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/ 22
CLASSIFICATION OF ELEMENTS AND
PERIODICITY IN PROPERTIES
Objectives
Mier s
able to
«lying this Unit, you will be
cclate how the concept of
dance to
the
grouping elements in ac
their properties led to
development of Periodie Table.
understand the Periodic Law:
nd the significance of
atomic number and electronic
configuration as the basis for
periodic classification:
* name the elements with
Z >100 according to IUPAC
nomenclature
© classify elements into s. p. d. f
blocks and learn their main
characteristics:
* recognise the periodic trends in
physical and chemical properiles of
elements
* compare the reactivity of elements
and correlate it with their
occurrence in nature:
+ explain the relationship between
ionization enthalpy and metallic
character;
* use selentifie vocabulary
appropriately to communicate ideas
related to certain important
properties of atoms e.g., atomic/
jonie radit, lontzation enthalpy.
electron gain enthalpy.
electronegativity, valence of
—~
The Periodic Table is arguably the most important concey
chemistry, both in principle and in practice. It is the ever|
support for students, it suggests new avenues of researg
professionals, and it provides a succinct organization o,
whole of chemistry. It is a remarkable demonstration of
fact that the chemical elements are not a random cluste,
entities but instead display trends and lie together in famiy,
An awareness of the Periodic Table is essential to anyoney,
wishes to disentangle the world and see how it is built
from the fundamental building blocks of the chemistry,
chemical elements.
Glenn T. Seay
In this Unit, we will study the historical development of,
Periodic Table as it stands today and the Modern Peri¢
Law. We will also learn how the periodic classificat
follows as a logical consequence of the electro
configuration of atoms. Finally, we shall examine som
the periodic trends in the physical and chemical proper
of the elements.
3.1 WHY DO WE NEED TO CLASSIFY ELEMENTS
*"e know by now that the elements are the basic units 0,
types of matter. In 1800, only 31 elements were known,
1865. the number of identified elements had more tl
doubled to 63. At present 114 elements are known,
them. the recently discovered elements are man-ma
Efforts to synthesise new elements are continuing. W
such a large number of elements it is very difficult to sti
individually the chemistry of all these elements and th
innumerable compounds individually. To ease out {
problem, scientists searched for a systematic way)
organise their knowledge by classifying the elements. |
only that it would rationalize known chemical facts ab,
elements, but even predict new ones for undertaking furt
study. a
— .
J iomie drerrols ~ ICCA END 2
(ABN)
psc TION OF ELEMENTS AND PERIODICITY IN PROMEITIS 15
2. GENESIS OF PERIODIC chemist, John Alexander Newlands in 1865
CLASSIFICATION profounded the Law of Octaves. He arranged
the clements in Increasing order of their atomic
classification of elements into groups and weights and noted that every eighth element
‘evelopment of Periodic Law and Periodic ~}jad properties similar to the first element
dee are the consequences of systemalising (Table 3.2), The relationship was just like every
theknowledge gained by number of scientists eighth note that resembles the first in octaves
ine ter observations and experiments. of music, Newlands's Lav of Octaves seemed
anchemist, Johann Dobereiner in {9 be true only for elements up to calelum,
The Germs .
cry 1800'S was the first to consider the idea
ewirends among properites of elements. By
1599 he noted a similarity among the physical
UE jchemical properties of several groups of
three elements (Triads). In each case, he
that the middle element of each of the
Triads had an atomic weight about half way
perween the atomic weights of the other two
{table 3.1). Also the properties of the middle
tiement were in between those of the other
notice
Table 3:1 Dobereiner's Triads
Although his idea was not widely accepted at
that Lime, he, for his work, was later awarded
Davy Medal in 1887 by the Royal Society.
London.
‘The Periodic Law, as we know it today owes
its development to the Russian chemist, Dmitri |
Mendeleev (1834-1907) and the German_
chemist, Lothar Meyer (1830-1895). Working
independently, both the chemists in 1869—
Element Element Atomic Element Atomic
weight weight
i 7 Ca 40 cl 35.5
Na 23 Sr 88 Br 80
K 39 Ba 137 I 127
two members. Since Dobereiner's relationship,
referred to as the Law of Triads, seemed to
work only for a few elements, it was dismissed
as coincidence. The next reported attempt to
dassify elements was made by a French
geologist, A.E.B, de Chancourtois in 1862. He
amranged the then known elements in order of
increasing atomic weights and made a
gllindrical table of elements to display the
periodic recurrence of properties. This also did
not attract much attention. The English
proposed that on arranging elements in the
increasing order of their atomic weights,
similarities appear in physical and chemical
“properties at regular intervals. Lothar Meyer
plotted the physical properties such as atomic
volume, melting point and boiling point
against atomic weight and obtained a
periodically repeated pattern) Unlike
Newlands, Lothar Meyer observed a change in
length of that repeating pattern. By 1868,
Lothar Meyer had developed a table of the
Table 3.2 Newlands’ Octaves
Element Li Be B c T N °o F
AL wt 7 9 11 12 14 16 19 |
Element Na Mg Al Si P s cl
AL wt 23 24 27 29 31 32 | 35.5
Element K Ca
At wt 39 40 76
elements that closely resembles the Modern
Periodic Table. However, his work was not
published until after the work of Dmitri
Mendeleev, the scientist who is generally
credited with the development of the Modern
Periodic Table.
While Dobereiner initiated the study of
periodic relationship, it was Mendeleev who
was responsible for publishing the Periodic
Law for the first time. It states as follows :
The properties of the elements are a
Periodic function of their atomic
weights.
Mendeleev arranged elements in horizontal
rows and vertical columns ofa table in order
of their increasing atomic weights in such a
way that the elements with similar properties
occupied the same vertical column or group.
Mendeleev’s system of classifying elements was
more elaborate than that of Lothar Meyer's.
