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ELECTRON AFFINITY

This page explains what electron affinity


is, and then looks at the factors that affect
its size. It assumes that you know about
simple atomic orbitals, and can write
electronic structures for simple atoms.

Important! If you aren't reasonable


happy about atomic
orbitalsand electronic structures you
should follow these links before you go
any further.

First electron affinity

Ionisation energies are always concerned


with the formation of positive ions.
Electron affinities are the negative ion
equivalent, and their use is almost always
confined to elements in groups 6 and 7 of
the Periodic Table.

Defining first electron affinity

The first electron affinity is the energy


released when 1 mole of gaseous atoms
each acquire an electron to form 1 mole of
gaseous 1- ions.

This is more easily seen in symbol terms.

It is the energy released (per mole of X)


when this change happens.

First electron affinities have negative


values. For example, the first electron
affinity of chlorine is -349 kJ mol-1. By
convention, the negative sign shows a
release of energy.

The first electron affinities of the group 7


elements

-328 kJ
F
mol-1
-349 kJ
Cl
mol-1
B -324 kJ
r mol-1
-295 kJ
I
mol-1

Note: These values are based on the


most recent research. If you are using a
different data source, you may have
slightly different numbers. That doesn't
matter - the pattern will still be the
same.

Is there a pattern?

Yes - as you go down the group, first


electron affinities become less (in the
sense that less energy is evolved when the
negative ions are formed). Fluorine breaks
that pattern, and will have to be accounted
for separately.

The electron affinity is a measure of the


attraction between the incoming electron
and the nucleus - the stronger the
attraction, the more energy is released.

The factors which affect this attraction are


exactly the same as those relating to
ionisation energies - nuclear charge,
distance and screening.

Note: If you haven't read


about ionisation energy recently, it
might be a good idea to follow this link
before you go on. These factors are
discussed in more detail on that page
than they are on this one.

The increased nuclear charge as you go


down the group is offset by extra screening
electrons. Each outer electron in effect
feels a pull of 7+ from the centre of the
atom, irrespective of which element you
are talking about.

For example, a fluorine atom has an


electronic structure of 1s22s22px22py22pz1. It
has 9 protons in the nucleus.

The incoming electron enters the 2-level,


and is screened from the nucleus by the
two 1s2 electrons. It therefore feels a net
attraction from the nucleus of 7+ (9
protons less the 2 screening electrons).

By contrast, chlorine has the electronic


structure 1s22s22p63s23px23py23pz1. It has 17
protons in the nucleus.

But again the incoming electron feels a net


attraction from the nucleus of 7+ (17
protons less the 10 screening electrons in
the first and second levels).

Note: If you want to be fussy, there is


also a small amount of screening by the
2s electrons in fluorine and by the 3s
electrons in chlorine. This will be
approximately the same in both these
cases and so doesn't affect the
argument in any way (apart from
complicating it!).

The over-riding factor is therefore the


increased distance that the incoming
electron finds itself from the nucleus as
you go down the group. The greater the
distance, the less the attraction and so the
less energy is released as electron affinity.

Note: Comparing fluorine and chlorine


isn't ideal, because fluorine breaks the
trend in the group. However, comparing
chlorine and bromine, say, makes things
seem more difficult because of the more
complicated electronic structures
involved.

What we have said so far is perfectly


true and applies to the fluorine-chlorine
case as much as to anything else in the
group,but there's another factor which
operates as well which we haven't
considered yet - and that over-rides the
effect of distance in the case of fluorine.

Why is fluorine out of line?

The incoming electron is going to be closer


to the nucleus in fluorine than in any other
of these elements, so you would expect a
high value of electron affinity.

However, because fluorine is such a small


atom, you are putting the new electron into
a region of space already crowded with
electrons and there is a significant amount
of repulsion. This repulsion lessens the
attraction the incoming electron feels and
so lessens the electron affinity.
A similar reversal of the expected trend
happens between oxygen and sulphur in
Group 6. The first electron affinity of
oxygen (-142 kJ mol-1) is smaller than that
of sulphur (-200 kJ mol-1) for exactly the
same reason that fluorine's is smaller than
chlorine's.

Comparing Group 6 and Group 7 values

As you might have noticed, the first


electron affinity of oxygen (-142 kJ mol-1) is
less than that of fluorine (-328 kJ mol-1).
Similarly sulphur's (-200 kJ mol-1) is less
than chlorine's (-349 kJ mol-1). Why?

It's simply that the Group 6 element has 1


less proton in the nucleus than its next
door neighbour in Group 7. The amount of
screening is the same in both.

That means that the net pull from the


nucleus is less in Group 6 than in Group 7,
and so the electron affinities are less.

First electron affinity and reactivity

The reactivity of the elements in group 7


falls as you go down the group - fluorine is
the most reactive and iodine the least.

Often in their reactions these elements


form their negative ions. At GCSE the
impression is sometimes given that the fall
in reactivity is because the incoming
electron is held less strongly as you go
down the group and so the negative ion is
less likely to form. That explanation looks
reasonable until you include fluorine!
An overall reaction will be made up of lots
of different steps all involving energy
changes, and you cannot safely try to
explain a trend in terms of just one of
those steps. Fluorine is much more
reactive than chlorine (despite the lower
electron affinity) because the energy
released in other steps in its reactions
more than makes up for the lower amount
of energy released as electron affinity.

Second electron affinity

You are only ever likely to meet this with


respect to the group 6 elements oxygen
and sulphur which both form 2- ions.

Defining second electron affinity

The second electron affinity is the energy


required to add an electron to each ion in 1
mole of gaseous 1- ions to produce 1 mole
of gaseous 2- ions.

This is more easily seen in symbol terms.

It is the energy needed to carry out this


change per mole of X-.

Why is energy needed to do this?

You are forcing an electron into an already


negative ion. It's not going to go in
willingly!

1st EA =
-142 kJ
mol-1
2nd EA =
+844 kJ
mol-1

The positive sign shows that you have to


put in energy to perform this change. The
second electron affinity of oxygen is
particularly high because the electron is
being forced into a small, very electron-
dense space.

Questions to test your understanding

If this is the first set of questions you have done,


please read the introductory page before you start.
You will need to use the BACK BUTTON on your
browser to come back here afterwards.

questions on electron affinites

answers

--------------------

electron affinity,
Energy required to detach an electron from the singly charged negative ion

(energy for the process ). The equivalent more common


definition is the energy released ( ) when an additional electron
is attached to a neutral atom or molecule.

---------------------------------------

Electron Affinity

Electron affinity is, essentially the opposite of the


ionization energy: Instead of removing an electron from
the element we add an electron to the element to create
an anion.

M + e- ---->
E.A.
M-
Generally, the energy that results from this process (the
electron affinity) is negative or close to zero. The more
negative this energy the more this process is favored. In
the figure below we see the trends in the electron
affinity for many of the elements.

Note that the noble gases, alkali metals and alkali earth
metals have E.A. close to zero - indicating that these
groups of elements do not particularly like to become
anions. However, the nonmetals and especially the
halogens are highly negative and thus readily become
anions. A periodic trend is evident, as was the case for
the ionization energy. This periodic trend can be
understood as a reflection of the underlying periodicity
in the electronic configuration of the elements.

=====================

Electron Affinity Trends


Electron Affinity is the energy associated with the addition of an electon to a gaseous atom.

Example:

Cl(g) + e- Cl-(g) E.A. = -349 kJ/mole


Notice the sign on the energy is negative. This is because energy is usually released in this process, as apposed to ionization energy,
whichrequires energy. A more negative electron affinity corresponds to a greater attraction for an electron. (An unbound electron has an
energy of zero.)

Trends:
As with ionization energy, there are two rules that govern the periodic trends of electron affinities:

Electron affinity becomes less negative down a group.

As the principal quantum number increases, the size of the orbital increases and the affinity for the electron is less. The change is small and there
are many exceptions.

Electron affinity decreases or increases across a period depending on electronic configuration.

This occurs because of the same subshell rule that governs ionization energies.

Example:

Since a half-filled "p" subshell is more stable, carbon has a greater affinity for an electron than nitrogen.

Obviously, the halogens, which are one electron away from a noble gas electron configuration, have high affinities for electrons:

(More negative energy = greater affinity)

Element Electron Affinity

I -295.2 kJ/mole
Br -324.5 kJ/mole

Cl -348.7 kJ/mole

F* -327.8 kJ/mole
*
Fluorine's electron affinity is smaller than chlorine's because of the higher electron - electron repulsions in the smaller 2p orbital compared to the
larger 3p orbital of chlorine.

-------------------------

Electron Affinities of the Main-Group


Elements*
The electron affinity is a measure of the energy change when an electron is added
to a neutral atom to form a negative ion. For example, when a neutral chlorine
atom in the gaseous form picks up an electron to form a Cl- ion, it releases an
energy of 349 kJ/mol or 3.6 eV/atom. It is said to have an electron affinity of -349
kJ/mol and this large number indicates that it forms a stable negative ion. Small
numbers indicate that a less stable negative ion is formed. Groups VIA and VIIA in
the periodic table have the largest electron affinities.

