CHAPTER 3

STRUCTURE OF THE ATOM AND THE PERIODIC LAW

Definition of terms:
Atom - the smallest unit of ordinary matter that forms a chemical element.
Periodic Table - a chart that organizes the chemical elements by their atomic number, electron
configuration, and chemical properties.

Objectives:
 Define the atom and its subatomic particles
 Describe the periodic law and how it is used to organize elements
 Explain the structure of the atom and how the subatomic particles interact.

About 450 BC, the Greek philosopher Democritus proposed that all matter is actually composed
of tiny, individual particles. He called these particles Atomos, from which we get the English word atom.
Unfortunately, Aristotle and other well-known Greek philosophers did not agree with Democritus' ideas
about atoms, so his ideas about atoms were rejected.
In 1803, a modest English school teacher named John Dalton developed an atomic theory of
matter. Dalton assumed all matter is made up of tiny, indivisible particles called atoms. He imagined that
atoms were hard and round like solid spheres. However, a series of discoveries beginning in the later part
of the 19th century showed that atoms were composed of even smaller bits of matter called subatomic
particles.

Subatomic Particles

Electrons
Much of our knowledge about the structure of atoms resulted from experiments involving the
passage of electricity through different gases at low pressures. A discharge tube, or Crookes tube, was
developed by Sir Williams Crookes (1832-1919). Crookes passed an electric current through a gas-filled
glass tube with electrodes sealed into both ends. As gas was pumped out of the tube, the pressure was
reached at which the remaining gas glowed. With more pumping, the gas ceased to glow. However, close
observation revealed that the glass at one end of the tube was glowing. Crookes suggested that this glow
was produced by negative particles, which he called cathode rays, passing from the negative electrode
(cathode) and moving toward the positive electrode (anode). Those particles that missed the anode hit the
glass and made it glow.

Cathode rays were shown to have the following characteristics:

1. They travel from the cathode in straight lines, as indicated by the fact that an object placed in
their path casts a sharp shadow on the end of the tube.
2. They cause a piece of metal foil to become hot by striking it for a period of time.
3. They are deflected by magnetic and electrical fields, and the direction of the deflection is the
same as that shown by negatively charged particles passing through such field (unlike charges
attract while like charges repel).

Beginning in 1896, the English physicist Sir J.J. Thomson conducted a series of systematic studies on
cathode rays. In 1897, he measured the deflection of cathode ray particles in both a magnetic field and an
electric field. From the strengths of the field, he determined the ratio of the electrical charge e, to the
mass, m, of the cathode ray particles, (e/m is 1.76 x 108 coulomb per gram). He found e/m to be identical
for all of these particles, irrespective of the metal the electrodes were made of and the kind of gas in the
tube. Thomson concluded that a cathode ray is composed of negatively charged particles and that these
particles come from the cathode.
This meant that atoms were not indivisible balls but instead had a substructure. He named these
negatively charged particles electrons. However, he was not able to compute the mass of an electron. The
charge was measured by an American physicist. R.A. Millikan in 1909. From the values of e/m, he found
the Likewise mass of the electron to be 1/1837 that of the hydrogen atom, or 0.00055 amu. the charge of a
single electron was determined to be 1.60 x 10-19 coulomb. This quantitative observation that all
electrons are identical, regardless of their source, along with the observation that they can be liberated
from any kind of atom, proves quite conclusively that electrons are parts of all types of matter.
Electrons emitted by some metals are heated to high temperatures. This process is called thermal
emission and is the source of electrons in X-ray tubes and cathode tubes such as television picture tubes.
Electrons are also emitted from metals, most readily from active metals such as cesium, sodium, and
potassium, when they are exposed to light. This type of emission is known as the photoelectric effect and
is the basis of the electric eye, or photoelectric cell, used in some automatic door openers.

Protons
In 1886 Eugen Goldstein, a German physicist, using a Crookes tube with holes in the cathode,
observed that another kind of ray was emitted from the anode and passed through the holes in the cathode.
Three years later, Wilhelm Wien showed these rays to be positively charged particles. Their charge-to-
mass ratio was found to be much smaller than that of electrons, and it varied with the kind of gas in the
tube. Since the ratio varied, follows that either the charge on each particle was found to be least when
hydrogen was used as the gas in the discharge tube. From the values of e and e/m for the positive particles
when hydrogen was used, the value of m was calculated as 1.0073 amu. These particularly charged are
called protons.

