Electronegativity and Polarity



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and Polarity N Goalby Chemrevise.org Definition: is the relative tendency of an atom in a molecule to attract electrons in a covalent bond to itself. is measured on the Pauling scale (ranges from 0 to 4). The most electronegative element is fluorine and it is given a value of 4.0. The higher the electronegativity value of an atom, the greater is the ability of an atom of that element to attract electrons to itself. 1

Electronegativities of elements INCREASING ELECTRONEGATIVITY DECREASING ELECTRONEGATIVITY 2.1 Li Be B C N O F 1.0 1.5 2 2.5 3.0 3.5 4.0 Na Mg Al Si P S Cl 0.9 1.2 1.5 1.8 2.1 2.5 3.0 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br 0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I 0.7 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5 Cs Ba La f Ta W Re Os Ir Pt Au g Tl Pb Bi Po At 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.2 2.2 2.4 1.9 1.8 1.8 1.9 2 2.2 Fr Ra Ac 0.7 0.9 1.1 Numbers refer to the Pauling Scaleof 4 3.5 3 2.5 2 1.5 1 0.5 Rb K Li Na Sr Ca Be Mg In B Al Ga C Si Ge Sn N P As Sb O S Se Te F Cl Br I 0 1 2 3 4 5 Group Number 6 7 2

Ionic or covalent bonds? Not all bonds are purelyionic or purelycovalent. Some covalent bonds have a partial ionic character: polar bonds. To deduce the degree of bond polarisation, we consider the differencein electronegativity between the two atoms in the bond. Pure covalent bond (non-polar) Difference in electronegativity is zero or very small(< 0.3). Each atom pulls on the electrons to the same extent and they are equally shared. E.g. Cl 2 (Cl) = 3.0 difference(cl Cl) = 3.0 3.0 = 0 Covalent bond Electrons shared equally N.B.Bonds between identical nonmetal atoms will always be nonpolaras the electronegativity difference will be zero. 3

Covalent with ionic character (Polar bond) Difference in electronegativity between atoms is around 0.3 to 1.7. One atom will pull electron pair closer to its end. E.g. Cl () = 2.1 (Cl) = 3.0 difference( Cl) = 3.0 2.1 = 0.9 δ Polar Covalent bond Electrons shared unequally Polar covalent bondor polar bondis a covalent bond with greater electron density around one of the two atoms. Representation of polar bonds Cl δ δ Polar Covalent bond Electrons shared unequally δ indicates a slight deviation from being neutral. The separation of charge induces a dipole: the bond is polar. The greater the electronegativity difference, the greater the bond polarity. δ resides on the more electronegative atom; on the less electronegative atom. 4

Pure ionic Difference in electronegativity between atoms is large (> 1.7). An electron is completely transferred from one atom to another. E.g. NaCl (Na) = 0.9 (Cl) = 3.0 difference(na Cl) = 3.0 0.9 = 2.1 + - Ionic bond Electrons are transferred Ionic bonds are generally formed between reactive metals and nonmetalswhere the difference in electronegativity is large. Non-polar, polar or ionic? In general if electronegativity difference between two bonded atoms is: < 0.3, usually between identical nonmetal atoms, called nonpolar covalent 0.3 to 1.7, 2 different nonmetals called polar covalent 1.7 or greater, usually nonmetals and reactive metals, is ionic Non polar Covalent bond Electrons shared equally Polar Covalent bond Electrons shared unequally Ionic bond Electrons are transferred Increasing ionic character Difference in electronegativity 0.4 1.7 5

Polar bonds and polar molecules For a moleculeto be polar it must have a net dipole. To work out if a molecule is polar we consider: the polarity of each of the individual bonds the shapeof the molecule. EXTRA Non-polar molecules A symmetric molecule (all bonds identical and no lone pairs) will not be polar even if individual bonds within the molecular ARE polar. e.g. CO 2 δ O = C = O δ The individual dipoles on the bonds cancel out due to the symmetrical shape of the molecule. There is no NET dipole moment: the molecule is NON POLAR EXTRA 6

Polar N- bonds Molecule non-symmetrical (lone pair) Polar molecules A non-symmetrical molecule (different bondsor the same bonds and having lone pairs) will be polarif individual bond(s) are themselves polar. N δ C Cl δ Polar C-Cl bond Molecule nonsymmetrical (different bonds) O Polar O- bonds Molecule nonsymmetrical (lone pairs) In each case, the dipoles do notcancel out. There is a net dipole moment and the molecule is polar. δ - EXTRA 7