* Alkali earth elements (Group IIA) and noble gases (Group VIIIA) do not form
stable negative ions.

Electron Affinities in kJ/mole


Period IA IIIA IVA VA VIA VIIA
H ... ... ... ... ...
Period 1
-73 ... ... ... ... ...
Li B C N O F
Period 2
-60 -27 -122 0 -141 -328
Na Al Si P S Cl
Period 3
-53 -44 -134 -72 -200 -349
K Ga Ge As Se Br
Period 4
-48 -30 -120 -77 -195 -325
Rb In Sn Sb Te I
Period 5
-47 -30 -121 -101 -190 -295
Cs Tl Pb Bi Po At
Period 6
-45 -30 -110 -110 -180 -270
Electron Affinities in Electron Volts
1 kJ/mol = .010364 eV/atom
Period IA IIIA IVA VA VIA VIIA
H ... ... ... ... ...
Period 1
-0.76 ... ... ... ... ...
Li B C N O F
Period 2
-0.62 -0.28 -1.27 0 -1.43 -3.41
Na Al Si P S Cl
Period 3
-0.55 -0.46 -1.39 -0.75 -2.08 -3.62
K Ga Ge As Se Br
Period 4
-0.50 -0.31 -1.25 -0.80 -2.02 -3.37
Rb In Sn Sb Te I
Period 5
-0.49 -0.31 -1.26 -1.05 -1.97 -3.06
Cs Tl Pb Bi Po At
Period 6
-0.47 -0.31 -1.14 -1.14 -1.87 -2.80
Periodic Table Chemical bonds

=======================

Factors Affecting Electron Affinity

The various factors which influence the electron affinity can be explained under following heads:-

1. NUCLEAR CHARGE

Greater the nuclear charge, greater will be the attraction for the incoming electron and as a result
larger will be the value of electron affinity.

2. ATOMIC SIZE

Larger the size of an atom, larger will be the distance between the nucleus and the incoming
electron. Thus, smaller will be force of attraction felt by incoming electron and hence smaller will be
the value of Electron affinity.

3. ELECTRONIC CONFIGURATION

Stable the configuration of an atom, lesser will be its tendency to accept an electron and hence lower
the value of its electron affinity.

=====================

What are the factors that affect electron affinity?

Factors affecting the value of electron affinity

(i) Atomic size: The value of electron affinity decreases with the increase in the
size of atom since the nuclear attraction decreases down a group as the atomic
number increases. Its value increases as we move along a period since the size
of atoms decreases along a period. The lower value of F than Cl is due to the
very small size of F in which negative charge is highly concentrated and repels
the incoming electron thereby reducing the force of attraction of the nucleus
towards the adding electron and hence decreasing the electron affinity. Thus,
chlorine has a highest value of electron affinity.
(ii) Nuclear charge: The value of electron affinity increases with increasing
nuclear charge. Thus, its value increases with increase in nuclear charge along a
period.
(iii) Screening or shielding effect: The value of electron affinity increases with
the decrease in shielding effect of inner electrons. Besides, the value of electron
affinity also depends to some extent upon the type of orbital in which electron is
added. The value is greater when electron enters 's' orbital and decreases
successively for p, d and f orbitals.

------------------------

Periodicity of electron affinity

Electron affinity is the amount of energy released when an electron is added to an isolated
gaseous atom.

Electron affinity is the ability of an atom to hold an additional electron. If the atom
has more tendency to accept an electron then the energy released will be large and
consequently the electron affinity will be high. Electron affinities can be positive or
negative. It is taken as positive when an electron is added to an atom. It is expressed
as electron volts per atom (eV per atom) or kilo joules per mole.
Factors affecting electron affinity
When the nuclear charge is high there is greater attraction for the incoming electron.
Therefore electron affinity increases as the nuclear charge increases.
With the increase in the size of the atom the electron affinity decreases because the
distance between the nucleus and the incoming electron increases.
Electron affinities are low or almost zero in elements having stable electronic
configurations (half filled and completely filled valence subshells) because of the small
tendency to accept additional electron.
Variation along a period
The size of an atom decreases and the nuclear charge increases on moving across a
period. This results in greater attraction for the incoming electron. Hence the
electron affinity increases in a period from left to right.
Variation down a group
As we move down a group the atomic size and nuclear size increases. As the effect of
increase in atomic size is more pronounced the additional electron feels less attracted
by the large atom. Consequently the electron affinity decreases.
However there are some irregularities observed in the above general trend. They are:

The halogens have highest electron affinity because they have only one electron less
than the stable noble gas configuration.They have a strong tendency to accept an
additional electron. This makes their electron affinity values high.
The electron affinity value of noble gases are zero because of the stable electronic
configuration of ns2np6 which has no tendency to take in additional electron. No energy is
released and their electron affinities are zero.

The electron affinity values for Be, Mg, N and P are almost zero because of the extra
stability of completely filled orbitals in Be and Mg and half filled orbitals in N and P.
Electron affinity of fluorine is unexpectedly less than that of chlorine. The low electron
affinity value of F is due to the very small size of F atom. This small size results in strong
inter electronic repulsions in the relatively compact 2p subshell of fluorine: thus the
incoming electron does not feel much attraction. Electron affinity for some third period
elements (e.g., P, S, Cl) are greater than corresponding second period elements (e.g., N, O, F)
because of the smaller atom size of second period elements, which produces larger electronic
repulsions for the additional electron.

Succesive electron affinities


The second electron is added to the negatively charged ion and the addition is
opposed by coulombic repulsions. The energy has to be supplied to force the second
electron into the anion.
First electron affinity

Second electron affinity

The second electron affinities in which energy is absorbed have negative values while the
first electron affinity have positive values as energy is released.

Problem
9. Arrange the following in the decreasing order of electron affinity: B, C, N, O.
Solution
All these elements belong to the same period. The size of an atom decreases and the
nuclear charge increases on moving across a period. This results in greater attraction
for the incoming electron. Hence the electron affinity increases in a period from left
to right O, C, B, N.
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Periodicity of ionization energy

The amount of energy required to remove the most loosely bound electron from an isolated
gaseous atom is called ionization energy (IE).

Ionization energy is also called as ionization potential because it is measured as the


minimum potential required to remove the most loosely held electron from the rest of the
atom. It is measured in the units of electron volts (eV) per atom or kilo joules per mole of
atoms (kJ mol-1).

1 eV per atom = 96.64 kJ mol-1 = 23.05 k cal mol-1


Thus, the ionization energy gives the ease with which the electron can be removed from an
atom. The smaller the value of the ionization energy, the easier it is to remove the electron
from the atom.

FACTORS GOVERNING IONIZATION ENERGY


Size of the atom
As the size of the atom increases the outermost electrons are held less tightly by the
nucleus (attractive force between the electron and the nucleus is inversely
proportional to the distance). As a result it becomes easier to remove the electron
and therefore the ionization energy decreases with the increase in atomic size.
Charge on the nucleus
The attractive force between the nucleus and the electron increases with the increase
in nuclear charge making it more difficult to remove an electron. The ionization
energy thus increases with the increase in the nuclear charge.
Screening effect
In multielectron atoms, the outermost electrons are shielded or screened from the
nucleus by the inner electrons. This is known as shielding or screening effect. The
outer most electrons do not feel the complete charge of the nucleus and the actual
charge felt is called the effective nuclear charge. When the inner electrons are more,
the screening effect will be large, the nuclear attraction will be less. Thus when the
inner electrons increase the ionization energy will decrease.
Penetration effect
The 's' electrons are more penetrating (maximum probability of finding near the
nucleus) towards the nucleus than the p electrons. The order of penetration power in
a given shell is s > p > d > f
If the penetration power of the electron is more, it will be closer to the nucleus and will be
held more firmly. Thus ionization energy will increase with the increase in the penetration
power of the electrons. For the same sub shell the ionization energy would be more to
remove an 's' electron than to remove a 'p' electron which in turn will be more than that for
removing a 'd' electron.

Electronic arrangement
Certain electronic configuration like half-filled and completely-filled shells have extra
stability. It is more difficult to remove electron from these stable configuration and
the ionization energy is very high. For example, the noble gases have the most stable
configuration and so have high ionization energy; elements like Be and Mg have
completely filled orbitals while N and P have exactly half-filled sub shells. Thus, their
ionization energies are high. The more stable the electronic configuration, the higher
is the ionization energy.
Variation along a period
The ionization energy increases with increasing atomic number in a period. This is
because
The nuclear charge increases on moving across a period from left to right.
The atomic size decreases along a period though the main energy level remains the
same.
Due to the increased nuclear charge and simultaneous decrease in atomic size, the valence
electrons are more tightly held by the nucleus. Therefore more energy is needed to remove
the electron and hence ionization energy keeps increasing. However some irregularities have
been noticed due to the extra stability of the half filled and completely filled configurations.

