(Shivani-2024) Periodic Properties 183

(v) The seventh period is considered to be incomplete period. It is

cted to contain
also expected to contain 32 elements corresponding to the filling of 16 orbitals
(i.e.,one 7s, seven 5f, five 6d and three 7p). It has elements starting with gpFr
onwards, Elements from atomic number 93 onwards are purely synthetic and
are known as
transuranium elements.
The number of elements and the corresponding orbitals are compiled in
the following table
Table 7.1 Number of Elements and Number of Orbitals Filled in
Different Periods

Orbitals being Number of Elements in the

Period (n) Electrons Period
Filled up
ls 2 2
First (1)
2+6 8
Second (2) 2s, 2p
2+6 8
Third (3) 3s, 3p
2+ 10 + 6 18
Fourth (4) 4s, 3d, 4p
2+ 10 +6 18
Fifth (5) 5s, 4d, 5p
2+ 14 + 10 +6 32
Sixth (6) 6s, 4f, 5d, 6p
2+ 14 + 10 + 6 32
Seventh (7) 7s, 5f, 6d, 7p
0.5. Write down the characteristics of modern periodic table.
Ans. Characteristics of modern periodic table are as follows -
(i) Metallic and non-metallic elements have been separated.
can
(ii) On the basis of filling of electrons in elements, all elements
be divided into s-block,p-block, d-block and f-block elements.
(ii) Two subgroups of the same group are placed separately.
(iv) Hydrogen is placed in group 1.
(v) Fe,Co, Ni are placed with transition elements.
(vi) Lanthanides and actinides are given appropriate places in modem
periodic table.
(vii) Strongly metallic elements (s-block elements) are placed on lett
Side of transition elements (d-block elements) in groups l and 2, transition
elements are placed between groups 3 to 12 and non-metallic elements (P
block elements) at the right of transition elements from groups 3to l7.
0.6. Draw the long form of periodic table or modern periodic table.
Ans. Refer table 7.2.
 en2024) Periodic Properties f85
Cessi elements according to the ype of orbital.
AnsTheelements, as arranged in the long form of the periodic table, can
dividedintofour blocks known ass, p, d- and fblock elements. This
e be
eeeoification depends upon the type of the orbital(s, p, dor f) into which the
elctron of the atom of the element enters.
à -Block Elements- Elements in which the last electron enters
orbital,are known asss-block elements. For example, among elements of
s numbers l0, 11,112 and 13 since the last electron enters the s-orbital
omic
elements with atomic numbers 11 and 12, only these are said to be the
nlyin
membersof the s-block elements.
Ne Is, 2s'p6
Na Is², 2s²p, 3s! s-block element (member of groups IA)
Mg Is?, 2s?p, 3s2 s-block element (member of groups IIA)
BAI ls, 2s-p, 3s²p!
Since an s-orbital can accommodate a maximum number of two electrons,
be s-block comprises of only two groups of the periodic table, i.e., group IA
alkali metals) having one electron in the outermost s orbital and group IIA
alkaline earth metals) having two electrons in the outermost s orbital. Thus
the electronic configuration of group IA and IIA elements may be represented
Bs ns and ns respectively where n is the number of the outermost shell.
Their (n-1) s, p and d orbitals are completely filled. Thus only the outermost
orbital of these elements is incomplete.
Group 1and 2 Group 3 to 12 Group 13to 18

Is Representative Elements
Gases
Inert
s-Block p-Block
Elements d-Block Elements Elements
ns or ns² (n-1) d1-10 ngl-2 ns² npl-6
-Block Elements
(n-2)fl-14 (n-1) 0-1 ns²
Fig. 7.1 Division of Periodie Table into s, p, d
() p-Block Elements - Elements in which
andFBlocks
gcively filled (i.e., elements in which last p-orbitals are being
Ae
known as p-block elements. For example, electronenters the p-orbital)
sB Ist, 2stp!
6C
1s, 2s²p
1st, 2sp² 1s, 2s'p
N Is, 2s'p 1ONe Is, 2sp
 186 Engineering Chemistry
In the long form of the
periodic table, (R.GPV., B. Tech.,-Yean
p-block consists of
mA IVA VA, VIA, VIIA and zero groups whose whose outermost
ns'np eneeandlregrynentslevels
have the configurations ns'np,
general
ns'np', ns²np'of, ns'np, of
respectively. Thus the configuration these
where n is the number of the outermost
are completely filled. Thus only the
shelL.
outermost orbital of and d pelements
(n 1) s, p is ngns' nf
Their
incomplete. Since their properties are dependent oron the
they are known as p-block elements. Elements having ns?p presencetheseof elemeontbtistals,is
also grouped separately as inert gases.
Elements of s- and p-blocks are called normal or conf i
gp-
uerl
aetc
io
representative elements
trons, are
(iii) d-Block Elements (Transition Elements)
last electron enters the d-orbital (i.e. elements in Elements
which d-orbitals arein which
progressively filled) are known as d-block elements. In these being
last electron is added to the penultimate shell (inner to the elementsshell),, the
outermost
Their two outermost orbitals are not complete or full. In the long
form of the
periodic table, d-block consists ofelements of IIIB, IVB, VB, VIB,
IB and IIB whosetwo outermost energy levels have the VIIB, VII,
configurations
from (n - 1) sp°d', ns² (in group IIB) to (n 1) s²p°alo, ns (in groupvarying
Since the properties of these elements are midway IIB).
between those of s-block
and p-block elements, they are known as transition elements. Their generl
nsl-2
electronic configuration is (n - l)dl-10
Transition (d-block) elements may again be divided into three series each
having 10 elements -
(a) First Transition Series- In these elements, the last electron
is added in the 3d orbital. This includes elements of fourth period from scandium
GSc) to zinc (30Zn).
(b) Second Transition Series - In these elements, the last
electron is added in the 4d orbital. This includes elements of fifth period from
yttrium (3g Y) to cadmium (4gCd).
(c) Third Transition Series- In these elements, the last electron
is added in the 5d orbital. This includes elements of sixth period i.e. lanthanum
(6La) and hafnium (zH)to mercury (go-Hg).
(iv) f-Block Elements- Elements in which the last electron isfilled) added
to any one of the seven f-orbitals (i.e. f-orbitals are
being progressively in
are called f-block elements. In all these the last electron is added
the antepenultimate (third orbit elements, n- 2) shell. Thus
f-block elements have their three from the orbits
outermost i.e.
incomplete. In these elements,
penultimate
the outermost shell (n) outermost
has only two electrons in s-orbital, the (n-2)
(n-1) shell has 0 or I electron antepenultimate
shell has 1to 14 electrons in in the d-orbital andthe outer shell electronic
configuration of f-block elementstheisf-orbital.
given as
Thus the

