the lattice energy is released.

26 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 II. Covalent bond
Covalent bond is formed between atoms (similar or dissimilar) by a mutual sharing of
electrons. The shared pairs of electrons are counted towards the stability of both the
participating atoms.
By definition
Covalent bond is the force of attraction arising due to sharing of electrons between the
two atoms. When the two atoms combine by mutual sharing of electrons, then each of the
atoms acquire stable configuration of the nearest noble gas.

Covalency
Covalency is the number of electrons which atom contributes towards mutual sharing
during the formation of chemical bond. Example of the covalency.
H2 H H, H:H
O2 O O, O::O
N2 N≡N, N⋮⋮N

Characteristics of covalent bond

i. Mode of formation:- covalent bonds are formed due to mutual sharing of one or
more pairs of electrons.
ii. Directional character:- covalent bonds are directional in nature, this is because
the shared electrons remains localized in a definite space between the nuclei of
the two atoms. This gives a directional character to the covalent bond.
Covalent bond can be formed either by sharing one electron or more electrons. Therefore we
have:-
a) Single bond (sigma (𝛿)-bond)
A covalent bond is formed by mutual sharing of one pair of electrons. A 𝛿 −bond is
represented by a small line (−) between the two atoms.
For example,
H + H H−H
Cl + Cl Cl−Cl
b) Multiple bond (pie (𝝅)-bond)
The covalent bonds developed due to mutual sharing of more than one pairs of electrons
are termed as multiple covalent bonds (𝝅-bond).
The multiple covalent bonds are
i. Double covalent bond
ii. Triple covalent bond
Double covalent bond is the bond between two atoms due to the sharing of two electron pairs. It
is called double bond.
Example,
O2 O=O
CO C=O
Triple covalent bond is the bond formed due to the sharing of three electron pairs.

27 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
Examples
N2 N≡N
C2H2 H−C≡C−H
A covalent bond is of two types depending on the type of overlapping between two atoms.
1. Sigma (σ) bond
This type of covalent bond results when there is end to end overlapping of atomic orbitals along
the internuclear axis. It is formed when s-s, s-p or p-p head-on overlapping takes place.
2. Pi (π) bond
This type of covalent bond results when there is sidewise overlap of half filled atomic orbitals. It
is formed when p-p sidewise overlapping takes place. This bond is weaker than sigma bond.

Comparison between single, double and triple bond

Triple bond length<double bond length<single bond length
Since a shorter bond means greater bond strength hence the energy required to separate the
bonded atoms (called bond energy) follows the order below:
Triple bond> 𝑑𝑜𝑢𝑏𝑙𝑒 𝑏𝑜𝑛𝑑 > 𝑠𝑖𝑛𝑔𝑙𝑒 𝑏𝑜𝑛𝑑

Polarity in covalent bond

Depending upon chemical nature of the combining elements, the following two types of covalent
bond are formed, that is
i. Non−polar covalent bond
ii. Polar covalent bond
Non−polar covalent bond
When a covalent bond is formed between two atoms of the similar electronegativity, the
electrons are share equally between the two atoms. The resulting molecule will be electrically
symmetrical. For instance H2. O2, Cl2, CH4.

Polar covalent bond

When a covalent bond is formed between two atoms of different electronegativity, the bonding
pair of electrons does not lie exactly midway between the two atoms. It lies towards the atom
which has more affinity for electrons.
The atom with higher affinity for electrons thus develops a slight negative charge and the atom
with lesser affinity for electrons a slight positive charge such molecules are polar molecules. HF
and H2O are examples of polar molecules.

𝐻 𝛿+ − 𝑂𝛿− − 𝐻 𝛿+

28 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Causes of polarity in bonds
The cause of polarity in bond is due to electronegativity difference. Electronegativity is the
measure of the attraction which an atom exerts on the electron pairs of a covalent bond. Example
of the electronegativty difference between hydrogen and halogen atoms is as follows:-
Halogen atoms (F, Cl, Br, I)
Electronegativity difference
F=4, H=2.1, Cl=3.0, Br=2.8, I=2.5
For H−F=(4-2.1=1.9)

Factors affecting the formation of covalent bond

The following are the factors that favour the formation of covalent bond
i. Higher ionization enthalpy
The element having higher ionization energy cannot lose electrons easily, so they tend to
share electrons.
ii. Nearly equal electron gain enthalpy or electron gain
The atoms of the two elements which have equal or nearly electron gain enthalpies tend
to complete their outer shells by mutual sharing of electrons.
iii. Nearlyor equal electronegativity
Nearly or equal electronegativity of the two combining elements does not permit the
transfer of electron(s) from one atom to another.
iv. High nuclear charge and small atomic size
High nuclear charge and small atomic size of the two combining elements favour
covalent bond because the transfer of electrons in such case will not be possible.