For example, the nuclear charge on Boron is more than Beryllium, yet there is slight
decrease in ionization energy from Be to B. This is because, in boron the last electron
goes to '2p' orbital which is at a slightly higher energy than '2s' orbital. Also, the
electronic configuration of B is less stable than that of Be (has completely filled
orbitals). Hence the ionization energy is less than that of Be. Similarly, nitrogen,
which has half filled '2p' orbitals, is more stable than oxygen. Therefore the
ionization energy of nitrogen is more than that of oxygen.

Fig: 4.7 - Variation of ionization energy with atomic number


Variation down a group
The ionization energy gradually decreases in moving from top to bottom in a group.
This is due to the fact that:
The nuclear charge increases in going from top to bottom in a group.
An increase in the atomic size due to an additional energy shell (level) 'n'.
Due to the increase in the number of inner electrons there is an increase in the
shielding effect on the outer most electron. The effect of increase in atomic size and the
shielding effect is much more than the effect of increased nuclear charge.
As a result , the electron becomes less firmly held to the nucleus and so the ionization
energy decreases as we move down the group.
Fig: 4.8 - The variation of ionization energy with atomic number
Successive ionization energies
The energies required to remove subsequent electrons from a gaseous atom is called
as successive ionization energies. They are termed as first ,second, third
ionization energy depending on the removal of the first, second, third electron
respectively.

The second ionization energies are higher than the first due to the fact that after the removal
of the first electron the atom changes into a monovalent positive ion. In this ion, the number
of electrons decreases but the nuclear charge remains same and so the remaining electrons
are held more tightly by the nucleus and it becomes difficult to remove the second electron.
Hence the value of the second ionization energy (IE2) is higher than the first (IE1). In the
same way the removal of the second electron will result in the formation of di-positive ion
making the attraction between the nucleus and the remaining electrons stronger. This results
in higher value of third ionization energy (IE3).

Problems
6. Calcium (Z = 20) loses electrons successively to form Ca+, Ca2+ and Ca3+ions.
Which step will have highest ionization energy?
Solution

The step, which involves the formation of Ca3+ from Ca2+ would have highest
ionization energy.

7. Consider the ground state electronic configurations given below:


(A) 1s2 2s2 2p6 (B) 1s2 2s2 2p4 (C) 1s2 2s2 2p6 3s2 (D) 1s2 2s2 2p6 3s1 (E) 1s22s2 2p5.

Which of the above configuration is associated with the lowest and which is
associated with highest ionization energy?
Solution
Lowest ionization energy = D
Highest ionization energy = A.

8. Why is the ionization energy of nitrogen unexpectedly high?


Solution
The electronic configuration of nitrogen (1s22s22p3) shows that it possesses exactly
half-filled 'p' orbitals as its outershell configurations. Since, half-filled orbitals are
extraordinarily stable, it is more difficult to remove an electron from this atom. Thus
nitrogen has unexpectedly high ionization energy.
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Periodicity of ionic radii

These are radii of ions in ionic crystals. Ionic radius may be defined as the effective distance
from the center of nucleus of an ion up to which it has an influence on its electron cloud. In
ionic compounds the inter nuclear distance may be taken as equal to the sum of the ionic
radii of the two ions. The inter nuclear distance in ionic crystals are obtained from X-ray
studies.

Fig: 4.6 - Internuclear distance and ionic radii

Radius of the cation


A cation is formed by the loss of one or more electrons from the gaseous atom. Thus,
the whole of the outer most shell of electrons is removed resulting in the smaller size
in the cation.
For example, in lithium atom, there is only one electron in the outermost '2s' shell. As the
lithium atom changes to Li+ ion the outer most '2s' shell disappears completely. This
disappearance results in the decrease in size.

With the removal of electrons from an atom the magnitude of the nuclear charge remains the
same while the number of electrons decreases. As a result the nuclear charge acts on less
number of electrons. The effective nuclear charge per electron increases and the electrons
are more strongly attracted and pulled towards the nucleus. This causes a decrease in the
size of the ion.

Radius of the anion


The negative atom is formed by the gain of one or more electrons in the neutral atom.
The number of electrons increases while the magnitude of nuclear charge remains
the same. The same nuclear charge acts on larger number of electrons than were
present in the neutral atom. The effective nuclear charge per electron is reduced and
the electron cloud is held less tightly by the nucleus. This causes an increase in the
size of the ion. Thus anions are larger in size than the corresponding atom.
Variation of ionic radii in a group
The ionic radii in a particular group increases in moving from top to bottom because
of the increase in the principal quantum number though the number of electrons in
the valence shell remains the same.
In isoelectronic series of ions, as the nuclear charge increases the electrons are pulled more
and more strongly and the size decreases.

Problem
5. Out of Na+ and Na which has the smaller size and why?
Solution
Na+ has a smaller size than Na. Na+ is formed by the removal of one electron from
Na. However both of these posses the same nuclear charge. Therefore electrons in
Na+ are more tightly held than in Na. The removal of one electron from Na also leads
to complete removal of the third shell so that in Na +, the outermost shell is second.
Hence Na+ has a smaller size than Na.
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Periodicity of atomic radii

When the elements are arranged in the order of increasing atomic numbers there is a
recurrence of similar properties after certain regular intervals. This regularity is called the
periodicity in properties. The distribution of electrons in the various shells determines their
physical and chemical character. It has been observed that the properties of the elements
depend more on the arrangements of the electrons in the outermost shell (valence shell) and
not on the inner shells. This repetition of similar electronic configuration in the outermost or
valence shell after certain regular intervals causes periodicity in the properties of elements.

Atomic radii
The size of the atom is significant in governing its property. If the atom is assumed to
be spherical, then the radius of the sphere gives the atomic radius. But it is difficult
to exactly determine the radius of the atom because
The probability of finding the electron is never zero even at large distances from the
nucleus and so the atom does not have a well defined boundary.
It is not possible to isolate an atom and measure its radius.
The size of the atom changes in going from one set of environment to another and
from one bonded state to another.
So, one can arbitrarily define atomic radius as the effective size which is the distance
of closest approach of one atom to another atom in a given bonding situation. This
approximate radius can be determined by measuring the inter-nuclear distance
between the two centres of the neighbouring atoms in a covalent molecule. This is
usually done by diffraction and spectroscopic techniques.

Fig: 4.3 - Calculation of atomic radius


The inter-nuclear distance corresponds to the diameter of the atom and therefore half of this
distance gives the atomic radius for a homonuclear molecule like Cl-Cl or Br-Br.

Hence, it may be defined as one half of the distance between the centers of the nuclei
of two similar atoms bonded by a single covalent bond. This is also called as covalent
radius.
For a hetero-nuclear molecule, the covalent radius is the distance between the center of the
nucleus of the atom and the mean position of the shared paired of electrons between the
bonded atoms.

The covalent radii are smaller than the atomic radii in the uncombined atoms
because the overlap region between atomic orbitals of two atoms becomes common
in a covalent bond.
The forces of attraction (Van der Waals forces) existing between non-bonded atoms and
molecules are weak and the atoms are held at larger inter-nuclear distances. Thus these radii
known as Van der Waals radii are always larger than covalent radii.

Van der Waals radius is defined as one half of the inter-nuclear distance between two
adjacent atoms belonging to the two nearest neighbouring molecules of the
substance in the solid state.
VARIATION OF ATOMIC RADII
Variation in a period
Atomic radii in general, decrease with increase in atomic number, going from left to
right in a period. This is explained on the basis of increasing nuclear charge along a
period. The nuclear charge increases progressively by one unit while the
corresponding addition of one electron takes place in the same principal shell. As the
electrons in the same shell do not screen each other from the nucleus, the nuclear
charge is not neutralized by the extra valence electron. Consequently the electrons
are pulled closer to the nucleus by the increased effective nuclear charge resulting in
the decrease in the size of the atom. In this way the atomic size goes on decreasing
across the period.
Fig: 4.4 - Variation of atomic radius with atomic number in a period
The atomic radius abruptly increases in the case of noble gas element Neon as it does not
form covalent bonds. So the value of Neon radius is Van der Waals radius which is
considerably higher than the value of other covalent radii.

Variation in a group
The atomic radii of elements increases from top to bottom in a group because the
nuclear charge increases with increasing atomic number. Although, there is an
increase in the principal quantum number from one atom to another, the number of
electrons in the valence shell remain the same. The effect of increase in the size of the
electron cloud out weighs the effect of increased nuclear charge and so the distance
of the valence electron from the nucleus increases down the group. Thus the size of
the atom goes on increasing down the group in spite of increasing nuclear charge.