(n-2)fr-4 (n -1) d0- ns

 Periodic Properties 187
Sman20P4)

cclementsare also known as inner transition elements because

fblock
series. There
The theyconstitute transition series within transition classified on
speaking
eraly offblock
elements each containing 14 elements
thenumber of?forbital (4f or 5h) being progressively filled.
basisof
he Lanthanides or Rare
Rare Earths -In these elements, the last
(a)
progressively added in the 4f orbital. This includes elements
is being part of sixth period.
elevtron
(sgCe)tolutetium( Lu) which form a
cerium last electron is being
fom
(b) Actinides - In these elements, theelements from thorium
prgressivelyadded in
the 5f orbital. This includes
lawrencium (103Lw) which form a part of seventh period.
to
lo
Th)
general characteristics of s-blockandp-block elements 2
Whatare the
General Characteristics of s-Block Elements-
Ans. melting and boiling points.
) They are soft metals with low provide univalent and bivalent
and
() They are highly reactive metals respectively.
one or two valence electrons
s
jons by losing
They have low ionization energies and thus are highly electropositive.
(m) agents.
(iv) They act as strong reducing block impart characteristic colours
(v) Most of the elements of this
to the flame.
(vi) They form ionic compounds.
Elements
General Characteristics of p-Block
p-block elements include both metals and non-metals. The
(i)
character decreases and non-metallicnature of elements increases as
metallic
right.
we move along a period from left to higher as compared to
relatively
(ü) Their ionization energies are
s-block elements.
(ii) They form covalent compounds. than one oxidation state in their
(iv) Majority of them show more
compounds. from top to bottom in a group
(v) Theirreducing character increases
in a period.
and their oxidising character increases from left to right
fFblock elements.
9. Write the characteristics of d-block and
Ans. General Characteristics of d-Block Elements
They are hard metals having high melting and boiling points.
)
() They exhibit several oxidation states. and p-block elements.
(ii) Their ionization energies lie betweens-
(Iv) They form both the ionic and covalent compounds.
electricity.
) They are good conductor of heat and
(Vi) They fotm coloured ions and complexes. paramagnetic
In nature. (vii) Metals andtheir ions having unpaired electrons arep
 188 Engineering Chemistry (R.GPV,B. Tech., -Yean)
(vii) Most of the transition metals such as V, Mn,.
Fe, Co, Ni,
ete. act as catalyst.
(ix) Transition elements form alloys.
Cu.
General Characteristics of -Block Elements
) They are heavy metals.
() They show high melting and boiling points,
(in) Theyshow variable oxidation states.
(iv) They have the tendency to form complexes.
(v) Their ions and complexes are generally coloured.
(vi) Elements of actinideseries are radioactive in nature
Q.10. What are the advantages and disadvantages offlong form of the
periodic table ?
Ans. Advantages - Since long form of the periodic table classifies the
elements on the basis of electronic configuration of their atoms, it has the
following advantages
) This classification is based on the atomic number of theelements
which is their fundamental property.
(ii) The elements in the same group show marked similarities in
properties due to their similar outer electronic configuration.
(ii) It is easy to remember them and reproduce.
(iv) The systematic grouping of elements into four blocks i.e. s. B.
dand f has made the study of these elements quite simple.
(v) Same position to the isotope of an element can be justifiedas
isotopes have sameatomic number but different atomic mass.
(vi) The position offew elements, which were misfit in Mendeleef's
table on the basis of their atomic mass is now justified on the basis of atomic
number. For example, argon is assigned position before potassium because
argon has atomic number 18 and potassium has 19.
(vii) The transition elements of fourth, fifth, sixth and seventh periods
are assigned proper positions in the periodic table.
(vii)Three triads consisting of nine elements have been placed n
groups 8, 9 and 10.
(ix) The lanthanides and actinides have been placed separately at ue
bottom of the table.
Disadvantages Although the long form of the periodic ttable has simplified
the study of chemistry of elements yet it suffers from the following
disadvantages)
Position of
hydrogen is not properly settled. It has been
alongwith alkali metals (group
both in hemical ) and halogens (group Vi) VI) as it
resembles
properties.
() 14 elements each of notbeen
accommodated in the main body of lanthanides and actinides have
the periodie table.
iant2024)
Poriodio Properties 189

