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Structure of an Atom
The atomic theory of matter was first proposed on a firm scientific basis by John Dalton in 1808.
His theory, called Dalton’s atomic theory, regarded the atom as the ultimate particle of matter.

Dalton's Atomic Theory (1808)

- Matter is composed of indivisible particles - atoms.
- An element is composed of only one kind of atom. These atoms in a particular element
have the same properties such as mass, size, or even shape.
- A compound is composed of two or more elements combined in fixed ratios or
proportions.
- In a chemical reaction, the atoms in the reactants recombine, resulting in products which
represent the combination of atoms present in the reactants. In the process, atoms are
neither created, nor destroyed. So a chemical reaction is essentially a rearrangement of
atoms.

Ramifications of Dalton’s Theory:

- The Law of Conservation of Mass states that mass is neither created nor destroyed in a
chemical reaction or physical change.
- The Law of Definite Proportions states that every chemical compound is made up of
elements in a definite ratio by mass.

Experimental observations made by scientists towards the end of nineteenth and beginning of
twentieth century established that atoms can be further divided into subatomic particles, i.e.,
electrons, protons and neutrons - a concept very different from that of Dalton. The major
problems before the scientists at that time were:
- To account for the stability of atom after the discovery of sub-atomic particles,
- To compare the behaviour of one element from other in terms of both physical and
chemical properties,
- To explain the formation of different molecules by the combination of different atoms,
- To understand the origin and nature of the characteristics of electromagnetic radiation
absorbed or emitted by atoms.

SUB-ATOMIC PARTICLES
Dalton’s atomic theory failed to explain the results of many experiments e.g. substances like
glass or ebonite when rubbed with silk or fur generate electricity.

Discovery of Electron
In mid 1850s, Faraday began to study electrical discharge in partially evacuated cathode ray
discharge glass tube containing two thin electrodes (Fig. 1). The pressure of different gases could
be adjusted by evacuation. When sufficiently high voltage was applied across the electrodes,
current started flowing through a stream of particles moving in the tube from the cathode to the
anode. These were called cathode rays or particles. The flow of current was further confirmed by
making a hole in the anode and coating the tube behind anode with phosphorescent material zinc
sulphide (ZnS). When the rays struck the ZnS coating, a bright spot was developed (same thing
happens in a television set) [Fig. 1(b)].
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The results of these experiments are summarized below:

i. The cathode rays start from cathode and move towards the anode.
ii. These rays themselves are invisible but can be observed with the help of certain kind of
materials (fluorescent or phosphorescent) which glow when hit by them.
iii. In the absence of electrical or magnetic field, these rays travel in straight lines (Fig. 2).

iv. In the presence of electrical or magnetic field, the cathode rays behave like negatively
charged particles, implying that cathode rays are negatively charged particles, electrons.
v. The behaviour of cathode rays (electrons) is independent of the material of electrodes and
the nature of the gas in the cathode ray tube. Thus, we can conclude that electrons are
basic constituent of all the atoms.
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Charge to Mass Ratio of Electron

In 1897, British physicist J.J. Thomson measured the ratio of electrical charge (e) to the mass of
electron (me) by using cathode ray tube and applying electrical and magnetic field perpendicular
to each other as well as to the path of electrons (Fig. 2). Thomson argued that the deviation of
the rays from their path in the presence of electrical or magnetic field depends upon:
i. The magnitude of the negative – the greater the magnitude of the charge on the particle,
the greater is the interaction with the field and thus greater deflection.
ii. The mass of the particle – lighter the particle, greater the deflection.
iii. The strength of the field – the deflection of electrons from its original path increases with
the increase in the voltage across the electrodes, or the strength of the magnetic field.