He fully recognized the significance of
periodicity and used broader range of physical
and chemical properties to classify the
elements. In particular, Mendeleev relied on
the similarities in the empirical formulas and
Properties of the compounds formed by the
¢lements. He realized that some of the elements
did not fit in with his scheme of classification
if the order of atomic weight was strictly
followed. He ignored the order of atomic
CHa,
weights, thinking that the |
measurements might be incorréct, jf!
the elements with similar properties, tog
For example, jodine with lower atomic wee
than that of tellurium (Group Vi) was 9.2
in Group VII along with Muorine, eng
bromine because of similarities in Proper
(Fig. 3.0). At the same time, keeping yt
primary aim of arranging the elements"
similar properties in the same group, {1
proposed that some of the elements were sq
undiscovered and, therefore, left several
in the table. For example, both gallium ayy
germanium were unknown at the tin,
Mendeleev published his Periodic Table. He et
the gap under aluminium and a gap unde
silicon, and called these elements Bky,
‘Aluminium and Eka-Silicon. Mendel,
Predicted not only the existence of gallium anj
germanium, but also described some of the;
general physical properties. These elements
were discovered later. Some of the propertie
predicted by Mendeleev for these elements ani
those found experimentally are listed is
Table 3.3.
The boldness of Mendeleev's quantitative
predictions and their eventual success matt
him and his Periodic Table famous
Mendeleev's Periodic Table published in 1905
is shown in Fig. 3.1.
Table 3.3 Mendeleev's Predictions for the Elements Eka-aluminium (Gallium) and
Eka-silicon (Germanium)
Property Eka-aluminium / Gallium | Eke-silicon | Germanium
(predicted) (found) (predicted) (found)
Atomic weight 68 70 72 72.6
Density / (¢/cm’) 5.9 5.94 55 5.36
Melting point /K Low 302.93 High 1231
Formula of oxide EO, Ga,0, EO, Geo,
Formula of chloride Ecl, Gacl, ECl, Gecl, ELEMENTS AND PERIODICITY IN PROPERTIES
aya PAUSHATIC-erAAL vee ee
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3.3 MODERN PERIODIC LAW AND ane
PRESENT FORM OF THE PERIOD!
TABLE
We must bear in mind that when Mendeleev
developed his Periodic Table, chemists knew
nothing about the internal structure of atom
However, the beginning of the 20" century
d profound developments in theories
ticles. In 1913, the
ry Moscleyobserved
cteristic X-ray spectra
witne:
about sub-atomic pz
English physicist, He
egularities in the chy
of the clements. A plot of Jy (where vis
frequency of X-rays emitted) against atomic
number (Z) gave a straight line and not the
plot of Vy vsatomic mass. He thereby showed
that the atomic number is a more fundamental
property of an element than its atomic mass.
Mendeleev's Periodic Law was, therefore,
accordingly modified. This is known as the
Modern Periodic Law and can be stated as:
The physical and chemical properties
of the elements are periodic functions
of their atomic numbers.
~ The Periodic Law revealed important
analogies among the 94 naturally occurring
elements (neptunium and plutonium like
actinium and protoactinium are also found in
pitch blende - an ore of uranium). It stimulated
renewed interest in Inorganic Chemistry and
has carried into the present with the creation
of artificially produced short-lived elements.
You may recall that the atomic number is
equal to the nuclear charge (ie., number of
protons) or the number of electrons in a neutral
atom. It is then easy to visualize the significance
of quantum numbers and electronic
configurations in periodicity of elements. In
fact, it Is now recognized that the Periodic Law
is essentially the consequence of the periodic
variation in electronic configurations, which
indeed determine the physical and chemi
properties of elements and their compounds.
wt
Oey,
Numerous forms of Periodic tay,
been devised from time to time. gor hy
emphasise chemical reactions ang”
whereas others stress the ¢ ath
configuration ofclements. A modern ye
the so-called “long form’ of the Periodic!
of the elements (Fig, 3.2), fs the most cone
and widely used. The horizontal OWS
Mendeleev called series) are called pe;
the vertical columns, groups) Elements he
similar outer electronie configurations ini!
atoms are arranged in vertical calug,
referred to as groups or families. Accorj,
to the recommendation of International Unig
of Pure and Applied Chemistry (IUPAG,
groups are numbered from 1 to 18 replace
the older notation of groups IA... VUA, Vin
... VIIBand0.
There are altogether seven periods,
period number corresponds to the highs
principal quantum number (n) of the elemen,
in the period. The first period contains
elements. The subsequent periods consists;
8,8, 18,18 and 32 elements, respectively. Te
seventh period is incomplete and like the sit
period would have a theoretical maximum |:
the basis of quantum numbers) of 32 clemers
In this form of the Periodic Table, 14 elemen
of both sixth and seventh periods (lanthanoii
and actinoids, respectively) are placed
separate panels at the bottom’.
3.4 NOMENCLATURE OF ELEMENTS Witt
ATOMIC NUMBERS > 100
The naming of the new elements had bet
traditionally the privilege of the discoverer
discoverers) and the suggested name wa
ratified by the IUPAC. In recent years this ht
Jed to some controversy. The new elements wil
very high atomic numbers are so unstable th!
only minute quantities, sometimes only a fe
atoms of them are obtained. Their synthes*
and characterisation, therefore, require high!
* Glenn T. Seaborg’s work in the middle of the 20"
those of all the transuranium elements from
below the lanthanoids. In 1951, Seaborg was awarded the
named Seaborgium (Sg) in is honour
century starting with the
94 to 102 led 10 reconfiguration of the periodic table
dliscovery of plutoniwn in 1940, follore®
i placins tne act
Nobel Prize in chemistry Jor is work. Element 100 tt
2 rary -spiouaye an
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sophisticated costly equipment and laboratory. which make up the atomte numbe
T ands
Such work is carried out with competitive spirit is added at the end. The IUPAC na; Tu
only in some laboratories in the world. elements with Z above 100 are showy!
f
Scientists, before collecting the reliabledataon Table 3.5.
the new clement, at times get tempted to claim
for its discovery. For example, both American Tle 3.4 of ine for TUPAC Nomenci,
and Soviet scientists claimed credit for
discovering element 104. The Americans
named it Rutherfordium whereas Soviets
named it Kurchatovium. To avoid such
Problems, the IUPAC has made
recommendation that until a new element's
discovery is proved, and its name is officially
recognised, a systematic nomenclature be
derived directly from the atomic number of the
element using the numerical roots for 0 and
numbers 1-9, These are shown in Table 3.4.
