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Electropositive elements, whose atoms give up one or more electrons easily, they have
low ionization potentials.
Electronegative elements, which can gain electrons. They have higher value of
electronegativity.
The octet rule:- The Lewis theory gave the first explanation of a covalent bond in terms of
electrons that was generally accepted. If two electrons are shared between two atoms, this
constitutes a bond and binds the atoms together. For many light atoms, a stable arrangement
is attained when the atom is surrounded by eight electrons.
This octet can be made up from some electrons which are totally owned and some electrons
which are shared. Thus atoms continue to form bonds until they have made up an octet of
electrons. This is called the octet rule. The octet rule explains the observed valencies in a
large number of cases. There are exceptions to the octet rule; for example, hydrogen is stable
with only two electrons. Other exceptions are discussed later.Today, the conventional Lewis
structure representation of a pair of bonded electrons is by means of a dash (-) usually called
a bond. Lone pairs or non-bonded electrons are represented by dots. Some structures are
represented below:
2.
The Valence Bond theory handles such species rather clumsily (odd-electron bonds
etc.) the molecular orbital theory copes much better.
3.
Species in which the central atom `expands' its octet (so to speak) PCl 5, SF6, many
transition metal compounds etc.
4.
Electron -deficient species like BCl 3, BeCl2, AlCl3, B2H6 etc. in which the central atom has
fewer than eight electrons.
Ionic Bonding
Electrovalency
Here potassium has one electron excess of its octet and chlorine has one deficit of octet. So
potassium donates its electron to chlorine forming an ionic bond.
Here the oxygen accepts two electrons from calcium atom. It may be noted that ionic bond is
not a true bond as there is no proper overlap of orbitals.
One of the species must have electrons in excess of octet while the other should be deficit of
octet. Does this mean that all substance having surplus electron and species having deficient
electron would form ionic bond? The answer is obviously no. Now you should ask why? The
reasoning is that in an ionic bond one of the species is cation and the other is anion. To form a
cation from a neutral atom energy must be supplied to remove the electron and that energy is
called ionization energy. Now it is obvious that lower the ionization energy of the element the
easier it is to remove the electron. To form the anion, an electron adds up to a neutral atom
and in this process energy is released. This process is called electron affinity.
So for an ionic bond one of the species must have low ionization energy and the other should
have high electron affinity. Low ionization energy is mainly exhibited by the alkali and alkaline
earth metals and high electron affinity by the halogen and chalcogens. Therefore this group of
elements are predominant in the field of ionic bonding.
of
gaseous
The energy required for this step is called ionization energy (I.E)
(b) Formation of gaseous anions
X(g) + e X(g) + E.A
The energy released from this step is called electron affinity (E.A.)
(c) Packing of ions of opposite charges to form ionic solid
A+(g) + X(g) AX(s) + energy
cations
The direct calculation of lattice enthalpy is quite difficult because the required data is often
not available. Therefore lattice enthalpy is determined indirectly by the use of the Born
Haber cycle. The cycle uses ionization enthalpies, electron gain enthalpies and other data for
the calculation of lattice enthalpies. The procedure is based on the Hesss law, which states
that the enthalpy of a reaction is the same, whether it takes place in a single step or in more
than one step. In order to understand it let us consider the energy changes during the
formation of sodium chloride from metallic sodium and chlorine gas. The net energy change
during the process is represented by H f.
The following are some of the general properties shown by these compounds
(i) Crystalline nature : These compounds are usually crystalline in nature with constituent
units as ions. Force of attraction between the ions is non-directional and extends in all
directions. Each ion is surrounded by a number of oppositely charged ions and this number is
called co-ordination number. Hence they form three dimensional solid aggregates. Since
electrostatic forces of attraction act in all directions, therefore, the ionic compounds do not
posses directional characteristic and hence do not show stereoisomerism.
(ii) Due to strong electrostatic attraction between these ions, the ionic compounds have high
melting and boiling points.
(iii) In solid state the ions are strongly attracted and hence are not free to move. Therefore, in
solid state, ionic compounds do not conduct electricity. However, in fused state or in aqueous
solution, the ions are free to move and hence conduct electricity.
(iv) Solubility : Ionic compounds are fairly soluble in polar solvents and insoluble in nonpolar solvents. This is because the polar solvents have high values of dielectric constant
which defined as the capacity of the solvent to weaken the force of attraction between the
electrical charges immersed in that solvent. This is why water, having high value of dielectric
constant, is one of the best solvents.
