COORDINATION CHEMISTRY AND COLORED COMPLEXES.

YR2 DP Chemistry HL
(Collins, A/Huron H.S. Ann Arbor, MI)

Coordination chemistry is the same concept as complex ions. In these chemical species there is a positively
charged metal cation that is surrounded by ligands. Ligands are formed via coordinate covalent bonds,
otherwise known as dative bonds. These bonds exist when the external species contributes both electrons in
the ligand. In reality, some of these may not be actual chemical bonds, but ligands forming due to ion/dipoles.
We studied this when we demonstrated hydration shells forming around a metal cation.

Typically, the number of positive charges on the metal cation correlates with the number of ligands that will
form. Two ligands per charge. Remember, all of these ligands can also be seen as Lewis acid/Base interactions.
Lewis bases donate electrons (free electrons on outer species) and Lewis acids accept electrons (cation).

Cu2+ + 4H2O ® Cu(H2O)42+

Fe3+ + 6H2O ® Fe(H2O)63+
Coordinated complexes are generally very soluble, have high Kf values and they are frequently brightly colored
when they have partially filled d-orbitals. Note, Sc3+ and Zn2+ are colorless as they have no unpaired d-orbital
electrons.

Ion Ion configuration Color

3+
Sc [Ar] Colorless
Ti3+ [Ar] 3d1 Violet
V3+ [Ar] 3d2 Green
Cr3+ [Ar] 3d3 Violet
Mn2+ [Ar] 3d5 Pink
Fe3+ [Ar] 3d5 Yellow
Fe2+ [Ar] 3d6 Green
Co2+ [Ar] 3d7 Pink
Ni2+ [Ar] 3d8 Green
Cu2+ [Ar] 3d9 Blue
Zn2+ [Ar] 3d10 Colorless

When these coordinated complexes are exposed to visible light they will absorb one wavelength and transmit,
or reflect, complementary wavelengths. If the transmitted wavelengths are in the visible region the observed
colors will be:

Color Wavelength Range /nm

Red 630 - 700
Orange 590 - 630
Yellow 560 – 590
Green 490 - 560
Blue 450 - 490
Violet 400 - 450
An example: Copper (II) Sulfate appears blue because it absorbs orange light. Orange and turquoise are
complementary colors, in that they are opposite each other in the color wheel.

White light is composed of all of the colors of the visible spectrum. Ions of transition metals display colors
because their ions absorb certain colored wavelengths. [Fe(H2O)6]3+, for example appears yellow because it
absorbed light in the blue region of the spectrum.

Transition metals absorb light because the d-orbitals split into two different sublevels. When transition metals
are isolated (not involved in bonding) their d-orbital electrons are said to be degenerate (all having the same
energy). When the ligands form, the electrical field produced by the free electrons will split these d-orbital
electrons into two sub-levels. The octahedral complex of [Ti(H2O)6]3+ has six water molecules oriented in the
x,y, and z axes. When light passes through this complex, one 3-d electron is excited from the lower to the
higher energy sublevel. A photon of green light is absorbed and the complimentary color (purple) is
transmitted. This accounts for the purple colored complex of [Ti(H2O)6]3+.
The energy separation between the orbitals is DE and the color of the complex depends on:

1. The nuclear charge and the identity of the central atom (remember high charge densities are required)
2. The geometry of the complex ion will determine the electrical field created by the ligand’s lone pair.
3. The number of d electrons present and the oxidation number of the central atom.

Charge Density of the Cation:

The strength of the coordinate/dative bond between the ligand and the central atom depends on the
Coulombic forces between the lone pair and the charge density of the cation. The higher the charge
density, the more energetic the photon absorbed will be.
Example:
[Mn(H2O)6]2+ and [Fe(H2O)6]3+ both have the same electron configuration, but iron has the
higher nuclear charge and will resultantly form stronger ligands.
• Manganese II compounds will appear to transmit pink colors (as they absorb in the
green region, 550 nm).
• Iron III compounds will appear to transmit yellow colors (as they absorb in the blue
region, 490 nm).

Remember, E = hc the longer the wavelength, the lower energy absorbed.

l

Charge Density of the Ligand:

Certain ligands, like ammonia (NH3) have higher charge densities than do water. If a hydrated copper II
ion, [Cu(H2O)6]2+ has some of its water molecules replaced with ammonia molecules,
[Cu(NH3)4(H2O)6]2+, the complex will absorb shorter, more energetic wavelengths. This will result in a
deeper blue color than it transmits as [Cu(H2O)6]2+. The following graph will demonstrate this:

The following table will highlight ligand types and the DE of the splitting:

LIGAND I- Br- S2- Cl- H2O OH- NH3 CN- CO

l MAX Longest Wavelength increasing Shortest

Wavelength ß---------------------------------------------- wavelength
DE Weakest DE increasing Strongest
Field -------------------------------------------------à Field
Geometry of the Complex:
In the classic Cobalt (II) chloride equilibrium:

Heat + [Co(H2O)6]2+ + 4Cl- ⇌ + 6H2O + [Co(Cl)4]2-

Pink Purple Blue

On the left side of the equation, the cobalt/water complex takes on an octahedral geometry. On the
right, the cobalt/chloride takes on a tetrahedral geometry. The splitting of d-orbital energy depends on
the relative orientation of the ligand and the d-orbitals.

The Number of d-Electrons and the Oxidation State of the Central Atom:
The strength of the interactions between the ligand and the central metal cation and the amount of
electron repulsion between the ligand and the d-electrons depends on the number of d-electrons and
hence the oxidation number of the metal. For example, [Fe(H2O)6]2+ absorbs violet light and so appears
green, whereas [Fe(H2O)6]3+ absorbs blue light and appears orange. The higher charge creates an
absorption of higher energy wavelengths, and the transmittance of lower energy wavelengths.
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Topic Page No.
INORGANIC CHEMISTRY

PERIODIC PROPERTIES
1. Classification of Elements and Periodicity in properties 01
2. Mendeleev’s Periodic Law 03
3. Modern Periodic Law 07
4. Effective Nuclear Charge 11
5. Atomic Size 12
6. Ionisation Potential 15
7. ElectronAffinity 18
8. Electronegativity 20
9. Density 27
10. Diagonal Relationship 28
11. Metallic Character 28
12. Non-metallic character 29
 Topic Page No.

13. Reactivity, Oxidation state, Valency 29

14. Acid-base behaviour of oxides and hydroxides 30
15. Atomic volume 30
16. Graphs of periodic properties 30
17. General Trend of different properties in the period and groups 35
18. Important facts of remember 36
19. Solved Examples 38
20 Exercise - 1 41
Exercise - 2 46
Exercise - 3 51
Exercise - 4 55
21. Answer Key 58
22. Hints/Solution 60
ACC- CH-PERIODIC PROPERTIES 1

PERIODIC PROPERTIES

CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES

Need for classification:

It is verydifficult to studyindividuallythe chemistry of all the elements and millions of their compounds,
hence to simplify and systematize the study of chemistry of the elements and their compounds, they are
classified into groups and periods. Early attempt to classify the elements:
Classification of Lavoiser
Elements had been classified into two major groups by Lavoiser
1. Metals 2. Non–metals
This classification was based on the differences in their properties.
The metal word itself can be considered an acronym in which each alphabet signifies a characteristic of
these substances:
1. M = malleability. The most malleable beingAu and Pt.
s–block < p–block < d–block > f–block.
M = melting point (also boiling point) of the metals in general is high. Metal having the highest melting
point is Tungsten (W) and the highest boiling point is Renium (Re).The lowest melting point is of Mercury
(Hg) and it is one of the two elements in the periodic table which are liquid at 25oC. (The other being
Bromine).
The element having highest mp is W.
Element having lowest mp and bp is He.

2. E stands for elasticity (Young’s modulus)

E is also for electropositive.
E also for good conductors of Electricity. Best isAg > Cu >Au. Metals are good conductors of electricity
and heat due to the presence of free mobile delocalized electrons.
Graphite and black phosphorous are also conductors of electricity but not of heat.
Whenever a compound of metal is electrolysed metal always deposited at cathode while non metal at
both anode as well as cathode.

3. T = Tenacity (Tensile/ductile means elongation) Most tensile/ductile–Au/Pt.

Least – Pb
T = Toughness/ Hardness. Hardest is W. Exception : diamond is the hardest material ever known.
Synthetic hard materials are called abrasive. These are
CorundumAl2O3, Carborundum SiC, Borazone BN, Boron carbide B4C (non stoichiometric), Tantalum
Carbide and Tungsten Carbide as hard as diamond.

4. A=Allotropy/polymorphism, shown mainly by nonmetals. Metals such as Sn show polymorphism.

=Atomicity, Number of atoms in the molecule of an [Link] is very significant for non–metals
because it reveals the shape of the molecules and physical properties (state) of the molecules.
A=Alloys formation.
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Alloys are homogeneous mixture of two or more metals. It may also have some non metals as well.
Every alloy is a solid solution except the alloys of Hg which is a solution of a solid into a liquid. The alloys
of mercuryare called [Link] of metals with at least a non–metal are called interstitial compounds.
Alloys of only metals of nearly similar character are called substitutional compounds. Steel is a
homogeneous mixture. It also is an interstitial compound.
Purpose of alloying a metal are:
a. To increase the utility of the metals eg. fuse wire (Pb+ Sn + Bi). It melts in boiling water.
b. To increase the hardness.
Alloying is property of metals not of nonmetals.

5. L = lustre, Shine property of metals. Each metal having a characteristic.

6. S = sonorous. Each metal gives special sound on beating.

Dobereiner’s law of traids:

It was first attempt towards classification. He arranged similar elements in a group of three elements
called triad and the atomic mass of the middle elements of the traid is approximately the arithmetic
mean of the other two.
e.g. Ca40 Sr87.5 Ba137
137 40
At. wt. of Sr = 88.5
2
88.5 is nearly similar to 87.5 of atomic wt. of Sr.
Such a group of elements is called Dobereiner’s triad.

