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In 1808, John Dalton published A New System of Chemical Philosophy, in which he proposed that;
…the ultimate particles of all homogeneous bodies are perfectly alike in weight, figure, etc.
and that atoms combine in simple numerical ratios to form compounds. The terminology he used has since
been modified, but he clearly presented the concepts of atoms and molecules, and made quantitative
observations of the masses and volumes of substances as they combined to form new substances. Only a
few years later, Avogadro used data from Gay-Lussac to argue that equal volumes of gas at equal
temperatures and pressures contain the same number of molecules. In the 1850s, Cannizzaro argued that
everyone should use the same set of atomic weights rather than the many different sets then being used. His
proposal was eventually accepted, and a consistent set of atomic weights and formulas evolved. In 1869,
Mendeleev and Meyer independently proposed periodic tables nearly like those used today, and from that
time the development of atomic theory progressed rapidly.

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Mendeleev and Meyer organized the elements in order of atomic weight and then identified groups of elements
with similar properties. The discovery of additional elements not known in Mendeleev’s time and the synthesis
of heavy elements have led to the modern periodic table. In the modern periodic table, a horizontal row of
elements is called a period and a vertical column is a group. The traditional designations of groups in the
United States differ from those used in Europe. The International Union of Pure and Applied Chemistry (IUPAC)
has recommended that the groups be numbered 1 through 18.

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During the 50 years after the periodic tables of Mendeleev and Meyer were proposed, experimental advances
came rapidly. Some of these discoveries are listed below.

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Parallel discoveries in atomic spectra showed that each element emits light of specific energies when excited
by an electric discharge or heat. In 1885, Balmer showed that the energies of visible light emitted by the
hydrogen atom are given by the equation

where

and the energy of the light emitted is related to the wavelength, frequency, and wavenumber of the light as
given by the equation

where

In addition to emission of visible light, as described by the Balmer equation, infrared and ultraviolet emissions
were also discovered in the spectrum of the hydrogen atom. The energies of these emissions could be
described
E = RH(1/nl2-1/nh2) (l for lower level, h for higher level)
These quantities, n, are called quantum numbers (these are the principle quantum numbers)

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The origin of this energy was unknown until Niels Bohr’s quantum theory of the atom. This theory assumed that
negatively charged electrons in atoms move in stable circular orbits around the positively charged nucleus with no
absorption or emission of energy. However, electrons may absorb light of certain specific energies and be excited
to orbits of higher energy; they may also emit light of specific energies and fall to orbits of lower energy. This
means that energy of the electron in a Hydrogen atom is quantized. The energy of the light emitted or absorbed
can be found, according to the Bohr model of the Hydrogen atom, from the equation
E = RH(1/nl2-1/nh2)
where R = 2π2μZ2e4/(4πε0)2h2
μ = reduced mass of the electron/nucleus combination:
1/μ = (1/me) + (1/mnucleus)
me = mass of electron
mnucleus = mass of the nucleus

Z = charge of the nucleus

e = electronic charge
4πε0 = permittivity of a vacuum
This equation shows that the Rydberg constant depends on the mass of the nucleus and on various fundamental
constants.

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Examples of the transitions observed for the
Hydrogen atom and the energy levels are
shown in Figure. As the electrons drop from
higher level to lower level, energy is
released in the form of electromagnetic
radiation. Conversely, if radiation of the
correct energy is absorbed by an atom,
electrons are raised from lower level to
higher level. When an electron occupies an
orbit n around the nucleus, its energy is
Balmer series
negative and it can be calculated by:
En = -2.179×10-18 J (Z2/n2)
Z = 1 for hydrogen
(n = integer that corresponds to the
energy level and Z is the atomic number)
When applied to the hydrogen atom and
other one-electron situations such as He+,
Li2+, and Be3+, Bohr’s theory worked well;
however, the theory failed when atoms with
two or more electrons were considered.