The roots are put together in order of digits
eoceruoe oes
0
1
2
3
4
iS
6
7
8
9
Table 3.5 Nomenclature of Elements with Atomic Number Above 100
Atomic Name according to [ Symbol TUPAC TUPAC
Number | IUPAC nomenclature Official Name Symbol
101 Unnilunium Unu Mendelevium Ma
102 Unnilbium Unb Nobelium No
103 Unniltrium Unt Lawrencium Lr
104 Unnilquadium Ung Rutherfordium RE
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unnilseptium Uns Bohrium, Bh
108 Unniloctium Uno Hassium Hs
io9 Unnilennium Une Meitnerium Mt
110 Ununnillium Uun Darmstadtium Ds
111 Unununnium Uuu Rontgenium Rg
112 Ununbium Uub Copernicium cn
113 Ununtrium Uut Nihonium Nn
114 Ununquadium Uuq Flerovium Fl
Ununpentium Uup Moscovium: Mec
Ununhexium Uuh Livermorium Ly
Ununseptium Uus Tennessine
Ununoctium Uuo Oganesson yr
[assificaTION ior
as
the new element first gets a
iy name, with symbol consisting of
riers. Lauter permanent name and
are given by a vole of TUPAC
bol atives from cach country, The
repre ent name might reflect the country (or
perme country) in which the element was
steered. oF pay tribute to a notable
getiet As of How, elements with atomte
seers up to 118 have been discovered.
nual names of all elements have been
Grnounced DY TUPAC.
problem 3.1
wnat would be the IUPAC name and
Fymbol for the element with atomic
number 120?
cm
solution
prom Table 3.4, the roots for 1, 2 and 0
jreun, biand nil, respectively, Hence, the
‘gmbol and the name respectively are Ubn
and unbinilium.
ee
je ELECTRONIC CONFIGURATIONS OF
ELEMENTS AND THE PERIODIC
TABLE
In the preceding unit we have learnt that an
¢jectron in an atom is characterised by a set of
four quantum numbers, and the principal
quantum number (n) defines the main energy
level known as shell, We have also studied
about the filling of electrons into different
subshells, also referred to as orbitals (s, p, d.
{finan atom. The.distribution of electrons into.
orbitals of an atom is called its electronic
configuration. An element's location in the
Periodic Table reflects the quantum numbers
ofthe last orbital filled. In this section we will
observe a direct connection between the
«lectronic configurations of the elements and
‘helong form of the Periodic Table.
9) Electronic Configurations in Periods
Be period d indicates the value of n for the
GtemosCor valence shell. In other words..
ee Period in the Periodic Table is.
praniited with the filling of the next. higher.
pal energy level.(n= 1, n=2, etc.). Itcan
MENTS AND PERIODICITY IN PROPERTIES
BI
+
be readily seen that thenumber of elements in
each period 1s twice the number of atomic.
orbitals avallable in the cnergy level that is
being filled The first pertod (= 1) starts with
the filling of the lowest level (1.5) and therefore
Nas two elements — hydrogen (1s!) and helium
(1s) when the first shell (K) is completed. The
second period (n= 2) starts with lithium and
the third electron enters the 2 orbital. The next
clement. beryllium has four electrons and has
the electronic configuration 1s’2s’. Starting
from the next element boron, the 2p orbitals
are filled with electrons when the L shell is
completed at neon (2s’2p"). Thus there are
8 clements in the second period. The third
period (n= 3) begins at sodium, and the added
electron enters a 3s orbital. Successive filling
of 3s and 3p orbitals gives rise to the third
period of 8 elements from sodium to argon. The
fourth period (n= 4) starts at potassium, and
the added electrons fill up the 4s orbital. Now
you may note that before the 4p orbital is filled,
filling up of 3d orbitals becomes energetically.
favourable and we come across the so called
3d transition series of elements. This starts,
from scandium (Z= 21) which has the electronic
configuration 3d' 4s’. The 3dorbitals are filled
at zinc (Z=80) with electronic configuration
3d'°4s? .\The fourth period ends at krypton
‘with the filling up of the 4p orbitals. Altogether
we have 18 elements in this fourth period. The
fifth period (n= 5) beginning with rubidium is
similar to'the fourth period and contains the.
4d transition series starting at yttrium
(Z = 39). This period ends at xenon with the
filling up of the 5p orbitals. The sixth period
(n= 6) contains 32 elements and successive
electrons enter 6s, 4f, 5d and 6p orbitals. in
the order — filling up of the 4forbitals begins
with cerium (Z = 58) and ends at lutetium_
(Z=71) to give the 4f-inner transition series _
which is called the lanthanoid series. The
seventh period (n = 7) is similar to the sixth
period with the successive filling up of the 7s,
5f, 6d and 7p orbitals and includes most of
the man-made radioactive elements. This
period will end at the element with atomic
number 118 which would belong to the noble
gas family. Filling up of the 5f orbitals after
actinium (Z= 89) gives the 5f-inner transition. 82
Known as the actinold series. The 4/
and 5/ inner transition series of clements are
> Periodic Table to
placed separately in the Periodic Tal
n and to preserve the
maintain its struct
principle of classification by keeping elements
With similar properties in a single column
Problem 3.2.
How would you justify the presence of 18.
elements in the 5” period of the Periodic
Table?
Solution
When n= 5, l= 0, 1, 2, 3. The order in
which the energy of the available orbitals
4d. 5s and 5p increases is 5s < 4d < 5p.