Triad of atoms Mean of first and last element

7 39
Li Na K 23
2
7 23 39
8 40
Be Mg Ca 24
2
8 24 40

Dobereiner could arrange only a few elements as triads and there are some such elements present in a
triad, whose atomic weights are approximately equal, e.g.
Fe Co Ni
Ru Rh Pd
There fore, this hypothesis was not acceptable for all elements.
Newland’s law of octaves:
When the lighter elements are arranged in order of their increasing atomic weights, then every eighth
element is similar to the first element in its properties, similarly as the eighth node of a musical scale
is similar to 1st one. e.g. Na 8th element resembles in their properties with Li. Similarly K the 8th
element with Na and so on.
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Name of element Li Be B C N O F
7 9 11 12 14 16 19
Name of element Na Mg Al Si P S Cl
23 24 27 28 31 32 35.5
It is clear from the above table that sodium is the eighth element from lithium, whose properties resemble
that oflithium.
This type of classification was limited up to only 20 elements.
Inert gas element were not discovered till then.
Lother Meyer arrangement: Cs
Rb
K
Br
Na Ca
Li Cl
Sr I
Ba
F
Be
Mg

Metalloid and transition metals

Atomic Weight

The graphs plotting the atomic volumes against atomic weights are known as Lothar Mayer volume
curves.
The alkali metals have highest atomic volumes.
Alkaline earth metals (Be, Mg Ca, Sr, Ba, etc.) which are relatively a little less electropositive. Occupy
positions on the descending part of the curve.
Halogens and the noble gases (except helium) occupy positions on the ascending part of the curve.
Transition elements have very small volumes and therefore these are present at the bottoms of the curve

Exercise

1. Lother Meyer attempt was based on plotting atomic mass vs

(A)Atomic size (B)Atomic volume (C) Density (D) Melting point
Ans. (B)

MENDELEEV‛S PERIODIC LAW

(i) Mendeleev’s Periodic Law - The physical and chemical properties of elements are the periodic
function of their atomic weight
(ii) Characteristic of Mendeleev’s Periodic Table -
(a) It is based on atomic weight (b) 63 elements were known, noble gases were not discovered.
(c) 12 Horizontal rows are called periods. (d) Vertical columns are called groups and there were 8
groups in mendeleev’s Periodic table. (e) Each group upto VIIth is divided into A & B subgroups.
‘A’sub groups element are called normal elements and ‘B’sub groups elements are called transition
elements. (f) The VIIIth group was consists of 9 elements in three rows (Transition metals group).
(g) The elements belonging to same group exhibit similar properties.

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MODIFIED MENDELEEF’S PERIODIC TABLE OF ELEMENTS

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ACC- CH-PERIODIC PROPERTIES 5

(iii) Merits or advantages of Mendeleev’s periodic table -

(a) Study of elements - First time all known elements were classified in groups according to their
similar properties. So study of the properties become easier of elements.
(b) Prediction of new elements - It gave encouragement to the discovery of new elements as some
gaps were left in it. Sc (Scandium), Ga (Gallium), Ge (Germanium),Tc(Technetium) were the elements
for whom position and properties were defined by Mendeleev even before their discoveries and he
left the blank spaces for them in his table.
e.g.- Blank space at atomic weight 72 in silicon group was called Eka silicon (means properties like silicon)
and element discovered later was named Germanium.
Similarly other elements discovered after mendeleev periodic table were.
Eka aluminium - Gallium (Ga) Eka Boron - Scandium (Sc)
Eka Silicon - Germanium (Ge) Eka Manganese - Technetium (Tc)
(c) Correction of doubtful atomic weights - Correction were done in atomic weight of some elements.
Atomic Weight = Valency × Equivalent weight.
Initially, it was found that equivalent weight of Be is 4.5 and it is trivalent (V = 3), so the weight of Be
was 13.5 and there is no space in Mendeleev’s table for this element. So, after correction, it was
found that Be is actually divalent (V = 2). So, the weight of Be became 2 × 4.5 = 9 and there was a
space between Li and B for this element in Mendeleev’s table.
– Corrections were done in atomic weight of elements are – U, Be, In, Au, Pt.
(iv) Demerits of Mendeleev’s periodic table -
(a) Position of hydrogen - Hydrogen resembles both, the alkali metals (IA) and the halogens (VIIA) in
properties so Mendeleev could not decide where to place it.
(b) Position of isotopes -As atomic weight of isotopes differs, they should have placed in different
position in Mendeleev’s periodic table. But there were no such places for isotopes in Mendeleev’s
table.
(c) Anomalous pairs of elements - There were some pair of elements which did not follow the
increasing order of atomic wts.
eg. Ar and Co were placed before K and Ni respectively in the periodic table, but having higher atomic
weights.
Ar K Te I Co Ni Th Pa
39.9 39.1 127.5 127 58.9 58.6 232 231
(d) Like elements were placed in different groups.
There were some elements like Platinum (Pt) and Gold (Au) which have similar properties but were
placed in different groups in mendeleev’s table.
Pt – VIII Au – IB
(e) Unlike elements were placed in same group.
st
I group

IA IB
Li
Na
More reactive K Cu Less reactive
Alkali metal Rb Ag Coin metal
Normal elements Cs Au Transition element
Fr
– Cu,Ag andAu placed in Ist group along with Na, K etc. While they differ in their properties (Only
similar in having ns1 electronic configuration)
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MODERN PERIODIC LAW

Mosley proved that the square root of frequency ( ) of the rays, which are obtained from a metal on
showering high velocityelectrons is proportional to the nuclear charge of the atom. This can be represented
by the following expression.
= a (Z–b) where Z is nuclear charge on the atom and a and b are constants.
The nuclear charge on an atom is equal to the atomic number.
According to modern periodic law. “The properties of elements are the periodic functions of their atomic
numbers”

Exercise

1. Which of the following expressions is correct ?

(A) = a(z–b) (B) 2 = a (z–b)2 (C) = a2 (z–b)2 (D) 2 = a2 (z–b)2
Ans. (C)

Cause of periodicity: It is due to the repetition of similar outer shell electronic configuration at a
certain regular intervals.

Structural features of the long form of the periodic table.

On the basic of the modern periodic law, a scientist named Bohr proposed a long form of periodic
table that was prepared by Rang and Warner.
(i) It consists of 18 vertial columns called groups and 7 horizontal rows called periods.
(ii) Elements of groups, 1, 2, 13 – 17 are called normal or representative elements.
(iii) Elements of groups 3 – 11 are called transition elements.
(iv) The 14 elements with atomic numbers (Z) = 58 – 71 (occurring after lanthanum 57La in the periodic
table) are called lanthanides or rare earth elements and are placed at the bottom of the periodic
table. The 14 elements with atomic numbers (Z) = 90 – 103 (Occurring after actinium 89Ac in the
periodic table) are called actinides and are placed at the bottom of the periodic table.
(v) The Eleven elements with Z = 93 – 103 (93Np – 103Lr) which occur in the periodic table after uranium
and have been prepared from it by artificial means are called transuranics. These are all radioactive
elements.
(vi) The elements belonging to a particular group are said to constitute a chemical family which is usually
named after the name of the first element. For example, Boron family (group 13), carbon family (group
14), nitrogen family (group 15), and oxygen family (group 16). In addition to this, some groups
have typical names. For example,
Elements of group 1 are called alkali metals
Elements of group 2 are called alkaline earth metals
Elements of group 16 are called chalcogens
Elements of group 17 are called halogens

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8 ACC- CH-PERIODIC PROPERTIES

Elements of group 18 are called zero group or noble gases.

The long form of the periodic table contains seven periods. These are :
1st period (1H – 2He) contains only two elements. This is the shortest period.
2nd period (3Li – 10Ne) and third period (11Na – 18Ar) contain 8 elements each and are called
short periods.
4th period (19K – 36Kr) and 5th period (37Rb – 54Xe) contain 18 elements each and are called long
periods.
6th period (55Cs – 86Rn) contains 32 elements and is the longest period.
7th period (87Li –) is, however, incomplete and contains at present only 24 elements.
In yet another classification, the long form of the periodic table has been divided into four blocks (i.e.,
s, p, d and f ), depending upon the subshell to which the last electron enters.

MERITS OF LONG FORM OF PERIODIC TABLE OVER MANDELEEF‛S PERIODIC TABLE

Positions of Isotopes and Isobars - Isotopes have same atomic number and the periodic table is
based on atomic numbers. Therefore, various isotopes of the same elements have to be provided the
same position in the periodic table. Isobars gave same atomic weights but different atomic numbers and
therefore they have to be placed at different positions.

The positions of actinides and lanthanides is more clear now because these have been placed in IIIB
groups and due to paucity of space, these are written at the bottom of the periodic table.

In the periodic table a diagonal line from B toAt separates the metals, nonmetals and metalloids from
one another. The elements like B, Si, As, Te, At, that are situated near this line are metalloids i.e. these
have characteristic of both metals and nonmetals.

The general electronic configuration of the elements remains same in group.

DEFECTS OF LONG FORM OF PERIODIC TABLE

The position of hydrogen is still disputable as it was there in Mendeleef periodic table in group IAas well
as IVA & VIIA.
Helium is an inert gas but its configuration is different from that of the other inert gas elements
Lanthanide and actinide series could not be adjusted in the main periodic table and therefore they had to
be placed in a separate block below the periodic table.

CLASSIFICATION IN BLOCKS

s-block elements.
Elements of groups 1 and 2 including He in which the last electron enters the s-orbital of the valence
shell are called s-block elements. There are only 14 s-block elements in the periodic table.