Fig: 4.5 - Variation of atomic radius with atomic number in a group


Problem
4.The atomic mass of germanium is 72.6 and its density is 5.47g cm -3. What is the
atomic volume of germanium?
Solution

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Periodicity of valency

The electrons present in the outer most shell are called valence electrons. The valency of an
element is defined as its 'combining capacity'.

Variation along the period


The number of valence electrons increase from left to right in a period. So, the
valency of the elements first increase from 1 to 4 and then decreases to zero.
Variation down the group
On moving down the group the number of valence electrons remain the same and
therefore all the elements in the group exhibit the same valency.
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Periodicity of physical properties

The recurrence of similar properties of the elements when they are arranged in the order of
increasing atomic number, after certain regular intervals, is called periodicity.

Cause of periodicity of elements


The modern periodic table is based on the electronic configuration of the elements.
The properties of an element are determined largely by the electrons in its outermost
or valence shell. Valence electrons interact with other atoms and take part in all
chemical reactions, while inner shell electrons have little influence on the properties
of elements.
When elements are placed in the order of their increasing atomic number, the elements
having the same number of valence shell electron is repeated in such a way, so as to fall
under the same group. Since, the electronic configuration of the valence shell electrons is
same they show similar properties.

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Division of elements into s,p, d and f blocks

Periodic Table

KEY ELEMENT CLASSIFICATION

Non-Metals Rare Earth Elements Semimetallic

s
Alkali Metals Transition Metals
Halogens

Alkaline-earth Metals Other Metals


Inert Gases

Radioactive Rare Earth Elements

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Advantages of modern Periodic table

1. The modern periodic table is divided into two main categories:


(i) Vertical columns called Groups and
(ii) Horizontal columns called Periods.
2. There are 18 vertical columns or groups. These are further sub-divided into A and
B (groups I to VII), VIII group and zero group.
3. Member of the same group have similar electronic configuration of the valence
shell and thus show same valency.
4. Elements of groups IA to VIIA are called groups of typical elements, representative
elements or normal elements.
5. Groups IA and IIA are strongly metallic and are called group of 'alkali metals and
alkaline earth metals'.
6. Groups IB to VII B and VIII lie in the middle of the table between IIA and IIIA
groups and are called groups of transition elements. They consist of metals.
7. The Zero group consists of 'Noble gases'.
8. There are 7 horizontal rows in the periodic table. These are called the periods.
9. In a period, the number of valence shell remains the same for all elements.
However, the number of electrons in the valence shell increases from left to right .
10. The number of elements present in each period is given in the following table.
Period Valence shell Type of Period Number of elements Atomic Number of elements

1st Period n=1 Short period 2 Atomic number 1 and 2

2nd Period n = 2 Short period 8 Atomic number 3 to 10

3rd Period n = 3 Long period 8 Atomic number 11 to 18

4th Period n= 4 Long period 18 Atomic number 19 to 36

5th Period n = 5 Long period 18 Atomic number 37 to 54

*6th Period n = 6 Long period 32 Atomic number 55 to 86


Period Valence shell Type of Period Number of elements Atomic Number of elements

*7th Period n = 7 Incomplete 23 Atomic number 87 to 109

11. The 6 th period consists of elements that have atomic numbers 58 to 71. They are
called Lanthanides. The 7th period consists of elements that have atomic numbers 90
to 105. They are called Actinides. Both of them are called inner transition elements.
12. The 7 th period is an incomplete period as it has only 23 elements.
13. Lanthanides and actinides are not accommodated in the main body of the
periodic table but are placed separately at the bottom of the table.
14. The position of hydrogen is not certain. Thus it can be placed in both group IA
and group VIIA.
15. Group VIIA elements are called halogens or salt producers. Representative
periodic table for eight groups up to calcium (atomic number 20) with their
electronic configuration is given in the table.
REPRESENTATIVE PERIODIC TABLE FOR ELEMENTS WITH ATOMIC NUMBER
FROM 1 TO 20 WITH THEIR ELECTRONIC CONFIGURATION

Group -->

1A 2A 3A 4A 5A 6A 7A 0

Period

1 H 2 He
Period 1
1 2

3Li 4 Be B
5 C
6 7N O
8 9F Ne
10
Period 2
2,1 2,2 2,3 2,4 2,5 2,6 2,7 2,8

Na
11 Mg
12 13Al 14Si 15P 16S 17Cl 18Ar
Period 3
2,8,1 2,8,2 2,8,3 2,8,4 2,8,5 2,8,6 2,8,7 2,8,8

K
19 20Ca
Period 4
2,8,8,1 2,8,8,2

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Modern periodic law, and modern periodic table

LATER, HENRY GYWN-JEFFREYS MOSELEY SHOWED THAT THE ATOMIC


NUMBER OF AN ELEMENT IS NUMERICALLY EQUAL TO THE NUMBER OF
ELECTRONS ROUND THE NUCLEUS. THE NUMBER OF ELECTRONS IN TURN
IS EQUAL TO THE NUMBER OF PROTONS IN THE NUCLEUS. HE SUGGESTED
THAT ATOMIC NUMBER IS A MORE FUNDAMENTAL PROPERTY OF AN
ELEMENT THAN ITS ATOMIC MASS. WHEN THE ELEMENTS ARE ARRANGED
IN THE INCREASING ORDER OF THEIR ATOMIC NUMBER, MOST OF THE
DEFECTS OF MENDELEEV'S CLASSIFICATION GET RECTIFIED.

The periodic law given earlier is now modified and followed today. It states that "the
properties of the elements are periodic functions of their atomic numbers."

The modern periodic table is also known as the long form of the periodic table or the
extended form of the periodic table.
In this table, the elements are arranged in the order of increasing atomic numbers in such
away that elements with similar properties fall in the same vertical column. These vertical
columns are referred to as 'Groups'. There are eight groups, which are further sub-divided
into eighteen sub-groups. There are 7 horizontal rows in the periodic table. These are called
the periods.

Noble (inert) gases are placed in the 18 or VIII A, which is at the extreme right of the
table. Halogens are placed in group 17 or VII A, just ahead of the noble gas elements.
The alkali metals (Na, K, etc.) are placed in group 1 or I A and the alkaline earth
metals (Ca, Ba, etc.) are placed in 2 or II A which is at the extreme left of the table.
Transition elements such as copper, iron, etc., are placed in the 3 to 12 groups, which
occur at the middle of the table. The inner transition elements, lanthanides and
actinides are placed in two separate series at the bottom of the main body of the
periodic table.
The recurrence of similar properties of the elements when they are arranged in the
order of increasing atomic number, after certain regular intervals, is called
periodicity.
Remember

Relation between Mass Number and Atomic Number Atomic Number (Z) is the number of
protons in the nucleus of an atom. It is also equal to the number of electrons since the atom is
electrically neutral. Mass Number (A) is the total number of neutrons and protons present in

the nucleus of an atom. = +

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Anamolies of Mendeleev's periodic table

(i) Position of hydrogen


The position of hydrogen is not correctly defined. It is still not certain whether to
place hydrogen in group I A or VII A.
(ii) Anomalous pair
In certain pairs of elements like, Ar (40) and K (39); Co (58.9) and Ni (58.6); Te
(127.6) and I (126.9) the arrangement was not justified. For e.g., argon was placed
before potassium whereas its atomic mass is more than potassium.
(iii) Position of isotopes
Isotopes are atoms of the same element having different atomic mass but same
atomic number. For e.g., there are three isotopes of hydrogen with atomic mass 1, 2,
and 3. According to Mendeleev's periodic table these should be placed at three
separate places. However isotopes have not been given separate places in the
periodic table.
(iv) Grouping of elements
Some similar elements are separated and dissimilar elements are grouped together
e.g., copper and mercury have similar properties but are placed in different groups.
On the other hand elements of group IA such as lithium, sodium and potassium were
grouped with dissimilar elements such as copper, silver and gold.
(v) Cause of periodicity
Mendeleev's table was unable to explain the cause of periodicity among elements.
(vi) Position of lanthanides and actinides
Fourteen elements that follow lanthanum called lanthanides and fourteen elements
following actinium called actinides were not given proper places in Mendeleev's
periodic table.
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Mendeleev's periodic law and periodic table

Later, Mendeleev arranged the sixty-three elements known at that time in the increasing
order of the atomic masses, in the form of a table called the Periodic Table. The periodic
table further classified the elements by arranging the elements with similar properties
together and separating the elements with dissimilar properties from one another.

Mendeleev stated the law of chemical periodicity as: "The physical and chemical
properties of elements are periodic functions of their atomic mass."
Mendeleev's periodic table contains eight vertical columns of elements called 'groups'
and seven horizontal rows called 'periods', Each group has two sub-groups A and B.
The properties of elements of a sub-group resemble each other more markedly than
the properties of those between the elements of the two sub-groups.
CONTRIBUTIONS OF MENDELEEV'S PERIODIC TABLE
(i) Systematic study of elements
Mendeleev's Periodic table simplified the study of elements. It became useful in
studying and remembering the properties of a large number of elements, in a simpler
way. This is because the elements showing similar properties
belonged to the same group.

