3. CLASSIEICATION OFELEMENTS.
AND
PERIODICITY IN PROPERTIES
Earlier classifications
1) Dobereiner's classification:
Johann Dobereiner classified elements into small groups each containing three elements. These
Small groups were called triads.
E.g. for triads are: i) 7Li 23Na 39K
ii) 40Ca 88Sr 137 Ba
In triads, the atomic mass of the middle element is approximately the average of the other two
elements. This is known as Law of Triads. This classification was rejected, since the law of triad is
applicable only to a very few elements.
2) Newlands classification:
Newland arranged elements in the increasing order of their atomic masses. He noted that the
properties of every eighth element, starting from a given element, are similar to that of the first
[Link] relationship is just like the resemblance of first and eighth musical notes. He named this as
law of octaves.
But his classification was rejected since the law of octaves was applicable to elements upto calcium.
A.E.B. de Chancourtois arranged elements in increasing order of atomic weights and made a
cylindrical table of elements to display the regular repetition of properties.
3) Lothar Meyer's classification: Lothar Meyer plotted the physical properties of elenments like
atomic volume, melting point and boiling point against atomic weight and obtained a periodically
repeated pattern. Based on this, he developed a periodic table similar to that of Mendeleev's.
4) Mendeleev's classification:
Dmitri Mendeleev (a Russian chemist) classified the elements in the increasing order of their atomic
weights. He found that the properties of elements repeat after a regular interval. Based on this
observation, he proposed a periodic law which states that "The properties of elements are the
periodic functions of their atomic weights." That is, when elements are arranged in the increasing
order of their atomic weights, their properties repeat after a regular interval.
Mendeleev's periodictable contains horizontal rows called series (periods) and vertical
columns called groups. Elements with similar properties are placed in the same group. He
mainly depends on the similarities in the empirical formulae and the properties of the
compounds formed by the elements. So he did not strictly obey the increasing order of
atomic weights. Alsohe corrected the wrong atomic masses of some elements.
When Mendeleev proposed his periodic table, some of the elements were not discovered. He
left some vacant places (gaps) for them in the periodic table and predicted some of their properties.
For e.g. both Gallium and Germanium were not discovered at that time. He named these elements as
Eka-Aluminium and Eka-Silicon respectively and predicted their properties. These elements were
discovered later and found that Mendeleev's predictions were correct.
Merits of Mendeleev's periodic table
1) It was the first comprehensive classification of elements.
2) He corrected the wrong atomic weights of some elements and placed them in correct
position in the periodic table.
3) He left vacant places for undiscovered elements and predicted some of their properties.
4) Elements with similar properties are placed in the same group.
Demerits of Mendeleev's periodic table
1) Elements with dissimilar properties are found in same group.
2) He could not give an exact position for hydrogen.
3) He could not give exact position for Lanthanoids and Actinoids and also for isotopes.
4) Mendeleev'speriodic table did not strictly obey the increasing order of atomic weights.
Modern Periodic table
Henry Moseley'swork on the X-ray spectra of elements proved that atomic number is a more
fundamental property than atomic mass. Based on this observation, he modified the Mendeleev's
periodic law as "the physical and chemical properties of elements are the periodic functions
of their atomic numbers". This is known as Modern Periodic law.
Based on the modern periodic law, numerous forms of periodic tables have been proposed. The
most commonly used is the long formn of periodictable.
In this periodic table, the elements are arranged in the increasing order of their atomic number.
It contains 7 horizontal rows called periods and 18 vertical columns called groups or families.
In the long form of modern periodic table, hydrogen has given a particular position at the top centre.
PERIODS
There are 7 periods in Modern periodic table. The period number corresponds to the highest
principal quantum number of the elements.
Period No. Elements No. of Elements Subshells filled Description
1H & 2He 2 1s Very short period
aLi to 1oNe o 2s & 2p
3s & 3p
Short periods
11Na to 18Ar o
V 19K to 36Kr 18 4s, 3d & 4p
Long periods
V 37Rb to 54Xe 18 5s, 4d & 5p
VI 55Cs to 86Rn 32 6s, 4f, 5d & 6p
VII 87Fr to 118Og
Longest periods
32 7s, 5f, 6d & 7p
The 14 elements each of sixth and seventh periods are placed in separate rows below the main
bodyof the periodictable. These are together called inner transition elements. The 14 elenments of
sixth period[from s7Ce (cerium)to 1lu (lutetium)] are called Lanthanides or Lanthanones or
Lanthanoids or rare earths. The 14 elements of seventh period [from 90Th (thorium) to 103Lr
(lawrencium)]are called Actinides or Actinones or Actinoids.