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ACC- CH-PERIODIC PROPERTIES 9

p-block elements.
Elements of groups 13–18 in which the last electron enters the p-orbitals of the valence shell are called
p-block elements.

d-block elements.
There are three complete series and one incomplete series of d-block elements. These are: 1st or 3d-
transition series which contains ten elements which atomic numbers 21–30 (21Sc – 30Zn).
2nd or 4d-transition series which contains ten elements with atomic numbers 39 – 48 (39Y – 48Cd).
3rd or 5d transition series which also contains ten elements which atomic numbers 57 and 72 – 80
(57La, 72Hf – 80Hg).

4th or 6d transition series which is incomplete at present and contains only nine elements. These are
89Ac, 104Rf, 105Ha, Unh (Unnihexium, Z = 106), 107Ns (Neilsobohrium), 108Hs (Hassium), 109Mt
(Meitherium), Uun (Ununnilium, Z = 110) and Uud (Unundium, Z = 112) or Ekamercury. The element,
Z = 111 has not been discovered so far. Thus, in all there are 39 d-block elements.

f-Block elements are called inner-transition elements. In these elements, the f-subshell of the
anti-penultimate is being progressively filled up. There are two series of f-block elements each
containing 14 elements. The fourteen elements from 58Ce – 71Lu in which 4 f-subshell is being
progressively filled up are called lanthanides or rare elements. Similarly, the fourteen elements from
90Th – 103Lr in which 5 f-subshell is being progressively filled up are called actinides.

Illustration

1. Which of the following is the period number of the element whose atomic number is 98
(A) 4 (B) 7 (C) 5 (D) 6
Ans. B
Sol. The electronic configuration of the element with atomic number 98 is as follow
1s2 , 2s2 , 2p6, 3s2, 3p6, 4s2 , 3d10, 4p6, 5s2, 4d10 , 5p6, 6s2, 4f14, 5d10, 6p6, 7s2, 5f 10
The last electron enters in f orbital, so it belongs to f block in the period.

2. The nuclei of elements X, Y and Z have same number of protons, but different numbers of neutrons.
According to Mendeleef periodic table, the elements X,Y and Z
(A) belong to same group and same period
(B) belong to different groups and different periods
(C) belong to same group and different periods
(D) are isotopes, which do not have different positions
Ans. D
Sol. Isotopes have same number of protons (i.e. same atomic number). So they occupy same position
in the periodic table. However, due to different numbers of neutrons their atomic weights are different.

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Exercise

1. Which of the following has the same number of electrons in its outermost shell and penultimate shell ?
(1) Al3+ (2) Ca2+ (3) F– (4) N3–
Ans. 2
2. Which of the following statement is not correct about the electronic configuration of chromium atom (Cr
with atomic number = 24)?
(1) It has five electrons in 3d - sub - shell
(2) It has one electrons in 4s-orbital
(3) The principal quantum numbers of its valence electrons are 3 and 4.
(4) It has six electrons in 3d-sub-shell
Ans. 4

TEMPORARY NOMENCLATURE

The IUPAC proposed a system for naming elements with Z > 100.
1. The names are derived by using roots for the three digits in the atomic number of the elements and
adding the ending -ium. The roots for the numbers are:
0 1 2 3 4 5 6 7 8 9
nil un bi tri quad pent hex sept oct enn
2. In certain cases the names are shortened; for example, bi ium and tri ium are shortened to bium and
trium, and enn nil is shortened to ennil.
3. The symbol for the element is made up from the first letters from the roots which make up the name. The
strange mixture of Latin and Greek roots have been chosen to ensure that the symbols are all different.

Illustration

1. According to the IUPAC system of naming elements, the symbol of the element of atomic number 121
will be
(A) Unu (B) Ubn (C) Ubu (D) Bus
Ans. (C)

Exercise

1. The IUPAC name of the element with atomic number Z = 109 is

(A) U np (B) U ns (C) U no (D) U ne
Ans. (D)

Anomalous behaviour of the first element of a group:

The first element of a group differs considerably from its congeners (i.e. the rest of the elements of
its group). This is due to (i) small size (ii) high electronegativity and (iii) non availability of d-orbitals
for bonding. Anomalous behaviour is observed among the second row elements (i.e., Li to F).
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ACC- CH-PERIODIC PROPERTIES 11

EFFECTIVE NUCLEAR CHARGE

In a polyelectronic atom, the internal electrons repel the electrons of the outermost orbit. This results in
decrease the nuclear attraction on the electrons of the outermost orbit.
Therefore, only a part of the nuclear charge is effective on the electrons of the outermost orbit. Thus, the
inner electrons protect or shield the nucleus and thereby decrease the effect of nuclear charge towards
the electrons of the outermost orbit.
Thus the part of the nuclear charge works against outer electrons, is known as effective nuclear
charge
Z* Z
Z* = effective nuclear charge
s = shielding constant and Z = nuclear charge
Ascientist named slater, determined the value of shielding constant and put forward some rules as
following.
(1) The shielding effect or screening effect of each electron of 1s orbital is 0.30.
(2) The shielding effect of each electrons of ns and np i.e. electron of the outermost orbit, is 0.35.
(3) The shielding effect of each electron of s or p orbitals of the penultimate orbit (n – 1) is 0.85.
(4) The shielding effect of each electron of s or p orbital of the prepenultimate orbit (n – 2) and below this is1.0.
Illustration

1. The screening effect of inner electrons of the nucleus causes

(A) Decrease in the ionisation energy (B) Increase in the ionisation energy
(C) No effect on the ionisation energy (D) Increases in the attraction of the nucleus to the electrons
Ans. (A)
Sol. The attraction of the nucleus with the electron decreases so it becomes easy to extract the electron.

Exercise

1. The screening effect of d - electrons is -

(A) equal to the p - electrons (B) much more than p - electron
(C) same as f - electrons (D) less than p - electrons
Ans. (D)
2. The increasing order of effective nuclear charge in Na,Al, Mg and Si atoms
(A) Na < Mg < Si < Al (B) Na < Mg < Al < Si (C) Mg < Na < Al< Si (D) Na = Mg = Al = Si
Ans. (B)

Periodic Properties: Properties which are directly or indirectly related to their electronic configuration and
show a regular gradation when we move from left to right in a period or from top to bottom in a group
are called periodic properties. Some important periodic properties are atomic size, ionization energy
electron affinity, electronegativity, valency, density, atomic volume, melting and boiling points etc.

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12 ACC- CH-PERIODIC PROPERTIES

(a) Atomic size : It refers to the distance between the centre of the nucleus of the atom to the outermost
shell containing electrons. Since absolute value of the atomic size cannot be determined, it is usually
expressed in terms of the following operational definitions.

X X

A B

1/2 AB = rcovalent
(of element X)

X H H X X
H
E F
G H

1/2 EF = rvan der Waals of hydrogen in HX molecule

1/2 GH = rvan der Waals of X in HX molecule

n 2a 0
rn
Z*
(i) Covalent radius. It is defined as one-half of the distance between the nuclei of two covalently bonded
atoms of the same element in a molecule.
Single Bond Covalent Radius, SBCR - (a) For Homolatomic molecules
dA–A = rA + rA or 2rA
dA A
rA =
2
(b) For hetrodiatomic molecules while electronegativity is approx same.
dA–B = rA + rB
For heteronuclear diatomic molecule.A–B, while difference between the electronegativity values of
atomAand atom B is relatively larger, (XA and XB) are the electron negativity in Pauling Scale.
dA–B = rA + rB – 0.09 |(XA –XB)| [Bond length or radius expressed in Å]
where XA and XB are electronegativityvalues of high electronegative elementAand less electronegative
element B, respectively. This formula was given by Stevenson & Schomaker.
Note : Covalent radius is slightly smaller then actual radius.
(ii) Van der Waals’radius. It is defined as one-half of the distance between the nuclei of two non-bonded
isolated atoms or two adjacent atoms belonging to two neighbouring molecules of an element in the solid
state.
By definition, van der Waals’radius of an element is always larger than its covalent radius.
Variation of atomic radii :
(i) Across the period atomic radii decreases
(ii) Where we move from 17th group to 18th atomic radii increases the period decreases

BANSAL CLASSES
ACC- CH-PERIODIC PROPERTIES 13

Illustration

1. Calculate the bond length of C–X bond, if C–C bond length is 1.54 Å, X–X bond length is 1.00 Å and
electronegativity values of C and X are 2.0 and 3.0 respectively
Sol. (1) C–C bond length = 1.54 Å
1.54
rC = = 0.77 Å
2

1.00
rX = = 0.50 Å
2
(2) C–X bond length
dC–X = rC + rX – 0.09 |XX – XC|
= 0.77 + 0.50 – 0.09 |3–2| = 0.77 + 0.50 – 0.09 × 1 = 1.27 – 0.09 = 1.18 Å
Thus C–X bond length is 1.18 Å

2. Which of the following should be the longest bond ?

(A) S–H (B) O–H (C) N–H (D) P–H
Ans. (D)
Sol. The atomic radius of P is largest out of O.S.N. and P. Therefore. P–H bond will be the longest one.