(ii) Prediction of new elements


While arranging the elements, in increasing order of atomic mass, Mendeleev left
three blanks for elements that were not discovered at that time. He was able to
predict the properties of these unknown elements more or less accurately. He named
them eka-boron, eka-aluminium and eka-silicon. He named them so, as they were
just below boron, aluminium and silicon in the respective sub-groups. Eka-boron
was later named as scandium, eka-aluminium as gallium and eka-silicon as
germanium.
A COMPARATIVE STUDY OF THE PROPERTIES OF THE ELEMENTS
PREDICTED AND LATER

DISCOVERED

Property Eka-boron Scandoum

Atomic weight 44 43.79


Oxide Eb2O3 Sc2O3
Specific gravity 3.5 3.864
Sulphate Eb2(SO4)3 Sc2(SO4)3

Property Eka-aluminium Gallium

Atomic weight 58 69.9


Specific gravity 5.9 5.94
Melting point Low 303. 15K
Formula of oxide Ea203 Ga203
Solubility in acid Dissolves slowly in both Dissolves slowly in
and alkali acid and alkali both acid and alkali

Property Eka-silicon Germanium

Atomic weight 72 72.32


Specific Gravity 5.5 5.47
Melting point High 958C
Valency 4 4
Reaction with Slightly attacked by Dissolves neither by
Property Eka-silicon Germanium

hydrochloric acid
acid acids, resists attack by
nor
and alkali alkali
sodium hydroxide

(iii) Correction of atomic masses


Mendeleev's periodic table helped in correcting the atomic masses of some of the
elements, based on their positions in the periodic table. For e.g., atomic mass of
beryllium was corrected from 13.5 to 9. Atomic masses of indium, gold, platinum
were also corrected.
MENDELEEV'S PERIODIC TABLE

Grp:1 Grp:2 Grp:3 Grp:4 Grp:5 Grp:6 Grp:7 Grp:8

H=1 - - - - - - -

Li=7 Be=9.4 B=11 C=12 N=14 O=16 F=19 -

Na=23 Mg=24 Al=27.3 Si=28 P=31 S=32 Cl=35.5 -

Fe=56
Co=58.9
K=39 Ca=40 - Ti=48 V=51 Cr=52 Mn=55
Ni=58.7
cu=63

- Zn=65 - - As=75 se=78 Br=80 -

Ru=104
Rh=104
Rb=85 Sr=87 Yt=88 Zr=90 Nb=94 Mo=96 -
pb=106
Ag=108

- cd=102 In=113 Sn=118 Sb=122 Te=127.6 I=126.9 -

Cs=133 Ba=137 Di=138 Ce=140 - - - -

Os=195
Ir=197
- - Er=178 La=180 Ta=82 W=184 -
Pt=198
Au=199

- Hg=200 Tl=204 pb=207 Bi=208 - - -

- - - Th=231 - U=240 - -

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Periodic Classification of Elements

At the turn of the nineteenth century, about 30 elements were known. 50 years later
by the 1850s, scientists had discovered sixty three chemical elements and the
numbers kept increasing. With the discovery and study of more and more elements
and their compounds, the various data about them also increased. It became
progressively difficult to organize all that was known about the elements and
scientists made several attempts to look for some pattern in their properties, on the
basis of which they could organize study such a large number of elements with ease.
Initially scientists had classified elements into metal and non-metals. However, some
elements possessed properties which could neither be classified as metals nor non-metals
called metalloids. This classification was found to be insufficient for scientific study. Later
on, a number of chemists attempted to make a rational and systematic classification of the
physical and chemical properties of elements and tabulate the results in the form of a table.

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Metallic solid

More than 80 elements in the periodic table are metals. Metals are solids at ordinary
temperature and pressure, with the exception (of mercury and gallium). Metals have
characteristic properties such as:

High thermal and electrical conductivity.


Luster and high reflectivity.
Malleability and ductility. They can be beaten or shaped without fracture.
Variability of mechanical strengths (ranging from soft alkali metals to Tungsten,
which is hard).
The force that binds together the atoms of metals is called metallic bond. The
properties of metals cannot be explained in terms of common types of bonds such as
ionic and covalent bonds. The inadequacy of these two type of bonds for metal
formation can be explained as under.
The atoms of metals are all alike therefore they cannot form ionic bonds. Moreover, ionic
compounds do not conduct electricity in the solid state and ionic compounds are brittle as
opposed to properties of metals. The atom of metallic elements contain only 1 to 3 valence
electrons, therefore these atoms cannot form covalent bonds, with noble gas configurations
as they will remain incomplete. Covalent compounds are bad conductors of electricity and
are generally liquids; properties opposed to metal formations. Thus, metals have a different
model of bonding.

Electron sea model for metallic bonding


To account for the bonding in metals, Lorentz proposed a model known as electron
gas model or electron sea model. This model is based on the following characteristic
properties of metals:
Low ionization energies
Metals generally have low ionization energies. This implies that the valence electrons
of metal atoms are not strongly held by the nucleus. Valence electrons can move
freely out of the influence of their kernels (atomic orbit/structure minus valence
electrons). Thus, metals have free mobile electrons.
Large number of empty orbitals
It has been observed that in metals a number of valence orbitals remain empty as the
number of valence electrons in metals is generally less than the number of valence
orbitals.
For example, lithium {(Li, Z = 3) 1s22s1} has 2p-orbitals vacant;

Sodium {(Na, Z = 11) 1s22s22p6 3s1} has 3p-and 5d-orbitals vacant;


Magnesium {(Mg, Z = 12) 1s22s22p6 3s2} has 3p-and 3d-orbitals vacant

The important features of electron sea model are:


The positively charged kernels of metal atoms are arranged in a regular fashion in a
metallic lattice.
Loosely held valence electrons, surround each kernel in metallic lattice. Being loosely
held to its kernel, the valence electrons enjoy complete freedom in the metallic lattice and
are regarded as mobile electrons.
In short, the metal may be regarded as 'a sea of electrons (common pool of electrons) in
which there is a three dimensional ordered arrangement of positively charged kernels,
surrounded throughout by mobile valence electrons'. This explanation is also responsible for
its name electron sea model.

Thus, the simultaneous force of attraction between the mobile electrons and the
positive kernels that binds the metal atoms together, is known as metallic bond.

Fig: 6.19 - Electron sea model


Comparison of Ionic bond Covalent bond and Metallic bond

Ionic Bond Covalent Bond Metallic Bond

The transfer of electrons This bond is formed by the This bond is formed due to
between two atoms having mutual sharing of electrons the attraction between kernels
different electro negativities between same or different and the mobile electrons in a
forms this bond. elements . metal lattice.
Ionic Bond Covalent Bond Metallic Bond

This is also a fairly strong This is a weak bond due to the


This is a strong bond due to
bond because the electron pair simultaneous attraction of the
electrostatic force of
is strongly attracted by two electrons by a large number of
attraction.
nuclei. kernels

This is a non-directional This is a non-directional


This is a directional bond.
bond. bond.

This bond makes substances This bond makes substances This bond make substances
hard and brittle. hard and incompressible. malleable and ductile.

Explanation of physical properties of metals


All the characteristic metallic properties can be explained on the basis of the electron.
Metallic lustre
The bright lustre of metals is due to presence of delocalised mobile electrons.
When light falls on the surface of the metal, the loosely held electrons absorb photons of
lights. They get promoted to higher energy levels (excited state), oscillating at a frequency
equal to that of the incident light. These oscillating electrons readily return from the higher
to the lower levels of energy by releasing energy, thus becoming a source of light radiations.
Light appears to be reflected from metal surface and the surface acquires a shining
appearance, which is known as metallic lustre.

Electrical conductivity
The presence of mobile electrons causes electrical conductivity of a metal. When a
potential difference is applied across the metal sheet, the free mobile electrons in the
metallic crystal start moving towards the positive electrode. The electrons coming
from the negative electrode simultaneously replace these electrons. Thus, the
metallic sheet maintains the flow of electrons from negative electrode to positive
electrode. This constitutes electrical conductivity.
Thermal conductivity
When a part of the metal is heated, the kinetic energy of the electrons in that region
increases. Since the electrons are free and mobile, these energetic electrons move
rapidly to the cooler parts and transfer their kinetic energy by means of collisions
with other electrons. Therefore, the heat travels from hotter to cooler parts of the
metals.
Malleability and ductility
Metals can be beaten into sheets (malleability) and drawn into wires (ductility).
Metallic bonds are non-directional in nature. Whenever any stress is applied on
metals, the position of adjacent layers of metallic kernels is altered without
destroying the crystal. The metallic lattice gets deformed but the environment of
kernels does not change and remains the same as before. The deforming forces
simply move the kernels from one lattice site to another.
Fig: 6.20 - Displacement of metal kernels in a metallic lattice
High tensile strength
Metals have high tensile strength. Metals can resist stretching without breaking. A
strong electrostatic attraction between the positively charged kernels and the mobile
electrons surrounding them is the reason for tensile strength.
Hardness of metals
The hardness of metals is due to the strength of the metallic bond. In general, the
strength of a metallic bond depends upon:
The greater the number of valence electrons for delocalisation the stronger is the
metallic bond.
Smaller the size of the kernel of metal atom, greater is the attraction for the
delocalised electrons. Consequently, stronger is the metallic bond.
For example, alkali metals have only one valence electron and larger atomic kernels, which
makes the metallic bonds weak. Consequently these metals are soft metals.