Coordinate bond/Dative bond bond

Dative bond is formed when the shared electron pair is provided by one of the combining
atoms. The atom which provides the electron pair is termed as the donor, while the other
atoms which accept are termed as the acceptor.
A coordinate bon is represented by an arrow ( )pointing towards the acceptor.

Formation of dative bond during the formation of a molecule or molecular ion

Consider the typical examples
a) Formation of ammonium ion (NH4+)
During the formation of ammonium ion nitrogen is the donor atom while H+ is the
acceptor ion.

29 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 b) Formation of coordinate bond between two molecules
Two or more stable molecules combine to form a molecular complex, in such a
complex molecule the constituent molecules are held together by coordinate bond.

The product above is ammonia boron trifluoride complex.

Intermolecular forces
Intermolecular forces are attractions between one molecule and a neighbouring molecule. The
strength of the molecules or atoms that compose a substance determines the state−solid, liquid,
or gas of the substance at room temperature. Strong intermolecular forces tend to result in liquids
and solids (high melting and boiling point). Weak intermolecular forces tend to result in gases
(low melting and boilng point).
There are three types of intermolecular forces:−
a) Van der Waal’s force (dispersion force)
b) dipole−dipole force
c) hydrogen bonding
I. Van der Waal’s force (Dispersion forces)
The default intermolecular force present in all molecules and atoms, is the dispersion
force (also called the London). Dispersion forces are caused by fluctuation in the electron
distribution within molecules or atoms. Since all atoms and molecules have electrons,
they all have dispersion forces. The electrons in an atom or molecule may, at any one
instant, be unevenly distributed.
Consider He−𝑎𝑡𝑜𝑚

30 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 Random fluctuations in the electron distribution of a helium atom cause instantaneous
dipoles (temporary dipoles). That is, the left side then acquires a slightly negative charge
(𝛿 − ). The right hand side of the atom, which is void of electrons acquires a slightly
positive charge (𝛿 + ).
Note
If all other factors are constant, the dispersion force increases with the molar mass. For
example, consider the boiling points of the noble gases:

Qn
Which halogen, Cl2 and I2, has the higher boiling point?

II. Dipole−dipole force

Is the one that exists in all molecules that are polar molecules have permanent dipoles
that interact with the permanent dipoles of molecules of neighbouring molecules. The
positive end of one permanent dipole is attracted to the negative end of another; this
attraction is the dipole-dipole force. Polar molecules, therefore, have higher melting point
and boiling point (including polar ones) have dispersion forces. In addition, polar
molecules have dipole-dipole forces. This additional attractive force raises their melting
point and boiling points relative to non-polar of similar mass. Consider the below which
shows the different m.p. and b.p. of polar and non-polar molecules:

III. Hydrogen bonding

A hydrogen bond is a weak type of force that forms a special type of dipole-dipole attraction
which occurs when a hydrogen atom bonded to a strongly electronegative atom exists in the
vicinity of another electronegative atom with a lone pair of electrons. These bonds are

31 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 generally stronger than ordinary dipole-dipole and dispersion forces, but weaker than true
covalent and ionic bonds.
A hydrogen bond is the electrostatic attraction between polar groups that occurs when a
hydrogen (H) atom bound to a highly electronegative atom such as nitrogen (N), oxygen (O)
or fluorine (F) experiences attraction to some other nearby highly electronegative atom.

Conditions necessary for the formation of hydrogen bond

i. Only the molecule in which hydrogen atom is linked to an atom is linked to a an atom of
highly electronegative element is capable of forming hydrogen bond.
ii. The atom of highly electronegative element should be small.

Some compounds showing hydrogen bonding

a) Water (H2O)
Water is a typical polar compound which exhibits hydrogen bonding as shown below.

b) Hydrogen fluoride (HF)

c) Ammonia (NH3)

The dotted line in all cases shows the H-bond

Types of hydrogen bonding

There are types of hydrogen bonding
i. Intermolecular hydrogen bonding
ii. Intramolecular hydrogen bonding
A. Intermolecular hydrogen bonding
When the hydrogen bonding is between the H-atom of one molecule and an atom of the
electronegative element of another molecule. For example, hydrogen bonding in water,
ammonia e.t.c.

32 | V i c e n t S a l u m 0 7 4 5 5 6 5 4 2 3
 B. The intramolecular hydrogen bonding
Intramolecular hydrogen bonding is between the hydrogen of one functional group and
the electronegative atom of the adjacent functional group in the same molecule. For
example the molecule of o-nitrophenol shows intramolecular hydrogen bonding. The p-
nitrophenol shows intermolecular hydrogen bonding.