GROUPS
Vertical columns in Long form of Modern periodic table are called groups or families. There are
18 groups and these are numbered from 1 to 18. Due to the similar outer electronic configuration and
same valency, the elements present inthe same group have similar properties.
Group General outer
No.
Elements Family name
Electronic configuration
1 Li, Na, K, Rb, Cs & Fr ns Alkali metals
2 Be, Mg, Ca, Sr, Ba & Ra ns² Alkaline earth metals
3to 12 4 rows of elements (n-1)di to 10 ns 0to 2 Transition elements
13 B, Al, Ga, In, TI& Nh ns² np Boron Family
14 C, Si, Ge, Sn, Pb & FI ns² np? Carbon Family
15 N, P, As, Sb, Bi& Mc ns' np Nitrogen Family
16 0, S, Se, Te, Po & Lv ns² np Oxygen Family
17 F,CI, Br, I, At, Ts ns² np Halogen Family
18 He, Ne, Ar, Kr, Xe, Rn, Og ns² np Noble gases
The Blocks in the Modern periodic table
The Modern periodic table is divided into 4 blocks based on the subshell in which
the last electron enters. They are s block, p block, d block and f block.
1. The s-block elements
These are elements in which the last electron enters in the outer most s sub shell.
They include elements of the groups 1 and 2. Their general outer electronic configuration
is ns' or ns². They are allreactive metals with low ionization enthalpies. They lose their
outer most electrons readily to form +1 and +2 [Link] metallic character and
reactivity increases down the group. They mainly form ionic compounds (except Li and Be).
2. The p-block elements
These are elements in which the last electron enters in the outer most psub shell.
They include elementsof the groups 13 to 18. Their general outer electronic configuration
is ns² np to 6. Their non-metallic character increases from left to right in aperiod and
metallic character increases from top to bottom ina group.
The 18th group elements are called Noble gases or inert gases. They have completely filled orbitals
andso they do not undergo chemical reactions at ordinary conditions.
sand p block elements are together called Representative elements, because these are the only
elements which show the general trends in the periodic table and also they contain metals, non-metals
and metalloids.
3. The d-block elements
These are elements in which the last electron enters in the penultimate d sub shell. They
include elements of the groups 3 to 12. They are also called Transition elements (Transition
metals),since they show a regular transition (change) from the most electropositive s block
elements to the least electropositive p block elements. Their general outer electronic
configuration is (n-1)d! to 10 nO to 2
Some properties of transition elements are:
a) They are allmetals.
b) They form coloured compounds or ions in aqueous solution.
c) They show variable oxidation states and valencies.
d) They are generally paramagnetic.
e) They show catalytic properties.
4. The f-block elements
These are elements inwhich the last electron enters in the anti-penultimate f sub
shell. They include lanthanides of 6th period and actinides of 7th period. They are also
called Inner transition elements. Their general outer electronic configuration is (n-2)f to
1(n-1)40 to l ns. They are all metals. Within each series the properties of these elements
are similar. Actinoid elements are radioactive. Elements after Uranium (z=92) in the actinide
series are called trans-uranium elementsor trans-uranic elements or artificial elements. [Neptunium
(93Np)and Plutonium (94Pu) are also found naturally in Pitch blende, an ore of Uranium].
Electronic configuration of an element and its position in the periodic table
From the electronicconfiguration of an element, we can assign its period, group and block in the
periodic table.
Block: The subshell in which the last electron enters.
Period number =the highest principal quantum number in itselectronic configuration.
Group number: For s-block elements=no. of valence s electrons
For p-block elements= no. of valence s electrons + valence p electrons + 10
For d-block elements = no. of valence s electrons + no. of penultimate d electrons.
Nomenclature of elements with atomic numbers >100
For naming elements with atomic number > 100, IUPAC has made some recommendations. A
systematic nomenclature be derived directly from the atomic number of the element using the
numerical roots for 0 and numbers 1-9.
Digit 1 2 5 6 7
Root name nil un bi tri quad pent hex sept Oct enn
Abbreviation n b t h
The roots are put together in order of digits which make up the atomic number and "ium" is added at
the end.