Opaqueness
The light that falls on metals is either reflected or completely absorbed by the
delocalised electrons. Because of this, no light is able to pass through metals and they
are termed as opaque.
Melting and boiling points
Metals have metallic bond strengths, which is intermediate to that of covalent and
ionic bonds. Therefore in general, metals have boiling and melting points in between
to that of covalent and ionic compounds.
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Molecular solid

In molecular solids, the constituents units are molecules, which do not carry any charge. The
attractive forces binding the molecules together are of two types:

Dipole-dipole interactions
These types of forces occur in molecular solids which have polar molecules. A polar
molecule has separate centres of positive and negative charges. These forces arise
due to electrostatic attraction of the other molecule and vice-versa (The positive end
of one molecule attracts the negative end of the other)
Van der Waal's forces
All molecules (polar and non-polar) exert a weak attraction upon the other, due to
the electrostatic attraction of the electrons of one molecule to the nuclei of the other.
These forces are known as van der Waals forces. They occur in all kinds of molecular
solids including non-polar molecules such as H 2, O2, Cl2, CH4, etc. and are present in
both solid and liquid states. It has been observed that even non-polar substances
such as hydrogen, chlorine, noble gases etc. can be liquefied due to these forces. The
existence of weak attractive forces among non-polar molecules in their liquid and
solid states was first proposed by J.D. Van der Waal's.
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Covalent solid

In covalent solids, the constituent particles are atoms of same or different kinds. Covalent
bonds network, forming a continuous giant interlocking structure of atoms throughout the
crystal that hold them together. They are also referred to as covalent network solids.
Because, covalent bonds are strong and directional, these solids are very hard. Diamond,
silicon carbide and graphite are the three important examples of covalent solids.

In diamond, each carbon atom is covalently linked to four other carbon atoms lying
at the four corners of a regular tetrahedron. This gives rise to a rigid three-
dimensional network of carbon atoms. This is also the reason why diamond is the
hardest substance known, with high density and melting point.

Fig: 6.15 - Structure of diamond


Silicon carbide has also three-dimensional structure as of diamond, with each silicon atom
surrounded by four carbon atoms and each carbon atom surrounded by four silicon atoms.

Graphite has carbon atoms arranged in hexagonal parallel layers. This results in a
double bond characteristic of graphite; each carbon atom is bonded to three others
by a sp2 covalent bond as well being bonded among the adjacent layers by Van der
Waal's forces.
Fig: 6.16 - Structure of graphite
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Ionic solid

In ionic solids, the constituent particles are ions. Coulombic forces of attraction hold
oppositely charged ions together, to form ionic bonds. Each ion is surrounded by a certain
fixed number of the ions of the opposite charge (as its nearest neighbour) to attain the
maximum stability and this regular arrangement extends continuously throughout the
crystal.

For example, in sodium chloride, Cl- ions have a definite regular arrangement. In this
arrangement, each Na+ is surrounded by six Cl- ions and each Cl- is surrounded by six
Na+ ions. Similar regular arrangements are also found in other ionic solids.

Fig: 6.14 - Structure of sodium chloride


Physical characteristics of ionic solids
Ionic solids are hard and brittle.
Ionic solids dissolve in polar solvents like water "The ions of the ionic solids are
pulled out of their lattice sites by the dipole movement of the polar solvent and dispersed
into solvent form in the solution.
Ionic solids have high melting and boiling points. To overcome the strong
electronegative forces that hold their ions together, considerable thermal energy has to be
applied to melt ionic solids. During melting, oppositely charged ions of the destroyed
crystal tend to stay together, thus molten ionic solids posses a quasilattice structure.
The ions in the molten stage of an ionic substance are free to move as opposed to
being fixed to their lattice sites as ionic solids. Therefore ionic solids do not conduct
electricity in a solid state but do so only in the molten state.
Ionic solids are anisotropic in nature. This means that properties like mechanical
strength, conductivity, refractive index etc. depend upon the direction along which they
are measured.
Ionic solids have negligible vapour pressure at room temperature.
The arrangement of ions in a particular ionic solid depends upon:
The relative sizes of the positive and negative ions.
Magnitude of the charges on the ions.
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Classification of crystalline solids

Crystalline solids can be further classified depending on the nature of the bonding as:

Ionic
Molecular
Covalent
Metallic
Classification of Crystalline solids

Types of
Constituent Particles Nature of forces Examples
Solids

Strong electrostatic KCl, BaSO4KNO3,


Ionic Positive and negative ions
forces of attraction LF

(I) Vander Waals forces


I2, CO2(solid) HCl
Molecular Molecules (ii) Dipole interaction
Ice
(iii) Hydrogen bonding

Covalent Atom Covalent bonds Diamond, silicon

Positive metal ions (kernels) All metals and


Metallic Metallic bonds
and mobile electrons some alloys

Some substances adopt different structural arrangements under different conditions.


Such arrangements are called Polymorphs.
Example: Diamond and graphite are two different polymorphic forms of carbon.
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Resonance and resonance hybrid structures of O3, SO3, SO2, CO3-2, SO4-2, PO4-2,NO3-

he phenomenon of resonance was put forward by Heisenberg to explain the properties of


certain covalent molecules. Most covalent molecules have a unique Lewis formula (dot
structure), which explains the bonding in that molecule. Some molecules lend themselves
two or more dot structures. None of these structures can exactly describe all the properties of
the molecule, but each structure contributes to the true structure of the molecule. Such
different structures are called 'resonance structures' and the actual molecule is termed as the
'resonance hybrid' of all these structures. In every case the actual molecule is found to be
energetically more stable than would be expected from any of its resonance structures.The
energy difference between the most stable resonating structure and the resonance hybrid
structure is termed as resonance energy.

Characteristics of resonance
The contributing structures do not have real existence. These are only imaginary
structures, proposed to explain the properties of the molecule. None of these 'resonance
structures' can be prepared in the laboratory. Only the resonance hybrid is the real
molecule structure.
Because of resonance, the bond lengths in resonating structures become equal. For
example, both the O-O bond lengths in O3 are equal. All the C-C bonds in benzene are
equal.
Resonance structure of ozone
Structure1

Structure2

Resonance hybrid structure of ozone

Both the O-O bond lengths are equal and intermediate of single and double bond.

Benzene

All the C-C bonds in the resonance hybrid structure are intermediates of single and double
bonds and the bond lengths are equal.

The resonance hybrid has lower energy and thus greater stability than any of the
contributing structures.
Greater the resonance energy, greater is the stability of the molecule.
Concept of resonance is theoretical.
Conditions for writing resonance structures
The contributing structures should:
Have the same atomic positions.
Posses the same number of unpaired electrons.
Have nearly the same energy.
Written in a way that negative charge is present on an electronegative atom and
positive charge is present on an electropositive atom.
Not place the like charges on adjacent atoms.
The resonance structures of a few more molecules and ions are given below:
NO-3 ion: The three possible resonance structures for the nitrate ion (NO -3) are

Benzene

Resonance energy is the difference between the actual bond energy of the molecule
and that of the most stable of the resonating structures (having least energy). For
example, the resonance energy of carbon dioxide is 138 kJ mol-1. This means that the
actual molecule of CO2 is about 138 kJ more stable than the most stable structure
among the contributing structures.

