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ELECTRON AFFINITY
-328 kJ
F
mol-1
-349 kJ
Cl
mol-1
B -324 kJ
r mol-1
-295 kJ
I
mol-1
Is there a pattern?
1st EA =
-142 kJ
mol-1
2nd EA =
+844 kJ
mol-1
answers
--------------------
electron affinity,
Energy required to detach an electron from the singly charged negative ion
---------------------------------------
Electron Affinity
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.
=====================
Example:
Trends:
As with ionization energy, there are two rules that govern the periodic trends of electron affinities:
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.
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:
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.
-------------------------
* Alkali earth elements (Group IIA) and noble gases (Group VIIIA) do not form
stable negative ions.
=======================
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.
=====================
(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.
------------------------
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.
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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The amount of energy required to remove the most loosely bound electron from an isolated
gaseous atom is called ionization energy (IE).
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.
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.
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.
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.
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.
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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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.
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.
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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'.
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.
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Periodic Table
s
Alkali Metals Transition Metals
Halogens
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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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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
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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.
DISCOVERED
hydrochloric acid
acid acids, resists attack by
nor
and alkali alkali
sodium hydroxide
H=1 - - - - - - -
Fe=56
Co=58.9
K=39 Ca=40 - Ti=48 V=51 Cr=52 Mn=55
Ni=58.7
cu=63
Ru=104
Rh=104
Rb=85 Sr=87 Yt=88 Zr=90 Nb=94 Mo=96 -
pb=106
Ag=108
Os=195
Ir=197
- - Er=178 La=180 Ta=82 W=184 -
Pt=198
Au=199
- - - Th=231 - U=240 - -
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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:
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.
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 bond makes substances This bond makes substances This bond make substances
hard and brittle. hard and incompressible. malleable and ductile.
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.
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.
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
Resonance and resonance hybrid structures of O3, SO3, SO2, CO3-2, SO4-2, PO4-2,NO3-
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
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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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 bonds can be classified into two types; Intermolecular hydrogen bond and
Intramolecular hydrogen bond.
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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
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.
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
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.
RELATED SEARCHES:
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.
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
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.
" The electronegativity of a bonded atom is defined as its relative tendency (or ability) to attract the shared electron
pair towards itself."
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.
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.
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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.
If the outermost electrons shields the nucleus effectively, the electronegativity of the element decreases.
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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.
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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.