Effects of hydrogen bonding

Hydrogen bonding affects the physical properties of compound appreciable. Some effects of H-
bonding are described below:-
a) Molecular association
Formation of aggregates containing two or more molecules due to weak electrostatic
interactions such as hydrogen bonding for example, water molecule undergoes molecular
association due to hydrogen bonding.
b) Increase in the melting point and boiling point
The interactions which affect the melting and boiling points of NH3, H2O and HF is
identified to be hydrogen bonding.
c) Influence on the physical state
Hydrogen bonding affects physical state of a substance also for example H2O is a liquid
while H2S is a gas under room temperature.
d) Solubility of covalent compound in water
Covalent compounds generally do not dissolve in water. However the covalent compound
which can form hydrogen bonds with water readily dissolved in it. For example ethanol,
ammines, lower aldehydes and ketones dissolve in water due to their tendency of forming
H-bonding with water.

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 Note
H-bond>dipole-dipole moment/force>dispersion force

LEWIS STRUCTURES
General Rules for Drawing Lewis Structures
1. All valence electrons of the atoms in Lewis structures must be shown.
2. Generally electrons are paired. Unpaired electrons are observed in odd electron
molecules such as NO and NO2.
3. Generally each atom acquires eight electrons in its valence shell except hydrogen
acquires only two electrons.
4. Multiple bonds (double and triple bonds) can be formed by C, N, O, P, and S.
5. Hydrogen atoms are terminal atoms. Hydrogen can accommodate a maximum of two
electrons in its valence shell. It can therefore only make one bond to one other atom.
There are only very few exceptions to this rule
6. Central atoms are generally less electronegative than terminal atoms. For example,
HCN is more stable than HNC because carbon is less electronegative then nitrogen.
Carbon atoms are generally central atoms. Oxygen has a relatively high electronegativity
and is observed to be a terminal atom in many molecules. In alcohols, the –O–H group is
attached to a carbon and even though hydrogen is less electronegative it must be a
terminal atom. Also, in peroxides such as hydrogen peroxide, H2O2, the oxygen atoms are
in the center (H–O–O–H).
7. In drawing Lewis structures for relatively small molecules and polyatomic ions, the
structures tend to be more stable when they are compact and symmetrical rather than
extended chains of atoms.

Qn

Note
Bonding pair of electrons is the electrons in molecules that participate in bond formation.

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 Lone pair of electrons is the pair of electrons that do not participate in bond formation.

Hybridization
Hybridization is the process of mixing of the atomic orbitals to form new hybrid orbital.
All hybrid orbitals of a particular kind have equal energy, identical shape and are
symmetrically oriented in space.

Characteristics of hybrid orbitals

i. The number of hybrid orbitals formed is equal to the number of the atomic
orbitals participating in hybridization.
ii. All hybrid orbitals are equivalent in shape and energy but different from
participating atomic orbitals.
iii. A hybrid orbital which takes part in the bond formation must contain only one
electron in it.
iv. A hybrid orbital, like atomic orbital cannot have more than two electrons. The
two electrons should have their spins paired.
v. Due to electrostatic repulsions between the hybrid orbitals they tend to remain at
the maximum distance from each other.
Types of hybridization
The types of hybridization shown by an atom depends upon the requirement of the reaction
a) sp3−hybridization
b) sp2−hybridization
c) sp−hybridization
d) s,p & d−hybridization
sp3−hybridization
Consider the CH4 molecule. Focusing only on the valence electrons, we can represent the orbital
diagram of 6C as

Promotion of electron

sp-Hybrid orbitals

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Another type of sp3−ℎ𝑦𝑏𝑟𝑖𝑑𝑖𝑧𝑎𝑡𝑖𝑜𝑛 is of NH3
The ground-state electron configuration of N is 1s22s22p3, so that the orbital diagram for the sp3
hybridized N atom is

sp−hybridization
The beryllium chloride (BeCl2) molecule is predicted to be linear by VSEPR. The orbital
diagram for the valence electrons in Be is

Promotion of electron

sp-Hybrid orbitals

Sp2-hybridization
Next we will look at the BF3 (boron trifluoride) molecule, known to have planar geometry based
on VSEPR. Considering only the valence electrons, the orbital diagram of B is

Promotion of electron

sp2-hybrid orbitals

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 Sp3d-hybridization

Sp3d2-hybridization
Consider the element below

Valence shell electron pair repulsion (VSEPR) theory

The VSEPR theory was proposed by R.J. Gillespie and R.S. Nyholm in 1957. The theory was
developed to predict the shapes of the molecule in which the atoms are bonded together. This
theory is based on the repulsions between the electron pairs in the valence shell of the atoms in
the molecule. The main postulates of the VSEPR theory are:
i. The geometry of a molecule is determined by the total number of electron pairs (bonding
and non-bonding) around the central atom of the molecule.
The shape of the molecule depends upon the orientation of these electron pairs in the
space around the central atom.
ii. The electron pairs (shared or lone pairs) around the central atom in a molecule tend to
stay as far away from each other as possible so as to minimize the repulsion between
them.
iii. The strength of repulsion between different electron pairs follows the order:-
Lone pair-lone pair>lone pair-shared pair>shared pair-shared pair electrons

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 The shared pair of electrons is also called bond pair of electrons. The presence of lone
pair (s) of electrons on the central atom causes some distortions in the expected regular
shape of the molecules.