,Howelectronic configuration is useful to place anelement in periodie

the definition and rends
(i)
offllowing in periodie table.
Electron afinity lonization energy
(R.GPV, Now, 2018)
Theelectron configuration
of
an atom is the representation the of
Ans.
t of
arnangemet electrons distributed among the orbital shells and subshells.
configuration is used to describe the orbitals of an
Comnonly,the electron but it can also be used to represent an atom that has
ground state,
gtominits a cation or anion by compensating with the loss of or gain of
into
ionized subsequent orbitals. Many of the physical and chemical
electronsin their
sofelements can be correlated totheir unique electron configurations.
properties
valence electrons, ellectrons in the
outermost shell, are the determining
The chemistry of the element.
bctor for the unique
Afinity Electron affinity
) Definition and Trends of Electronaneutral atom (in the gaseous
defined as the change inenergy (in kJ/mole) of form a negative ion. In other
phase) when an
electron is added to the atom to
gaining an electron.
Mords. the neutral atom's likelihood of groups and from left to right
Electron affinity increases upward for the
of a periodic table because the electrons added to energy levels
across periods attraction between the nucleus
become closer to the nucleus, thus a stronger distance, the less of an attraction:
electrons. Remember that greater the
and its electron is added tothe outside orbital.
thus, less energy is released when an
element has, the more likely it is to
In addition, the more valence electrons an valence electrons an atom has,
gain electrons to form a stable octet. The less
the least likely it will gain electrons. to left across
Electron affinity decreases down the groups and from right in a higher
the periods on the periodic table because the electrons are placed
pull. However, one
energy level far from the nucleus, thus a decrease from its down
might think that since the number of valence electrons increase goingaffinity.
electron
he group, the element should be more stable and have higher
the period, the
Une fails toaccount for the shielding affect. As one goes down electrons. This
elding effect increases, thus repulsion occurs between the one
BWhy the attraction between the electron and the nucleus decreased as
Boes down the group in the periodic table.
As we go down the group, first electron affinities become less. Fluorine
separately. The electron
breaks that pattern, and will have to be accounted forincoming
:
electron andthe
atlinity is a measure of the attraction between the isreleased.
ucleus The factors
thethisstronger
Mhich affect the attraction,
attraction are exactlythe
the more
sameenergy
as those relating to inonization
Ehergies- nuclearthe group,distance The increased nuclear charge
Swe go down charge, is offsetandbyscreening.
extra screening electrons. Each outer
Clectron in effect feels apull of7+ from the centre of the atom, irrespective of
Which element you are talking about.
 190 Engineering Chemistry

theenergy
initial
()

remove one
Definition
requiredto
inonization
mole of
and Trendssoflonization Energy -

electrons
togetherwith
of an atom or molecule is
energy or E,from
atomnic
one m
and ionic radius,
(R.GPVlo.,nBiz.Tatateioctonhms.r,eLquiYenerergdy
removean clectron from a gaseous atom or
the ion. The first iox
energy or to
mole of isolated gaseous
lonization,
aftinityand metallicity,
generally increases moving from left
lonization energy This is because the atomic radius toelectronegalirivegilthteym,eacrntso.ss
follows a trend on the periodic table of
eleYonsctr ,

attractgenerional ybetwdecreeneases
(row). an
element period period, so there is a greater effective
moving across a electrons and positively-charged nucleus. the
negatively charged the alkali metal onthe left side of the table
for noblevalue
minimum
its the
for and has
gas on the far right side of a period. The noble gas
electron removal.
a is at
afilled Lonizatmaxiion mum
valence shell, so it resists bottom down aan n
lonization decreases moving top to
principal quantum number elementgroup (column)
of the outermost electron
This is because the are more protons in atoms mnoving increases
moving down a group. There down amaking
(greater positive charge), yet the effect is to pull in the electron shhells, group
them smaller and screening outer electrons from the attractive force of the
nucleus. More electronshells are added moving down a group, so the outermost
from the nucleus.
electron becomes increasingly distance
June 202),
0.12. Write brief noteon electron affinity, (R.GP., May 2019,
Ans. Refer toQ.11 ().
group and
0.13. What is periodic table ? Write trends offollowing in a
in a periodgiving suitable reason - (i) Electron affiniy:
) Electronic configuration (i) Atomicsize (R.GPV., Nov. 2019)
Ans. Periodic Table Refer to Q.1.
electronic configuration of an
() Electronic Configuration - The ofelectrons distributed
atom is the numerical representation of the arrangement
orbitals of the atom. This determines the position of an element in the
in the explains how the atoms are
periodic table and in turn its chemical behaviour. It trends which are observed
held Itogether by the chemical bonds, and the peculiar
in the rows and columns of the periodic table.
Electronic Configurationin Periods - the valence
(a) The value ofn, the principal quantum number, for
number
shell is the period of the element.
accommodate different
(b) Different energy levels can
of electrons. energylevel
given thefirst
(c) The maximum number of electrons that a level. So hold
can accommodate is given by 2n', where n is the energy can
shell) on.
level(L s
energy level (K shell) can hold up to 2 electrons, second electrons and
so

up to 8 electrons, and third level (M shell) can also hold18

Shhant-2024) Periodlo Properties 191
NThus, the first period with n=1 can hold up to 2elements by
thelowest
level1s. The elements are Hydrogen and Helium with electronic
configuration1s' and Is² This marks the complete filling of Kshell.
illing
(e) The second period starts with Lithium and Beryllium which
and.4electrons and| hencethe last electrons enter the level 2s and they
3
haveanelectronicconfiguration of 1s'2s and
have