Exercise
1. The van der Waal’s radii of O, N, Cl, F and Ne increase in the order
(A) F, O, N, Ne, Cl (B) N, O, F, Ne, Cl (C) Ne, F, O, N, Cl (D) F, Cl, O, N, Ne
Ans. (C)

2. Whenever a list of radii is given, we find that the size of the noble gases is larger than the size of their
adjacent halogens. The reason is
(A) Noble gases have a complete octet
(B) Theyhave a higher inter electronic repulsion
(C) In halogens it is covalent radii and in noble gases it is vander waals radii
(D) Noble gases cannot be liquified
Ans. (C)

Variation in Period :
Li Be B C N O F Ne
Z 3 4 5 6 7 8 9 10
Z * 1.30 1.95 2.60 3.25 3.90 4.55 5.20 5.85
n 2 2 2 2 2 2 2 2
rn (pm) 123 90 80 77 75 74 72 160
(covalent) (Van der Waals)

BANSAL CLASSES
14 ACC- CH-PERIODIC PROPERTIES

Ionic size. An atom can be changed to a cation by loss of electrons and to an anion by gain of
electrons. A cation is always smaller than the parent atom because during its formation effective
nuclear charge increases and sometimes a shell may also decrease. On the other hand, the size of
an anion is always larger than the parent atom because during its formation effective nuclear charge
decreases e.g..
Mg2+ < Mg, Cl– > Cl
The size of a cation is smaller in comparison to the size of its corresponding atom. This is because of the
fact that an atom on losing electrons/s form a cation, which has lesser number of electrons/s than the
number of proton/s. This results in increase in the effective nuclear charge.
1
Size of cation
Amount of positive ch arg e or Z eff

Examples - (1) Mn > Mn+2 > Mn+3 > Mn+4 > Mn+6 > Mn+7 (size)
(2) Pb+2 > Pb+4

The size of an anion is greater than the size of its corresponding atom, because the number of electrons
present in the anion gets larger than the number of protons due to gain of electron/s. This results in
decrease in the effective nuclear charge.
Size of anion Amount of negative charge
O0 < O–1 < O–2

Size of Isoelectronic Series

Isoelectronic ions or species are the neutral atoms, cations or anions of different elements which have
the same number of electrons but different nuclear charge e.g..
The size of the isoelectronic species depends upon their nuclear charge Greater the nuclear charge,
lesser the radii.
The ionic radii decrease moving from left to right across any period in the periodic table
Na+ Mg2+ Al3+
102 pm 72 pm 53.5 pm

1
Size in an isoelectronic series
Nuclear charge
No. of protons

Illustration

1. What should be the order of size of H–1 , H+1 and H ?

H–1 H+1 H
1p 1p 1p
2e 0e 1e
Sol. +1
H <H<H –1

BANSAL CLASSES
ACC- CH-PERIODIC PROPERTIES 15

Exercise

1. Which of the following has the largest size

(A) N–3 (B) O–2 (C) K+1 (D) Ca+2
Ans. (A)

2. Which one of the following is correct order of the size of iodine species?
(A) I > I– > I+ (B) I > I+ > I– (C) I+ > I– > I (D) I– > I > I+
Ans. (D)

IONISATION POTENTIAL

The energy required to remove the most loosely bound electron from the outermost orbit of one mole of
isolated gaseous atoms of an element, is called ionisation potential (IP). This ionisation is an endergonic
or energy-absorbing process.
An electron cannot be removed directly from an atom in solid state. For this purpose, the solid state is
converted to gaseous state and the energy required for this is called sublimation energy.
A Ist IP A+1 II nd IP A+2 III rd IP A+3

The energy required to remove one electron from a neutral gaseous atom to convert it to monopositive
cation, is called first ionisation potential (Ist IP). The energy required to convert a monopositive cation to
a diapositive cation is called second ionisation potential (IInd IP) of an atom
Ist IP < IInd IP < IIIrd IP because as the electrons go out of the atom, the ionic size goes on decreasing
and the amount of positive charge goes on increasing.
Factors Affecting Ionisation Potential
(i) Atomic size : When the size of an atom is very large the electron of the outermost orbit bound to the
nucleus by weaker attractive forces. Such an electron will be readily removed from the atom. Therefore.
The value of ionisation potential will be low.

1
Ionisation potential
atomic size

(ii) Effective Nuclear Charge : Atomic size decreases with increase in effective nuclear charge because,
higher the effective nuclear charge stronger will be the attraction of the nucleus towards the electron of
the outermost orbit and higher will be the ionisation potential
Ionisation potential Effective nuclear charge

(iii) Shielding Effect : The electrons of internal orbits repel the electrons of the electron of the outermost
orbit due to which the attraction of the nucleus towards the electron of the outermost orbit decreases and
thus atomic size increases and the value of ionisation potential decreases.

1
Ionisation potential
shielding effect

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16 ACC- CH-PERIODIC PROPERTIES

(iv) Stability of half filled and fully filled orbitals : The atoms whose orbitals are half-filled (p3, d5, f7) or
fully-filled (s2 , p6 , d10 , f14) have greater stability than the others. Therefore, they required greater
energy to for removing out electron. However stability of fully filled orbitals is greater than that of the
half filled orbitals
[Link] fully filled orbitals I.P. of half filled orbitals

(v) Penetration power : In any atom the s orbital is nearer to the nucleus in comparison to p, d and f
orbitals. Therefor, greater energy is required to remove out electron from s orbital than from p, d and f
orbitals. Thus the decreasing order of ionisation potential of s, p, d and f orbitals is as follows
s > p > d> f
Io n is a tio n p o te n tia l p e n e tra tio n p o w e r

Periodic Table & Ionisation Potential

(a) In a Period : The value of Ionisation potential normally increase on going from left to right in a period,
because effective nuclear charge increases and atomic size decreases.
Exceptions :
In second period ionisation potential of Be is greater than that of B, and in the third period ionisation
potential of Mg is greater than that ofAl due to high stability of fully filled orbitals.
In second period ionisation potential of N is greater than O and in the third period ionisation potential of
P is greater than that of S, due to stability of half filled orbitals.
The increasing order of the values of ionisation potential of the second period elements is
Li < B < Be < C < O < N < F < Ne
The increasing order of the values of ionisation potential of the third period elements is
Na < Al < Mg < Si < S < P < Cl < Ar
InnerTransition Elements : The size of inner transition elements is greater than that of d block elements.
Therefore the value of ionisation potential of f block elements is smaller than that of d block elements
and due to almost constant atomic size of f block elements in a period the value of their ionisation
potential remains more constant than that of d block elements.
In a Group
The value of ionisation potential normally decreases on going from top to bottom in a group because
both atomic size and shielding effect increase.
Exception :
The value of ionisation potential remains almost constant from Al to Ga in the IIIAgroup.
(B>Al , Ga > In)
IP1(Sn) < IP1(Pb)
IP1(In) < IP1(Tl)
In the periodic table the element having highest value of ionisation potential is He.
The values of ionisation potential of noble gases are extremely high, because the orbitals of outermost
orbit are fully-filled (ns2 , np6) and provide great stability.
In a period, the element having least value of ionisation potential is an alkali metal (group IA) and that
having highest value is inert gas (Group 0)

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ACC- CH-PERIODIC PROPERTIES 17

Applications of Ionisation Potential

The elements having high values of ionisation potential have low reactivity, e.g. inert gases.
The value of ionisation potential decreases more on going from top to bottom in a group in comparison
to a period. Therefore, reactivity of metal increases and the atom forms a cation by loss of electron.
1
Ionisation potential
Re activity of metal
The elements having low value of ionisation potential readily lose electron and thus behave as strong
reducing agents.
1
Ionisation potential
Re ducing property
The elements having low value of ionization potential readily lose electron and thus exhibit greater
metallic property.
1
Ionisation potential
Metallic property

The elements having low value of ionisation potential readily lose electron and thus have basic property.
1
Ionisation potential Basic property

Illustration

1. Which of the following should be the order of increasing values of second ionisation potential of C6, N7,
O8 and F9
(A) C > N > F > O (b) C < F < N < O (C) C < F < N < O (D) C < N < F< O
Ans. (D)
Sol. The second ionisation potential means removal of electron from a cation
C+1 (5e) = 1s2 , 2s2 , 2p1
N+1 (6e) = 1s2, 2s2, 2p2
O+1 (7e) = 1s2, 2s2, 2p3
F+1 (8e) = 1s2, 2s2 , 2p4
Therefore C < N < F < O
2. Which of the following should be correct for Z1 and Z2 in the following two processes
M+ + Z1 M+2 + e–
M+2 + Z2 M+3 + e–
1 1
(A) Z = Z2 (B) Z1 = Z2 (C) Z1 = Z (D) Z1 < Z2
2 1 2 2
Ans. (D)
Sol. Z1 = second ionisation potential and Z2 = Third ionisation potential.
Second ionisation potential is always less than the third ionisation potential.

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18 ACC- CH-PERIODIC PROPERTIES

Exercise

1. One mole of magnesium in the vapour state absorbed 1200 kJ of energy. If the first and second ionization
enthalpies of magnesium are 750 and 1450 kJ mol–1 respectively, the final composition of the mixture is
(A) 69% Mg+, 31% Mg2+
(B) 59% Mg+, 41% Mg2+
(C) 49% Mg+, 51% Mg2+
(D) 29% Mg+, 71% Mg2+
Ans. (A)

2. The incorrect statement in the following is

(A) The third ionisation potential of Mg is greater than the third ionisation potential ofAl
(B) The first ionisation potential of Na is less than first I.P of Mg
(C) The first I.P. of Al is less than the first I.P. of Mg
(D) The second I.P. of Mg is greater than the second I.P. of Na
Ans. (D)

ELECTRON AFFINITY (EA)

The energy released on adding up one mole of electron to one mole of neutral atom (A) in its gaseous
state to form an anion (A–) is called electron affinity of that atom. In general, electron affinity is
associated with an exothermic process.
A(g) + e– A– (g) , Heg = –En

When one electron adds up to a neutral atom, it gets converted to a unit negative ion and energy is
released. On adding one more electron to the mononegative anion, there is a repulsion between the
negatively charged electron and anion. In order to counteract the repulsive forces, energy has to be
provided to the system. Therefore, the value of the second electron affinity is positive.
A– (g) + e– A–2 (g) , Heg = + En Heg : Electron gain enthalpy

Factors Affecting Electron Affinity

Effective Nuclear charge : When effective nuclear charge is more, then the atomic size less. Hence
EA increases.
Electron affinity Effective nuclear charge

Atomic Size orAtomic Radius : When the size or radius of an atom increases, the electron entering the
outermost orbit is more weakly attracted by the nucleus and the value of electron affinity is lower.