Problems
7. Identify the atoms which do not obey the octet rule in the following compounds
and draw their Lewis structures? SO2 or SF6
Solution
SO2
Here all atoms obey the octet rule. Oxygen and sulphur atoms have six electrons in
their outermost shells. The Lewis structure of SO2 is,

S is attached to one O atom through a double bond while to the other O atom through
a coordinate bond. All atoms have eight electrons in their outer most shells. The octet
rule is obeyed.
SF6
S does not obey the octet rule. The Lewis Structure of SF6 gives 12 electrons (6 pairs
of electrons) around S. Thus, S does not obey the octet rule.
(Only the sharing electron of F is shown)
8. Write and explain the Lewis Structure for (I) H2SO4 (II) H3PO4 (III)
BCl3compounds.
Solution
(I) Sulphur atom has six valence electrons. The two hydrogens in this compound are
present as OH groups. The possible Lewis structure of H2SO4 is,

(II) Phosphorous has 5 valence electrons. The three hydrogens are present as three
OH groups. The possible Lewis Structure of H3PO4 is

(III) Boron atom (B) has 3 electrons in its outermost shell, and Cl has 7. B does not
obey the octet rule. The possible Lewis structure for BCl3 is

Thus, there are only six electrons around B. The octet rule, thus is not obeyed by B.
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vander Waal's bond

Van der Waal's forces


All molecules (polar and non-polar) exert a weak attraction upon the other, due to
the electrostatic attraction of the electrons of one molecule to the nuclei of the other.
These forces are known as van der Waals forces. They occur in all kinds of molecular
solids including non-polar molecules such as H 2, O2, Cl2, CH4, etc. and are present in
both solid and liquid states. It has been observed that even non-polar substances
such as hydrogen, chlorine, noble gases etc. can be liquefied due to these forces. The
existence of weak attractive forces among non-polar molecules in their liquid and
solid states was first proposed by J.D. Van der Waal's.
Origin of Van der Waal's forces
In order to understand the origin of these forces, consider two helium atoms very
close to each other. The ground state electronic configuration of helium is 1s 2 .Each
helium atom is uncharged because its electron cloud is symmetrically distributed
around the nucleus. In the most favoured arrangement in the helium atom, the two
electrons tend to stay as far apart as possible. Thus, they are present diametrically
opposite to each other and the centres of positive and negative charges coincide.
However, due to the motion of the electrons, we can imagine that for a fraction of
time, the electron distribution is not symmetrical i.e. the centres of positive and
negative charges do not coincide. As a result of instantaneous asymmetrical
distribution of electrons in the atom, there is a small temporary dipole known as
instantaneous dipole. This instantaneous asymmetry influences the electron
distribution in the neighbouring atom and induces a dipole known as instantaneous
induced dipole

Fig: 6.17 - Instantaneous dipole and instantaneous induced dipole in an atom


The attractive forces between the instantaneous dipole and instantaneous induced
dipoles are called Van der Waal's forces.
Fig: 6.18 - Dipole - dipole forces in molecular solids
The Van der Waal's forces are responsible for the condensation of noble gases and
other gases such as H2, O2, Cl2, CH4, etc., which have no residual bonding capacity. In
all such cases, solids and liquids are formed through the Van der Waals' type of
interactions. However, these forces are very weak forces.
The strength of Van der Waal's forces depends upon:

Larger size of the interacting molecules. As large molecules have much diffused
charged clouds there are great chances of its distortion and producing instantaneous
dipoles.
Increase in number of electrons present in the molecule, leads to greater chances of
distortion of electron clouds. For example, the boiling points of monoatomic noble gases
increase from helium to radon.
Molecular structure.
The lowering of temperature.
Increase in pressure.
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metallic bond

The attractive force, which binds various metal atoms, is called metallic bond. The metallic
bond is neither a covalent nor an ionic bond.

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hydrogen bond and its types

Hydrogen bonds can be classified into two types; Intermolecular hydrogen bond and
Intramolecular hydrogen bond.

Intermolecular hydrogen bond


This occurs when the hydrogen bonding is between H-atom of one molecule and an
atom of the electronegative element of another molecule. For example (i) hydrogen
bond between the molecules of hydrogen fluoride. (ii) hydrogen bond in alcohol or
water molecules.
Intermolecular hydrogen bond results into association of molecules. Hence, it usually
increases the melting point, boiling point, viscosity, surface tension, solubility, etc.

Intramolecular hydrogen bond


This bond is formed between the hydrogen atom and an atom of the electronegative
element (F,O,N) , of the same molecule .
Intramolecular hydrogen bond results in the cyclization of the molecules and prevents their
association. Consequently, the effect of this bond on the physical properties is negligible. For
example, intramolecular hydrogen bonds are present in molecules such as

o-nitrophenol, o-nitrobenzoic acid, etc.

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Dipole moments and its application

Molecules having two equal and opposite charges separated by certain distance are said to
possess an electric dipole. In the case of such polar molecules, the centre of negative charge
does not coincide with the centre of positive charge. The extent of polarity in such covalent
molecules can be described by the term Dipole moment.

Dipole moment can be defined as the product of the magnitude of the charge and the
distance of separation between the charges.
It is represented by the Greek letter 'm'. Mathematically it is equal to

dipole moment (m) = charge (e) x distance of separation (d).


It is expressed in the units of Debye and written as D

(1 Debye = 1 x 10-18e.s.u cm)


Dipole moment is a vector quantity and is represented by a small arrow with tail at the
positive centre and head pointing towards a negative centre.
For example, the dipole moment of HCl molecule is 1.03 D and that of H 2O is 1.84 D.
The dipole of HCl may be represented as:

DIPOLE MOMENT AND MOLECULAR STRUCTURE


Diatomic molecules
A diatomic molecule has two atoms bonded to each other by a covalent bond. In such
a molecule, the dipole moment of the bond gives the dipole moment of the molecule.
Thus, a diatomic molecule is polar if the bond formed between the atoms is polar.
Greater the electronegativity difference between the atoms, more will be the dipole
moment.
The dipole moment of hydrogen halides decreases with decreasing

electronegativity of halogen atom.


Polyatomic molecules
In polyatomic molecules the dipole moment not only depends upon the individual
dipole moments of the bonds but also on the spatial arrangement of the various
bonds in the molecule. In such molecules the dipole moment of the molecule is the
vector sum of the dipole moments of various bonds.
For example, Carbon dioxide (CO2) and water (H2O) are both triatomic molecules but the
dipole moment of carbon dioxide is zero whereas that of water is 1.84 D. This is because
CO2 is a linear molecule in which the two C=O (m=2.3D) bonds are oriented in opposite
directions at an angle of 180. Due to the linear geometry the dipole moment of one C = O
bond cancels that of another. Therefore, the resultant dipole moment of the molecule is zero
and it is a non-polar molecule.
Water molecule has a bent structure with the two OH bonds oriented at an angle of
104.5. The dipole moment of water is 1.84D, which is the resultant of the dipole
moments of two O-H bonds.
Similarly in tetra-atomic molecules such as BF3 and NH3, the dipole moment of BF3 molecule
is zero while that of NH3 is 1.49 D. This suggests that BF3 has symmetrical structure in which
the three B-F bonds are oriented at an angle of 120 to one another. Also the three bonds lie
in one plane and the dipole moments of these bonds cancel one another giving net dipole
moment equal to zero.

NH3 has a pyramidal structure. The individual dipole moments of three N-H bonds
give the resultant dipole moment as 1.49 D.
Thus, the presence of polar bonds in a polyatomic molecule does not mean that the
molecules are polar.

Importance of dipole moment


Dipole moment plays very important role in understanding the nature of chemical
bonds.
Importance of dipole moment and problems
The measurement of dipole moment helps in distinguishing between polar and non-
polar molecules. Non-polar molecules have zero dipole moment while polar molecules
have some value of dipole moment.
For example:

Non-polar molecules: O2, Cl2, BF3, CH4


Polar Molecules: HF (1.91 D), HCl (1.03 D), H2S (0.90 D)

Dipole moment measurement gives an idea about the degree of polarity in a diatomic
molecule. The greater the dipole moment the greater is the polarity in such a molecule.
Dipole moment is used to find the shapes of molecules. This is because the dipole
moment not only depends upon the individual dipole moment of the bonds but also on
the arrangement of bonds.
It is possible to predict the nature of chemical bond formed depending upon the
electronegativities of atoms involved in a molecule. The bond will be highly polar if the
electronegativities of two atoms is large. However, when the electron is completely
transferred from one atom to another, an ionic bond is formed (ionic bond is an extreme
case of polar covalent bonds). The greater the difference in electronegativities of the
bonded atoms, the higher is the ionic character. When the electronegativity difference
between two atoms is 1.7, then the bond is 50% ionic and 50% covalent. If the
electronegativitv difference is more than 1.7, then the chemical bond is largely ionic
(more than 50% ionic character) and if the difference is less than 1.7, the bond formed is
mainly covalent.
The percentage of ionic character can be calculated from the ratio of the observed dipole
moment to the dipole moment for the complete electron transfer (100% ionic character).

In HCl molecule, the observed dipole moment is 1.03 D and its bond length is 1.275.
Assuming 100% ionic character, the charge developed on H and Cl atoms would be
4.8 x 10-10e.s.u.
Therefore, dipole moment for 100% ionic character will be

= q x d = 4.8 x 10-10e.s.u x 1.275 x 10-8cm


=6.12x 1O-18e.s.u.cm

= 6.12 D (1D = 10-18 e.s.u. cm.)

