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What is electronegativity and how does it vary around the Periodic Table? What is the reason of its variation? It will also tell that differences in electronegativity affect bond type and also explain what are polar bonds and polar molecules. To understand all this in details, please go through the page.
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of electrons. It can also be defined as the power of ability of an atom to attract the shared pair of electrons towards itself in a molecule. Shared pair means bonding pair of electrons. Two scales of electronegativity are used commonly: the Pauling scale (proposed in1932) and the Mulliken scale (proposed in 1934). Another proposed scale is the Allred-Rochow scale. The Pauling scale is the most commonly used to measure electronegativity and it is based on bond energy data. Fluorine is the most electronegative element having value of 4.0, but caesium and francium are the least electronegative having value 0.7. Pauling pointed out that the difference in electronegativities lхA – хBl = 0.102√∆
The Mulliken scale is related to the values of electron gain enthalpy and ionization enthalpy of the concerned atoms. This scale explains that an atom with
high value of ionization enthalpy and low electron gain enthalpy will have greater tendency of attracting the electrons and thus will have high value of electronegativity. It is represented as:
Electronegativity depends on the atomic size:
Smaller the size of an atom, greater will be the attraction for the bonding electron and larger will be the value of electronegativity. Example: Atomic radius of oxygen is less than that of nitrogen. Therefore electronegativity of oxygen (3.5) is more than that of nitrogen (3) Polar character of covalent bond : It can be explained with the help of three combinations. 1) Combination of atoms having equal electronegativity: Consider a bond between two atoms, A and B. having same electronegativity.
If the atoms are of equal electronegativity, then both have the same tendency to attract the bonding pair of electrons, and then this bond pair will be found on average mid way between the two atoms .For example, bond formation between H2 and Cl2 molecules.
This type of bond could be considered of as a "pure" covalent bond - where the electrons are shared evenly between the two atoms. 2) Combination of atoms having different electronegativity: Again consider two atoms A & B. B is more electronegative than A. So B will attract the electron pair more strongly than A.
B end of the bond will have large share of electron density as compared to that of A. So it becomes slightly negative ( -). At the same time, the A end will become slightly positive ( +) due to the shortage of electrons.
3) Combination of atoms, in electronegativity than the other:
Consider two atoms A&B forming a bond between them. B atom has very large electronegativity as compared to A. Then B atom has complete control on both the electrons and drags these electrons towards it. With this two ions are formed.
Polar Bond - It is the covalent bond, which develops a partial ionic character
as a result of the difference of electronegativities of the atoms forming the bond. Formation of polar covalent bond occurs due to the unequal distribution of electron charge density. The more electronegative atom acquires a partial negative charge ( -) where as the less electronegative atom will acquire a partial positive charge ( +).
Examples: The hydrogen-chlorine bond in HCl or the hydrogen-oxygen bonds in water are typical examples of polar covalent bond
In a pure covalent bond, the shared pair of electrons lies midway between the nuclei of two atoms. But in a polar bond, the shared pair of electrons has been dragged slightly towards one end, which is more electronegative. Let’s take the example of Lithium iodide, which is ionic with some covalent character. In this case, the shared pair of electron hasn't moved entirely over to the iodine end of the bond. Unlike other ionic compounds Lithium iodide is soluble in non-polar solvents like ethanol. The above three combinations can be summarized as: • • • No electronegativity difference between two atoms formation of pure nonpolar covalent bond. A small electronegativity difference forms polar covalent bond. A large electronegativity difference forms an ionic bond.
Some complicated examples of polar bond:
In CCl4, each bond is polar but not the molecule.
The molecule as a whole isn't polar because it doesn't have an end or a side, which is slightly either negative or positive. All external ends of the molecule are negative, but there is no overall separation of charge from top to bottom or from left to right in a molecule. In contrast to above, CHCl3 is polar molecule.