The solubility in polar solvents like water can also be explained by the dipole nature of water
where the oxygen of water is the negative and hydrogen being positive, water molecules pull
the ions of the ionic compound from the crystal lattice. These ions are then surrounded by
water dipoles with the oppositely charged ends directed towards them. These solvated ions
lead an independent existence and are thus dissolved in water. The electrovalent compound
dissolves in the solvent if the value of the salvation energy is higher than the lattice energy
of that compounds.
AB + Lattice energy A+ + B
These ions are surrounded by solvent molecules. This process is exothermic and is called
salvation.
A+ + x(solv.) [A(solv.)x]+ + energy
(v) Ionic reactions: Ionic compound furnish ions in solutions. Chemical reactions are due to
the presence of these ions. For example
Na2SO4 2Na+ + SO42
BaCl2 Ba2+ + 2Cl
Covalancy
This type of valency involves sharing of electrons between the concerned atoms to attain the
octet configuration with the sharing pair being contributed by both species equally. The atoms
are then held by this common pair of electrons acting as a bond, known as covalent bond. If
two atoms share more than one pair then multiple bonds are formed. Some examples of
covalent bonds are
A covalent bond is formed by overlapping of valence shell atomic orbitals of the two atoms
having unpaired electron. As a result of overlapping, there is maximum electron density
between the bonding atoms and large part of bonding force arises due to electrostatic force of
attraction between accumulated electron cloud and two nuclei. Greater the overlapping of
atomic orbitals higher is the strength of chemical bond. The paired electron of valence shell
of an atom can take part in covalent bonding subject to availability of vacant orbitals of
slightly higher energy of the same main energy shell and availability of energy for unpairing
of paired electron and their shifting to vacant orbitals. This point explains the trivalency of
boron, tetravalency of carbon, pentavalency of phosphorous hexavalency of S and hepta
valency of Cl, Br, I.
Depending on type of overlapping atomic orbitals covalent bond can be classified into two
types
1. Sigma (s) 2. Pi (p) bond
When two hydrogen atoms form a bond, their atomic orbitals overlap to produce a greater
density of electron cloud along the line connecting the two nuclei. In the simplified
representations of the formation of H 2O and NH3 molecules, the OH and NH bonds are also
formed in a similar manner, the bonding electron cloud having its maximum density on the
lines connecting the two nuclei. Such bonds are called sigma bonds (-bond).
A covalent bond established between two atoms having the maximum density of the electron
cloud along the line connecting the centre of the bonded atoms is called a -bond. A -bond
is thus said to possess a cylindrical symmetry along the internuclear axis.
Let us now consider the combination of two nitrogen atoms. Of the three singly occupied porbitals in each, only one p-orbital from each nitrogen (say, the p x may undergo head on
overlap to form a s-bond. The other two p-orbitals on each can no longer enter into a direct
overlap. But each p-orbital may undergo lateral overlap with the corresponding p-orbital on
the neighbour atom. Thus we have two additional overlaps, one by the two p y orbitals, and the
other by the two pz orbitals. These overlaps are different from the type of overlap in as-bond.
For each set of p-orbitals, the overlap results in accumulation of charge cloud on two sides of
the internuclear axis. The bonding electron cloud does no more posses an axial symmetry as
with the s-bond; instead, it possess a plane of symmetry. For the overlap of the p z atomic
orbital, the xy plane provides this plane of symmetry; for the overlap of the p yatomic orbitals,
the zx plane serves the purpose. Bonds arising out of such orientation of the bonding electron
cloud are designated as -bonds.
The bond formed by lateral overlap of two atomic orbitals having maximum overlapping on
both sides of the line connecting the centres of the atoms is called a -bond. A -bond
possess a plane of symmetry, often referred to as the nodal plane.
-Bond : When covalent bond is formed by overlapping of atomic orbitals along the same
axis it is called s - bond. Such type of bond is symmetrical about the line joining the two nuclei
e.g.
(a) s-s
overlapping
(b) s-p
overlapping
(c) p-p
overlapping
- Bond: This type of bond is formed by the sidewise or lateral overlapping of two half filled
atomic orbitals.
|The strength of a bond depends upon the extent of overlapping of half-filled atomic orbitals.
The extent of overlapping is between two atoms is always greater when there is end to end
overlapping of orbitals than, when there is sidewise overlapping of oritals. Hence s-bond is
always stronger than p-bond.