The total number of orbitals available are
‘9. The maximum number of electrons that
can be accommodated is 18; and therefore
18 elements are there in the 5" period.
eee
() Groupwise Electronic Configurations
Elements in the same vertical column or. ‘group
haye similar valence shell electronic
configurations, the same number of electrons
in the outer orbitals, and similar properties,
For example, the Group 1 elements (alkali
metals) all have ns’ valence shell electronic
configuration as shown below. .
CHa,
M
theoretical foundation for the
sifleation. The elements in a verti.
of the Periodic Table constitute ;
family and exhibit stiaiiar chemient ye
This similarity arises because these a.
have the same numberand same disiys
of electrons in their outermost orbital
classify the elements into four blocs
s-block, p-block, d-block and fy)’
depending on the type of atomic orbiaie
are being filled with electrons. This i illus.
in Fig. 3.3. We notice two exceptions ig,
categorisation. Strictly, helium belongs,
s-block but its positioning in the p-blocksy,
With other group 18 clements is just
because it has a completely filled valence:
(1s4) and as a result, exhibits propen,
characteristic of other noble gases) The
exception is hydrogen. It has only
s-electron and hence can be placed in grou
(alkali metals); It can also gain an electron
achieve a noble gas arrangement and hen:
can behave similar to a group 17 (halo
family) elements. Because it is a special cas
we shall place hydrogen separately at thet:
of the Periodic Table as shown in Fig. 3.2.
Fig. 3.3. We will briefly discuss the sale:
features of the four types of elements marked
Atomic number Symbol Electronic configuration
3 Li 18°28! (or) [Hel2s!
M1 Na 1s*2s*2p/35' (or) [Ne]3s!
19 K 1s*28*2 7333 p"4s! (or) [Arl4s
37 Rb 18*2s*2p°3s'3p'3d"°4s"4p'5s! (or) [Kr]5s'
55 cs 1s'2s*2p°3s*3p"3d°4.5°474d"°5s°5p'6s! (or) [Xel6s!
87 Fr [Rn}7s!
‘Thus it can be seen that the properties of
an clement have periodic dependence upon its,
atomic number and not on relative atomic
mass.
3.6 ELECTRONIC CONFIGURATIONS
AND TYPES OF ELEMENTS:
Sp d-, f BLOCKS
The aufbau (build up) principle and the
electronic configuration of atoms provide a
the Periodic Table. More about these elemet
will be discussed later. During the descripti
of their features certain terminology has be
used which has been classified in section 3!
3.6.1 The s-Block Elements
The elements of Group 1 (alkali metals)
Group 2 (alkaline earth metals) which have! yr
a3
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aS
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wootay
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BH {eV} ad | | so fod) | eL ]JH | eT | Ps
PI] By | Pd} wa) ma] oL ow] AN | 3Z] A | Pr
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wom Ol 6 8 £ 9 § b
caTION OF ELEMENTS AND PERIODICITY IN PROF
ji
r
ass 4
and ns? outermost electronic configuration
belong to the s-Block Element: hey are all
reactive metals with low ionization enthalpies.
‘They lose the outermost electron(s) readily 0
form I+ ion (in the case of alkali metals) or 2+
on (in the case of alkaline earth metals). The
metallic character and the reactivity increase
as we go down the group. Because of high
found pure in nature.
sblock elements, with
reactivity they are nev
s of th
The compoun
the exception of those of ithitnrand beryllium
are predominantly ionic.
3.6.2 The p-Block Elements
The p-Block Elements comprise those
belonging to Group 13 to 18 and these
together with the s:Block Elements are called
the Representative Elements or Main Group
Elements. The outermost electronic
configuration varies from ns*np! to ns*np? in
each period. At the end of each period is a noble
gas clement with a closed valence shell ns*ny?
configuration. All the orbitals in the valence
shell of the noble gases are completely filled
by electrons and it is very difficult to alter this
stable arrangement by the addition or removal
of electrons. The noble gases thus exhibit very
low chemical reactivity. Preceding the noble gas.
family are two chemically important groups of
non-metals. They are the halogens (Group 17)
and the chaleogens (Group 16). These two.
groups of elements have highly negative
electron gain enthalpies and readily add one
or two electrons respectively to attain the stable
noble gas configuration? The non-metallic
character increases as we move from left to right
across a period and metalllic character increases
as we go down the group.
3.6.3 The d-Block Elements (Transition
Elements)
‘These are the elements of Group 3 to 12 in the
centre of the Periodic Table. These are
characterised by the filling of inner d orbitals
by electrons and are therefore referred to as
dBlock Elements. These elements have the
general outer electronic configuration
(r-1)d' “ns? . They are all metals, They mostly
form coloured ions, exhibit variable valence
(oxidation states), paramagnetism and oftenly
used as catalysts. However, 7;
which have the electronic cong tat
(01) d¢nsédo not show most ofthe #8
of transition elements, In a way Py,
metals form a bridge between the of
active metals of s-block elements ay
active elements of Groups 13 and 14
lake their familiar name “Treat
Element:
3.6.4 The fBlock Elements
(nner-Transition Elements)
The two rows of elements at the bottoms,
Periodic Table, called the Lanthann
GelZ = 58) - Lu(Z = 71) and Acting,
Th(Z= 90) ~ Lr (Z= 103) are characterises
the outer electronic configuration (n3;
(n-I)eP'ns®, The last electron added toe,
clement is filled in f- orbital. These two sex
of elements are hence called the Inge
Transition Elements (fBlock Elemen,
They are all metals. Within each series,
properties of the elements are quite similar}
chemistry of the early actinoids is me
complicated than the correspond:
lanthanoids, due to the large number
oxidation states possible for these actim
elements. Actinoid elements are radioacty
Many of the actinoid elements have been m:
only in nanogram quantities or even lesst
nuclear reactions and their chemistry ist
fully studied. The elements after uranium:
called Transuranium Elements.
