CHAPTER 4

ELEMENTS AND PERIODICITY

Definition of terms:
Elements - a substance that cannot be broken down into simpler substances by chemical means.
They are the basic building blocks of matter.
Compound - a substance that is made up of two or more elements that are chemically combined.
Group - is a vertical column of elements that have similar shells of the atom.
Substances - a material with uniform composition and properties.

Objectives:
 Understand the basic concepts of elements and periodicity
 Be able to use the periodic table to predict the properties of elements
 Understand the different types of elements
 Be able to apply the concepts of elements and periodicity to solve problems in chemistry

The elements are found in various states of matter and define the independent constituents of
atoms, ions, simple substances, and compounds. Isotopes with the same atomic number belong to the
same element. When the elements are classified according to the similarity of their properties as atoms
or compounds, the periodic table of the elements emerges.
Chemistry has accomplished rapid progress in understanding the properties of all the elements.
The periodic table has played a major role in the discovery of new substances, as well as in the
classification and arrangement of our accumulated chemical knowledge. The periodic table of
elements is the greatest table in chemistry and holds the key to the development of material science.
Inorganic compounds are classified into molecular compounds and solid-state compounds according to
the types of atomic arrangements.

The Periodic Table

It became evident early in the development of chemistry that certain elements could be grouped
together by reason of their similar properties. The members of one such grouping are lithium, sodium, and
potassium. These elements all look like metals, conduct electricity well, react with chlorine, forming
white, water-soluble compounds with one chlorine atom per metal atom, and all react with water, giving
hydrogen gas and metal hydroxides with one hydroxide (OH) group per metal. If M is used to represent a
metal atom, the formulas of the chlorides and hydroxides would be MCI and MOH, respectively. A
second grouping includes calcium, strontium, and barium, which also look like metals and conduct
electricity well. However, when they react with chlorine, they give white solids that contain two chlorine
atoms per metal atom, or MC1₂.
When they react with water, they give hydrogen gas and hydroxide with two hydroxide groups
per metal atom, or M(OH)2. Halogens, such as fluorine, chlorine, bromine, and iodine Hot also exhibit
similar properties. They do not conduct electricity and are nonmetallic. They react with hydrogen to form
compounds that contain one hydrogen atom and one halogen atom: HF, HCI, HBr, and HI. When they
react with sodium, they form compounds that contain one sodium atom per halogen atom: NaF, NaCI,
NaBr, and Nal.

In 1896, Dimitri Mendeleev in Russia and Lothar Meyer in Germany, working independently,
observed that the properties of the elements are periodic functions of their atomic weights. As an
understanding of the structure of the atom and electronic o configuration developed, it became apparent
that the properties of atoms were actually periodic functions of their atomic numbers rather than their
atomic weights. The modern statement of this periodic relationship, the periodic law is: the properties of
the elements are periodic functions of their atomic numbers.

The shape of the periodic table comes in part from the periodic law. Elements that have similar
properties are aligned in vertical columns, called groups or families. The horizontal rows in the table are
called periods. The periodic table has 7 periods and 18 labeled groups.
Take a close look at the periodic tables seven periods, or horizontal rows. Notice that each period
contains more and more elements. The first period has only 2 elements: hydrogen (H) and helium (He).
The second and third periods each have 8 elements: lithium (Li) through neon (Ne) in the second period
and sodium (Na) through Argon (Ar) in the third period. The fourth and fifth periods each have 18
elements. The sixth period has 32 elements. To keep the periodic table from being too wide, 14 of the
elements in the sixth period are placed under the main part of the table, together with the 14
corresponding elements from the seventh period.
 The vertical columns called groups are numbered from I A to VIII-A. (The representative group
elements). Elements in any one group have the same number of electrons in their outermost shell: lithium
and sodium have only one, beryllium and magnesium have two, and fluorine and chlorine have seven
electrons in the valence shell (the outer shell containing the valence electrons). The similarity in chemical
properties among elements of the same group occurs because they have the same number of valence in
electrons, and the number of electrons in the valence shell of an atom determines its chemical properties.
It is the loss, gain, or sharing of valence electrons that determine how elements react.
However, there are changes in the properties of the elements in a vertical column, so the chemical
behaviors of these elements while similar are not identical. A given vertical group is often referred to as a
family of elements. For example, the elements in Group IA are called alkali metals; Grouped IIA are the
alkaline earth metals; Group VIIA are the halogens; and those in Group 8A are called the noble gases.
Other families are sometimes identified by the name of the first element in the group, This, Group IVA is
sometimes called the carbon family.