1
Electron affinity
Atomic size

BANSAL CLASSES
ACC- CH-PERIODIC PROPERTIES 19

Shielding Effect : Shielding effect is directly proportional to atomic size and atomic size is inversely
proportional to electron affinity.

1
Electron affinity
Shielding effect

Stability of Fully-Filled and Half-Filled Orbitals :

The stabilityof the configuration having fully-filled orbitals (p6, d10, f14) and half-filled orbital (p3 , d5 , f7)
is relativelyhigher than that of other configurations.

Periodic Table and Electron Affinity :

In a period, atomic size decreases with increase in effective nuclear charge and hence increase in
electron affinity.

Exception :
On going from C6 to N7 in the second period, the values of electron affinity decreases in stead of
increasing. This is because there are half-filled (2p3) orbitals in the outermost orbit of N, which are more
stable. On the other hand, the outermost orbit in C has 2p2 configuration.

In the third period, the value of electron affinity of Si is greater than that of P. This is because electronic
configuration of the outermost orbit in P atom is 3p3 , which being half-filled, is relatively more stable

The values of electron affinity of inert gases are zero, because there outermost orbit has fully-filled p
orbitals.

In a period, the value of electron affinity goes on decreases on going from group IA to group IIA. The
value of electron affinity of the elements of group IIA is zero because ns orbitals are fully-filled and such
orbitals have no tendency to accept electrons.

In a Group
The values of electron affinity normally decrease on going from top to bottom in a group because the
atomic size increases which decreases the actual force of attraction by the nucleus.

Exceptions (E.A. 2nd period p-block element < E.A. 3rd period p-block element)

The value of electron affinity of F is lower than that of Cl, because the size of F is verysmall and compact
and the charge density is high on the surface. Therefore, the incoming electron experiences more repulsion
in comparison to Cl . That is why the value of electron affinity of Cl is highest in the periodic table.

The values of electron affinity of alkali metals and alkaline earth metals can be regarded as zero, because
they do not have tendency to form anions by accepting electron.

BANSAL CLASSES
20 ACC- CH-PERIODIC PROPERTIES

Illustration

1. O(g) + 2e–1 O–2 (g) –E = + 744.7

The reason for the positive value of E is
(A) endothermic reaction (B) exothermic reaction
(C) both 1 and 2 (D)All of the above are wrong
Ans. (A)
Sol. When electron is brought near O–1 there will be repulsion between them, and therefore the energy
will be positive i.e there will be absorption of energy during the process.

2. The increasing order of electron affinity values of O,S and Se is

(A) O < S < Se (B) S < O < Se (C) O < S > Se (D) Se < O > S
Ans. (C)
Sol. Atomic size of Se is very large.

Exercise

1. The least electron affinityis found in

(A) Kr (B) O (C) N (D) B
Ans. (A)
2. Of the following element of which electronic configuration will have the highest electron affinity
(A) 1s2 2s2 2p3 (B) 1s2 2s2 2p5 (C) 1s2 2s2 2p6 3s2 3p5 (D) 1s2 2s2 2p6 3s2 3p3
Ans. (C)

ELECTRONEGATIVITY

The measure of the capacity or tendency of an atom to attract the shared pair of electrons of the covalent
bond towards itself is called electronegativity of that atom.
Electronegativity is a relative value that indicates the tendency of an atom to attract shared electrons
more than the other atom bonded to it. Therefore it does not have any unit. Pauling was the first scientist
to put forward the concept of electronegativity.
The numerical value of electronegativity of an atom depends on its ionisation potential and electron
affinityvalues.

Factors Affecting Electronegativity

Atomic size – Electronegativity of a bonded atom decreases with increase in its size.
1
Electronegativity
Atomic size

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38 ACC- CH-PERIODIC PROPERTIES

SOLVED EXAMPLES

Q.1 For the element X, student Surbhi measured its radius as 102 nm, [Link] as 113 nm and [Link]
as 100 nm using same apparatus. Their teacher explained that measurements were correct by saying that
recorded values by three students were
(A) Crystal, vander Waal and covalent radii (B) Covalent, crystal and vander Waal radii
(C) Vander Waal, ionic and covalent (D) None is correct
Ans. (A)
Sol. Order of radius is – Vander Waal’s radius > Metallic radius > Covalent radius

Q.2 Which oxide of N is isoelectronic with CO2 -

(A) NO2 (B) NO (C) N2O (D) N2O3
Ans. (C)
Sol. N2O
Total electrons 14 + 8 = 22
CO2
Total electrons 6 + 16 = 22

Q.3 Give the correct order of initials T (true) or F (false) for following statements.
(I) Top positions of Lother-Mayer’s atomic volume curve are occupied byAlkali metals.
(II) Number of elements presents in the fifth period of the periodic table are 32.
(III) 2nd I.P. of Mg is less than the 2nd I.P. of Na.
(IV) A p-orbital can take maximum of six electrons.
(A) TFTF (B) TFFT (C) FFTF (D) TTFF
Ans. (A)
Sol. (II) 5s 4d 5p
Orbital 1 5 3
Total orbitals = 9
Total element = 18
(III) Mg+ 1s2 2s2 2p6 3s1
Na+ 1s2 2s2 2p6
Na+ attained inert gas configuration
IE2 of Na is greater than Mg.
(IV) p-orbital can have 2 electrons but p-subshell can have 6 electrons.

Q.4 The electronic configuration of an element is 1s2, 2s22p6,3s13p33d2. The atomic number of the element
present just below this element in the periodic table -
(A) 36 (B) 34 (C) 33 (D) 32
Ans. (B)
Sol. At. No. = 16(S)
Next element below this element has atomic number = 16 + 18 = 34

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ACC- CH-PERIODIC PROPERTIES 41

EXERCISE-1 (Exercise for JEE Mains)

[SINGLE CORRECT CHOICE TYPE]

Q.1 The correct order of ionic radius is -

(A) Ce > Sm > Tb > Lu (B) Lu > Tb > Sm > Ce
(C) Tb > Lu > Sm > Ce (D) Sm > Tb > Lu > Ce [2010110651]

Q.2 The Zeff for

3d electron of Cr
4s electron of Cr
3d electron of Cr3+
3s electron of Cr3+ are in the order respectively
(A) 4.6, 2.95, 4.95, 8.05 (B) 4.95, 2.95, 4.6, 8.05
(C) 4.6, 2.95, 5.3, 12.75 (D) none of these [2010110575]

Q.3 According to the Periodic Law of elements, the Variation in properties of elements is related to their ?
(A) Nuclear masses (B)Atomic numbers
(C) Nuclear neutron-proton number ratio (D)Atomic masses [2010112297]

Q.4 Atomic radius decreases in a period, but after halogens, the atomic radius suddenly increases. Thus,
inert gases has almost highest radius in a period. The explanation for such an increase is-
(A) Inert gases has most stable configuration
(B) Inert gases do not take part in bonding
(C) Vander Wall’s radius is reported in case of inert gases
(D) None of these
[2010110748]
Q.5 Which one of the following groups represent a collection of isoelectronic species ?
(At. no. Cs = 55, Br = 35)
(A) N3–, F–, Na+ (B) Be, Al3+, Cl– (C) Ca2+, Cs+, Br (D) Na+, Ca2+, Mg2+
[2010110847]

Q.6 Consider the following statements:

I. The radius of an anion is larger than that of parent atom
II. The I.E. increases from left to right in a period generally
III. The electronegativity of an element is the tendency of an isolated atom to attract an electron
The correct statements are -
(A) I alone (B) II alone (C) I and II (D) II and III
[2010110542]

Q.7 The atomic numbers of vanadium (V). Chromium (Cr), manganese (Mn) and iron (Fe) respectively 23,
24, 25 and 26. Which one of these may be expected to have the higher second ionization enthalpy ?
(A) Cr (B) Mn (C) Fe (D) V
[2010111695]

BANSAL CLASSES
46 ACC- CH-PERIODIC PROPERTIES

EXERCISE-2 (Exercise for JEE Advanced)

[PARAGRAPH TYPE]

Paragraph for Question Nos. 1 to 2

Four elements P, Q, R & S have ground state electronic configuration as:
P 1s2 2s2 2p6 3s2 3p3 Q 1s2 2s2 2p6 3s2 3p1
R 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3 S 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p1
[2010111148]
Q.1 Comment which of the following option represent the correct order of true (T) & false (F) statement
I size of P < size of Q II size of R < size of S
III size of P < size of R (appreciable difference) IV size of Q < size of S (appreciable difference)
(A) TTTT (B) TTTF (C) FFTT (D) TTFF

Q.2 Order of IE1 values among the following is

(A) P > R > S Q (B) P < R < S < Q (C) R > S > P > Q (D) P > S > R > Q

Paragraph for Question Nos. 3 to 4

The electron affinity is a inherent property of the atom and it depends upon several factors.
[2010111642]
Q.3 The correct electron affinity order is
(A) F > Cl (B) Cl > F (C) S < P (D) N > O

Q.4 Choose the incorrect statement.

(A) 1st I.E. ofA¯ is equal to electron affinity of A
(B) 2nd electron affinity is always greater than 1st electron affinity.
(C) O O2– process is endothermic
(D) Li Li+ process is endothermic.