ee
Problem 3.3
The elements Z 17 and 120 have no
yet been discovered. In which family /
group would you place these elements
and also give the electronic configuration
in each case,
the,
an
My
Solution
We see from Fig. 3.2, that element with2
= 117, would belong to the halogen family
(Group 17) and the electroni¢
configuration would be _ [R®l
5/"6d'°7s"7p*. The element with Z= 120.
will be placed in Group 2 (alkaline eart
metals), and will have the electronl¢
configuration (Uuo]8s?. yr
LAsSIFICAT
yas Metals. Non-metals and Metallolds
jgaition to displaying the classification of
ements Into SP d-. and fdlocks. Fig. 3.3
lene another broad classification of elements
ov on their properties, The elements can
eSjpvded into Metals and Non-Metals. Metals
bet pnse more than 78% of all known elements
cop appear on the left side of the Pertodie
fable Metals are usually solids at room
Mperarure [mercury {s an exception: gallium
cei eaesium also have very low melting points,
Ask and 302K. respectively)]. Metals usually
fave high melting and boiling points. They are
xi conductors of heat and electricity. They
Sr malleable (can be flattened into thin sheets
SRyammering) and ductile (can be drawn into
res). In contrast. non-metals are located at
hetop right hand side of the Periodic Table.
jn ict. in a horizontal row. the property of
Hements change from metallic on the left to
metallic on the right. Non-metals are
ceually solids or gases at room temperature
sath low melting and boiling points (boron and
sbon are exceptions). They are poor
conductors of heat and electricity. Most non-
setallic solids are brittle and are neither
saleable nor ductile. The elements become
‘ore metallic as we go down a group: the non-
iallic character increases as one goes from
to right across the Periodic Table. The
change from metallic to non-metallic character
's not abrupt as shown by the thick zig-zag
ine in Fig, 3.3. The elements (e.g.. silicon,
gmanium, arsenic. antimony and tellurium)
bordering this line and running diagonally
acmss the Periodic Table show properties that
xe characteristic of both metals and non-
‘neuals, These elements are called Semi-metals
Metalloids.
—
Problem 3.4
Considering the atomic number and
position in the periodic table, arrange the
following elements in the increasing order
of metallic character : Si, Be. Mg. Na. P.
Solution
Metallic character increases down a group,
and decreases along a period as we move
ee. |
JON OF ELEMENTS AND PERIODICITY IN PROPERTIES
85,
from left to right. Hence the order of
increasing metallic character {s: P < Si <
Be < Mg < Na.
SS
3.7 PERIODIC TRENDS IN PROPERTIES
OF ELEMENTS
‘There are many observable patterns in the
physical and chemical properties of elements
as we descend in a group or move across a
period in the Periodic Table. For example.
within a period, chemical reactivity tends to be
high in Group 1 metals. lower in elements
towards the middle of the table, and increases
to a maximum in the Group 17 non-metals.
Likewise within a group of representative
metals (say alkali metals) reactivity increases
on moving down the group. whereas within a
group of non-metals (say halogens). reactivity
decreases down the group. But why do the
properties of elements follow these trends? And
how can we explain periodicity? To answer
these questions, we must look into the theories
of atomic structure and properties of the atom.
In this section we shall discuss the periodic
trends in certain physical and chemical
properties and try to explain them in terms of
number of electrons and energy levels.
3.7.1 Trends in Physical Properties
‘There are numerous physical properties of
elements such as melting and boiling points.
heats of fusion and vaporization. energy of
atomization, etc. which show periodic
variations. However. we shall discuss the
periodic trends with respect to atomic and ionic
radii, ionization enthalpy. electron gain
enthalpy and electronegativit
(a) Atomic Radius
You can very well imagine that finding the size
of an atom is a lot more complicated than
measuring the radius of a ball. Do you know
why? Firstly. because the size of an atom
(~ 1.2 Aie.. 1.2 x 10° m in radius) is very
small. Secondly, since the electron cloud
surrounding the atom does not have a sharp
boundary. the determination of the atomic size
cannot be precise. In other words, there is no 86
which the size of an individual
asured. However, an estimate
ofthe atomic size can be made by knowing the
atoms in the combined
h to estimate the
practical way by
atom can be mei
distance between the
state, One practical approac!
size of an atom ofa non-metallic element Is (0
measure the distance between two atoms when
they are bound together by a single bond i
covalent molecule and from this value
“Covalent Radius” of the clement car
calculated, For example, the bond distance in
the chlorine molecule (C1, is 198 pm and half
this distance (99 pm). is taken as the atomic
radi of chlorine. For metals, we define the
term “Metallic Radius” which is taken as half
the internuclear distance separating the metal
cores in the metallic crystal. For example, the
distance between two adjacent copper atoms
in solid copper is 256 pm: hence the metallic
radius of copper is assigned a value of 128 pm.
For simplicity, in this book, we use the term
Atomic Radius to refer to both covalent or
metallic radius depending on whether the
element is a non-metal or a metal. Atomic radii
can be measured by X-ray or other
spectroscopic methods.
‘The atomic radii ofa few elements are listed
in Table 3.6 . Two trends are obvious. We can
ina
the
be
Hens,
explain these trends in terms of nucteay
and energy level. The atomic size 4.4
decreases across a period as illustrat"!
Fig, 3.4(a) for the elements of the secon!
It Is because within the period the
electrons are in the same valence shell ang
effective nuclear charge increases as the at,”
number Increases resulting in the incre
attraction of electrons to the nucleus, With;
family or vertical column of the periodic tay,
the atomic radius increases regularly yi
atomic number as illustrated in Fig. 3.4(5)
alkali metals and halogens, as we descend,
groups. the principal quantum number ;,
increases and the valence electrons are fart,
from the nucleus. This happens because th,
inner energy levels are filled with electron
which serve to shield the outer electrons fros
the pull of the nucleus. Consequently the siz
of the atom increases as reflected in the aton:
radii.