Shapes of molecules having bond pair of electrons

a) Molecules with two bond pairs
In a molecule having two bond pair of electrons around its central atom, the bond
pairs are located in opposite side (at an angle of 180°) of the central atom so that
the repulsion between them is maximum.

The shape is linear

b) Molecules with three bond pairs
In a molecule having three bond pairs of electrons around its central atom, the
electron pair form an equilateral triangular arrangement around central atom.
Thus the three bond pairs at 120° with respect to each other. The molecule having
three bond pairs around its central atom have trigonal planar shape.

c) Molecules having four bond pairs

In a molecule having four bond pairs of electrons, four bond pairs are arranged in
tetrahedral around the central atom. Thus the four bond pairs are at an angle of
109°28’.

The shape is tetrahedral

d) Molecule with five bond pairs
Five bond pairs orient themselves around the central atom in a trigonal
bipyramidal way. Three bond pairs are in a plane called equatorial plane and
oriented at an angle of 120° with respect to each other. Thus a molecule having
five bond pairs around its central atom has trigonal bipyramidal way shape.

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 Therefore the molecule of the type AB5 is trigonal bipyramidal example PCl5,
PF5, SbCl5
e) Molecules with six bond pairs
Six bond pairs are distributed octahedral around the nucleus. Thus a molecule
having six bond pairs around its central atom has an octahedral shape. Thus
molecule SF6 has an octahedral shape.

The table below shows the geometry of molecules which has no lone pairs

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 Shapes of the molecules having bond pairs and lone pairs
a) Molecules having three bond pairs and one lone pairs.
A molecule having three bond pairs and one lone pair of electrons thus has in all
four pairs of electrons around its central atom. Therefore the four pairs of
electrons are distributed tetrahedral around the central atom. The bond angle is
107°28’.

The shape is tetrahedral.

Typical molecules of this type are NH3, NF3, PCl3 and H3O+.
b) Molecules with two bond pairs and two lone pairs
The two bond pairs are distributed tetrahedral around the central atom. The two
lone pairs on the central atom repel the bond pairs slightly inwards due to greater
lone pair-bond pair repulsion. As a result the bond angle in such a molecule is
less than the tetrahedral value of 104°28’. Example, H2O, H2S, F2O, SCl2.

c) Molecules with four bond pairs and two lone pair

The four bond pairs are in a square planar distribution. The two lone pairs are in
direction at right angles to this plane.

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 Note other shape check on the table below

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NB
On determining the shape/geometry of molecule the Lewis structure must be drawn first. This
will enable you to know the central atom better.
Example
Predict the shape of the following molecule SF4
Solution
The Lewis structure of SF4

Since SF4 has four bond pairs and one lone, it is trigonal bipyramidal.
Qn
Predict the shapes of the following molecules by using the VSEPR theory
a) NH3
b) BeCl3
c) H2O
d) SiCl4
Other questions
1. Explain briefly the meaning of the following quantum numbers
i. n
ii. l
iii. ml
iv. ms
2. In a tabular form, specify the four quantum numbers for each electron in an atom whose n-
value is 2. Given all the orbitals are full of electrons.
3. Briefly explain why the following quantum numbers are not allowed
1
i. n=1, l=1, ml=0, ms=− 2
1
ii. n=1, l=0, ml=2, ms=+ 2
1
iii. n=4, l=3, ml=4, ms=+ 2
1
iv. n=0, l=-1, ml=1, ms=− 2
1
v. n=2, l=-1, ml=1, ms=− 2
4. An electromagnetic radiation was emitted in the Balmer’s series as a result of electron
transfer between 2 and 5, calculate the
i. Energy of the radiation in Kj/mol
ii. Frequency of the radiation in Hz
iii. Wavelength of the radiation in metre
5. Predict the hybridization of the following
i. PCl5

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 ii. SF6
iii. CO2
iv. BCl3
6. Arrange the following in order of increasing melting points, CO2, H2O, CO, H2 and Ar.
7. Use VSEPR theory to predict the molecular geometry of the species
i. PCl3
ii. NH3
iii. PCl5

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