The hydrogen at the top of the molecule is less electronegative meaning thereby it is slightly positive as compared to carbon. Carbon has slightly negative charge. This shows that the molecule is slightly positive at "top" and slightly negative at "bottom", and therefore it is a polar molecule. A polar molecule will need to be "asymmetrical" in some way.
Periodic Trends of Electronegativity:
The most electronegative element in periodic table is fluorine and as we know that electronegativity is a periodic function of atomic number of elements. It should always increase towards fluorine in the Periodic Table.
Trends in electronegativity across a period:
As we move across a particular period till the elements of group 17 the electronegativity of the elements increases because size of the atom decreases and force of attraction for the bonding electrons increases. Consequently the value of electronegativity increases. In a periodic table the electronegativity of group 17 elements is found to be the highest. The following chart depicts electronegativities from sodium to chlorine, which is increasing.
Trends in electronegativity down a group:
As we move down in a group, electronegativity decreases because the size of the atom increases due to the addition of new shell. As a result the force of attraction for the electrons decreases. With this electronegativity also decreases. (If it increases up to fluorine, it must decrease as you go down.) The graph below depicts the patterns of electronegativity in Groups 1 and 7.
Values of electronegativities given by Pauling & Mulliken:
Note: Values in the bracket are on Mulliken scale while others are on Pauling scale As we observe from the table, values of electronegativity decrease down a particular group and increase across a particular period. Increase in electronegativities can be explained by taking an example of sodium chloride (across a period). Taking sodium the first element of period 3 and chlorine the last (except noble gas - argon), assuming that sodium chloride was covalently bonded.
Both sodium and chlorine have their bonding electrons in the 3rd level. The electron pair is shielded from both the nuclei by the 1s, 2s and 2p electrons, but the force of attraction of chlorine nucleus is more due to the presence of 6 protons in it. So electron pair gets dragged towards the chlorine and ions are formed. Increase in the number of charges on the nucleus increases the electronegativity that attracts the bonding pair of electrons more strongly. Decrease in electronegativities down a group can be explained with the help of an example of hydrogen fluoride and hydrogen chloride.
The bonding pair of electrons is shielded from the fluorine's nucleus by the 1s2 (2 electrons). But In case of chlorine the bonded pair is shielded by 1s22s22p6 (10 electrons).
There is a net force of attraction from the centre of the fluorine or chlorine of +7 electrons in both the cases. But fluorine has the bonding pair in the 2nd level whereas chlorine has 3rd level. If the bonded pair is closer to the nucleus then it will have greater attraction. Electronegativity decreases down a group because the bonding pair of electrons is at a large distance from the nucleus and is not experiencing force of attraction.
Covalent character in ionic bond:
As we have discussed covalent bond develops ionic character due to the difference of electronegativities of bonded atoms. Similarly the ionic bond also develops covalent character.
When two oppositely charged ions come close the positive ion tends to distort the electron cloud of negative ion towards itself. As a result the electron cloud of negative ions gets polarized and electron density is pulled in between the nuclei of the 2 atoms. It means the ionic bond dies not remain 100% ionic but develops some covalent character
The polarisability It is the ability of anion to undergo distortion.
Polarising power The power of the cation to cause distortion in the electron cloud of negative ion is called polarizing power. Fajan rules The extent of covalent character in ionic bond depends on the polarizing power of cation and polarisability of anion which are decided on the set of rules. These are called Fajan Rules.
1) Smaller the size of cation, larger will be the polarizing power. For example: Li+< K+ ions. Therefore LiCl is more covalent than KCl.
2) For 2 cations of similar size the one with pseudo nobel gas configuration ns2np6nd10 has larger polarizing power than with actual noble gas configuration. For example – CuCl is more covalent in nature than NaCl because polarizing power of Cu+ is greater than Na+.
3) Larger the size of an anion, higher will be the polarizability e.g. LiI is more covalent than LiF. Similarly AlF3 is more ionic but AlCl3 is covalent. Aluminium fluoride is ionic because the aluminium ion can't polarize the small fluoride ion sufficiently to form a covalent bond.
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