Note that the atomic radii of noble gases
are not considered here. Being monoatomi:
their (non-bonded radii) values are very larg:
In fact radii of noble gases should be compart
not with the covalent radii but with the vand:
Waals radii of other elements.
gener
he
Out,
Table 3.6(a) Atomic Radii/pm Across the Periods
————
Atom (Period IN) Li Be B c N ° F
Atomic radius 152 1 88 77 74 66 64
Atom (Period mm) | Na Mg a | si P s cL
Atomic radius 186 160 143 117 110 104 99
Table 3.6(b) Atomic Radii/pm Down a Family
Atom Atomic Atom
(Group D Radius (Group 17) Radius
i 152 F 64
Na 186 cI 30
K 231 Br are
Rb 244 T 738
Cs 262
At
wo LEMENTS AND PE
asst aTion OF
a
160
5
8
Be
8
B
Sn
Atomic radius/pm.
8
OF
2 4 6 8 10
Atomic number (2)
Variation of atomic radius with
atomic number across the second
period
) Ionic Radius
Fig. 9-4 (2)
qheremoval ofan electron from an atom results
inthe formation of a cation, whereas gain of
‘nelectron leads to an anion, The ionic radii
can be estimated by measuring the distances
petween cations and anions in ionic crystals.
ingeneral, the ionic radii of elements exhibit
the same trend as the atomic radii. A cation is
smaller than its parent atom because it has
feverelectrons while its nuclear charge remains
the same. The size of an anion will be larger
than that of the parent atom because the
addition of one or more electrons would result
in increased repulsion among the electrons
and a decrease in effective nuclear charge. For
eample, the ionic radius of fluoride ion (F ) is
136 pm whereas the atomic radius of fluorine
isonly 64 pm. On the other hand, the atomic
radius of sodium is 186 pm compared to the
jonic radius of 95 pm for Na’.
When we find some atoms and ions which
contain the same number of electrons, we call
them, isoelectronic species*. For example.
ate Na’ and Mg” have the same number of
rons (10). Their radii would be different
canst ofthetr different nuclear charges. The
q nwith the greater positive change will have
Snuller radius because of the greater
"nari,
‘less of the nature of elements involved.
i
HODICITY IN PROPERTIES a
€s(262)
a ‘aan Rb(244)
2 ‘Na(186)
150
E052)
z 11133)
§ 100 Br(114)
=
Atomic number (2)
Fig. 3.4 (6) Variation of atomic radius with
atomic number for alkali'metals
and halogens
attraction of the electrons to the nucleus. Anion:
with the greater negative charge will have the
larger radius. In this case, the net repulsion of
the electrons will outweigh the nuclear charge
and the ion will expand in size.
Problem 3.5
Which of the following species will have
the largest and the smallest size?
Mg. Mg, Al, AI".
Solution
Atomic radii decrease across a period.
Cations are smaller than their parent
atoms. Among isoelectronic species, the
one with the larger positive nuclear charge
will have a smaller radius.
Hence the largest species is Mg: the
smallest one is Al"
(c) Ionization Enthalpy
A quantitative measure of the tendency of an
element to lose electron is given by its
Ionization Enthalpy. It represents the energy
required to remove an electron from an isolated
gaseous atom (X) in its ground state. In other
words, the first ionization enthalpy for an
Wo oF more species with same number of atoms, same number of valence electrons and same structure, 88.
element Xis the enthalpy change (4,4) for the
reaction depicted in equation 3.1.
Xg) > XW +e 60)
‘The ionization enthalpy is expressed In
units of kJ mol, We can define the second
ionization enthalpy as the energy required to
remove the second most loosely bound
electron; it is the energy required to carry out
the reaction shown in equation 3.2.
X@ox*g™te (3.2)
Energy is always required to remove
electrons from an atom and hence ionization
enthalpies are always positive. The second
ionization enthalpy will be higher than the first
ionization enthalpy because it is more difficult,
to remove an electron from a positively charged
ion than from a neutral atom. In the same way
the third ionization enthalpy will be higher than
the second and so on. The term “ionization
enthalpy”, ifnot qualified, is taken as the first
ionization enthalpy.
The first ionization enthalpies of elements
having atomic numbers up to 60 are plotted
in Fig. 3.5. The periodicity of the graph is quite
striking, You will find maxima at the noble gases
which have closed electron shells and very
stable electron configurations. On the other
hand, minima occur at the alkali metals and
their iow ionization enthalpies can be correlated
A\H/ks mol
Atomic number(2)
3.6 (a)
Fig. 3.6(a) First ionization enthalpies (4,
we
HPA mot
‘Norte mudora
Fig. 3.5 Variation of first ionization enthaip,
44H) with atomic number Jor eleres
with Z = 1 to 60
with their high reactivity. In addition, you yy
notice two trends the first ionization enthaj,
generally increases as we go across a peri
and decreases as we descend in a group. They
trends are illustrated in Figs. 3.6(a) and 3.6},
respectively for the elements of the secon:
period and the first group of the periodic tab
You will appreciate that the ionization enthaly
and atomic radius are closely relait
properties. To understand these trends, »
have to consider two factors : (i) the attractin
of electrons towards the nucleus, and (ii) *
repulsion of electrons from each other. Te
effective nuclear charge experienced bj:
valence electron in an atom will be less the
550
Li(520)
gs
S
Na(496)
A.H/ki- mol"
2
g
Rb(403)
400
Cs(374)
350
0 102030405060
= Atomic number(2)
3.6 (b)
HH) of elements of the second period as"
function of atomic number (2) and Fig. 3.6(b) AH of alkali metals as a | function of 2
* bh Py
caTioN OF ELEMENTS AND PERIODICITY IN
cuss
jreharge on the nucleus because of
ing” or “screening” of the valence
rom the nucleus by the intervening
"rons. For example, the 2s electron tn
‘x shielded from the nucleus by the
¢ of Is electrons. As a result, the
et .
ioc electron experiences a net positive
valewhiclt 8 Tess than the actual charge of
chart general. shielding is effective when the
usin the inner shells are completely filed,
ituation occurs in the case of alkali metals
fy have single outermost ns-eleetron
by a noble gas electronic
onbila
mhis
whiel
receded
configuration.