Neutrons
The existence of the neutron, a particle with a mass close to that of the proton but with no charge,
had been postulated for more than ten years before the English physicist James Chadwick detected this
third basic unit of the atom in 1932. He showed that Otto uncharged particles (neutrons) are emitted when
atoms of beryllium (and other elements) are bombarded with high-velocity helium atoms with all
electrons removed (alpha particles). Neutrons were determined to have a mass of 1.0087 amu. They are
unstable outside of an atom and slowly disintegrate to form a proton and an electron.

The Nuclear Atom

Although the experiments described above indicated that an atom can be characterized as
assemblies of electrons, protons, and neutrons, they gave no clue as to how these particles are arranged.
Until then, scientists had accepted Thomson's so-called "plum pudding" model of an atom, named after a
popular English dessert. According to this model, negative charges are distributed evenly throughout an
atom's positively charged interior, similar to the way fruits are distributed in plum pudding. The first
insight into the architecture of atoms resulted from particle scattering experiments by Ernest Rutherford.

When Rutherford projected a beam of positively charged alpha particles from a radioactive
source onto the gold foil, he found that most of the particles passed through the foil without deflection.
However, a few were diverted from their paths, and a very few were deflected back toward their source.
From the results of a series of such experiments, Rutherford concluded that (1) the volume occupied by
an atom must be largely empty space because most of the alpha particles passed through the foil
undeflected and (2) the atom must contain a heavy, positively charged body (the nucleus) because of the
abrupt change in path of some of the alpha particles as they hit this nucleus.

The atom then, was presumed to consist of a very small, positively charged nucleus, in which
most of the mass of the atom is concentrated, surrounded by the electrons necessary to produce an
electrically neutral atom. Rutherford's nuclear theory of the atom, proposed in 1911, is the model we still
use today. Rutherford determined the diameter of the nucleus to be at least 100,000 times smaller than the
diameter of the atom. The diameter of an atom is of the order of 108 cm. Thus a nucleus is almost
unbelievably small. If the nucleus of an atom were as large as the period at the end of this sentence, the
atom would have a diameter of about 40 yards.

From this same series of experiments, Rutherford found that, for many of the lighter elements, the
number of positive charges in the nucleus (the number of protons in the nucleus) is approximately equal
to half of the atomic mass of the elements. In 1914 another English physicist, Henry Moseley, reported a
method for determining the number of protons in the nucleus of any atom, and hence the number of
positive charges in the nucleus. This is the atomic number of the atom. The atom contains the same
number of protons as electrons, thus the atomic number represents the number of electrons for a neutral
atom as well.
Moseley measured the X-rays produced by the elements in a modern X-ray tube which is a
modified cathode-ray tube in which electrons are produced by thermal emission from a filament heated by
an electric current. When a solid target is placed in the beam of electrons, very penetrating rays, called X-
rays, are produced by the elements in the target. This fact was used to determine the atomic numbers of
the heavier elements. We know that the nuclei of atoms contain both protons and neutrons (except for the
nucleus of the common hydrogen atoms, which contain only a proton). For a given element, the number
of protons does not vary, but the number of neutrons may vary within a limited range. Atoms with the
same atomic number but different numbers of Isotopes are identified with the atomic number as neutrons
are called isotopes. subscript and the mass number (the sum of the number of protons and neutrons) as
superscript to the left of the symbol for the element. The naturally occurring isotopes of magnesium
would be indicated as 12 24Mg, 1225Mg, and 1226Mg.

When an atom loses or gains one or more electrons, it acquires a net electrical charge and is called an ion.
The net charge of an ion is found by :

Charge of ion = number of protons - number of electrons

Sample Problem:

1. Determine the number of electrons, protons, and neutrons in each of the following isotopes of
chlorine:

a. 35
17
36 37
Cl 17Cl 17Cl

2. A neutral magnesium atom has 12 protons and 12 electrons. If the atoms loses 2 electrons, it
becomes an ion with a charge of 2+