The average distance between the nuclei of the two bonded atoms in a molecule is called
bond length and the energy required to break one mole of bonds of particular type in gaseous
state is called Bond energy or Bond strength. The same amount of energy is released in
formation of one mol of particular bond.
Limitation: VBT cannot explain the paramagnetic properties of B2,O2 etc.
Co-ordinate Covalency
A covalent bond results from the sharing of pair of electrons between two atoms where each
atom contributes one electron to the bond. It is also possible to have an electron pair bond
where both electrons originate from one atom and none from the other. Such bonds are
called coordinate bond or dative bonds. Since in coordinate bonds two electrons are shared by
two atoms, they differ from normal covalent-bond only in the way they are formed and once
formed they are identical to normal covalent bond.
It is represented as []
Atom/ion/molecule donating electron pair is called Donor or Lewis base. Atom / ion /
molecule accepting electron pair is called Acceptor or Lewis acid, [] points
donor to acceptor
NH4+, NH3 has three (N H) bond & one lone pair on N atom. In NH 4+ formation this lone pair
is donated to H+ (having no electron) NH3 + H+ NH4+
2.
3.
Each combining atom must contribute at least one electron to the shared pair.
4.
The combining atoms should attain the noble gas configuration after bond formation.
Covalent bonds can be classified into following two groups depending on the electronegativity
difference between the bonded atoms..
1.
2.
Polar covalent bond is formed between two atoms which have large difference in
electronegativity. The electronegativity difference disturbs the distribution of shared pair of
electrons between the two atoms as the electron density would be more toward the element
which is more electronegative. This will develop partial positive charge on more
electronegative element and partial positive charge on less electronegative one. For example,
bond between H and F would be polar covalent bond.
Maximum Covalency
Elements which have vacant d-orbital can expand their octet by transferring electrons, which
arise after unpairing, to these vacant d-orbital e.g. in sulphur.
In excited state sulphur has six unpaired electrons and shows a valency of six e.g. in SF 6. Thus
an element can show a maximum covalency equal to its group number e.g. chlorine shows
maximum covalency of seven.
Dipole Moment
The dipole moment is defined as the product of the distance separating charges of equal
magnitude and opposite sign, with the magnitude of the charge. The distance between the
positive and negative centres called the bond length.
Thus, = = electric charge bond length = q d
As q is in the order of 1010 esu and d is in the order of 108 cm, is the order of1018 esu cm.
Dipole moment is measured in Debye unit (D)
1D = 1018 es cm = 3.33 1030 coulomb metre
Note:
1.
2.
moment
is
vector
quantity.
3.
4.
Unsymmetrical non-linear polyatomic molecules have net value of dipole moment. For
example, H2O, CH3OH, NH3 etc.?
Let AB and AC are two polar bonds inclined at an angle their dipole moments are 1 and 2.
when =
the
resultant
is
maximum R = 1 + 2
Due to the symmetrical structure of CCl4 the resultant of bond dipoles comes out to be zero.
But in case of CHCl3 it is not possible as the presence of hydrogen introduces some
dissymmetry.
Bond Characteristics
1. Bond Length
The bond length of the homonuclear diatomic molecules are twice the covalent radii.
2.
The lengths of double bonds are less than the lengths of single bonds between the
same two atoms, and triple bonds are even shorter than double bonds.Single bond >
Double bond > Triple bond (decreasing bond length)
3.
Bond length decreases with increase in s-character since s-orbital is smaller than a p
orbital.
sp3 C H = 1.112:
sp2 C H = 1.103;
sp C H = 1.08;
(25% s-character as in alkanes) (33.3% s-character as in alkenes) (50% s-character as in
alkynes)
4.
Bond length of polar bond is smaller than the theoretical non-polar bond length.
The magnitude of the bond energy depends on the type of bonding. Most of the
covalent bonds have energy between 50 to 100 kcal mol1 (200-400 kJ mol1). Strength of
sigma bond is more than that of a -bond.
2.
A double bond in a diatomic molecules has a higher bond energy than a single bond
and a triple bond has a higher bond energy than a double bond between the same
atoms. C C > C = C > C C (decreasing bond length)
3.
The magnitude of the bond energy depends on the size of the atoms forming the bond,
i.e. bond length. Shorter the bond length, higher is the bond energy.
4.
5.
The bond energy decreases with increase in number of lone pairs on the bonded atom.