fthe2p
orbital filling. It start with Boron (1s'2s²2p') and ends with
startof
Neon
(1,s²2s'2p) which marks the completion of Lshell. Thus 8 elements
presentin the second period.
are () The third period starts with Sodium and ends at Argon while
SUccessively.filling 3sand13p orbitals. 8elementsare present in this period too.
(g) The fourth period with n =4 starts by filling the level 4s. It
begins withPotassium.
However, we know that 3d orbital is to be filled before
the beginning of the 3d transition elements
fllingof4porbitalIstarts. This marks
hScandium (electronic configuration - [Ar] 3d'4s). At Zinc (electronic
configuration - [Ar]3d °4s), the 3d orbital is filled.
(h) The fifth period with n =5 starts by filling the level 5s. This
soriod consists of the 4d transition series which starts with Yttrium. Xenon
ends the period()byThecompletely filling the Sp orbital.
sixth period with n=6 holds 32 elements with electrons
Fling 6s,4f, 5d and 6p orbitals. Cerium marks the electrons entering 4forbital
oiving rise to the 4f-inner transition elements, called the lanthanide series.
(i) The seventh period withn =7 includes the man-made
radioactive elements with electrons filling 7s, 5f, 6d and 7p orbitals. Similar to
period 6, this period also leads to the filling of electrons to 5f orbital, giving
rise to the 5f-inner transition elements known as the actinide series.
Electronic Configuration in Groups -Elements in the same group have
the same number of electrons in their outermost shell leading to similar valence
shell electronic configuration. Thus, we observe a similar trend in the properties
and chemistry of the elements in the same group.
(i) AtomicSize - The atomic radius or atomic size is an indication
of the size of an atom. Although the concept of adefinite radius of an atom is
abit fuzzy, atoms behave as if they have a certain radius. Such radii can be
estimated from various experimental techniques, such as the X-ray
crystallography of crystals.
As you go down a column of the periodic table, the atomic radii increase.
This is because the valence electron shell is getting a larger and there is a
larger principal quantum number, so the valence shelllies physically farther
away from the nucleus. This trend can be summarized as follows
as PT, atomic radius ‘
where PT stands for periodic table. Going across a row on the periodic table,
et to right, the trend is different. This is because although the valence shell
 192 Engineering Chemistry
quantum number, the number of
(R.GPV, B.Tech.,-Yean
same principal
maintainsthe
tphreotonrosw,-nd
charge-is increasing as you go across
hence the nuclear charge casts a tighter grip on the valence
increasing positiveperiodic table, the atomic radii decrease, The
yougo across the
summarizethis trend as follows
atomic radius
elAgaiectronn,s, s0 a%
we Can
as > PT,
Qll).
(i) Electron Afinity - Refer to
understand by periodic properties of
Q.14 What do you
Discuss is importantproperties. elemen
Ans. Most of the properties of the elements such as valency, atomic
ts ?
ionisationenergyand electron affinity andlelectronegativity aredirectly related to
properties
the electronic configuration of atoms. These period undergo periodicc
with the changein atomic number within
a
indirectly controlthe physical propertiessuchaas
or a group.
These vari ation
properdensity
melting point, boilingpoint, ties
below
etc. of elements. Some important properties are discussed
(i) Valencyand Oxidation State--Combining capacity of an element
is known as its valency. It is generally expressed in terms of the number ot
hydrogen atoms or the number of chlorine atoms or double the number of
Oxygen atoms that combine with an atom of the element. As discussed earlier,
the properties of an element usually depend upon the number of electrons
present in the valence shell i.e., the number of electrons present in the last
orbit. Therefore, the electrons present in the outermost shell are called valence
electrons and these electrons determine valency of the atom.
In case of s-block and d-block elements (known as representative
elements) the valency is generally equal to the either the number of valence
electrons or equal to eight minus the number of valence electrons. However,
the transition elements (d-block elements) and inner transition elements (f
block elements) exhibit variable valency.
(a) Variation of Valency in the Periodic Table - The number
of valency electrons increases from Ito 8 on moving across a period from
left to right. However, valency of element along a period with respect to
hydrogen or chlorine increases from 1to 4 and then decreases to zero. 1his
may be illustrated by taking the elements of second and thirdperiods as shown
below in table 7.3.
Table 7.3 Variation of Valency of Elements of Second and Third Periods
Elements of Second Period
|Elements of 2nd period Li Be B N
F Ne
Compounds with hydrogen LiH BeH, BH,CH.NH,H,0| HF
BelH, BH,
|Compounds with chlorine LiCI BeCl,BCHcL.INCHCIHo|CIF
Valency w.r.t. H orCI 2 3 4 3210
4
Shian-2024)
Periodic Properties 193
Elements of Third Period
period Na Mg A
plementsof3rd P aAr
Compounds with hydrogen NalH
Compounds with chlorine
|MgH,|AIH SiH, PH H,S H
Valency w.rt
Hor CI NaCl|M2gC,|AIC|SiC PCI|SC,Ch
1 2 3 4
210 2
(b) Variation of Valency in a Group - On
number of valency electrons moving down a
group, the remain the same, therefore, all the
elementsin a group exhibitsame valency. For example, all elements of group
ie.alkaliimetals) and of group 2(i.e. alkaline earth metals) have
valency1
and2respectively. Similarly, al noble; gases present in group 18 are chemically
inertand exhibit zero valency.
The arbitrary charge assigned to an atom in a compound is known as its
idation number or Oxidation state. Transition and inner transition metals
exhibit variable oxidation numbers.
(i) Atomic and lonic radii - The radius of an atom (known as
Romic radius) is the distance between the centre of its nucleus and electron in
the outermost orbit. Although atomic radius or atomic size is very important
Droperty of an atom because most of the chemical and physical properties
shown by an atom are related to its atomic size yet it is not possible to find out
the exact radius of the atom because of the following reasons.
(a) Size of an atom is very small and hence it is not possible to
isolate a single atomn to measure its radius.
(b) According to probability distribution of electrons, an atom
does not have well defined boundary. Furthermore, the probability of finding
the electron is never zero even at large distance from the nucleus.
(c) The probability distribution is alsoaffected by the presence
of other atoms in its neighbourhood.
(d) Atomic radius also changes from one bonding state to another.
(ii) lonization Energy (or lonization Potential) - When an atom
Bbsorbs energy,the electrons from the outermost orbit are promoted to higher