Paragraph for Question Nos. 5 to 7

Atoms of metals have only a few electrons in their valence shells while atoms of non-metals generally
have more electrons in their valence shells. Metallic character is closely related to atomic radius and
ionization enthalpy. Metallic character increases from top to bottom in a group and decreases from left to
right in a period. Metallic character is inverselyrelated to electronegativity.
[2010111495]
Q.5 Which of the following groups contains metals, non-metals and metalloids -
(A) Group 1 (B) Group 17 (C) Group 14 (D) Group 2

Q.6 Non-metals belong to -

(A) s-blockelements (B) p-block elements (C) d-blockelements (D) f-block elements

Q.7 Considering the elements B, C, N, and F the correct order of their non-metallic character is -
(A) B > C > N > F (B) C > B > N > F (C) F > N > C > B (D) F > N > C > B
BANSAL CLASSES
ACC- CH-PERIODIC PROPERTIES 51

EXERCISE-3 (Miscellaneous Exercise)

Subjective Type
Q.1 Use the following system of namingelements in which first alphabets of the digits are written collectively,
0 1 2 3 4 5 6 7 8 9
nil uni bi tri quad pent hex sept oct enn
to write three-letter symbols for the elements with atomic number 101 to 109.
[Example : 101 is Unu....] [2010110901]

Q.2 Mg2+, O2–, Na+, F–, N3– (Arrange in decreasing order of ionic size) [2010110877]

Q.3 Why Ca2+ has a smaller ionic radius than K+. [2010110043]

Q.4 Arrange in decreasing order of atomic size : Na, Cs, Mg, Si, Cl. [2010110195]

Q.5 Why the first ionisation energy of carbon atom is greater than that of boron atom whereas, the reverse is
true for the second ionisation energy. [2010110601]

Q.6 The IE do not follow a regular trend in II & III periods with increasing atomic number. Why?
[2010110943]

Q.7 Explain whya few elements such as Be (+0.6), N(+0.3) & He(+0.6) have positive electron gain enthalpies
while majorityof elements do have negative values. [2010110599]

Q.8 Which bond in each pair is more polar

(a) P – Cl or P – Br (b) S – Cl or S – O (c) N – O or N – F
[2010110441]

Q.9 From among the elements, choose the following: Cl, Br, F,Al, C, Li, Cs & Xe.
(i) The element with highest electron gain enthalpy.
(ii) The element with lowest ionisation potential.
(iii) The element whose oxide is amphoteric.
(iv) The element which has smallest radii.
(v) The element whose atom has 8 electrons in the outermost shell. [2010110597]

Q.10 In the ionic compound KF, the K+ and F– ions are found to have practically radii, about 1.34 Å each.
What do you predict about the relative covalent radii of K and F? [2010110350]

Q.11 Which oxide is more basic, MgO or BaO? Why? [2010110301]

Q.12 The basic nature of hydroxides of group 13 (III-A) decreases progressively down the group. Comment.
[2010110596]

Q.13 Based on location in P.T., which of the following would you expect to be acidic & which basic.
(a) CsOH (b) IOH (c) Sr(OH)2 (d) Se(OH)2 (e) FrOH (f) BrOH
[2010110868]

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ACC- CH-PERIODIC PROPERTIES 55

EXERCISE-4

SECTION-A
(IIT JEE Previous Year's Questions)

Q.1 Moving from right to left in a periodic table, the atomic size is: [JEE 1995]
(A) increased (B) decreased (C) remains constant (D) none of these
[2010112001]

Q.2 The increasing order of electronegativity in the following elements: [JEE 1995]
(A) C, N, Si, P (B) N, Si, C, P (C) Si, P, C, N (D) P, Si, N, C
[2010110537]

Q.3 One element has atomic weight 39. Its electronic configuration is 1s2, 2s2 2p6, 3s2 3p6 4s1. The true
statement for that element is:
(A) Highest value of IE (B)Transition element
(C) Isotone with 18Ar 38
(D) None [JEE 1995]
[2010111632]

Q.4 The number of paired electrons in oxygen atom is: [JEE 1995]
(A) 6 (B) 16 (C) 8 (D) 32
[2010112648]

Q.5 The decreasing size of K+, Ca2+, Cl– & S2– follows the order: [REE 1995]
(A) K+ > Ca +2 > S–2 > Cl– (B) K+ > Ca +2 > Cl– > S–2
(C) Ca >K > Cl > S
+2 + – –2
(D) S–2 > Cl– > K+ > Ca+2
[2010111675]

Q.6 Which of the following oxide is neutral? [JEE 1996]

(A) CO (B) SnO2 (C) ZnO (D) SiO2
[2010111977]

Q.7 Which of the following has the maximum number of unpaired electrons [JEE 1996]
(A) Mg2+
(B) Ti3+
(C) V 3+
(D) Fe2+

[2010111613]

Q.8 The following acids have been arranged in the order of decreasing acid strength. Identify the correct
order [JEE 1996]
ClOH(I) BrOH(II) IOH(III)
(A) I > II > III (B) II > I > III (C) III > II > I (D) I > III > II
[2010110900]

Q.9 The incorrect statement among the following is: [JEE 1997]
(A) the first ionisation potential ofAl is less than the first ionisation potential of Mg
(B) the second ionisation potential of Mg is greater than the second ionisation potential of Na
(C) the first ionisation potential of Na is less than the first ionisation potential of Mg
(D) the third ionisation potential of Mg is greater than the third ionisation potential ofAl
[2010112041]

BANSAL CLASSES
ACC- CH-PERIODIC PROPERTIES 57

Q.20 Identify the correct order of acidic strengths of CO2, CuO, CaO, H2O: [JEE 2002]
(A*) CaO < CuO < H2O < CO2 (B) H2O < CuO < CaO < CO2
(C) CaO < H2O < CuO < CO2 (D) H2O < CO2 < CaO < CuO
[2010111496]

SECTION-B
(AIEEE Previous Year's Questions)
Q.21 In which of the following arrangements, the sequence is not strictly according to the property written
against it ? [AIEEE-2009]
(A) H2O < H2S < H2Se < H2Te : Increasing acidic strength
(B) HF < HCl < HBr < HI : Increasing acidic strength
(C*) NH3 > PH3 < AsH3 < SbH3 : Increasing basic strength
(D) B < C < O < N : increasing first ionization enthalpy
[2010113518]

Q.22 The set representing the correct order of ionic radius is – [AIEEE-2009]
+ 2+
(A) Li > Be > Na > Mg+ 2+ + + 2+
(B) Na > Li > Mg > Be 2+
2+ +
(C) Li > Na > Mg > Be 2+ 2+ (D) Mg2+ > Be2+ > Li+ > Na+
[2010113569]

Q.23 The correct sequence which shows decreasing order of the ionic radii of the elements is
[AIEEE-2010]
3+ 2+ +
(A) Al > Mg > Na > F > O – 2– (B) Na > Mg > Al > O > F–
+ 2+ 3+ 2

(C) Na+ > F– > Mg2+ > O2– > Al3+ (D) O2– > F– > Na+ > Mg2+ > Al3+
[2010113620]

Q.24 Which one of the following ordered presents the correct sequence of the increasing basic nature of the
given oxides ? [AIEEE-2011]
(A) Al2O3 < MgO < Na2O < K2O (B) MgO < K2O < Al2O3 < Na2O
(C) Na2O < K2O < MgO < Al2O3 (D) K2O < Na2O < Al2O3 < MgO
[2010113671]

Q.25 The increasing order of the ionic radii of the given isoelectronic species is [AIEEE-2012]
(A) Ca2+, K+, Cl–, S2– (B) K+, S2–, Ca2+, Cl–
(C) Cl–, Ca2+, K+, S2– (D) S2–, Cl–, Ca2+, K+ [2010113722]

Q.26 The first ionisation potential of Na is 5.1 eV. The value of electron gain enthalpy of Na+ will be:
(A*) –5.1 eV (B) –10.2 eV (C) +2.55 eV (D) –2.55 eV
[JEE MAIN-2013]
[2010113967]

Q.27 Which of the following represents the correct order of increasing first ionization enthalpy for Ca, Ba, S,
Se and Ar?
(A) S < Se < Ca < Ba < Ar (B*) Ba < Ca < Se < S < Ar
(C) Ca < Ba < S < Se < Ar (D) Ca < S < Ba < Se < Ar [JEE MAIN-2013]
[2010114018]

BANSAL CLASSES
58 ACC- CH-PERIODIC PROPERTIES

EXERCISE-1

Q.1 (A) Q.2 (C) Q.3 (B) Q.4 (C)

Q.5 (A) Q.6 (C) Q.7 (A) Q.8 (D)
Q.9 (D) Q.10 (A) Q.11 (B) Q.12 (B)
Q.13 (B) Q.14 (C) Q.15 (B) Q.16 (B)
Q.17 (C) Q.18 (D) Q.19 (D) Q.20 (D)
Q.21 (D) Q.22 (C) Q.23 (B) Q.24 (C)
Q.25 (B) Q.26 (A) Q.27 (D) Q.28 (A)
Q.29 (A) Q.30 (B) Q.31 (C) Q.32 (A)
Q.33 (A)

EXERCISE-2

Q.1 (B) Q.2 (A) Q.3 (B) Q.4 (B)

Q.5 (C) Q.6 (B) Q.7 (C) Q.8 (B)
Q.9 (A) Q.10 (C) Q.11 (C) Q.12 (B)
Q.13 (D) Q.14 (A) Q.15 (A) Q.16 (C)
Q.17 (A) Q.18 (C) Q.19 (C) Q.20 (C)
Q.21 (D) Q.22 (A) Q.23 (D) Q.24 (A), (C)
Q.25 (A), (B), (C) Q.26 (B), (D) Q.27 (A), (B), (C) Q.28 (A), (C), (D)
Q.29 (A), (C), (D) Q.30 (A), (C)
Q.31 [(A) S (B) R (C) P (D) Q ] Q.32 [(A) Q, (B) S, (C) P, Q]
Q.33 [(A) Q,R; (B) P,S; (C) S; (D) Q,R ] Q.34 [(A) Q (B) P,Q,R (C) P (D) R,S ]
Q.35 [(A) Q,R (B) R (C) P (D) S] Q.36 [(A) P,Q,R (B) R,S (C) Q,R (D) P,Q ]