This is due to electrostatic repulsion of lone pairs of electrons of the two bonded atoms.
6.
Homolytic and heterolytic fission involve different amounts of energies. Generally the
values are low for homolytic fission of the bond in comparison to heterolytic fission.
7.
8.
Bond
s
CC
energy
<
increase
p
<
>
in
the
sp
following
<
NN
order:
sp <
2
>
sp3
OO
3. Bond angles
Angle between two adjacent bonds at an atom in a molecule made up of three or more atoms
is known as the bond angle.
Hybridization
Bond angle
Example
sp3
109o28'
CH4
120o
BCl3
180o
BeCl2
sp2
sp
Generally s- character increase in the hybrid bond, the bond angle increases.
(ii) Lone pair repulsion: Bond angle is affected by the presence of lone pair of electrons at
the central atom. A lone pair of electrons at the central atom always tries to repel the shared
pair (bonded pair) of electrons. Due to this, the bonds are displaced slightly inside resulting in
a decrease of bond angle.
(iii) Electronegativity: If the electronegativity of the central atom decreases, bond angle
decreases.
4. Resonance
There may be many molecules and ions for which it is not possible to draw a single Lewis
structure. For example we can write two electronic structures of O 3.
In (A) the oxygen - oxygen bond on the left is a double bond and the oxygen-oxygen bond on
the right is a single bond. In B the situation is just opposite. Experiment shows however, that
the two bonds are identical. Therefore neither structure A nor B can be correct.
One of the bonding pairs in ozone is spread over the region of all the three atom rather than
associated with particular oxygen-oxygen bond. This delocalised bonding is a type of bonding
in which bonding pair of electrons is spread over a number of atoms rather than localised
between two.
Structures (A) and (B) are called resonating or canonical structures and C is the resonance
hybrid. This phenomenon is called resonance, a situation in which more than one plausible
structure can be written for a species.
Atoms gain or lose electrons to attain a more stable noble gas - like electron configuration
(octet rule). There are two ways in which atoms can share electrons to satisfy the octet rule:
Ionic Bonding - occurs when two or more ions combine to form an electrically-neutral
compound
The
positive
cation
"loses"
an
The
negative
anion
"gains"
the
The anion steals the electrons from the cation.
electron
electron
(or
(or
2
2
or
or
3)
3)
Covalent Bonding - occurs when two or more atoms combine to form an electrically-neutral
compound
The electrons are shared between the two atoms. Both atoms don't have charge in the
beginning and the compound remains with zero charge.
The chemical activity of an atom is determined by the number of electrons in its valence shell.
With the help of concept of chemical bonding one can define the structure of a compound and
is used in many industries for manufacturing products in which the true structure cannot be
written at all.
Some other examples
(i) CO32 ion
Example
(ii) Carbon-oxygen bond lengths in carboxylate ion are equal due to resonance.
(iii) Benzene
Difference in the energies of the canonical forms and resonance hybrid is called resonance
stabilization energy and provides stability to species.
Solution: Out of the structures listed above, the structure (III) is wrong since the number of
electron pairs on oxygen atoms are not permissible. Similarly, the structures (II) has very little
contribution towards the hybrid because one of the oxygen atoms (electronegative) is show to
have positive charge. Carbon dioxide is best represented by structures (I) and (IV).
Hybridization
The mixing or merging of dissimilar orbitals of similar energies to form new orbitals is known
as hybridizationand the new orbitals formed are known as hybrid orbitals.
Orbitals belonging to the same atom or ion having similar energies get hybridized.
2.
Number of hybrid orbitals is equal to the no. of orbitals taking part in hybridization.
3.
4.
The hybrid orbitals form more stable bond than the pure atom orbital.
5.
The reason hybridization takes place is to produce equivalent orbitals which give
maximum symmetry.
6.
It is not known whether actually hybridization takes place or not. It is a concept which
explains the known behaviour of molecules.
7.
The hybrid orbitals are directed in space in same preferred direction to have some
stable arrangement and giving suitable geometry to the molecule.
sp2 hybridization: In this case one s and two p orbitals mix together to form three sp 2 hybrid
orbitals and are oriented in a trigonal planar geometry.
The remaining p orbital if required form side ways overlapping with the other unhybridized p
orbital of other C atom and leads to formation of p2C = CH2 bond as in H
sp hybridization: In this case, one s and one p orbital mix together to form two sp hybrid
orbitals and are oriented in a linear shape.