When we move from lithium to fluorine
cross the second period, successive electrons
ve added (0 orbitals in the same principal
quantum level and the shielding of the nuclear
dharge by the inner core of electrons does not
inerease very much to compensate for the
increased attraction of the electron to the
qucleus. Thus. across a period, increasing
nuclear charge outweighs the shielding.
Consequently. the outermost electrons are held
nore and more tightly and the ionization
enthalpy increases across a period. As we go
down a group. the outermost electron being
increasingly farther from the nucleus, there is
an increased shielding of the nuclear charge
bythe electrons in the inner levels. In this case,
increase in shielding outweighs the increasing
nuclear charge and the removal of the
cutermost electron requires less energy down,
a group.
From Fig. 3.6(a), you will also notice that
the first ionization enthalpy of boron (Z= 5) is
slightly less than that of beryllium (Z= 4) even
though the former has a greater nuclear charge.
When we consider the same principal quantum
level. an s-electron is attracted to the nucleus
more than a p-electron. In beryllium, the
‘letron removed during the fonization is an
tess whereas the electron removed during
nization of boron is a p-electron. The
fetation of a 2s-electron to the nucleus is
de that of a 2p-electron; hence the 2p
cae oO boron is more shielded from the
select °y the inner core of electrons than the
Tons of beryllium. Therefore, it is easier
>.
Prop
89.
{o remove the 2p-electron from boron compared
{0 the removal ofa 2s-electron from beryllium.
Thus. boron has a smaller first tonization
enthalpy than beryllium, Another “anomaly”
is the smaller first ionization enthalpy of oxygen
compared (o nitrogen. This arises because in
the nitrogen atom, three 2p-cleetrons reside in
different atomic orbitals (Hund’s rule) whereas
in the oxygen atom, two of the four 2pelectrons
must occupy the same 2p-orbital resulting in
an increased clectron-electron repulsion.
Consequently. it is casicr to remove the fourth
2p-electron from oxygen than it is. to remove
one of the three 2p-electrons from nitrogen.
Problem 3.6
The first ionization enthalpy (4,1) values
of the third period elements, Na, Mg and
Si are respectively 496, 737 and 786 kJ
mot". Predict whether the first 4,H value
for Al will be more close to 575 or 760 kJ
mol" ? Justify your answer.
Solution
It will be more close to 575 kJ mol’ The.
value for Al should be lower than that of
Mg because of effective shielding of 3p
electrons from the nucleus by
3s-electrons.
(4) Electron Gain Enthalpy
When an electron is added to a neutral gaseous
atom (X) to convert it into a negative ion, the
enthalpy change accompanying the process is
defined as the Electron Gain Enthalpy (4,,H).
Electron gain enthalpy provides a measure of,
the ease with which an atom adds an electron
to form anion as represented by equation 3.3.
XQ +e > X1g (3.3)
Depending on the element, the process of
adding an electron to the atom can be either
endothermic or exothermic. For many elements
energy is released when an electron is added
to the atom and the electron gain enthalpy is.
negative. For example, group 17 elements (the
halogens) have very high negative electron gain
enthalpies because they can attain stable noble
gas electronic configurations by picking up an
electron. On the other hand, noble gases have CHa,
90
4:7 Electron Gain Enthalpies* / (kJ mot!) of Some Main Group Elemene,
Table 3.7 Electron Gi
Group 0
| Group 17| AH 7
4H [Group 16] 4.¥ .
Group 1] 4H | a =
H -73
Li 60 - 141 F = 928 Ne ‘i
Na - 53 8 = 200 cl - 349 Ar a)
K 48) Se = 195) Br ~ 325 Kr tas
7 — 190) T = 295 xe 7
Rb =47__| Te L
Cs | ~46 Po ~174 At = 270 Rn +68
— =
large positive electron gain enthalpies because ““probiem ay
the electron has to enter the next higher
principal quantum level leading to a very
unstable electronic configuration. It may be
noted that electron gain enthalpies have large
negative values toward the upper right of the
periodic table preceding the noble gases.
‘The variation in electron gain enthalpies of
elements is less systematic than for ionization
enthalpies. As a general rule, electron gain
enthalpy becomes more negative with increase
in the atomic number across a period. The
effective nuclear charge increases from left to
right across a period and consequently it will
be easier to add an electron to a smaller atom
since the added electron on an average would
be closer to the positively charged nucleus. We
should also expect electron gain enthalpy to
become less negative as we go down a group
because the size of the atom increases and the
added electron would be farther from the
nucleus. This is generally the case (Table 3.7).
However, electron gain enthalpy of O or F is
less negative than that of the succeeding
element. This is because when an clectron is
added to O or F, the added electron goes to the
smaller n = 2 quantum level and suffers
significant repulsion from the other electrons
present in this level. For the n= 3 quantum
level (S or Cl), the added electron occupies a
larger region of space and the electron-electron
repulsion is much less.
+n many book:
he negative of the enthalpy change for the
Which of the following will have the most
negative electron gain enthalpy and which
the least negative?
P,S, CLF.
Explain your answer.
Solution
Electron gain enthalpy generally becomes
more negative across a period as we move
from left to right. Within a group, electron
gain enthalpy becomes less negative down
a group. However, adding an electron ta
the 2p orbital leads to greater repulsion
than adding an electron to the larger
3p-orbital. Hence the element with most
negative electron gain enthalpy is chlorine;
the one with the least negative electron
gain enthalpy is phosphorus.
() Electronegativity
A qualitative measure of the ability of an atom
in a chemical compound to atiract shared
electrons to itself is called electronegativity.