EXERCISE-3

Q.1 [101 102 103 104 105 106 107 108 109
Unu Unb Unt Unq Unp Unh Uns Uno Une]
Q.2 [N > O > F > Na > Mg2+]
3– 2– – + Q.3 [Isoelectronic Ca+2(Value of Zeff is higher)]
Q.4 [Cs > Na > Mg > Si > Cl] Q.5 [Zeff & half filled config.]
Q.6 [half filled & fullyfilled orbitals] Q.7 [half filled and fullyfilled orbitals]
Q.8 [(a) P–Cl (b) S–O, (C) N–F] Q.9 [(i) Cl (ii) Cs (iii) Al (iv) F (v) Xe]
Q.10 [rk > 1.34Å > rF] Q.11 [BaO]
Q.12 [False]
Q.13 [(a) basic (b) acidic (c) basic (d) acidic (e) basic (f) acidic ]
Q.14 [CaO < CO < CO2 < N2O5 < SO3] Q.15 [EN1 > EN2]
Q.16 [5.919 Å] Q.17 [1.21 Å]
Q.18 [4.64 Å ; b = 3.28 Å] Q.19 [IE2 = 1825 kJ/mole, IE3 = 2737.5 kJ/mol]
Q.20 [3.476 eV] Q.21 [3.03 (Pauling)]
Q.22 [3.8752] Q.23 [3.2]
BANSAL CLASSES
60 ACC- CH-PERIODIC PROPERTIES

EXERCISE-1

Q.1 [Due to lanthanide contraction; left to right atomic size decreases. ]

Q.2 [Cr = 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Zeff =Atomic no
s for 4s electron (valance shell e¯ –1) × 0.35 +
Penultimate shell e¯ × 0.85 + remaining e¯
= (1 – 1) × 0.35 + 13 × 0.85 + 10
= 0 + 11.05 + 10 = 21.05
Zeff = 24 – 21.05 = 2.95
Zeff for 3d electron
for 3de¯ = (valance shell e¯ –1) × 0.35 + remaining e¯
= (5 – 1) × 0.35 + 18
= 1.4 + 18 = 19.4
= 24 – 19.4 = 4.6 ]

Q.3 [Atomic no.]

Q.5 [Isoelectronic species = Total no. of electrons are same ]
Q.6 [After the removal of one electron Cr acquired half filled stable d-orbital configuration ]
Q.7 [Basic characters electropositive / metallic character ]
Q.8 [Metals oxide are basic as well as they are electropositively in nature ]
Q.10 [( Heg)2 is an endothermic process ]
Q.11 [Due to the half filled stable configuration of N its ionisation potential is maximum]
Q.12 [Correct order is B < C < O < N]
Q.13 [Correct order of IE1
Li < B < Be < C]
Q.14 [Poorer shielding of 5d electrons by 4f electron. ]
z
Q.15 [ Atomic size ]
e
Q.22 [rc + rF = 1.33 Å
rsi + rF = 1.54 Å
----------------------
rc + rsi + 2rF = 2.87 Å

rc + rsi = 1.87 Å

1.87Å + 2 rF = 2.87 Å
2 rF = 1.00 Å
rF = .5 Å]

1
Q.23 [Electronegativity atomic size ]

BANSAL CLASSES
Examples:

ANS:

ANS:
ANS:
PEARSON'S HARD & SOFT ACIDS &
BASES (HSAB) THEORY
Hard and Soft Acids and Bases (HSAB) Theory is a qualitative concept
introduced by Ralph Pearson to explain the thermodynamic stability of
metal complexes that depends on the properties of the ligand and the metal
ion and on the type of bonding. Also, the mechanisms of metal complex
reactions can be explained by HSAB theory.

According to this theory, the Lewis acids and bases can be further divided
into hard or soft or border line types.

Hard Lewis acids are characterized by small ionic radii, high positive
charge (i.e they have higher charge-to-radius ratio), strongly solvated, and
empty orbitals in the valence shell and with high energy LUMOs.

Soft Lewis acids are characterized by large ionic radii, low positive
charge (i.e., lower charge-to-radius ratio), and completely filled atomic
orbitals and with low energy LUMOs.

Hard Lewis bases are characterized by small ionic radii, strongly

solvated, highly electronegative, weakly polarizable and with high energy
HOMOs.

Soft Lewis bases are characterized by large ionic radii, intermediate

electronegativity, highly polarizable and with low energy HOMOs.

The Border line Lewis acids and bases have intermediate properties.

In short, Hard acids and bases are small and non-polarizable, whereas Soft
acids and bases are larger and more polarizable.

HSAB Principle: According to HSAB concept, hard acids prefer binding

to the hard bases to give ionic complexes, whereas the soft acids prefer
binding to soft bases to give covalent complexes.
* The large electronegativity differences between hard acids and hard
bases give rise to strong ionic interactions.

* The electronegativities of soft acids and soft bases are almost same and
hence have less ionic interactions. i.e., the interactions between them are
more covalent.

* The interactions between hard acid - soft base or soft acid - hard base
are mostly polar covalent and tend to be more reactive or less stable. The
polar covalent compounds readily form either more ionic or more
covalent compounds if they are allowed to react. The interactions between
acids and bases are controlled by the relative energies of the participating
HOMO and LUMO.

CHARACTERISTICS OF HARD, SOFT & BORDERLINE ACIDS & BASES

Type of
CHARACTERISTICS EXAMPLES
Acid/Base

* Atomic centres of small

ionic radii (<90 pm). H+, Li+, Na+, K+, Be2+, Mg2+,
* High positive charge. Ca2+, Sr2+, Sn2+
* Empty orbitals in their
valence shells. Al3+, Ga3+, In3+, Cr3+, Co3+,
Hard acids * Low electronegativity Fe3+, Ir3+, La3+, Si4+, Ti4+,
(0.7-1.6) and low electron Zr4+, Th4+, VO2+ , UO22+
affinity.
* Likely to be strongly BeMe2, BF3, BCl3, B(OR)3,
solvated. AlMe3
* High energy LUMO.

* Large radii (>90 pm). Cu+, Ag+, Au+, Hg+ , Cs+ ,

Soft acids * Low or partial positive Tl+ , Hg2+ , Pd2+, Cd2+ ,
charge. Pt2+
 * Completely filled orbitals
in their valence shells. Metal atoms in zero
* Intermediate oxidation states
electronegativities (1.9-2.5)
* Low energy LUMO's with
large magnitude of LUMO
coefficients.

* Small radii (around

120pm) & highly solvated . Fe2+ , Co2+ , Ni2+ , Cu2+ ,
Border line * electronegative atomic
Zn2+ , Pb2+ , B(CH3)3, SO2,
acids centres (3.0-4.0). NO+
* Weakly polarizable
H2O, OH-, F-, Cl-, CH3CO2-,
* Weakly polarizable. PO43-, SO42-, CO32-, NO3-,
Hard bases * Difficult to be oxidized.
ClO4-, ROH, RO-, R2O, NH3,
* High energy HOMO. RNH2, N2H4

* Large atoms (>170 pm)

with intermediate
electronegativity (2.5-3.0).
RSH, RS-, R2S, I-, CN-, SCN-,
* High polarizability
Soft bases S2O3-, R3P, R3As (RO)3P,
* Easily undergo oxidation.
RNC, CO, C2H4, C6H6, R-, H-
* Low energy HOMO's but
large magnitude HOMO
coefficients.

Border line Aniline, pyridine, N3-, Br-,

bases NO2-, SO32-, N2
APPLICATIONS OF HSAB PRINCIPLE

In hydrogen bonding: The strong hydrogen bond is possible in cases

of H2O, NH3 and HF, since the donor atoms (F, O & N) are hard lewis
bases and their interactions with partially positively charged H, which is
a hard acid, are stronger.

Stability of complexes:

Because the interaction between hard acids and hard bases is primarily
electrostatic in nature, the stability of complexes involving hard acids and
hard bases increases as the positive charge on the metal ion increases and
as its radius decreases. For example, the complex of Al 3+ (r = 53.5 pm)
with four fluoride ligands (AlF4−) is about 108 times more stable than
InF4−, the corresponding fluoride complex of In 3+ (r = 80 pm). In general,
the stability of complexes of divalent first-row transition metals with a
given ligand varies inversely with the radius of the metal ion, as shown in
Table

complex stability Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+
ionic radius (pm) 83 78 74.5 69 73 74

Because a hard metal interacts with a base in much the same way as a
proton, by binding to a lone pair of electrons on the base, the stability of
complexes of hard acids with hard bases increases as the ligand becomes
more basic. For example, because ammonia is a stronger base than water,
metal ions bind preferentially to ammonia. Consequently, adding
ammonia to aqueous solutions of many of the first-row transition-metal
cations results in the formation of the corresponding ammonia complexes.
In contrast, the interaction between soft metals (such as the second- and
third-row transition metals and Cu+) and soft bases is largely covalent in
nature. Most soft-metal ions have a filled or nearly filled d subshell, which
suggests that metal-to-ligand π bonding is important. Complexes of soft
metals with soft bases are therefore much more stable than would be
predicted based on electrostatic arguments.
Linkage of ambidentate ligands to metal atoms: The ambidentate
ligand, SCN- can bind either by S end or N end. The bonding mode can
be determined by using HSAB principle.
It bonds through sulfur atom (soft base) when bonded to Pt 2+, a soft acid.
However it bonds through nitrogen atom (a hard base) when linked to
Cr3+, a hard acid.
Site preference in organic reactions: RCOX is a hard acid and reacts
with the nitrogen end of SCN- ion to form an acyl isothiocyanate.

Whereas the softer methyl group bonds to the Sulfur atom and forms
methyl thiocyanate.