The remaining two unhybridised p orbitals overlap with another unhybridised p orbital leading
to the formation of triple bond as in HC CH.
Shape
Hybridisation
Linear
sp
Trigonal planar
sp2
Tetrahedral
sp3
Trigonal bipyramidal
sp3d
Octahedral
sp3d2
Pentagonal bipyramidal
sp3d3
Molecular geometry
Requirement = 3 bonds + 1
lone pair
Hybridization = sp3
Shape = pyramidal
Hybridisation: sp2
Shape: angular
Requirement = 3 bonds
Hybrdisation = sp2
Shape: planar trigonal
In the structure one bond is a double bond and the other 2 are
single. The position of the double bonds keeps changing in the
figure. Since peripheral atoms are isovalent, so contribution of
the resonanting structures are equal. Thus it is seen that none of
the bonds are actually single or double. The actual state is
valence
O=C=O
Requirement: 2 bonds
Hybridisation: sp
Shape: linear
valence
4 bonds
+1
Hybridization : sp3d
Shape: Distorted TBP (sea-saw
geometry)
3 bonds
Hybridization: sp3
Shape: Pyramidal
valence
5 bonds
Hybridization: sp3d2
Shape: square pyramidal.
Geometry of the molecules in which the central atom has no lone pairs are regular and can be
predicted simply.
Bond ange of any molecule with regular geometry = 360o /Number of bond pairs
Number of
electron pairs
Arrangement of electrons
Molecular geometry
Examples
BeCl2, HgCl2
2
BAB
Linear
3
BF3, AlCl3
= 120
= 120
5
PCl5, PF5
SF6
Geometry of the molecules having lone pair of electrons can not be predicted simpley using
above mentioned method. The geometric arrangement of atoms in molecules and ions may
be predicted by means of the valence-shell electron-pair repulsion (VSEPR) theory. This type
includes molecules which may or may not obey the octet rule but have only single bonds.
Postulates of VSEPR theory:
1.
The shape of the molecule is determined by repulsions between all of the electron pairs
present in the valence shell.
2.
A lone pair of electrons takes up more space around the central atom than a bond-pair,
since the lone pair is attracted to one nucleus whilst the bond pair is shared by two
nuclei. It follows that repulsion between two lone pairs is greater than repulsion between
a lone pair and a bond pair, which in turn is greater than the repulsion between two
bond pairs. Thus the presence of lone pairs on the central atom causes slight distortion
of the bond angles from the ideal shape. If the angle between a lone pair, the central
atom and a bond pair is increased, it follows that the actual bond angle between the
atoms
must
be
decreased.The
descending
order
of
repulsion
is
(lplp)
>
where lp-Lone pair; bp-bond pair
(lpbp)
>
(bpbp)
3.
4.
Double bonds cause more repulsion than single bonds and triple bonds cause more
repulsion than double bonds.
5.
6.
With very few exceptions, the predictions based on the VSEPR theory have been shown
to be correct.
Molecule
Type
No. of
Bonding
pairs
No. of
lone pair
Arrangement of
electrons pairs
Shape
(Geometry)
AB2E
Examples
SO2, O3
AB3E
Bent
AB2E2
H2O
See saw
SF4
AB4E
Bent
AB3E2
T shaped
CIF3
Square pyramidal
BrF5
Square planar
XeF4
AB5E
AB4E2
Identify the central atom and count the number of valence electrons.
2.
3.
If it is an ion, add negative charges and subtract positive charges. Call it total N
4.
Divide N by 2 and compare the result with chart I and obtain the shape.
Total N/2
Example
Linear
HgCl2/BeCl2
Triangular planar
BF3
Angular
SnCl2, NO2
Tetrahedral
CH4, BF4-
Trigonal Pyramidal
NH3, PCl3
Angular
H2O
Trigonal bipyramidal
PCl5, PF5
Irregular tetrahedral
SF4, IF4+
T-shaped
CIF3, BrF3
Linear
XeF2, I3-
Octahedral
SF6, PF6-
Square Pyramidal
IF5
Square planar
XeF4, ICI4
As mentioned above, when a pair of atomic orbitals combine they give rise to a pair of
molecular orbitals, the bonding and the anti-bonding. The number of molecular orbitals
produced must always be equal to the number of atomic orbitals involved. Electron density is
increased for the bonding MOs in the inter-nuclear region but decreased for the anti-bonding
MOs, Shielding of the nuclei by increased electron density in bonding MOs reduces inter
nuclei repulsion and thus stabilizes the molecule whereas lower electron density even as
compared to the individual atom in anti-bonding MOs increases the repulsion and destabilizes
the system.