Atomic Number Name according to Symbol IUPAC Official Name
IUPACnomenclature and Symbol
101 Unnilunium Unu Mendelevium (Md)
102 Unnilbium Unb Nobelium (No)
103 Unniltrium Unt Lawrencium (Lr)
104 Unnilquadium Ung Rutherfordium (Rf)
105 Unnilpentium Unp Dubnium (Db)
106 Unnilhexium Unh Seaborgium (Sg)
107 Unnilseptium Uns Bohrium (Bh)
108 Unniloctium Uno Hassium (Hs)
109 Unnilennium Une Meitnerium (Mt)
110 Ununnilium Uun Darmstadtium (Ds)
111 Unununium Uuu Rontgenium (Rg)
112 Ununbium Uub Copernicium (Cp)
113 Ununtrium Uut Nihonium (Nh)
114 Ununquadium Uuq Flerovium (FI)
115 Ununpentium Uup Moscovium (Mc)
116 Ununhexium Uuh Livermorium (Lv)
117 Ununseptium Uus Tennessine (Ts)
118 Ununoctium Uuo Oganesson (Og)
119 Ununennium Uue
120 Unbinilium Ubn
Periodic properties of Elements
The properties which repeat after a regular interval are called periodic properties. Some of the
important periodicproperties of elements are atomic and ionic radi, ionization enthalpy, electron gain
enthalpy,electropositivity, electronegativity etc.
1. Atomic Radius
It isdefined as the distance from the centre of the nucleus to the outermost shell having
electrons. Atomic radius of individual atoms cannot be determined. So it is expressed in any of the
following methods:
a) Covalent radius: It is half of the inter nuclear distance between two covalently bonded (single
bonded) atoms. It isused to express the atomic radius of non-metal atoms. For e.g. the bond
distance of Cl2 molecule is 198 pm. So the covalent radius is 99 pm.
b) Metallic radius: It is the half of the inter nuclear distance between two metallic ions in a metal
crystal.
c) van der Waal's radius: It is definedas the half of the inter nuclear distance between two non
bonded atoms of separate molecules in the solid state.
Atomic radius is commonly expressed in picometre (pm) or angstrom (A) unit. [1 pm = 1012m and
1 A° = 1010 m]. It is measuredby x-ray diffraction method or by spectroscopic method.
Variation of atomic radius along agroup anda period
The atomic size decreases from left to right ina period. This is because ina period,
the electrons are added to the same valence shell. Thus the number of shells remains the
same, but the effective nuclear charge increases. So the atomic radius decreases. In a given
period, alkali metals (group 1) have the maximum size and halogens (group 17) have the minimum size.
In agroup, the atomic radius increases from top to bottom. This is because of the
increase in no. of shells and shielding effect. (Inatoms with higher atomic number,the inner
electrons partially shieldthe attractive force of the nucleus. So the outer electrons do not experience
the full attraction of the nucleus and this is known as shielding effect or screening effect).
Aradtoiums/pc
160
140
12o
Li
Aratdoiums/pc 300
250
200 -
K(231) Rb(244)
Cs(262)
Be
Na(186)
100 150T(152) I(133)
100 Br(114)
80 CI(99)
50 F(72)
60
4 10
Atomic number ( Atomic number (Z)
Variation of atomic radii along 2nd period Variation of atomic radii along 1t and 17th groups.
Atomic radius of noble gases is larger than that of halogens. This is because noble
gases are monoatomic. So van der Waal'sradius is used toexpress their atomic radius
which is greater than covalent radius or metallic radius.
2. lonic radius
It is defined as the half of the inter nuclear distance between cations and anions of an ionic crystal.
The variationof ionic radius is same as that of atomic radius.
Generally a cation is smaller than its parent atom(e.g. Nat is smaller than Na atom).
This is because a cation has fewer electrons, but its nuclear charge remains the same as
that of the parent atom.
An anion is larger than its parent atom (e.g. Ct is larger than Cl atom). This is because
the addition of one or more electrons would result in an increased electronic repulsion and
a decrease in effective nuclear charge.
Isoelectronic species:
Species (atoms and ions) having the same number of electrons are called isoelectronic
species. E.g. N,O,F,Ne, Na', Mg,A`* etc. (All these contain 10 electrons).
Among isoelectronic species, the cation with greater positive charge willhave the
Smaller radius. This is because of the greater attraction of electrons to the nucleus. The anion with
greater negative charge will have the larger radius. Here the repulsion between electrons is
greater than the attraction of the nucleus. So the ion willexpand in size.
Thus among the isoelectronicspecies N, 0, F, Ne, Nat, Mg*and AI, the largest ion is N and
the smallest ion is A³*.
3. lonisation enthalpy(AH)
It is defined as the energy required to remove an electron from the outer most shell
of an isolated gaseous atom in its ground state. Or, it is the energy requiredto convert agaseous
neutral atom to a gaseous unipositive ion. It may be represented as:
Xig) + AiH ’ X*) +e
Its unit is kJ/mol or J/mol.