energy levels. If supplying of energy is continued, the electron goes off
pletely from the influence of nucleus. Such removal of electron from an
alom will result in the formation ofa cation (i.e. apositive ion) andthe amount
of
energ y required for ionization of electron is termed as ionization energy or
ionization potential.
where M(g) + Energy’ M'(g) te
Slate. M(g) and M'(g) represent metal atom and mnetal cation in gaseous
o Thus,, ionization energy may be defined as the amount of energy required
rBAseeousmovestatean. electron from the outermost orbit of an isolated atom in the
 194 Engineering Chemistry (R.GPV, B.Tech.,
corresponding to-Yoatnh)e
- The energy
Successive lonization Energy
most loosely bound electron from an atom in
ionization ofthe
called its first
ionization energy denoted by IE e.g.,
M(g) +IE M(g) +e
gaseous
state is
Similarly, the amount of energy required to remove one more
firom unipositiveion istermed second ionization energy. it is denoted by 1E
enerRy required to knock
out third and fourth electron
Likewise the
dipositive and tripositive ions are calledIE3 and IE4 respectively.
’ M²(g) + e
electrons
from
M'(g) + IE,
M²*(g) + IE ’ M(g) + e
M(g) + I IE4E ’ M(g) +
> E,
It may be noted that IE > IE3 > IE,
(iv) Electron Afinity- It is defined asas the amounttof energy released
when an extra electron is taken up by a neutral gaseous atom to form monovalen
gaseous anion, e.g.,
X(g) + e ’ X + Energy
the atom ear
The magnitude of electron affinity is the force with which
hold an extra electron i.e., greater the electron affinity value greater is the
tendency of atom to accept the electron.
Unitsof Electron Affinity Electron affinity values are expressed either
the
in electron volt (eV) or kJ mole. Its values are determined indirectly with
help of Born-Haber cycle.
Successive Electron Affinities When an electron is added to gaseous
anion.
atom, the energy is released and the atom becomes negative iron or
However, the addition of second electron to an anion is opposed by electrostatic
of second
repulsion and hence the energy has to besupplied for the addition an
electron. Therefore, the second and successive electron affinities ofelement
are negative. For example,
First E.A. - Og) +e ’ O (g); EA, =+ 141.0 kJ mole
(Energy is released)
780.0 kJ mole-
Second E.A. - 0 (g) +e’o (g); EA, =-
(Energy is absorbed)
an atom in a compoundto
() Electronegativity- The tendency of electronegativity
attract a pair of bonded electrons towards itself is known as
of the atom. It is and
electronegativity
important
both measure the electrons
to note that electron affinity an
isolated
attracting refers to:
power but the former electronaftinity
gaseous atom while the latter to an atom in a compound. Thus ofbonded
is attraction for a single electron while electronegativity is forra a pair tendency
electrons. Further, electron affinity isisenergy
e
is a
while electronegativity electronic
(b)
Electronegativity
configuration. depends upon (a) the size of the atom and
a
Shianh2024) Periodic Properties 195
Smallatoms attract electron more than the larger one and are therefore
electronegative, Secondly, atoms with nearly filled shells of electrons, will
more
have higher electronegativity than those which are sparsely occupied.
endto (a)Variationnof Electronegativityyin a Period- Along aperiod
electronegativityincreases from left to right. This is due to decrease in size
increasein nuclear charge. Thus alkali metals possess the lowest values,
and
while
halogenshavethe highest. Inert gases have zero electronegativity,.
(b) Variation of Electronegativity in aGroup- Within agroup
electronegativity decreases from top to bottom. This is due to increase in
atomicsize.
element exhibits various oxidation states, the atom in the higher
If an
oxidationstate will be more electronegative due to greater attraction
for the
electron,i.e. Sn II (1.30) and Sn IV (1.90).
Concept of electronegativity may predict following properties -
(a) If the two atoms have similar electronegativities, the bond
kobueen them will be covalent (i.e., a weak bond), while a large difference in
lectronegativities leads to an 1onic bond (i.., a strong bond). It is observed
fhat when the difference between the electronegativities of the two atoms is
17.the bond formed between them will be 50% ionic in character.
(b) Sinceacovalent bond is a weaker bond, while an ionic bond
is astronger bond, greater the ionicpercentage character of a bond more is its
stability. Percent ionic character of a bond may be calculated using Hannay
and Smyth equation.
%lonic character = 16 (ZA - XB) +3.5 (XA - XB
where (ZA -Xa) are electronegativities difference between Aand B. For example,
the percent ionic character between Hand F bond can be calculated as follows.
Electronegativities of F and H are 4.0 and 2.1l respectively.
%lonic character in HF = 16 (4.0 - 2.1) +3.5 (4.0 - 2.1) = 43%
(c) Greater the electronegativity of an element, greater is its
tendency to gain electrons (greater oxidising power) and hence more is its
non-metallic properties.
Conversely, the electropositive character (the tendency of an atom to
SValence electrons) decreases across the period and increases down the
Boups. Alkali metals (group l) are the most electropositive followed by alkaline
metals (group 2).Oxides of these elements become increasingly acidie
OSS a period, but increasingly basic down a group.
Since eleelectronegativity is a relative property, it has no units.
ElvaleucetrMuloneglaiktien'vitys
of
may be expressed on the Mulliken's scale.
Scale - Mulliken regarded electronegativity as the average
ionization potential and electron affinity of an atom.
lonization potential + Electron affinity
Electronegativity = 2
 196 Engineering Chemistry (R.GPV., B.
0.15. Whine brief note on
electronegativity.(R. GPV, Noy, .Tech., kYean)
Ans. Refer to Q.14 (V).
radius or size.
2019, 2022)
QI6 Eylain the opes of atomic
Ans, In order to explainradii, chemical properties of
various
in tems of atomic or
ionic three operational concepts of differentatomielcements
are widely in use. radius
() Covalent Radins - It iscovalently
defined as one half of
between the centres of nuclei of two bonded atoms theof the distance
element. Thus covalent radius of carbon in a compound having C-C same
bond (i.e. homonuclear diatomic molecule) can be determined by single
bond length by two i.e.
dividing the
1
[Internuclear distance between two covalently bondedl
Toovalent2
Since the internuclear distance between two bonded atoms is known
atoms)
bond length,
1
Toovalent= 2
[Bond length]
H-H 1
or TH-H cOvalent = i.e. Bond distance between two H atomsl
or H-Hbond distance = 2rcovalent 144 A=
For example, the internuclear distance
between two hydrogen atoms in H2
molecule is 0.74 Å (or 74 pm). Hence the
covalent radius of hydrogen atom is equal
to 0.37 ¢ (or 37 pm). Similarly, atomic Covalent
1.44
Radius.
radius of fluorine is =