In simple homonuclear diatomic molecules the order of MO's based on increasing energy is :
This order is true except B2, C2 & N2. If the molecule contains unpaired electrons in MOs it will
be paramagnetic but if all the electrons are paired up then the molecule will be diamagnetic.
Bond order
Bond order is a number which indicates the no. of bonds a molecule possesses and the
stability of the molecule in comparison to another. An integral value implies that so many
bonds exist in the molecule. Anything fractional indicates that the bond is intermediate.
Bond-order = 1/2 (no. of bonding electrons - No. of antibonding electrons).
1.
Application
Molecules
of
MOT
to
Homonuclear
Diatomic
2.
BO = 1/2 (2-0) = 1
Therefore No. of bonds = 1
3.
4.
As, paramagnetism arises due to unpaired electron. Therefore B 2is paramagnetic molecule.
The molecular orbitals of heteronuclei diatomic molecules should differ from those of
homonuclei species because of unequal contribution from the participating atomic orbitals.
Lets take the example of CO.
The M.O. energy level diagram for CO should be similar to that of the isoelectronic molecule
N2. But C & O differ much in electronegativity and so will their corresponding atomic orbitals.
But the actual MO for this species is very much complicated since it involves a hybridisation
approach between the orbital of oxygen and carbon.
HCl Molecule: Combination between the hydrogen 1s A.Os. and the chlorine 1s, 2s, 2p & 3s
orbitals can be ruled out because their energies are too low. The combination of H
1s1 and 3p1x gives both bonding and anti-bonding orbitals, and the 2 electrons occupy the
bonding M.O. leaving the anti-bonding MO empty.
NO Molecule: The M.O. of NO is also quite complicated due to energy difference of the atomic
orbitals of N and O.
As the M.O.s of the heteronuclei species are quite complicated, so we should concentrate in
knowing the bond order and the magnetic behaviour.
Molecules/Ions
Magnetic behaviour
CO
14
Diamagnetic
NO
15
Paramagnetic
NO+
14
Diamagnetic
NO
16
Diamagnetic
CN
13
Paramagnetic
CN
14
Diamagnetic
Fajan's Rule
Although atomic bond in a compound like M+X- is considered to be 100% ionic, actually it also
has some covalent character. An explanation for the partial covalent character of an ionic
bond has been given by Fajan. According to Fajan, if two oppositely charged ions are brought
together, the nature of the bond between them depends upon the effect of one ion on the
other.
When two oppositely charged ions (say A + and B- ) approach each other the positive ion
attracts electrons on the outermost shell of the anion and repels its positively charged
nucleus. This results in the distortion,deformation or polarization of the anion. If the
polarization is quite small, an ionic bond is formed, while if the degree of polarization is large,
a covalent bond results.
Thus the power of an ion (cation) to distort the other ion is known as its polarization
power and the tendency of the ion(anion) to get polarized by the other ion is known as
its polarisability. Greater the polarization power or polarisability of an ion, greater will be its
tendency to form a covalent bond.
The polarising power, or polarisability and hence formation of covalent bond is
favoured by the following factors:
1.
2.
Large Negative Ion (Anion): The larger the anion, the greater is its polarisability, i.e.
susceptibility to get polarised. It is due to the fact that the outer electrons of a large
anion are loosely held and hence can be more easily pulled out by the cation. This
explains why iodides, among halides, are most covalent in nature.
3.
Large Charge on Either of the Two Ions: As the charge on the ion increases, the
electrostatic attraction of the cation for the outer electrons of the anion also increases,
with the result its ability for forming the covalent bond increases. Thus covalency
increases in the order : Na+ Cl-, Mg2+ (Cl2)2-, Al3+ (Cl3)3 -
4.
Electronic Configuration of the Cation : For the two ions of the same size and
charge, one with a pseudo noble gas configuration (i.e., 18 electrons in outer-most shell)
than a cation with noble gas configuration (i.e. 8 electrons in outermost shell) will be
more polarising. Thus copper (I) chloride is more covalent than sodium chloride
although Cu+ ion (0.96A) and Na+ ion (0.95A) have same size and charge.