Hydrogen (H) is separated slightly from the other squares in Group IA. The reason for this
separation is that hydrogen is really not a member of the alkali metals, in fact, hydrogen is definitely a
nonmetal. Hydrogen is listed in Group IA because it has the same number of outermost electrons as the
alkali metals.

The s-, p-, d-, and f- Block Elements

The key to understanding the shape of the periodic table is to examine the element's electron
configurations. The simplest way to look at these electron configurations is to divide the periodic table
into four sections, or blocks:

1. The s-block elements - are composed of hydrogen, helium, and the elements of groups IA and
IIA. Valence electrons are in s orbitals only - group IA has one’s electron and group IIA has two
s electrons. The s block contains only two groups because an s orbital can hold a maximum of 2
electrons.
2. The p block elements - groups III A to VIII A are termed p electron groups because the p
orbitals are being filled that is, group IIIA elements have one p electron; and so on to group VIII
A elements, which have six p electrons. The p- block is 6 elements wide because p orbitals can
hold up to 6 electrons.
3. The d-block elements - this block takes up most of the middle of the table constituting the B
groups or the transition elements. As you move from left to right across this block, the elements'
electrons fill the d orbitals. A d orbital can hold up to 10 electrons, which is why the d-block is 10
elements wide. The first d orbital is the 3d orbital, which begins filling with scandium (Sc),
element number 21.
4. The f-block elements - this block is the inner transition metals. Electrons fill the f orbitals. The
first f orbital is the 4f orbital, which begins filling with elements in the sixth period. Essentially,
the f-block elements are the 28 elements that are placed below the main body of the periodic
table. It is 14 elements wide because an f sublevel can hold up to 14 electrons.

The Origin of Elements and Their Distribution

All substances in the universe are made of elements. According to the current generally accepted theory,
hydrogen and helium were generated first immediately after the Big Bang ,some 15 billion years ago.
Subsequently, after the elements below iron(Z=26) were formed by nuclear fusion in the incipient stars,
heavier elements were produced by the complicated nuclear reactions that accompanied stellar generation
and decay.
In the universe, hydrogen (77%weight) and helium (21% weight) are overwhelmingly abundant and the
other elements combined amount to only 2%. Elements are arranged below in the order of their
abundance,
1
H >4He >>16O >>12C >20Ne >28Si >27Al >24Mg >56Fe
1 2 8 6 10 14 13 12 26

The atomic number of a given element is written as a left subscript and its mass number as a left
superscript.

Discovery of elements
 The long-held belief that all materials consist of atoms was only proven recently, although
elements, such as carbon, sulfur, iron, copper, silver, gold, mercury, lead, and tin, had long been
regarded as being atom-like. Precisely what constituted an element was recognized as modern
chemistry grew through the time of alchemy, and about 25 elements were known by the end of the 18th
century. About 60 elements had been identified by the middle of the 19th century, and the periodicity
of their properties had been observed.

The element technetium (Z = 43), which was missing in the periodic table, was synthesized by
the nuclear reaction of Mo in 1937, and the last undiscovered element promethium (Z = 61) was found
in the fission products of uranium in 1947. Neptunium (Z=93), an element of atomic number larger
than uranium (Z=92), was synthesized for the first time in 1940. There are 103 named elements.
Although the existence of elements Z = 104-111 has been confirmed, they are not significant in
inorganic chemistry as they are produced in insufficient quantity.

All trans-uranium elements are radioactive, and among the elements with an atomic number
smaller than Z=92, technetium, promethium, and the elements after polonium are also radioactive. The
half-lives (refer to Section 7.2) of polonium, astatine, radon, actinium, and protactinium are very short.
Considerable amounts of technetium 99Tc are obtained from fission products. Since it is a radioactive
element, handling 99Tc is problematic, as it is for other radioactive isotopes, and their general chemistry
is much less developed than those of manganese and rhenium in the same group.

Atoms are equivalent to alphabets in languages, and all materials are made of a combination of
elements, just as sentences are written using only 26 letters.