Unlike ionization enthalpy and electron gait
enthalpy, it is not a measureable quantit
However, a number of numerical scales 0
electronegativity of elements viz., Pauling scale,
Mulliken-Jafe scale, Allred-Rochow scale have
been developed. The one which is the most
process depicted in equation 3.3 is defined as
the electron afta bs eke ain lnder consideration. I energy ts released when an elecion ie eka wan aX
the electron affinity ts taken as positive,
contrary to thermodynam
electron 1 an atom. then the electron affinity of the atom ty
convention. f energy has to be supplied to edd
signed negative sign, However eleetron alfiild ©
Ie eee aro and therefore at anyother temperature (heal capclice vend reactants andl the prods®
have to be taker into account in A, 1 = -A. 5/2 RT
eee Yr
ipicaTion OF ELEMENTS AND PERIODICHTY IN
cuss!
psec the Pauling seate, Lins Pauling
adel an sclenitst, 1922 assigned
an Amer gate of 4 Ot0 Mtorine, the clement
astra ra have the greatest ability to attract
caitte. Approximate values for the
cle att oF ew elements are given in
able 3810)
me electroncgativity of any given clement
_ pot constant: Ht varies depending on the
ss Ment to which i 8 ound. Though tis not
able quantity, It does provide a means
ng the nature of force
a pair ofatoms together
you will
cl
ameasut
of predict
at holds
tt dationship that
explore later
Electronegativity generally
incr across a period from left
to right (say from lithium to
fuorine) and decrease down.a group
jay from fluorine to astatine) in
the periodic table, How can these
trends be explained? Can the
clectronegativity be related to
gtomie radii, which tend to
decrease across each period from
left to right, but increase down
each group ? The attraction
between the outer (or valence)
Table 3.8(a) Electronegativity Values
PRovennies o
trons and the nucleus Increases as the
mic radius decreases in a period, The
clectroncgativity also Increases. On the same
account clectronegativity values decrease with
the increase in atomic radii down a group. The
trend is similar to th:
of ionization ent
py.
Knowing the relationship between
electronegativity and atomic radius, ean you
now visualise the relationship between
electronegativily and non-metallic properties?
Fig. 3.7. The periodic trends of elements in the periodic table
(on Pauling scale) Across the Periods
Atom (Period II) | Li 2 ‘Be B c N oO ¥F
Electronegativity 1.0 ‘Ls 2.0 25. 3.0 35 4.0
Atom (Period II) Na Mg Al Si 7 s cl
| Electronegativity 0.9 1.2 15 18 a LL 2.5 .0 4S
Table 3.8{b) Electronegativity Values (on Pauling scale) Down afamiy "> Bud
Atom Electronegativity Atom Electronegativity
(Group 1) Value (Group 17) Value
i 1.0 F 4.0
Na 0.9 a 3.0
K 0.8 Br 2.8
Rb 0.8 1 25
Cs 0.7 At 2.2
ae —————aorT————rlc (at
92
jon-metallic elements have strong eI
to gain electrons. Theretore, eleetroncuall ty
is directly related to that non-metalll
eleme! It can be further
properties of elements. is
extended to say that the eleetronegativity is
inversely related to the metallic properties o}
elements. Thus, the increase in
clectronegativities across a period is
aceompanied by an inerease In non-metallic
properties (or decrease in metallic properties)
of elements. Similarly, the decrease in
clectronegativity down a group is accompanied
by a decrease in non-metallic properties (or
increase in metallic properties) of elements.
All these periodic trends are summarised
in figure 3.7.
3.7.2 Periodic Trends in Chemical
Properties
Most of the urends in chemical properties of
elements, such as diagonal relationships, inert
pair effect. effects of lanthanoid contraction etc.
will be dealt with along the discussion of each
group in later units. In this section we shall
study the periodicity of the valence state shown,
by elements and the anomalous properties of
the second period elements (from lithium to
fluorine).
(a) Periodicity of Valence or Oxidation
States
The valence is the most characteristic property
ofthe elements and can be understood in terms
of their electronic configurations. The valence
of representative elements is usually (though
not necessarily) equal to the number of
clectrons in the outermost orbitals and / or
equal io eight minus the number of outermost
electrons as shown below.
Nowadays the term oxidation state is
frequently used for valence. Consider the two
oxygen containing compounds: OF, and Na 0,
The order of electronegativily of the three
elements involved in these compounds is F >
O> Na. Each of the atoms of fluorin
Ne
with outer
Sd
a
CHE
electronic configuration 25!2p, shar,
electron with oxygen in the OF, molec %
highest electronegative e
,
given oxidation state -1. Since moe
fluorine atoms in this molecule, oxy
outer electronic configuration 2s‘2p' shar!
two electrons with fluorine atoms and then
exhibits oxidation state +2. In Na, Ory
being more electronegative accepis i
electrons, one from each of the two sogiy!
atoms and, thus, shows oxidation state~ 6°
ihe other hand sodium with electroy,
configuration 3s! loses one electron (o oxyyq
and is given oxidation state +1. Thus, 4,
oxidation state of an element in a partiey,
compound can be defined as the charg
acquired by its atom on the basis
electronegative consideration from other atom,
in the molecule.
“Problem 3.8
Using the Periodic Table, predict the
forniulas of compounds which might be
formed by the following pairs of elements;
(a) silicon and bromine (b) aluminium and
sulphur.
Solution
(a) Silicon is group 14 element with a
valence of 4; bromine belongs to the
halogen family with a valence of 1.
Hence the formula of the compound
formed would be SiBr,
(b) Aluminium belongs to group 13 with
a valence of 3; sulphur belongs to
group 16 elements with a valence of
2. Hence. the formula of the compound
formed would be Al,S,
Some periodic trends observed in the
valence of elements (hydrides and oxides) a®
shown in Table 3.9. Other such periodic trends
which occur in the chemical behaviour of the
elements are discussed elsewhere in this book
_ ee
Group 1 2 13 14 15 16 pt 18
| Number of valence 1 2
electron : i = ; .
Valence 1 2 3 4 3.5 L7 0.8_S Yr