2
=0.72 Å
Bond distance between F- F 144 Fig. 7.2 Covalent Radius of
2 2 Fluorine Atom
=72 pm (or 0.72 Å)
Bond distance between Cl -Cl
Atomic radius of chlorine =
2
198
= 99 pmn (or 0.99 A)
2
(ii) Vander Waal's Radius -It is defined as one-halfofthe distance
between the centres of nuclei of two adjacent non-bonded atoms belongingto
two neighbouring molecules of an element in the
solid state. chlorine
For examnple, the adjacent
atoms of the two internuclearCl, distance between two
state is 360 pm.
neighbouring
Therefore, the Vander Waal's radius of
molecules in the solid
360 l80pmor
pm=
chlorine atom is 2
Shvant-2024) Periodic Properties 197
Similarly,the internuclear distance between two adjoining H-atoms of
eghbouringhydrogen molecules in the solid state is 240 pm (or 2.4 A).
18A

240
Theretore,Vander Waal's
hydrogen radii ==2 120 pmor 1.2 A.
(ii) Metallic Radius - It is defined as one half of the internuclear
betweenthe centres of two adjacent atoms in the metallic crystal.
distance
internuclear distance between the two adjacent atoms in a metallic crystal
The than the internuclear distance between the two atoms linked by a
longer
is of?
cOvalentbond. Due to overlapping fatomic orbitals, the covalent bond becomes
suggeststhat metallic bondis weaker than acovalent bond. Therefore,
short.It
metallicradius of an element is greater than its covalent radius. For example,
metallicand covalent radius of potassium are 2.31 and 2.03 Árespectively.
0.17.Compare covalent radius with Vander Waal's radius.
Ans. Vander Waal's forces between two non-bonded isolated atoms is
weak and its magnitude depends upon the packing of atoms when the element
sin the solid state. Contrary to it, acovalent bond is formed by overlapping of
atomic orbitals and the
Overlap region becomes
common between the
two atoms, therefore, the
covalent radii is always
shorter than the atomic
radii of non-bonded Tcovalent rVander Waal's

adjoining atoms (i.e. Fig. 7.3 Comparison of Covalent and Vander

Vander Waal's radii). Waal's Radius
Q18. Write explanatory note on ionic radi.
Ans. lons are formed when neutral atoms either lose or gain electrons.
When a neutral atom loses one or more electrons a cation is formed whereas
Bain of one or more electrons by a neutral atom results in the formation of
0n. Ihus radius of an ion decreases by lose of electron and increases by
gain of electron. Therefore, ionic radius may be defined as the effective distance
from the centre of
its electron cloud. the nucleus of the ion upto which it exerts its influence on
Acation (formed by the
is removal of one or more electrons from an atom)
alwaysof felectronssmaller
number
much than the corresponding atom. Further, greater the
removed smaller will be the size of the resulting positive
ion. For example,
Atomic radius of Fe = 1.26 A
lonic radius of Fe2+ = 0.76 Å
lonic radius of Fet= 0.64 Å
198 Engineering Chemistry
(RGPV, B.1Tech..,EYear)
following wo factors
This is)dueAtocation formed by the loss of electrons may result in the
complete disappearance ofthe outershellandI sincethe remaining iinner shels
space,the cation is much
smaller than the
do not extendso
farin metal atom
For example, Sodium atom (Na) ’ Sodium ion (Na)
(2, 8, 1) (2,8)
() Whenever a cationis forned, the ratio of nuclear charge to the
number ofelectrons(Z/eratio)isincreased with the resultthe effective nuclear
charge is increasedand electrons are pulled towards the nucleus. Consequently.
the cation becomes smaller. Table 7.4 illustrates the comparative size of atoms
and their cations.
Atoms and their Cations
Table 7.4 Comparative Size of
Na K Be Mg Ca A Fe
Atom
Atomic radii(Å) L231.54 2.02 |0.89| 1.36| 1.97 1.251.26
Corresponding cation Lt Nat Kt Be2+ Mg?+Ca² AP+ Fe3
lonic radii (¢) 0.600.951.33 0.39|0.65 |0.990.500.64
An anion (formed by gain of one or more electrons) is always larger than
the corresponding atom. For example,0.99 ¢
Atomic radius of Cl=
lonic radius of CI = 1.81Å
The reason for increase in ionic radius is due to following factors.
) Due to addition of one or more electrons, the electron cloud
expands and the ionic size increases.
(ü) In the formation of anion the effective nuclear charge decreases
which results in expansion of electron cloud. Thus the anion becomes larger
than the corresponding atom.
Comparative sizes of atoms and their anions may be illustrated in table 7.5.
Table 7.5Comparative Sizes of Atoms and their Anions
Alom F Br S N
Atomic radii (Å) 0.72 0.,99 1.14 1.33 0,74 1.02 0.75
Corresponding anion F CI Br S2 N
lonic radii (A) 1.36 1.81 2.16 142 1.84 17L
1.95
0.19. Givethe reason for increase ofsuccessive ionization energy Wrie
the units of
ionization energy.
Ans. After the removal of first electron, the atom changes tounipositive
ion. In unipositive ionic state, the number of electrons have reducedbutthe
Shiant2024) Periodic Properties 199
muckearcharge remains the same. As a result of this the effective nuclear
ohargeperclectronincreases and the electrons are held more firmly by the
mNcleus.Therefore, greater amount of energy is required to removethe second
elevtronie.IE, >IE,. Similarly, successive removal of electrons further
incTeAsesthe effective nuclear charge per electron and hence successive
Aonizationenergies increase. Thus,,IE, >IE, >IE.
Thevalues of IE, IE, and IE, for the first ten elements are tabulated in
Bble76.
Table 7.6 Values of IE, IE, and IE, for the First Ten Elements
Atomic Valence
Symbol lonization Potential
Number Configuration
1 H 13.6
2 He 24.0 54.5
3 2s! 5.4 75.6 122.4
4 Be 282 9.3 18.2 153.8
5 B 28? 2p' 8.3 25.1 38.0
6 C 2s? 2p 11.2 24.3 48.0
N 2s 2p³ 14.5 29.6 57.0
8 2s 2pt 13.6 35.1 55.0
F 2s 2p 17.4 35.0 63.0
10 Ne 2s2 2p 21.6 41.0 64.0