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The development of quantum theory took place in two stages. In the older theories (1900–1925), the electron
was treated as a particle, and the achievements of greatest significance to inorganic chemistry were the
interpretation of atomic spectra and assignment of electronic configurations. In more recent models, the
electron is treated as a wave (hence the name wave mechanics). The de Broglie equation, proposed in the
1920s, accounted for the electron’s wave nature. According to de Broglie, all moving particles have wave
properties described by the equaion
λ = h/mν
λ = wavelength of the particle
h = Planck constant
m = mass of the particle
ν = velocity of particle
According to the de Broglie equation, electrons have observable wave properties because of their very small
mass. Also, electrons moving in circles around the nucleus, as in Bohr’s theory, can be thought of as
standing waves. However, no longer believe that it is possible to describe the motion of an electron in an
atom so precisely. This is a consequence of another fundamental principle of modern physics, Heisenberg’s
uncertainty principle, which states that there is a relationship between the inherent uncertainties in the
location and momentum of an electron. The x component of this uncertainty is described as
∆x ∆px ≥ h/4π
∆x = uncertainty in the position of the electron
∆px = uncertainty in the momentum of the electron

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This means that we cannot treat electrons as simple particles with their motion described precisely, but we
must instead consider the wave properties of electrons, characterized by a degree of uncertainty in their
location. In other words, instead of being able to describe precise orbits of electrons, as in the Bohr theory,
we can only describe orbitals, regions that describe the probable location of electrons. The probability of
finding the electron at a particular point in space, also called the electron density, can be calculated- at least
in principle.

Diffraction of X-rays by metal foil Diffraction of electrons by metal foil

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In 1926 and 1927, Schrödinger and Heisenberg published papers on wave mechanics, descriptions of the
wave properties of electrons in atoms. Schrödinger’s differential equations are more commonly used to
introduce the theory which describe the wave properties of an electron in terms of its position, mass, total
energy, and potential energy. The equation is based on the wave function, Ψ (psi), which describes an
electron wave in space; in other words, it describes an atomic orbital. In its simplest notation, the equation is
HΨ = EΨ
H = Hamiltonian operator
E = energy of the electron
Ψ = wave function
The Hamiltonian operator includes derivatives that operate on the wave function. When the Hamiltonian is
carried out, the result is a constant (the energy) times Ψ. The operation can be performed on any wave
function describing an atomic orbital. Different orbitals have different wave functions and different values of
E. This is another way of describing quantization in that each orbital, characterized by its own function Ψ, has
a characteristic energy. In the form used for calculating energy levels, the Hamiltonian operator for one-
electron systems is

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This operator can be applied to a wave function Ψ

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 The covalent radius is one-half the distance between the nuclei of two identical atoms joined by a
single covalent bond. The ionic radius is based on the distance between the nuclei of ions joined by an
ionic bond. For metals, we define a metallic radius as one-half the distance between the nuclei of two
atoms in contact in the crystalline solid metal. Similarly in the solid sample of a noble gas the distance
between the centres of neighboring atoms is called the van der Waals radius. Atomic radius increases
from top to bottom through a group of elements. The atomic radius decreases from left to right through
a period of elements.

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 An important property related to the electron configurations of atoms and ions is their behavior in a
magnetic field. In a diamagnetic atom or ion, all electrons are paired and a diamagnetic species is
weakly repelled by a magnetic field. A paramagnetic atom or ion has unpaired electrons and these
electrons possess a magnetic moment that causes the atom or ion to be attracted to an external
magnetic field.

For example;

Na: 1s2 2s2 2p6 3s1 paramagnetic (it has one unpaired electron)

Mg: 1s2 2s2 2p6 3s2 diamagnetic (it has no unpaired electron)

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 Some metal oxides, such as Li2O, react with water to produce the metal hydroxide. These metal oxides
are called basic oxides or base anhydrides.

Li2O + H2O → 2 Li+ + 2 OH-

Some nonmetal oxides react with water to produce an acidic solution. These are acidic oxides or acid
anhydrides. SO2 reacts with water to produce H2SO3, a weak acid.

SO2 + H2O → H2SO3

Al2O3, however, can act as either an acidic or a basic oxide. Oxides with this ability are called
amphoteric.

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