Chem U 2 G 11
Chem U 2 G 11
Chem U 2 G 11
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 .
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.
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.
This ratio has a value of – 5.686 × 10–12kg C–1(kilograms per coulomb).
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 as e = –1.602 × 10–19 C.
From this value and the value for me /e, we can calculate the mass of an electron.
In 1923, Millikan was awarded the Nobel Prize in physics for his oil-drop experiment.
2.3.2 Radioactivity and Discovery of Nucleus
Radioactivity
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,
Frequency (, 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 .............................(2.1)
In vacuum, light travels at a speed of 2.99792458 × 108 m s–1 (3.00 × 108 m s–1to 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 …………………...(2.2)
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.
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 2.6).
The electromagnetic waves inthe different spectral region travel at the same speed but
differ in frequency andwavelength.
The long wavelength, low-frequency portion of the spectrum comprises the
microwaveand radio wave regions.
The infrared (IR) region overlaps the microwave region onone end and the visible region
on the other.
We perceive different wave lengths (or frequencies) of visible light as differentcolours,
from red (λ = 750 nm) to violet (λ = 400 nm).
Light of a single wavelengthis called monochromatic (Greek “one colour”), whereas
light of many wavelengths ispolychromatic (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 andgamma ray (γ-ray)
regions.
Thus, a TV signal, Infrared (IR) light, and a gamma ray emitted by a radioactiveelement
differ principally in frequency and wavelength.
2.5.2 The Quantum Theory and Photon
The quantum theory is concerned with the rules that govern the gain or loss of
energyfrom an object.
In 1900, the German physicist Max Planck came to an entirely newview of matter and
energy. He proposed that a hot glowing object could emit(or absorb) only certain
amounts of energy.E = nhv
where E 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)
The essence of Planck’s quantum theory is that there is such a thing as a smallest
allowable gain or loss of energy.
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.
Planckassumed that the amount of energy gained or lost at the atomic level by the
absorptionor emission of radiation had to be a whole-number multiple of a constant,
times thefrequency of the radiant energy.
ΔE = hv, 2hv, 3hv, ...(2.3) where Δ nE is the amount of energy gained or
lost. The smallest increment of energy ata given frequency, hv is the quantum of
energy.
2.5.4 The Bohr Model 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.
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.
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
The Bohr radius, denoted by ao (ao = 0.0529 nm) can be calculated using the formula
r
ao = where n is a positive integer which is called quantum number.
n2
r is the radius of the orbit and is given by:
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.
When the electron is in the orbit closest to the nucleus (n = 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:
∆E = Ee – Eg...(2.10) 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.
Since a larger orbit radius means a higher atomic energy level, the farther the electron
drops, the greater is the energy (higher v, 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 state (ni) to the final state (nf) becomes smaller and smaller as the
distance from the nucleus increases.
A very useful result from Bohr’s work is an equation for calculating the energy levels of
an atom,
2.5.5 Limitations of the Bohr Theory
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.
Exercise 2.6
Higher level s-orbitals (3s, 4s, ...) have similar overall shapes, that is, spherical symmetry.
The second principal energy level (n = 2) consists of four different orbitals. One having l = 0,
is the 2s orbital just described. The other three orbitals of the n = 2 level have l = 1. They are
described by dumb bell-shaped regions (Figure 2.10).
Higher - level p-orbitals (that is 3p, 4p, ...) have similar overall shapes.
The third principal energy level (n = 3) is divided in to three sublevels: one 3s orbital, three
3p orbitals, and five 3d orbitals.
The d orbitals are much more complex in shape than p orbitals.
The actual values are 124, 124, and 125 pm, respectively, for Fe, Co and Ni.
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.
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.
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 which occur at Groups IIIA and VIA in period 2
(at B and at O) and in period 3 (at Al and at S).
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.
For the representative elements, removing a core electron requires much
more energy compared to removing a valence electron.
Exercise 2.11
Electron Affinity (EA)
The corresponding atomic property for the formation of a gaseous negative ion
is electron affinity, the energy change that occurs when an electron is added to a
gaseous atom or ion.
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 smaller the atom the closer an added electron can approach the atomic
nucleus and the more strongly it is attracted to the nucleus.
In these cases a stable anion for group IIA and VIIIA does not form.
We can write a separate electron affinity for each step. For oxygen atom, it can
be written as:
O(g) + e– → O– (g); EA1 = –141 kJ mol–1
O–(g) + 1e– → O2–(g); EA2 = +744 kJ mol–1
Electronegativity
On an electronegativity 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.
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Within a group, electronegativity decreases from top to bottom.
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.
Down a group, the metallic character increases, due to the lesser attraction from
the nucleus to the valence electrons.
2.8. 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.