Problem
12. Calculate the ionic character of HCl. Its measured dipole moment is 3.436 x 10 -
30
coulomb meter. The HCl bond length is 2.29 x 10-10 meter.
Solution
Dipole moment corresponding to 100 % ionic character of HCl
= 1.602 x 10-19 C x 1.29 x 10-10 m

= 20.67 x 10-30 Cm
Actual dipole moment of HCl = 3.436 x 10-30 Cm

13. The C-Cl bond is polar but CCl4 molecule is non-polar. Explain.

Solution
The C-Cl bond is polar because the chlorine atom being more electronegative pulls
the shared electron pair towards itself. In CCl4, there are four C-Cl bonds. Since these
polar bonds are symmetrically arranged, the polarities of individual bonds cancel
each other resulting in a zero dipole moment for the molecule. The net result is that
CCl4 molecule is non-polar.
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Partial ionic characters of covalent compounds. Non-polar and polar covalent molecules

Two types of covalent bonds are formed depending upon the electronegativity of the
combining elements.

Non-polar covalent bond


When a covalent bond is formed between two atoms of the same element, the shared
electron pair will lie exactly midway between the two atoms i.e. the electrons are
equally shared by the atoms. The resulting molecule will be electrically symmetrical
i.e., centre of the negative charge coincides with the centre of the positive charge.
This type of covalent bond is described as a non-polar covalent bond. The bonds in
the molecules H2, O2, Cl2 etc., are non-polar covalent bonds.

Polar covalent bond


The bond between two unlike atoms, which differ in their affinities for electrons is
said to be a polar covalent bond. When a covalent bond is formed between two atoms
of different elements, the bonding pair of electrons will lie more towards the atom,
which has more affinity for electrons. As the said electron pair do not lie exactly
midway between the two atoms, the atom with higher affinity for electrons develops
a slight negative charge and the atom with lesser affinity for electrons, a slight
positive charge. Such molecules are called 'polar molecules'.
In the hydrogen chloride (HCl) molecule, the bonding of hydrogen and chlorine atoms lies
more towards Cl atom (because Cl is more electronegative) in the shared pair of electrons.
Therefore, Cl atom acquires a slight negative charge, and H atom a slight positive charge.
This causes the covalent bond between H and Cl to have an appreciable ionic character.
The compounds having polar bonds are termed polar compounds. Polar substances in their
pure forms, do not conduct electricity, but give conducting solutions when dissolved in polar
solvents.

Cause of polarity in bonds


A pure covalent bond is formed when the shared pair of electrons is shared equally
by the two atoms. Conversely when the two combining atoms share the shared pair of
electrons unequally, the bond formed is a polar covalent bond. Unequal sharing of
the shared pair of electrons arises due to an unequal electron-attracting tendency of
the two atoms. The electron-attracting tendency of the atoms in a molecule is
described in terms of electronegativity. 'Polarity in a bond arises due to the difference
in the electronegativities of the combining atoms'. Thus, the atom of an element
having higher electronegativity has greater electron attracting tendency.
For example, two atoms of hydrogen combine to form a molecule of hydrogen in which H-H
is a pure covalent bond. But, when the atoms of different elements (with different
electronegativities) combine, the atom of the more electronegative element attracts the
shared pair of electrons more towards it. This leads to the formation of a polar bond.

Hydrogen and chlorine react to give hydrogen chloride (HCl). HCl is a polar molecule
because of the difference in the electronegativity values of hydrogen and chlorine.
The greater is the difference in the electronegativity values of the combining atoms, greater is
the polar character in the bond so formed.

For example, in the series H - X (X=F, Cl, Br,I), the electronegativity difference
between H and X atom follows the order:
H- F > H - Cl > H - Br > H - I

Therefore, the polarity in the H - X bond follows the order,

H - F > H - Cl > H - Br > H I i.e., H - F bond is the most polar and


H -I bond is the least polar in this series of compounds.

http://chem-guide.blogspot.in/2010/04/periodicity-of-electron-affinity.html

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Electronegativity Trends
The long form of periodic table carries elements according to the increasing order of their atomic numbers. This in
turn, is actually the increasing number of outermost electrons. When we look at the arrangements though, there are certain
properties of these elements which are also periodic in nature.

These are called periodic properties and are discussed and understood before going over to chemical bonding or the nature of
compounds formed by any group of elements.
Define Electronegativity

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Consider the formation of a covalent bond between two similar atoms of a molecule like Hydrogen. In this molecule the electron
pair participating in the formation of covalent bond is shared equally by both hydrogen atoms, that is, the electron pair lies
exactly in the center of the molecule.

On the other hand, consider the formation of a covalent bond between two dissimilar atoms of a molecule like HCl. In this
molecule the electron pair participating in the formation of covalent bond is not shared equally by the two atoms, the hydrogen
and chlorine. The electron pair tends to lie nearer the Cl atom than the Hydrogen atom.

The reason for this unequal sharing of electron pair is given by the fact that Cl atom has a greater tendency than the hydrogen
atom to attract the shared electron pair between them towards itself.

Thus, we can also say that the Cl atom has more electronegativity than the Hydrogen atom.

From the above fact, electronegativity can be defined as

" The electronegativity of a bonded atom is defined as its relative tendency (or ability) to attract the shared electron
pair towards itself."

Electronegativity of an atom, A is generally expressed as xA.

The concept of electronegativity was proposed by the American chemist Linus Pauling in 1932. Electronegativity is a relative
quantity. It is basically written in comparing two atoms involved in the covalent bond formation. It does not have any unit.

Some of the scales suggested for measuring the electronegativity are

1. Pauling's bond energy scale

Where bond energies or the energy required to break a bond, to get neutral atoms, is employed to measure

electronegativity of an element.

2. Mullikan's scale

According to this scale, electronegativity is taken as a mean difference between ionization potential of an element and its

electron affinity.

Factors Affecting Electronegativity Value

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The electronegativity of an element is influenced by following factors.


1. Nuclear charge

The higher the nuclear charge, more will be the electronegativity value of an element, since the nucleus will be able to attract or
pull more electrons towards itself.

2. Atomic size

Size of the atom is inversely proportional to electronegativity value. The smaller the element, higher is its nucleus's reach
towards the outer shell. Thus, more will be the electronegativity. An example of this is Fluorine, the first member of the halogen
series.

Fluorine is the most highest electronegative element available and is the smallest one too.

3. Screening effect or shielding effect

If the outermost electrons shields the nucleus effectively, the electronegativity of the element decreases.

Electronegativity Trend Periodic Table

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In a period

Electronegativity increases on moving in a period of the periodic table from left to right. This is due to the increase in nuclear
+ -
charge as a result of which the added electrons can be held more tightly. Thus, C-N bond should be shown as C - N or
CN, the arrow head being towards the more electronegative element, N.

In the same period, on moving from left to right, the electronegativities increase with the increase in the number of outer
electrons. An example of this can be shown with the help of the second period.

Element Li Be B C N O F

Electronegativity 1. 1. 2. 2. 3. 3. 4.
value 0 5 0 5 0 5 0

In a group

In moving down a group, from top to bottom, a new shell is added from the top element to the bottom one. Also, the nuclear
charge increases from top to bottom.
The increase in the nuclear charge indicates that the electronegativity of the lower element should be more than that of the top
element. This is not the case though.

The reason is because of the increase in the atomic radii as we move down the group. The increase in atomic radii increases
the electron shielding effect, and it is much more than the increase in the nuclear charge. Consequently, the lower elements are
less electronegative than the top elements. Thus, as we move down a group. electronegativity decreases.
The most electronegative elements, say, Fluorine for example, are present at the top right hand corner of the periodic table.
while the most electropositive elements or the less electronegative elements are present at the bottom left hand corner, for
example, Cs.

Trend for Electronegativity

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Electronegativity value of elements follows the below mentioned trend:

1. Electronegativity increases as we move down from left to right across a period. This is because the atomic size
decreases across the period and nuclear attraction over electrons increases.

2. On moving down a group, the atomic size increases and the nuclear attraction over outer electrons decreases.
Consequently, electronegativity decreases as we move from top to bottom in a group.

3. On comparing the elements based on their group, Halogens are the most electronegative elements in their respective
periods.

4. Alkali metals, have the least electronegativity value in their periods. The last group in the periodic table, the 18th
group consists of Noble gases. They have zero electronegativity value because of their completely filled outer shells.

5. Fluorine, the smallest element has the highest electronegativity value among all elements and Helium has the lowest
electronegativity value.

6. The 15, 16, and 17th group of elements are comparatively more electronegative due to the almost filled outermost
shells.

7. The first and second group, alkali metals and alkaline earth metals are least electronegative. These are
electropositive in nature.

8. Electronegativity value is only applicable for bonded atoms, and not for the isolated gaseous atoms.

9. It is usually calculated from experimentally determined values of bond energies compared to a reference.