Similarities and Differences of Elements within Groups and Periods

1. VARIATION IN COVALENT RADII.

There are several ways to define the radii la of atoms and thus determine their relative sizes. We
will use the covalent radius, which is defined as half the distance between the nuclei of two identical
atoms when they are joined by a single covalent bond. The radius is one measure of the size of an atom.
In general, from left to right across a period of the periodic table, each element has a smaller covalent
radius than that of the one preceding it can be attributed to the increasing nuclear charge across the
period, with the added electrons going into partially occupied shells. Each element in the periodic table
has one more electron and a nuclear charge that is one higher than the preceding element. Within a
period, however, the number of shells is constant. In general, within a given period, the larger nuclear
charge results in a larger force of electrostatic attraction between the nucleus and the electrons, because
the additional electrons are in the same shell. This causes a decrease in covalent radii across the period.

The covalent radii are based on interatomic distances between two identical atoms held together
by chemical bonds. Noble gases, however, do not bond this way. Thus covalent radii are not available for
the noble gases.

Proceeding down a group of the periodic table, succeeding elements have larger covalent radii as
a result of greater numbers of electron shells. The total number of shells increases down a group, and
shells with larger principal quantum numbers have larger radii. The larger size of the shells coupled with
repulsions between the increasing numbers of electrons overcome the increased nuclear attraction, so that
the atoms increase in size down a group.

2. VARIATION IN IONIC RADII.

The covalent radius of a positive ion is less than the covalent radius of its parent atom. A positive
ion forms when one or more than one electron is removed from an atom. Usually, the representative
elements form positive ions by loss of all their valence electrons. The loss of all electrons from the
outermost shell results in a smaller radius, because the remaining electrons occupy shells with smaller
principal quantum numbers (and smaller radii). In fact, even the radii of these remaining filled electron
shells decrease (relative to their size in the neutral atom), because of the decrease in the total number of
electron-electron repulsions within the atom. The decreasing repulsions give rise to a greater average
attraction of the nucleus per remaining electron, an effect spoken of as an increase in Thus the covalent
radius of a sodium atom and the effective nuclear charge. (1s²2s 2 2p6 3s2) is 1.86 A, whereas the ionic radii
of a sodium ion (1s²2s²2p6) are 0.95 Å. Proceeding down the groups of the Periodic Table, positive ions of
succeeding elements have larger radii, corresponding to greater numbers of shells.
A simple negative ion is formed by the addition of one or more electrons to the valence shell of
an atom. This results in a greater force of repulsion among the electrons and a decrease in the effective
nuclear charge per electron. Both effects cause the radius of a negative ion to be greater than that of the
 parent atom. For example, a chlorine atom ([Ne] 3s²3p') has a covalent radius of 0.99 Å, whereas the ionic
radius of a chloride ion ([Ne] 3s 3p) is 1.81 A. For succeeding elements proceeding down the groups,
negative ions have more electron shells and larger radii.
Ions and atoms that have the same electron configuration, such as those in the series N³ -, 0²-, F-,
Ne, Na+, Mg2+, and those in the series P 3-, S2-, CI-, Ar, K+, Ca²+, and Sc³+, are termed isoelectronic. The
greater the nuclear charge, the smaller the ionic radius in a series of isoelectronic ions and atoms.

3. VARIATION IN IONIZATION ENERGIES.

The amount of energy required to remove the most loosely bound electron from a gaseous atom,
atom is called its first ionization energy. This change may be represented for any element X by the
equation.
X(g) + energy => X+ (g) + e-

The energy required to remove the second most loosely bound electron is called the second ionization
energy; to remove the third electron, the third ionization energy; and so forth. First ionization energies
increase in an irregular way from left to right across a period. Ionization energies show two important
trends: Ionization energies decrease as you move down a group and increase as you move from left
to right across a period.

4. VARIATION IN ELECTRON AFFINITIES

The electron affinity is a measure of the energy involved when an electron is added to a gaseous
atom to form a negative ion. A negative value for electron affinity indicates that energy is produced when
an electron is added to an atom. The change is expressed for any element X by the equation.

X(g) + e- => X- (g) electron affinity = - KJ/mol

A positive value for electron affinity indicates that energy must be added to force the electron
onto the atom, as represented in the equation.

Elements to the left (metals) within a period have little tendency to form negative ions; thus their
electron affinities tend to be small or negative. Elements to the right (non-metals) within the period tend
to have larger electron affinities.

5. ELECTRONEGATIVITY
ability of an atom to attract electrons in a chemical bond. Electronegativity values have no units
because it is not an amount of energy nor is it a property of an atom that can be directly measured.
Fluorine (F) is the most electronegative element, with an electronegativity of 4.0. the least electronegative
elements are in the lower left corner of the periodic table. Both cesium and francium have
electronegativities of 0.7. Electronegativity increases as you move from left to right across a period
and decrease as you move down a group.