Inorganic reactions: HSAB principle is used to predict the outcome of

some of the reactions.
1) The following reaction is possible because As is softer than P and I- is
softer than F-.

Remember that both As and P are soft but relatively As is softer.

2) The following reaction is possible since Mg2+ is harder acid than Ba2+
and O2- is harder base than S2-.

Precipitation reactions: The softer acids like Ag+, Hg+, Hg2+ etc., and
border line acids like Fe2+, Ni2+, Cu2+, Zn2+, Pb2+ etc., can be precipitated
as sulfides from their aqueous solutions since S2- ion is a softer base.
PEARSON’S HARD & SOFT ACIDS & BASES (HSAB) THEORY

Type of
CHARACTERISTICS EXAMPLES
Acid/Base
* Atomic centers of small ionic radii
H+, Li+, Na+, K+, Be2+, Mg2+,
(<90 pm).
Ca2+, Sr2+, Sn2+
* High positive charge.
* Empty orbitals in their valence
Al3+, Ga3+, In3+, Cr3+, Co3+,
Hard acids shells.
Fe3+, Ir3+, La3+, Si4+, Ti4+, Zr4+,
* Low electronegativity (0.7-1.6)
Th4+,U4+, VO2+ , UO22+
and low electron affinity.
* Likely to be strongly solvated.
BeMe2, BF3, BCl3, B(OR)3, AlMe3
* High energy LUMO.

* Large radii (>90 pm).

Cu+, Ag+, Au+, Hg+ , Cs+ , Tl+ ,
* Low or partial positive charge.
Hg2+ , Pd2+, Cd2+ , Pt2+
* Completely filled orbitals in their
valence shells.
Soft acids Metal atoms in zero oxidation
* Intermediate electronegativities
states
(1.9-2.5)
* Low energy LUMOs with a large
BH3
magnitude of LUMO coefficients.

Borderline Fe2+ , Co2+ , Ni2+ , Cu2+ , Zn2+ ,

acids Pb2+ , B(CH3)3, SO2, NO+

* Small radii (around 120pm) &

highly solvated.
* electronegative atomic centres H2O, OH-, F-, Cl-, CH3CO2-, PO43-
Hard bases (3.0-4.0). , SO42-, CO32-, NO3-, ClO4-, ROH,
* Weakly polarizable. RO-, R2O, NH3, RNH2, N2H4
* Difficult to be oxidized.
* High energy HOMO.
* Large atoms (>170 pm) with
intermediate electronegativity (2.5-
S2-, RSH, RS-, R2S, I-, CN-, SCN-
3.0).
, S2O3-, R3P, R3As,
Soft bases * High polarizability
(RO)3P, RNC, CO, C2H4, C6H6, R-
* Easily undergo oxidation.
, H-
* Low energy HOMOs but large
magnitude HOMO coefficients.
Borderline Aniline, pyridine, N3-, Br-, NO2-,
bases SO32-, N2

According to this theory, the Lewis acids and bases can be further divided into hard or soft
or border line types.
HSAB principle: According to HSAB concept, hard acids prefer binding to the hard bases to
give ionic complexes, whereas the soft acids prefer binding to soft bases to give covalent
complexes.
APPLICATIONS OF HSAB PRINCIPLE:
There are numerous applications of the HSAB principle. It helps in understanding
organic reaction mechanisms, metal-ligand interactions in metal complexes, ore
processing in metallurgy, precipitations in qualitative analysis etc.

1. In hydrogen bonding:

The strong hydrogen bond is possible in cases of H2O, NH3, and HF, since the
donor atoms (F, O & N) are hard Lewis bases and their interactions with partially
positively charged H, which is a hard acid, are stronger.

2. Linkage of ambidentate ligands to metal atoms:

It is one of the important applications of the HSAB principle. The SCN- ligand is an
ambidentate ligand and can be S-bound to metal (M-SCN) and referred to as
thiocyanate or can be N-bound to metal (M-NCS) and is referred to as isothiocyanate.
The choice among S-bound or N-bound is decided by soft or hard acid-base behavior.
S is a comparatively soft base than N atom. Hence soft metal ions are S-bound while
hard metal ions are N-bound.
1) SCN- bonds through sulfur atom (soft base) when bonded to Pt2+, a soft acid.
2) It bonds through nitrogen atom (a hard base) when linked to Cr3+, a hard acid.
3) When Fe2+ reacts with SCN- a bright red [Fe(SCN)]+ ion is formed, whereas
Cr forms [Cr(NCS)]2+.
3+

Reason: Fe2+ is a borderline acid and is S-bound. Whereas Cr3+ is hard acid and
prefers to be N-bound.
4) The molecule (CH3)2NCH2PF2 would bond to BF3 through N whereas it would
bond to BH3 through P.
 Reason: BF3 is a hard acid and prefers to bind with N atom - a hard base. Whereas,
BH3 is a soft acid and preferentially bonded to soft base, P atom.
Symbiotic effect: The hard-soft character of the metal ion is altered by the other
groups attached. It is referred to as a symbiotic effect.
For example, the isolated Co3+ is a hard acid and is expected to make the bond
with SCN- ion through N atom as observed in [Co(NH3)5(NCS)]3-.
However, when bound to five soft base ligands like CN- ions, the hardness of cobalt
ion (Co3+)is reduced. Thus [Co(CN)5]2- behaves as a soft acid and prefers to bind with
SCN- ion through S atom to form [Co(CN)5(SCN)]3-.

3. To predict the direction of Inorganic reactions:

HSAB principle is used to predict the outcome of few of the reactions. We can
predict whether a reaction proceeds to the right or left based on soft or hard acid/base
interactions.
1) The reaction between AsF3 and PI3 is possible and proceeds to the right since
As is softer than P3+ and I- is softer than F-.
3+

Remember that both As3+ and P3+ are soft but relatively As3+ is softer due to larger
size.
2) The reaction between MgS and BaO as shown below is possible since Mg2+ is
harder acid than Ba2+ and O2- is harder base than S2-.

3) P2F4 can be prepared by treating PF2I with mercury as shown below.

2PF2I + 2Hg ------>• Hg2I2 + P2F4
In this reaction, it is iodine rather than fluorine that is removed from PF2I.
Explanation:Hg22+ ion is a soft acid that prefers soft base I - rather than hard base F-.

4. Solubility in water:

The compound formed due to soft acid-soft base combination is more covalent
and less soluble in polar solvents like water. For example, Silver iodide, AgI is insoluble
in water as it has covalent nature since it is the combination of soft acid, Ag+ and soft
base, I-.
On the other hand, Lithium iodide, LiI is the result of a combination of Li + (hard
acid) and I- (soft base). Thus it is polar covalent and thus soluble in water.

5. Hard Soft interactions - Types of ores:

We know that the hard metals prefer to bind with hard anions and thus they are
available as oxides or fluorides or carbonates or silicates in nature. Whereas, the soft
metals prefer to bind with soft anions and hence are found in nature as sulfides or
phosphides or selenides.
 E.g. Aluminium is mostly found in nature as alumina, Al2O3 - an oxide ore, since
Al3+ is a hard metal which prefers to combine with hard oxide anion rather than the
soft sulfide ion.
Silver & copper metals exist as sulfide ores since both Ag+ and Cu2+ are soft
metals.
The f-block elements are found in nature as silicate minerals since the trivalent
lanthanides are actinides are hard acids and tend to bind with hard oxygen bases as
in silicates.

6. Precipitation reactions & Qualitative analysis:

The softer acids like Ag+, Hg+, Hg2+ etc., and borderline acids like Fe2+, Ni2+, Cu2+,
Zn , Pb2+ etc., can be precipitated as sulfides from their aqueous solutions since
2+

S2- ion is a softer base. Following table illustrates the separation of cations based on
their hardness or softness.
HSAB and Qualitative Analysis
Separation Table
Group-1 Group-2 Group-3 Group-4 Group-5
HSAB acid Soft Borderline & soft Borderline Hard Hard
Reagent HCl H2S (acidic) H2S (basic) (NH4)2CO3 Soluble
AgCl HgS MnS CaCO3 Na+
PbCl2 CdS FeS SrCO3 K+
Hg2Cl2 CuS CoS BaCO3 NH4+
Precipitates SnS NiS
As2S3 ZnS
Sb2S3 Al(OH)3
Bi2S3 Cr(OH)3

7. Site preference:

1) RCOX is a hard acid and reacts with the nitrogen end of SCN - ion to form an
acyl isothiocyanate.

2) Whereas the softer methyl group bonds to the Sulfur atom and forms methyl
thiocyanate.

8. Nucleophilic addition of α,β-unsaturated carbonyl compounds:

The α,β-unsaturated carbonyl compounds have two types of carbon electrophilic

centers.
1) Carbonyl carbon - Hard electrophilic center.
2) β-carbon - Soft electrophilic center.
 Therefore, the hard nucleophiles like Grignard reagents attack the carbonyl carbon
(hard electrophile) resulting in 1,2-nucleophilic addition to C=O group.

E.g.,

Whereas, the soft nucleophiles like Lithium organocuprates, thiols etc. attack
the β-carbon (soft nucleophile) resulting in 1,4-conjugate addition.

LIMITATIONS (DRAW BACKS) OF PEARSON'S HSAB MODEL

Pearson's HSAB theory is in direct contradiction with Fajan's rules. For example, the
later predict the nature of Beryllium salts to be more covalent. But according to the
HSAB principle, the Be2+ ion is hard acid and is expected to show charge controlled
bonding that results in more ionic nature for beryllium compounds. But this is not
true.
Since hydrogen ion, H+ is a hard acid and hydride ion, H- is a soft base, according
to HSAB principle the interactions between them must be polar covalent and H 2 must
be unstable. Indeed H2 is a stable molecule with pure covalent nature.