The Bohr Model of the Atom

Rutherford's nuclear model of the atom, with its very small massive nucleus surrounded by
lightweight electrons, accounted for the properties of the atom as revealed by the discharge-tube
experiments of Crookes and others, by the alpha particle scattering experiments, and by the 'varying mass
of the elements due to the presence of isotopes. However, one serious problem remained. According to
the physical principles known at the time, such an atom should not be stable. Since there is an attractive
force electrons would be expected to fall into the nucleus. If it were assumed that the electrons would
counterbalance the force of ‘attraction, the electrons would stay in their orbits would radiate energy
continuously, since this would mean that it was continuously losing energy, it should move in smaller and
smaller orbits and finally fall into the nucleus.
In 1913 Neils Bohr, a Danish scientist, proposed a solution to the problem by suggesting a new
theory for the behavior of matter. He proposed that the energy of an electron in an atom cannot vary
continuously, but is quantized; that is; it is restricted to discrete or individual values. The success of this
theory in explaining the spectra of the hydrogen atom and of hydrogen-like ions, which contain only one
electron moving about a nucleus, led to its general acceptance.
The Bohr model of a hydrogen atom or a hydrogen-like ion assumed that the single electron
moved about the nucleus in a circular orbit and that the centrifugal force due to this motion
counterbalanced the electrostatic attraction between the nucleus and the electron. The energy of the
electron was assumed to be restricted to certain values, each of which corresponds to an orbit with a
different radius. Each of these orbits could be characterized by an integer, n. Bohr showed that the energy
of an electron in one of these orbits is given by the equation E=-kZ2/n2.

The Quantum Mechanical Model of the Atom

The Bohr model cannot satisfactorily explain the behavior of chemical bonding of an atom or ion,
thus the Bohr model has been supplanted by more mathematical theories of quantum mechanics.

The quantum mechanical model of the hydrogen atom consists of one proton (as a nucleus) and
one electron moving about the proton. Larger atoms have several electrons moving about a positive
nucleus. Although the electrons are known to move about the nucleus, the exact path they take cannot be
determined. The German physicist Werner Heisenberg expressed this in a form that has come to be
known as Heisenberg's uncertainly principle: it is impossible to determine accurately both the momentum
and the position of a small particle simultaneously.

The more accurately we measure the momentum of a moving electron, the less accurately we can
determine its position. Accurately determining the position of an electron will alter its momentum, and an
experiment designed to measure the exact momentum of an electron will unavoidably change its position.
If position and momentum are measured at the same time, the values are inexact for one or the other or
both. Although we cannot pinpoint an electron's position or path, we can calculate the probability of
finding an electron at a given location within an atom. In spite of the limitations described by the
uncertainty principle, the behavior of electrons can be determined in a useful way, using the mathematical
tools of quantum mechanics. Both the energy of an electron in an atom and the region of space in which it
may be found can be determined.

The results of a quantum mechanical treatment of the problem developed by an Austrian

physicist, Erwin Schrodinger, show that the electron may be visualized as being in rapid motion within
one of several regions of space located around the nucleus. Each of these regions is called an orbital, or
atomic orbital. Although the electron may be located anywhere within an orbital at any instant in time, it
spends most of its time in certain high-probability regions.

For example, in an isolated hydrogen atom in its ground state, the single electron effectively
occupies all the space. Within this spherical orbital, the electron has the greatest probability of being at a
distance of 0.529 A from the nucleus. Note that an orbit and a quantum mechanical orbital are very
different. An orbit is a circular path: an orbital is a three-dimensional region of space. Some chemists
describe the occupancy of an orbital in terms of electron density.
The electron density is relatively high in those regions where the probability of finding an
electron is high, and low in those regions of the orbital where the probability is low. Each electron in an
atom can be described by a mathematical expression called a wave function. The general results of the
quantum mechanical model of the atom may be summarized as follows:

1. The location of an electron cannot be determined exactly. All that can be identified is the region
or volume of space where there is a relatively high probability of finding the electron - that is, the
orbital occupied by the electron.
2. Orbitals are characterized by n, the principal quantum number, which may take on any integral
value; n= 1,2,3,4,5... as n increases, the orbitals extend farther from the nucleus, and the average
position of an electron in these orbitals is farther from the nucleus. The energies of the orbitals
increase as the value of n increases.

For values of n greater than 1, there are several different orbitals with the same value of n. A shell
contains orbitals with the same value of n, Shells may be identified by either the values of n or the letters
K, L, M, N, O,... respectively (for example, an n=2 shell may be called an L shell).