The conditions of electron filling

Pauli principle: The number of electrons that are allowed to occupy an orbital must be
limited to one or two, and, for the latter case, their spins must be anti-parallel (different direction).
Hund's rule: When there are equal-energy orbitals, electrons occupy separate orbital and their
spins are parallel (same direction). The order of orbital energy of a neutral atom is 1s <2s< 2p < 3s<3p
< 4s < 3d< 4p … and the electron configuration is determined as electrons occupy orbital s in this
order according to the Pauli principle and Hund's rule. An s orbital with one ml can accommodate 2
electrons, a p orbital with three ml 6 electrons, and a d orbital with five ml 10 electrons.
 Fig.1.3.1Shapes of s , p , and d orbitals.

Table1.3.1 Periodic table of elements. The values are atomic weights.

1 2 3 4 5 6 7 8 9
1 1.008
1H
2 6.941 9.012
3Li 4Be

3 22.99 24.31
11Na 12Mg

4 39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.85 58.93

19 K 20Ca 21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co

5 85.47 87.62 88.91 91.22 92.91 95.94 (99) 101.1 102.9

37Rb 38Sr 39Y 40Zr 41Nb 42Mo 43Tc 44Ru 45Rh

6 132.9 137.3 Lantha- 178.5 180.9 183.8 186.2 190.2 192.2

55Cs 56Ba noid 72Hf 73Ta 74W 75Re 76Os 77Ir

7 (223) (226) Acti-

87Fr 88Ra noid

Lanthanoid 138.9 140.1 140.9 144.2 (145) 150.4 152.0

57La 58Ce 59Pr 60Nd 61Pm 62Sm 63Eu

Actinoid (227) 232.0 231.0 238.0 (237) (239) (243)

89Ac 90Th 91Pa 92U 93Np 94Pu 95Am

10 11 12 13 14 15 16 17 18
4.003
2He

10.81 12.01 14.01 16.00 19.00 20.18

5B 6C 7N 8O 9F 10Ne

26.98 28.09 30.97 32.07 35.45 39.95

13Al 14Si 15P 16S 17Cl 18Ar

58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80

28Ni 29Cu 30Zn 31Ga 32Ge 33As 34Se 35Br 36Kr

106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3

46Pd 47Ag 48Cd 49In 50Sn 51Sb 52Te 53I 54Xe

195.1 197.0 200.6 204.4 207.2 209.0 (210) (210) (222)

78Pt 79Au 80Hg 81Tl 82Pb 83Bi 84Po 85At 86Rn

157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0

64Gd 65Tb 66Dy 67Ho 68Er 69Tm 70Yb 71Lu

(247) (247) (252) (252) (257) (258) (259) (262)

96Cm 97Bk 98Cf 99Es 100Fm 101Md 102No 103Lr
Block Classification of the Periodic table and elements

Starting from hydrogen, over 100 elements are constituted as electrons are successively
accommodated into 1s, 2s, 2p, 3s, 3p, 4s, and 3d orbitals one by one from lower to higher energy
levels. When elements with similar properties are arranged in columns, the periodic table of the
elements is constructed. The modern periodic table of the elements is based on one published by D.I.
Mendeleev in 1892, and a variety of tables have since been devised. The long periodic table
recommended by IUPAC is the current standard, and it has the group numbers arranged from Group 1
alkali metals through Group 18 rare gas elements (Table 1.1).

Based on the composition of electron orbitals, hydrogen, helium, and Group 1 elements are
classified as s-block elements, Group 13 through Group 18 elements p-block elements, Group 3
through Group12 elements d-block elements, and lanthanoid and actinoid elements f-block elements.
(Fig. 1.2). s-Block, p-block, and Group 12 elements are called main group elements, and d-block
elements other thanGroup12andf-block elements are called transition elements. The characteristic
properties of the elements that belong to these four blocks are described in Chapter 4 and thereafter.
Incidentally, periodic tables that denote the groups of s-block and p-block elements with Roman
numerals (I, II,, VIII) are still used, but they will be unified into the IUPAC system in the near future.
Since inorganic chemistry covers the chemistry of all the elements, it is important to understand the
features of each element through reference to the periodic table.

Fig.1.4 Block classification of elements in the periodic table.