The orbital overlapping involved in covalency reduces, the charge on each ion and so weakens
the electrovalent forces throughout the solid, as is evident from the melting point of lithium
halides.
LiF = 870C LiCl = 613C
LiBr = 547C LiI = 446C
From the above discussion, we find that greater the possibility of polarisation, lower is
the melting point and heat of sublimation and greater is the solubility in non-polar
solvents.
Example: The melting point of KCl is higher than that of AgCl though the crystal radii of
Ag+ and K+ ions are almost the same.
Solution : Now whenever any comparison is asked about the melting point of the
compounds which are fully ionic from the electron transfer concept it means that the
compound having lower melting point has got lesser amount of ionic character than the other
one. To analyse such a question first find out the difference between the 2 given compounds.
Here in both the compounds the anion is the same. So the deciding factor would be the
cation. Now if the anion is different, then the answer should be from the variation of the
anion. Now in the above example, the difference of the cation is their electronic configuration.
K+ = [Ar]; Ag+ = [Kr] 4d10. This is now a comparison between a noble gas core and pseudo
noble gas core, the analysis of which we have already done. So try to finish off this answer.
Every ionic compound having some percentage of covalent character according to Fajans
rule. The percentage of ionic character in a compound having some covalent character can be
calculated by the following equation.
The percent ionic character = Observed dipole moment/Calculated dipole moment
assuming 100% ionic bond 100
Example: Dipole moment of KCl is 3.336 1029 coulomb metre which indicates that it is
highly polar molecule. The interatomic distance between k + and Cl is 2.6 1010 m. Calculate
the dipole moment of KCl molecule if there were opposite charges of one fundamental unit
located at each nucleus. Calculate the percentage ionic character of KCl.
Solution: Dipole moment = e d coulomb metre
For KCl d = 2.6 1010 m
For complete separation of unit charge
e = 1.602 1019 C
Hence = 1.602 1019 2.6 1010 = 4.1652 1029 Cm
KCl = 3.336 1029 Cm
% ionic character of KCl = 3.3361029/4.1651029 = 80.09%
Example. Calculate the % of ionic character of a bond having length = 0.83 and 1.82 D as
its observed dipole moment.
Solution: Tocalculate considering 100% ionic bond
= 4.8 1010 0.83 108esu cm
Metallic Bonding
Metals are characterised by bright, lustre, high electrical and thermal conductivity,
malleability, ductility and high tensile strength. A metallic crystal consists of very large
number of atoms arranged in a regular pattern. Different model have been proposed to
explain the nature of metallic bonding two most important modules are as follows
The electron sea Model In this model a metal is assumed to consist of a lattice of positive ion
(or kernels) immersed in a sea of mobile valence electrons, which move freely within the
boundaries of a crystal. A positive kernel consists of the nucleus of the atom together with its
core on a kernel is, therefore, equal in magnitude to the total valence electronic charge per
atom. The free electrons shield the positively charged ion cores from mutual electrostatic
repulsive forces which they would otherwise exert upon one another. In a way these free
electrons act as glue to hold the ion cores together.
The forces that hold the atoms together in a metal as a result of the attraction between
positive ions and surrounding freely mobile electrons are known as metallic bonds.
Through the electron sea predated quantum mechanics it still satisfactorily explains certain
properties of the metals. The electrical and thermal conductivity of metals for example, can
Hydrogen Bonding
Intramolecular hydrogen bonding: This type of bonding occurs between atoms of the
same molecule present on different sites. Intramolecular hydrogen bonding gives rise to a
closed ring structure for which the term chelation is sometimes used. Examples are
o-nitrophenol, salicylaldehyde.
2.
3.
Boiling point
4.
large size and less electronegativity of S. So its boiling point is equal to that of an isolated H 2S
molecule and therefore it is a gas.
Example.Ethyl alcohol (C2H5OH) has got a higher boiling point than dimethyl ether (CH 3-OCH3) although the molecular weight of both are same.
Solution: Though ethyl alcohol and dimethyl ether have the same molecular weight but in
ethyl alcohol the hydrogen of the O-H groups forms intermolecular hydrogen bonding with the
OH group in another molecule. But in case of ether the hydrogen is linked to C is not so
electronegative to encourage the hydrogen to from hydrogen bonding.
HOHOHO
|
|
|
C2H5
C2H5
C2H5
Due to intermolecular H-bonding, ethyl alcohol remains in the associated form and therefore
boils at a higher temperature compared to dimethyl ether.