 When only electric field is applied, the electrons hit the cathode ray tube at point A.
 When only magnetic field is applied, electron strikes the cathode ray tube at point C.
 Carefully balancing of the field strengths brings back the electron to hit the screen at point B.
 Thomson was able to determine the value of e/m by accurate measurements on the amount of
deflections observed by the electrons on the electric or magnetic field strength,

Where m is mass of the electron in kg and e is the magnitude of the charge on the electron in
coulomb (C).

Charge on the Electron

R.A. Millikan (1868-1953) devised a method known as oil drop experiment (1906-14), to
determine the charge on the electrons. He found the charge on the electron to be – 1.6 x 10-19 C.
The present accepted value of electrical charge is – 1.6022 x 10-19 C. The mass of the electron
(me) was determined by combining these results with Thomson’s value of e/me ratio.

Millikan’s Oil Drop Method

Oil droplets in the form of mist, produced by the atomizer, were allowed to enter through a tiny
hole in the upper plate of electrical condenser and their motion viewed through a telescope. The
air inside the chamber was ionized by passing a beam of X-rays through it. The electrical charge
on these oil droplets was acquired by collisions with gaseous ions. The fall of these charged oil
droplets can be retarded, accelerated or made stationary depending on the charge of the droplets
and the polarity and strength of the voltage applied to the plate. From the rate of fall of the
droplets, Millikan was able to measure the mass of oil droplets. By carefully measuring the
effects of electrical field strength on the motion of oil droplets, Millikan concluded that the
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magnitude of electrical charge, q, on the droplets is always an integral multiple of the electrical
charge, e, that is, q = n e, where n = 1, 2, 3….

Discovery of Protons and Neutrons

Electrical discharge carried out in the modified cathode ray tube led to the discovery of particles
carrying positive charge, also known as canal rays. The characteristics of these positively
charged particles are listed below.
- The positively charged particles depend on the nature of gas used in the cathode ray tube.
- The charge to mass ratio of the particles depends on the gas from which these originate.
- Some of these particles carry a multiple of the fundamental unit of electrical charge.
- Their behaviour in magnetic or electrical field is opposite to that observed for electrons.

The smallest and lightest positive ion was obtained from hydrogen and was called proton,
characterized in 1919. Later, Chadwick (1932) discovered the presence electrically neutral
particles by bombarding a thin sheet of beryllium by α-particles, where electrically neutral
particles (neutrons) having a mass slightly greater than that of the protons were emitted. The
important properties of these fundamental particles are given below.

A BS O L UT E RE L A T I V E A P P RO X .
N A M E S Y M BO L MASS/KG MASS/U
C HA RG E / C C HA RG E MASS/U
Electron e -1.6022×10-19 -1 9.10939×10-31 0.000554 0

Proton p +1.6022×10-19 +1 1.67262×10-27 1.00727 1

Neutron n 0 0 1.67493×10-27 1.00867 1

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ATOMIC MODELS
The first atomic theory by John Dalton in 1808 regarded atom as the ultimate indivisible particle
of matter. Towards the end of the nineteenth century, it was proved experimentally that atoms
are divisible and consist of three fundamental particles: electrons, protons and neutrons. The
discovery of sub-atomic particles led to the proposal of various atomic models to explain the
structure of atom.

Thomson in 1898 proposed that an atom consists of uniform sphere of positive electricity with
electrons embedded into it. This model considered the mass of the atom to be evenly spread over
the atom but was proved wrong by Rutherford’s famous alpha-particle scattering experiment.

Rutherford’s scattering experiment (1909) led to the conclusion that atom is made of a tiny
positively charged nucleus, at its centre with electrons revolving around it in circular orbits.
Rutherford model, which resembles the solar system, was no doubt an improvement over
Thomson model but it could not account for the stability of the atom i.e., why the electron does
not fall into the nucleus.

Fig. 5: Rutherford’s scattering experiment. When a beam of alpha particles is “shot” at a thin
gold film, most of them pass through without effect. Some are, however deflected.
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Rutherford was also silent about the electronic structure of atoms i.e., about the distribution and
relative energies of electrons around the nucleus. The difficulties of the Rutherford model were
overcome by Niels Bohr in his model of the hydrogen atom.