The energy required to remove the first electron from the outer most shell of a neutral atom is called
first ionisation enthalpy (AiHi).
X(B) + AiH1’ X*) +e
Second lonisation enthalpy (AiH2) is the amount of energy required to remove an electron from a
unipositive ion.
X*e) + AiH2 ’ X) + er
Energy isalways required to remove an electron from an atom or ion. So 4,H is always positive.
The second ionisation enthalpy is always higher than first ionization enthalpy. This is
because it ismore difficult to remove an electron froma positively charged ion than from
a neutral atom.
Similarly third ionisation enthalpy is higher than second ionisation enthalpy and so on.
i.e. AH1< AH2 < AjH3........
As the ease of removal of electron increases, the ionisation enthalpy decreases.
Factors affecting ionisation enthalpy
The important factors which affect ionisation enthalpy are:
a) Atomic size: Greater the atomic size (atomicradius), smaller willbe the ionisation enthalpy.
b) Nuclear charge: The value of ionisation enthalpy increases with nuclear charge.
c) Shielding effect: As the shielding effect increases, the electrons can easily be removed and so the
ionisation enthalpy decreases.
d) Presence of half-filled or completely filled orbitals increases ionisation enthalpy.
[As the ease of removal of electron increases, ionisation enthalpy decresaes].
Variation of AH along a period and a group
Along a period, ionisation enthalpy increases from left to right. This is because of the
decrease in atomicradius and increase in nuclear charqe. Thus alkali metals have the least
AH and noble gases have the most.
Down agroup, AH decreases due to increase in atomic radius and shielding effect.
Thusamong alkali metals, lithium has the highest AH and francium has the lowest.
2500 550
Li(520)
molA,H/k'J 2000
Ne
(2080) molA,H/kJ' 500 Na(496)
F
1500
(1681)
450
(1402)
Be (1314) K
Rb(403)
1000 (899) 400
1086) (419)
Li
Cs(374)
(520) (801)
500 350|
2 4 6 10 0 10 20 30 40 50 60
60 Atomic number(
Atomic number(2)
Variation of ionisation enthalpy along 2nd period Variation of ionisation enthalpy along 1st group
In the secondperiod of modern periodic table, the first ionisation enthalpy of Boron
is slighthy less than that of Beryllium. This is because after the removal of one electron
from boron,it gets the stable configuration (1s2s'). So Bloses one electron faster.
Similarly the first ionisation enthalpy of nitrogen is greater than that of oxygen.
This is because N has half filled electronic conf iguration (1s²2s2p), which is more stable
and so more energy is required to remove an electron.
4. Electron gain enthalpy (AegH)
It isthe heat change (enthalpy change) when an electron is added to the outer most
shell of an isolated gaseous atom. It can be represented as X(g) +e’Xe)
Its unit is kJ/mol. It may be positive ornegative depending on the nature of the element. For
most of the elements, energy is released when electron is added totheir atoms. So AeghH is negative.
Noble gases have large positive electron gain enthalpy because of their stable
completely filled electronic configuration.
Electron gain enthalpy also depends on atomic size, nuclear charge, shielding effect etc. As the
atomicsize increases, AegH becomes less negative. When nuclear charge increases, electron gain
enthalpy becomes more negative. As shielding effect increases, AegH becomes less negative. Presence of
half-filled or completely filled orbitals make AegH less negative.
[As the ease of addition of electron increases,electron gain enthalpy becomes more negative].
Periodic variation of AegH
From left to right across a period, AegH become more negative. Thisis because of decrease in
atomicradius and increase in nuclear charge. So the ease of addition of electron increases.
Down a group,AegH becomes less negative. This is due to increase in atomic radius and shielding effect.
Electron qain enthalpy of fluorine is less negative than chlorine, This is because,
when an electron is added to F, it enters into the smaller 2nd shell. Due to the smaller size,
the electron suffers more repulsion from the other electrons. But for Cl, the incoming
electron goes to the larger 3rd shelI. So the electronic repulsion is low and hence Cl adds
electron more easily than F [OR, Due to the compactness of the 2p subshell of F, electronic
repulsion is greater in Fand hence it does not easily add electron]. Due to the same reason AegH of
oxygen is less negative than sulphur.
Thusin modern periodic table, alkalimetals have the least negative AegH and halogens have the
most negative [Link] halogens, AegH becomes less negative in the order: Cl> F> Br >|
[The negative electron gain enthalpy is also called electron affinity].