Units of Ionization Energy - lonization energy is measured in units of

klocalories/mole or kilojoules/mole. It is also measured in units of electron
vOls (eV) where one electron volt is the energy acquired by an electron while
toving under apotential difference of one volt. These units are interrelated to
each other as follows -
I electron volt (eV) per atom =23,05 kCal mol = 96.49 kJ mot!
L20. Discuss various fuctorsaffecting the values of ionization energy.
Ans. lonization energy depends upon the following factors
(0) Atomic size or radius
(6) Nuclear charge
(i) Penetration effect of the electron
(iv) Sereening effect
() Stable electronic configuration.
200 Engineering Chemistry (R.GPV., B. Tech. I
(i) Atomic Size or Radius- The larger the atomic
the atomn size, -Year)
is the ionization energy. As the size of
the outer electrons lie farther away from the
increases down the smaller
nucleus and thus
attraction towards the nucleus. Hence electron can be exertgroup,less
Similarly, as we move along a period from leftt to right, atomic easily removed.
size
and the nuclear charge increases. As a result of this
increases along a period. lonization energies of alkali onizatareiondecrenereasgeys
imetals
table 7.7. given in
Table 7.7 First I.E. of Alkali Metals in kJ mole-1
Element Li Na K Rb Cs
LE. (kJ mole-l) 520 495 418 403
374
(i) Nuclear Charge The
effective nuclear charge of a neutral
atom or ion is defined as the net nuclear
attraction towards the valence shell
electrons. Greater is the effective nuclear charge, more tightly the electrons
are held with the nucleus and thus
more energy will be required to
electrons from the atom. remove
On moving along the period the
atomic number increases while the charge on nucleus increases as the
thus effective nuclear charge valence shell remains the same and
increases which leads to higher ionization
energy. Therefore, ionization energy
disorders. increases along the period with some
Increase in positive charge on the ion
charge which in turn increases the ionization increases the effective nuclear
in negative charge on the ion energy. On the other hand, increase
turn decreases the decreases the effective nuclear charge which in
ionization energy.
First I.E. of the elements of
second period are compiled in table .0.
Table 7.8 First L.E. of
Second Period Elements
Elements Li Be B C N F Ne
Nuclear charge +3 +4 +5 +6 +7 +8 +9 +10
L.E. (kJ mole-) 520 900 800 |1086 1403 1314| 1681|2081
First ionization
table 7.9. energies (in eV) of representative elements are givenin
ian2024) Periodic Properties 201
Thble79First lonization Energies of Representative Elements
s-block p-block Elements
Gronp
Period 2 13 14 1S 16 17 18
H He
13.6 24.6
Li Be B C N
5.4 9.3 8.3 Ne
11.2 14.5 13.6 174|21.6
Na Mg AI Si P S CI Ar
3 7.6 6.0
5.1 8.1 11.0 10,4 13.0 15.8
K Ca Ga Ge As Se Br Kr
4 6.1 6.0
4.3 7.8 9.8 9.8 11.8 14.0
Rb Sr In Sn Sb Te Xe
4.2 5.7 5.7 7.3 8.6 9.0 10.4 12.1
Cs Ba TI Pb Bi Po At Rn
6
3.9 5.2 6.1 7.4 7.2 8,4 10.7

ii) Penetration Effect of Electrons lonization energy increases

ethe nenetration effect of electrons increases in an atom. In a multielectron
alom, the electrons of s-orbital is more close to nucleus than the p-orbital
of the same orbit. Therefore, s electrons will experience more attraction
than p-electrons. Hence their removal is difficult leading to higher L.E.
Likewise L.E. of p-electrons will be more than I.E. of d-electrons and so
0n.

In general, the ionization energy follows the following order.

S>p>d>forbital of the same orbit.
For example, first I.E. of Al is lower than that of Mg. This differencein
lE. can be explained due to penetration effect of the outermost electron.
IMg 1s² 2s? 2p 3s?
13Al 1s² 2s? 2p 3s 3p!
is hence, during ionization of one electron from Alto form Al", the electron
ionized p-orbital whereas in case of Mg the electron is knocked out
tom s-orbifrom
ta l of the same energy shell. Since the energy required to remove
PelAisectron is less than the s-electron of the same energy shell, the first L.E. of
lower that of Mg. Similarly, the first LE. of B(1s? 2s 2p') is lower
an that ofthan Be (1s 2s).
(iv)nedSereening
effect is defi las the effectEffectcaused
(or Shielding Effec)- onSereening
byinner electrons or shielding
the attraction ofthe
 202 Engineering Chemistry

outermost electrons by the

nucleus. As
(R.GPV., B.
the screening effect Tech., I-Yean)
ionization energy decreases.

electrons in the outer

in the inner shell,
Larger the number of electrons(valency) shell. greater is the
Thus electron
increases, the
effect on the
less attraction from the
lower value of ionizationand
nucleus and can be easily
potential. Now as we move downremoved
a
s cre n ing
leadiexnpgerietoncethes
of inner shells increases
hence the group,tothedecrease.
ionization potential tends number
The actual charge felt by the valence shell electrons is
nuclear charge (Ze). Therefore, the effective nuclear chargecalledis given
effectivase
Total nuclear charge (Z) -
=

Screening constant (S)

where screening constant (S) takes into account the number of
electinner
present in the inner shell. Thus greater the number of electrons in the rons
shells, more will be the screening effect. Obviouslyit will result in less attraction
by the nucleus for the valence shell electrons and hence I.E. decreases.
Slater gave a set of empirical rules for calculating S, i.e. screening constant
in apolyelectronic systemn. The Slater rules are as under
(a) Electrons present in higher quantum shells are incapable of
shielding electrons in the lower shells and thus give no contribution towards
screening constant.
(b)All electrons in the ns, np group contribute to the extent of
0.35 each to screening constant (S).
(c) Allelectrons in the (n1)th shell contribute 0.85 each to the
screening factors (S).
(d) All electrons in (n - 2)th shell or lower shells shield the
electrons in the nth shell completely. Their contribution to the screening constant
is 1.0 each.
(e) Allthe electrons in the groups lying left to the nd or nforbital
shield the d or f electrons completely and contribute 1.0 each to S.
(v) Stable Electronic Configuration - According to Hund's rule,
orbitals have extra
filled
atoms containing exactly half filled or completely atom requires
stability. Obviously the removal of an electron from such an
more energy than expected. For example,
filled orbitals(ie.
(a) I.E. of Be >I.E. of B- Since Be has fully Similarly,
Is? 2s?), the knocking of electron needs higher ionization energy.
I.E. of Mg is greater than I.E. of Al. nitrogen
of
(b) I.E. of N>I.E. of O- Electronic configuration
(1s?2s²2p 2p, 2p,) shows that its valence electrons aré exactly e
 2024) Periodic Properties 203
provide extra stability to the atom. As aresult,the removal of electron
oh becomes dificult and its 1.E. becomes higher than that of oxygen.
larly,LE.
ofPis greater than I.E. of S.
(c) Inert Gas Electronic Configuration of Atom or lon - If
gtomorranion has ns-np configuration, its ionization energy is extremely
tothe presence of the so-called octet arrangement. To sum up, we
saythat greater the stability of electronic configuration of atom, greater is
onizationenergy.