Niels Bohr (1913) postulated that electron moves around the nucleus in circular orbits. Only
certain orbits can exist and each orbit corresponds to a specific energy. He calculated the energy
of electron in various orbits and for each orbit predicted the distance between the electron and
nucleus. Bohr model, though offering a satisfactory model for explaining the spectra of the
hydrogen atom, could not explain the spectra of multi-electron atoms. This is because he
regarded an electron as a charged particle moving in a well defined circular orbit about the
nucleus. He ignored the wave character of the electron.

An orbit is a clearly defined path and this path can completely be defined only if both the exact
position and the exact velocity of the electron at the same time are known. This is not possible
according to the Heisenberg uncertainty principle. Bohr model of the hydrogen atom, therefore,
not only ignores the dual behaviour of electron but also contradicts Heisenberg uncertainty
principle.

The Heisenberg Uncertainty Principle (1927) by Werner Heisenberg (1901–1976): It is

impossible to determine accurately both the momentum and the position of an electron (or any
other very small particle) simultaneously.

Erwin Schrödinger (1926) proposed an equation called Schrödinger equation to describe the
electron distributions in space and the allowed energy levels in atoms. This equation incorporates
de Broglies concept of wave-particle duality and is consistent with Heisenberg uncertainty
principle. When Schrödinger equation is solved for the electron in a hydrogen atom, the solution
gives the possible energy states the electron can occupy [and the corresponding wave function(s)
(ψ) (which are the mathematical functions) of the electron associated with each energy state].

Wave nature for electron: De Broglie (1925) proposed that not only does light have the dual
properties of waves and particles, but also particles of matter have properties of waves. The
wavelength of those particle waves is given by:

λ = h/ mv

where m and v are the mass and velocity of the particle. Planck’s constant, h, is so small that the
wavelengths are in an observable range only for particles of atomic or subatomic mass.
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Basic ideas of quantum mechanics:

- Atoms and molecules can exist only in certain energy states. In each energy state, the
atom or molecule has a definite energy. When an atom or molecule changes its energy
state, it must emit or absorb just enough energy to bring it to the new energy state (the
quantum condition).
- When atoms or molecules emit or absorb radiation (light), they change their energies.
The energy change in the atom or molecule is related to the frequency or wavelength of
the light emitted or absorbed by the equations:

- The allowed energy states of atoms and molecules can be described by sets of numbers
called quantum numbers.
- The mathematical approach of quantum mechanics involves treating the electron in an
atom as a standing wave.

Orbitals:
- A solution to the Schrödinger equation for an electron must satisfy three quantum
conditions corresponding to the three dimensions of space.
- Each quantum condition introduces an integer, called a quantum number, into the
solution.
- A separate solution, describing a probability distribution of finding the electron at various
locations, exists for each allowed set of three quantum numbers.
- Such a solution is called an orbital.
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Quantum number:
- Principal quantum number (n) denotes the energy level of electrons. The larger the
principal quantum number is, the larger the energy.
- The orbital size depends on n. This means that the larger the n value, the larger the
orbital. Orbitals with the same n belong to the same shell.

- Angular momentum quantum number (l) denotes the shape of the orbital. The values
range from 0 to n – 1.
- The angular momentum quantum numbers correspond to different subshells.

- Magnetic quantum number (ml) defines the different spatial orientations of the orbitals.
The values range from –l to +l.
- There are three p orbitals corresponding to ml = 1, 0, and −1. However, it is usually more
convenient in chemistry to use a new set of three orbitals oriented along the x, y, and z
axes to display the shapes and directions of these orbitals.
- Further, there are 5 d orbitals and 7 f orbitals having different shapes and orientations in
space.
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- Spin quantum number (mS) has to do with the spin orientations of an electron. The two
possible spins are denoted by the spin quantum numbers + ½ and - ½.