5. Electronegativity
Electronegativity of an atom in a compound is the ability of the atom to attract
shared pair of electron of electrons. It is not ameasurable quantity and so it has no unit. There are
different scales for measuring the Electronegativity of elements. The most commonly used one is the
Pauling Electronegativity scale developed by Linus Pauling. The other electronegativity scales are
Mulliken-Jaffe scale, Allred-Rochow scale etc.
Electronegativity depends on atomicsize and nuclear charge. As the atomic radius increases,
electronegativity decreases. Greater the nuclear charge, greater will be the electronegativity.
Generally electronegativity increases across a period and decreases along a group. So in modern
periodic table, Fluorine isthe most electronegative element and Francium is the least electronegative
element. Since francium is radioactive, caesium is the least electronegative stable element. In Pauling
Scale, electronegativity of Fluorine is 4.0and that of Oxygen is3.5.
The electronegativity of an element is not constant. It varies depending on the element to which it is
bound. It is directly related to the non-metallic character of elements. An increase in electronegativity
across a period indicates an increase in non-metallic character and decrease in metallic character.
6. Electropositivity
It isthe tendency of an atom to lose the most loosely bound electron (valence
electron). It is directly related to the metallic character of elements. It depends on atomic size and
nuclear charge. As the atomic radius increases, electropositivity increases.
Along a period, electropositivity decreases from left to right. But downa group,it increases. So
francium is the most electropositive element and fluorine is the least electropositive element.
7. Valency
It isthe combining capacity of anelement. Or, it is the number of electrons lost or
gained by anatom during a chemical reaction.
Along aperiod, valency first increases upto the middle and then decreases (for s and p block
elements only). In a group, valency remains constant. Transition elements can show variable valency.
Valency is numerically equal to oxidation number of the element. The difference is that oxidation
number has a positive or negative sign but the valency doesn't.
Anomalous Properties of Second Period Elements
The first element in groups 1 (lithium) and 2 (beryllium) and groups 13 to 17 (boron
tofluorine) differs from the other members of their respective group in their properties.
This is known as anomalous properties. This is due to their small size, large charge to
radius ratio, highelectronegativity and absence of vacant d-orbitals.
Some of the anomalous properties are:
They can form multiple bonds with themselves (e.g. C=C, N=Netc.) and with other
elements of the second period (e.g. C= 0, C= Netc.).
Their maximum co-valency is 4, due to the absence of vacant d-orbitals. But other
elements of the respective groups can expand their covalency beyond 4 (due tothe presence of
vacant d-orbitals). For this reason, Aluminium forms [AIF6l whereas boron cannot form[BF63
but forms only [BFa. Similary, Phosphorus forms PCls while nitrogen cannot form NCIs.
Diagonal relationship
The similarities in properties shown by the diagonally placed elements of the 2nd and
3rd periods in the Modern periodic table are called Diagonal relationship. This is due to
their similar atomic radii, ionisation enthalpy, electronegativity etc.
E.g. Lithium shows similarities with Mg, Be with Al, Bwith Si etc.
Group 1 Group 2 Group 13 Group 14
Li Be B
Na Mg Al
Periodic Trends and Chemical Reactivity
The periodicity in properties of elements is related to electronic configuration. That is, elements
having similar outer electronic configuration show similarities in chemical and physical properties.
The atomic and ionic radii, generally decrease in a period from left to right. As a consequence,
the ionization enthalpies generally increase and electron gain enthalpies become more negative across a
period. This results into high chemical reactivity at the two extremes and the lowest in the centre. Thus,
the maximum chemical reactivity at the extreme left (among alkalimetals) is exhibited by the loss of an
electron leading to the formation of acation and at the extreme right (among halogens) shown by the
gain of an electron forming an anion. This property can be related with the reducing and oxidizing
behaviour of the elements. i.e. Elements at the extreme left (alkali metals) of the periodic table are good
reducing agents and those at the extreme right (halogens) are good oxidising agents.
The chemical reactivity of an element can be explained by its reactions with oxygen. Elements on
two extremes ofaperiod (1$* and 17th groups)easily combine with oxygen to form oxides. The normal
Oxide formed by the element on extreme left (1 group) is the most basic (e.g. Naz0), whereas that
formed by the element on extreme right (17th group) is the most acidic (e.g. Cl,0,). Oxides of elements
in the centre are amphoteric(e.g. Alz03, Asz03) or neutral (e.g. C0, NO, No). Amphoteric oxides behave
both as acidic (with bases)and basic (with acids), while neutral oxides have no acidic or basic properties.