3. Orbitals with the same value of n may have different shapes. The different shapes of orbitals are
distinguished by a second quantum number, I, called the azimuthal, or subsidiary quantum
number. In atoms with two or more electrons, electrons with different I values will have different
energies. An electron with 1=0 occupies a spherical orbital. Such an orbital is called an s orbital
and the electron occupying it is an 's electron. An electron with 1=1 occupies a dumbbell-shaped
region of space and is called a p electron; a d electron, with 1=2, occupies a volume of space
usually drawn with four lobes, and an f electron, with 1=3, occupies a rather complex - looking
volume of space usually shown with eight lobes. Letters corresponding to the values continue
alphabetically following f. Although I value higher than 3 is possible, electrons greater than 3 are
not found unless they have been excited by the absorption of energy by an atom.

L 0 1 2 3 4 5 6
Letter designation s p d f g h i

In an atom with two or more electrons, the energies of electrons in the orbitals within a given
shell increase in the following order: s electrons < p electrons < d electrons< f electrons.

The mathematical expression of quantum mechanics tells us that there are limits on the values
that ı can have: an electron for which the principal quantum number has a value of n may have an
integral value ranging from 0 to (n-1). These limits have been verified experimentally from the spectra of
atoms. Thus an electron in a K shell, for which n = 1, can only have an [value of zero. An electron in a
shell with n=3 can have an [value of zero (an s electron), an [value of I (a p electron), or an [value of 2 ( a
d electron), but cannot have an f value higher than 2.
4. For [values larger than zero, orbitals with the same value of fin in any given shell have the same
shape and the same energy but differ in their orientation. Each orientation is characterized by a
third quantum number, m, the magnetic quantum number, which may have any integral value
from - 1 through zero to +1.
5. Electrons have a fourth quantum number, s, the spin quantum number. Electrons behave as if
each were spinning about its own axis. The spin quantum number specifies the direction of spin
of an electron about its own axis. The spin can be either counterclockwise or clockwise and is
designated arbitrarily by either s=+ ½ or s 1/2. Electrons with the same spin quantum number are
 said to have parallel spins. For every possible combination of n, 1, and m, there can be two
electrons differing only in the direction of spin about their own axes. Each orbital can contain a
maximum of two electrons that have identical n, 1, and m, values but differ in their s values.
6. The energy of electrons in an atom is limited to discrete values. Mathematics in the quantum
mechanical model is far more complicated than in the Bohr model, but the energy can be
determined from the wave function that describes the behavior of the electron.
7. The maximum number of electrons that may be found in a shell with the principal quantum
number, n, is 2n².

As the principal quantum number, n, increases the energies of atomic orbitals also increase. The
orbital with electrons of lowest energy is the Is orbital, followed by the 2s orbital, and so on. As electrons
fill higher orbitals their energies overlap. The electron configuration of the atom shows the arrangement
of electrons in the orbitals. This is described by a number that designates the main shell, a letter that
designates the subshell, and a superscript that designates the number of electrons in that subshell. For
example, the notation 3p5 (three-p-five) indicates that five electrons are in the p subshell of the third main
shell. The electron configuration of nitrogen (the atomic number is seven) is 1s² 2s² 3p³. For Rotor larger
atoms the electron configurations are abbreviated. For example, the electron configuration of chlorine, Cl,
is abbreviated to [Ne] 3s² 3p5. The symbol [Ne] represents the configuration of Ne (neon), 1s² 2s²2p6.

According to the Pauli exclusion principle, no two electrons in the same atom can have the same set
of four quantum numbers. The maximum number of electrons in an orbital is limited to two. Thus, a 1s
orbital is filled when it contains two electrons: one with n=1, 1-0, m=0, and s=-1/2; the other with n=1,
1=0, m=0, and s= +1/2.
Subshells containing more than one orbital are filled following Hund's rule: every orbital in a subshell
is singly occupied or filled before an orbital is doubly filled and all electrons in a singly filled orbitals
have the same spin. For example, a 3p³ electron configuration has one unpaired electron each in the three
different p orbitals.
To show the systematic variations in the electronic structure of elements, chemists build them in
atomic order. Starting with hydrogen one proton is added at a time to the nucleus and one electron to the
proper subshell until the electron configuration of all elements is described. This process of building up is
called Aufbau principle after the German word Aufbau meaning building up. Subshells of lower energy
are filled to capacity first before electrons can enter the higher-energy subshell.