- The values of n, l, and ml describe a particular atomic orbital. Each atomic orbital can
accommodate no more than two electrons, one with mS = +½ and another with mS = -½.
- A set of quantum numbers: (n, l, ml, ms).

Permissible Values of the Quantum Numbers

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In an atom, many such orbitals are possible and electrons are filled in those orbitals in order of
increasing energy in accordance with Pauli exclusion principle (no two electrons in an atom can
have the same set of four quantum numbers) and Hund’s rule of maximum multiplicity (pairing
of electrons in the orbitals belonging to the same subshell does not take place until each orbital
belonging to that subshell has got one electron each, i.e., is singly occupied). This forms the
basis of the electronic structure of atoms.

In excited state the energies of 2s and 2p come further close and hence the four electrons (all in
2s and 2p) divide themselves between four orbitals. Thus covalency of carbon is four.

Electron configurations by the Aufbau Principle

- No two electrons in an atom may have identical sets of four quantum numbers (Pauli
exclusion principle).
- Orbitals are filled in the order of increasing energy (Klechkowski´s rule).
- Electrons occupy all the orbitals of a given subshell singly before pairing begins. These
unpaired electrons have parallel spins (Hund´s rule).
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Example:
Iron has atomic number 26. Electronic configuration according to Aufbau principle will be: 1s2,
2s2, 2p6, 3s2, 3p6, 4s2, 3d6.
But empty (p0 d0), half filled (p3 d5) and completely filled (p6 d10) orbitals of a sub shell provide
symmetry and are more stable as compared to other arrangements. Thus, the other stable
configuration for iron will be: 1s2, 2s2, 2p6, 3s2, 3p6, 4s2, 3d5, 4p1.

Deviations from Aufbau Principle:

The deviations from regularity may occur due to one of the following reasons:
a) half filled and completely filled orbitals are more stable than partially filled orbitals,
b) diamagnetic nature of atom,
c) to explain the observed properties of elements like lanthanides and actinides.

Electron configurations
Two general rules help us to predict electron configurations:
- Electrons are assigned to orbitals in order of increasing value of (n + l).
- For subshells with the same value of (n+l), electrons are assigned first to the subshell
with lower n.

1s < 2s < 2p <3s < 3p<4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d...

Degenerate orbitals – The orbitals having equal energy are called degenerate orbitals. So p has
three equivalent energy orbitals or three fold degeneracy, d orbital has 5 fold degeneracy and f
has seven fold degeneracy. While filling the orbitals, no differentiation is made between three p,
five d or seven f levels.
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Electromagnetic spectrum
Visible light, infrared radiation, microwaves, radio waves, ultraviolet, x-rays and gamma rays are
all types of electromagnetic radiation.

Wave character of light

- The distance between two waves, usually measured from the peak of the waves, is the
wavelength, given the symbol lambda, λ.
- The frequency is a statement of the number of waves passing a point in space per second;
it is given the symbol nu, ν. (The hertz is commonly used as the unit for frequency; 1 Hz
= 1 s−1)
- The product of the wavelength and the frequency is equal to the velocity of light, usually
designated by c:
c = λν
(The value of c can be rounded to c=2.998 × 108 m/s for most calculations.)
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Particle character of light

- The energy of light is emitted, absorbed, or converted to other forms of energy in
individual units referred to as quanta (singular: quantum).
- The unit of light energy is often referred to as the particle of light called the photon.
- The energy of a photon is proportional to the frequency:
ε = hν = (6.626 × 10−34 J · s)ν
Planck’s constant, h, is the universal proportionality constant.

Atomic spectra
- In the late 19th century, Johann Balmer (1825–1898) and Johannes Rydberg (1854–1919)
showed that the wavelengths of the various lines in the hydrogen spectrum can be related
by a mathematical equation:

- Here R is 1.097 x 107 m-1 and is known as the Rydberg constant. The n’s are positive
integers, and n1 is smaller than n2.