Q21. What are the factors influencing the value of electron affinity ?
Ans. Important factors which influence the electron affinity of an atom
ediscussed below -
) Size of the atom (i) Nuclear charge (ii) Electronic configuration.
()) Size of the Atom With the increase in size of the atom, the
stance between the nucleus and the last orbit which receives the incoming
ctron also increases. Asa result of this the force of attraction between the
ncleus and the incoming electron decreases. Thus the electron affinity
ecreases with increase in size of atom.

(ii) Nuclear Charge - Greater the magnitude of nuclear charge

reater will be the force of attraction between the nucleus and incoming
lectron. Thus, electron affinity increases with increase in nuclear charge.

(iiü) Electronic Configuration - Atoms having stable electronic

onfiguration (i.e. halffilled or completely filled orbitals) show no tendency to
almost zero,
acept additional electron. Hence their electron affinity is
electronegativity.
0.22. Distinguish between electron affinity and
electronegativity are oiven
Ans. Differences between electron affinity and
as follows

S.No.
Electron Afinity Electronegativity
tendency of isolated atom It is the tendency of an atom in
It is the
attract an electron.a molecule to attract the bonded
state to
in gaseous electrons.

absolute value of an atom. It is relative value of an atom.

the
() It is the
change regularly in a It changes regularly in a period
(ii) It does not or a grOup.
period or a group.
eV/atom or kJ mole It has no unit,
measuredin
It iskcal mole-!
(iv) or
 204 Enoineering Chemistry
028. Wht ik polarizabili ? Give its examples
Or
(RGPV, B. Tech Yean
HHine short note on polarizability. (R.GRE, May 2019, J
Or
Wie briefnote on polarizability. June 201y
Ans. Polarizability is a measure ofhow
electron cloud will
(R.GPV June 2023)
easily an electron cloud i
is
by an electric field. Typically the
example,by an datistoomrted
molecule or ion. Theelectric field couldI be caused, for belong to an of
ora neaby cation or anion.
Ifan electron cloudis easy to distort, we saythat the electrode
species it
is polarizable. Polarizability. which is represented bythe Greek
is experimentally measured as the ratio of induced dipole let er,beallopngsha, ta,o
electric field E that induces it momentp to the
E
The units of a are cm²V-!,
Examples -
() Large, negatively charged ions, likel and Br, are highly polarizahle
() Small ions with high positive charge, like Mg and AP* hae
low polarizability, but they have a high ability to polarize polarizable species
like I andBr.
(ii) In ordinary usage polarizability refers to the mean polarizability.
ie., the average over the x, y, z axes of the molecule. Polarizabilities in different
directions (e.g. along the bond in Cl,, called longitudinal polarizability, and in
the direction perpendicular to the bond, called transverse polarizability) can be
distinguished, at least in principle.
Q.24. What are the factors that affect polarizability ?
Ans. The relationship between polarizability and the factors of electron
density, atomic radiand molecular orientation is as follows -
0 The greater the number of electrons, the less control the nuckear
charge has on charge distribution, and thus the increased polarizability of the aon.
(u) The greater the distance of electrons from nuclear charge, e
less control the nuclear charge has on the charge distribution, and thus the
increased polarizability of the atom.
(i) Molecular orientation with respect to an electric field canattèct
polarizability(labeled orientation-dependent), except for molecules that This are-

tetrahedral, important orforicosahedral

factor is moreoctahedral unsaturated(labeled
orientation-independent).
molecules that contain areasofelectron
dense regions, like 2-4 hexadiene. Greatest polarizability in these moleculesiS
achieved when the molecule rather
than
perpendicular to theelectric
field is
molecule. applied
Iparallel to the mol
Shivan-2024) Periodic Propertles 205
Q25 Wrie generic definition of oxidation state.
Ans.The oxidation state is the atom's charge after ionic approxímation of
bonds. Theterms to be clarified are the atom's charge, its bonds, and the
onicapproximation.
Theatom's charge is the usual count of valence electrons relative to the
Theeoxidation state is aquantitative concept that operates on integer
heeatom.
alesofcounted electrons. This mayrequire idealizing visual representations
rroundingoff numerical results.
orr
Approximatingall bonds to be ionic may lead to unusual results. If the
N=Nbondin N,O were extrapolated to be ionic, the central nitrogen atom
la have an oxidation state of +5 and the terminal one -3. To obtain less
nenme values, bonds between atoms of the same element should be divided
oqually upon ionic approximation.
Several criteria were considered for the ionic approximation -
() Extrapolation of the bond's polarity -
(a) from the electronegativity difference
(b) from the dipole moment
(c) from quantum-chemical calculations of charges.
(ii) Assignment of electrons according to the atom's contribution
to the molecular orbital (MO).
NUMERICAL PROBLEMS

Prob. 1. Write the electronic configuration of the following elements

and predict their group, block and period.
(i) Atomic number = 12
(ii) Atomic number = 26
(ii)Atonic number = 36
(iv) Atomic number = 17
(v) Atomic number = 58.
Sol.
SAtomic Electronic Configuration Group
Number
No.Number
0) 12 1s2s2p°3s 2

(ü) 26 1s2s2p'3s'3p°3d°48? 8

(i) 36 1s2s2p°3s3pb3d 04s?4p 18

(iv) 17 1s22p3s3p 17
(V) 58 1s2s'2p3s3p'3d 04s°4p°4d104f'5s²spsd'6s? Lanthanides