Bohr's Model of Hydrogen Atom (1913)

The radius is given by r= n2a0
a0 =5.292 x 10-11 m = 0.5292 Å (Bohr radius)
The potential energy is given by:

where h Planck’s constant, m the mass of the electron.

Each line in the emission spectrum represents the difference

in energies between two allowed energy levels for the electron.

(Comparing this to the Balmer-Rydberg equation)

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Example:
The figure shows the line spectra and the electron transitions of the hydrogen atom with its
characteristic three spectral series, Lyman, Balmer and Paschen. Calculate the wavelength (in
nm) of spectral line associated with the n = 6 to n = 3 electron transition in a hydrogen atom.

Solution:
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The Periodic Table

- The properties of elements are periodic functions of their atomic numbers
- The vertical columns of elements represented in the periodic table are called groups, and
the horizontal rows are called periods.
- There are seven periods in the periodic table. The groups are usually designated by roman
numerals followed by the letter A or B as shown in the periodic table.

- The groups IA through VIIA are called the representative elements. These elements have
either s or p orbital valence electrons. The last group in the periodic table is the noble gas
group otherwise known as the zero group.
- The groups ranging from IB through VIIIB are called transition metals, and finally the
metals from lanthanum through hafnium and metals from actinium onward are called the
inner transition metals.
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Period 1

Period 2

Period 3
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Period 4

Periodicity of Atomic Properties

As principal quantum number n increases, atomic orbitals become larger and less stable. As
atomic number Z increases, any given atomic orbital becomes smaller and more stable.
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Atomic size

Exercise: Arrange the following elements in terms of increasing atomic radius: Mg, Cl, K and
Cs.

Ionization energy (IE) is the minimum amount of energy required to remove an electron from
an atom.
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First IE < Second IE < Third IE < Fourth IE < ...

Electron affinity is the energy change associated with the addition of an electron to a gaseous
atom.
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Electronegativity
The relative tendency of an atom to attract the bonding electrons to itself is called
electronegativity. The popularly used electronegativity scale is based on a system called
Pauling's scale, according to which fluorine (the most electronegative element) has an
electronegativity value of 4.0. Nonmetals are the most electronegative elements.
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Electronegativity Values of the Elements:

Atomic Number and Mass Number

The presence of positive charge on the nucleus is due to the protons in the nucleus. The number
of protons present in the nucleus is equal to atomic number (Z). For example, the number of
protons in the hydrogen nucleus is 1, in sodium atom it is 11. In order to keep the electrical
neutrality, the number of electrons in an atom is equal to the number of protons (atomic number,
Z). For example, number of electrons in hydrogen atom and sodium atom are 1 and 11
respectively.

(Z) = number of protons in the nucleus = number of electrons in a nuetral atom

Mass number (A) = number of protons (Z) + number of neutrons (n)
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Atomic mass unit (amu)

Atomic mass unit (amu) is defined as exactly 1/12 the mass of a 12C atom. The mass of the 12C
atom is taken to be exactly 12 amu.

Isobars and Isotopes

- Isobars: atoms with same mass number but different atomic number e.g., and .
- Isotopes: atoms with identical atomic number but different atomic mass number. For
example, considering of hydrogen atom again, 99.985% of hydrogen atoms contain only
one proton. This isotope is called protium ( ). Rest of the percentage of hydrogen atom
contains two other isotopes; deuterium ( , 0.015%) and tritium ( ).
- The atomic mass of an element is the weighted average of the masses of the individual
isotopes of the element.
Example: Naturally occurring copper consists of 69.17% 63Cu and 30.83% 65Cu. The
mass of 63Cu is 62.939598 amu, and the mass of 65Cu is 64.927793 amu. What is the
atomic mass of copper?

Chemical properties of atoms are controlled by the number of electrons, which are
determined by the number of protons in the nucleus. Therefore, all the isotopes of a given
element show same chemical behaviour.