FACTORS GOVERNING POLARIZATION AND POLARISABILITY (FAJANS RULE)

Cation Size: Smaller is the cation more is the value of charge density () and hence more its polarising power. As a result more covalent character will develop. Let us take the example of the chlorides of the alkaline earth metals. As we go down from Be to Ba the cation size increases and the value of decreases which indicates that BaCl 2 is less covalent i.e. more ionic. This is well reflected in their melting points. Melting points of BeCl2 = 405C and BaCl2 = 960C. Cationic Charge: More is the charge on the cation, the higher is the value of and higher is the polarising power. This can be well illustrated by the example already given, NaBr and AlBr3. Here the charge on Na is +1 while that on Al in +3, hence polarising power of Al is higher which in turn means a higher degree of covalency resulting in a lowering of melting point of AlBr3 as compared to NaBr. Noble Gas vs Pseudo Noble Gas Cation:A Pseudo noble gas cation consists of a noble gas core surrounded by electron cloud due to filled d-subshell. Since d-electrons provide inadequate shielding from the nuclei charge due to relatively less penetration of orbitals into the inner electron core, the effective nuclear charge (ENC) is relatively larger than that of a noble gas cation of the same period. NaCl has got a melting point of 800C while CuCl has got melting point of 425C. The configuration of Cu + = [Ar] 3d10 while that of Na+ = [Ne]. Due to presence of d electrons ENC is more and therefore Cl is more polarised in CuCl leading to a higher degree of covalency and lower melting point. Anion Size:Larger is the anion, more is the polarisability and hence more covalent character is expected. An e.g. of this is CaF2 and CaI2, the former has melting point of 1400C and latter has 575C. The larger size of I ion compared to F causes more polarization of the molecule leading to a lowering of covalency and increasing in melting point. Anionic Charge:Larger is the anionic charge, the more is the polarisability. A well illustrated example is the much higher degree of covalency in magnesium nitride (3Mg++ 2N3) compared to magnesium fluoride (Mg++ 2F). This is due to higher charge of nitride compare to fluoride. These five factors are collectively known as Fajans Rule. Example: The melting point of KCl is higher than that of AgCl though the crystal radii of Ag+and K+ ions are almost 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 cation is different, then the answer should be from the variation of the cation. 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.

Example: AlF3 is ionic while AlCl3 is covalent. Solution: Since F is smaller in size, its polarisability is less and therefore it is having more ionic character. Whereas Cl being larger in size is having more polarisability and hence more covalent character. Example: Which compound from each of the following pairs is more covalent and why? (a) CuO or CuS (c) PbCl2 or PbCl4 Solution: (a) CuS (c) PbCl4 (b) AgCl or AgI (d) BeCl2 or MgCl2 (b) AgI (d) BeCl2

DIPOLE MOMENT
Difference in polarities of bonds is expressed on a numerical scale. The polarity of a molecule is indicated in terms of dipole moment (). To measure dipole moment, a sample of the substance is placed between two electrically charged plates. Polar molecules orient themselves in the electric field causing the measured voltage between the plates to change. 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 of10 18 esu cm. Dipole moment is measured in Debye unit (D) 1D = 1018 es cm = 3.33 1030 coulomb metre Note: (i) Generally as electronegativity difference increase in diatomic molecules, polarity of bond between the atoms increases therefore value of dipole moment increases. (ii) Dipole moment is a vector quantity (iii) A symmetrical molecule is non-polar even though it contains polar bonds. For example, CO2, BF3, CCl4 etc. because summation of all bond moments present in the molecules cancel each other.

(iv) Unsymmetrical non-linear polyatomic molecules have net value of dipole moment. For example, H2O, CH3OH, NH3 etc.

Calculation of Resultant Bond Moments

Let AB and AC are two polar bonds inclined at an angle their dipole moments are 1 and 2.

Resultant dipole moment may be calculated using vectorial method. = 12 + 22 + 212 cos when = 0 the resultant is maximum R = 1 + 2

when, = 180, theresultant is minimum R = 1 2 Example. The compound which has zero dipole moment is

(A) CH2Cl2 Solution: (C)

(B) NF3

(C) PCl3F2

(D) ClO2

Example. Sketch the bond moments and resultant dipole moment in

(i) SO2

(ii) CisC2H2Cl2 and

(iii) trans-C2H2Cl2

Solution:

Resultant m = 0

Example. CO2 has got dipole moment of zero. Why?

Solutions: The structure of CO2 is.This is a highly symmetrical structure with a plane of symmetry passing through the carbon. The bond dipole of CO is directed towards oxygen as it is the negative end. Here two equal dipoles acting in opposite direction cancel each other and therefore the dipole moment is zero.

Example. Dipole moment of CCl4 is zero while that of CHCl3 is non zero.

Solution: Both CCl4 & CHCl3 have tetrahedral structure but CCl4 is symmetrical while CHCl3 is non-symmetrical.

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.

Example: Compare the dipole moment of H2O and F2O. Solution: Lets draw the structure of both the compounds and then analyse it.

In both H2O and F2O the structure is quite the same. In H2O as O is more electronegative than hydrogen so the resultant bond dipole is towards O, which means both the lone pair and bond pair dipole are acting in the same direction and dipole moment of H2O is high. In case of F2O the bond dipole is acting towards fluorine, so in F2O the lone pair and bond pair dipole are acting in opposition resulting in a low dipole.

In C-H, carbon being more electronegative the dipole is projected towards C. Now the question comes whether hybridization has anything to do with the dipole moment. The answer is obviously yes. If yes, why? Depending on the hybridization state the electronegativity of carbon changes and therefore the dipole moment of C-H bond will change. As the s character in the hybridized state increases, the electronegativity of C increases due to which C attracts the electron pair of C-H bond more towards itself resulting in a high bond dipoles.

Now as we have said about carbon hydrogen bonds, the question that is coming to your mind is whether we would be dealing with organic compounds or not. Yes we would be dealing with the organic compounds.

For instance but -2- ene. It exists in two forms cis and Trans.

The trans isomer is symmetrical with the 2 methyl groups in anti position. So the bond dipoles the two Me C bonds acting in opposition, cancel each other results into a zero dipole. Whereas in cis isomer the dipoles do not cancel each other resulting in a net dipole.

Example: The molecule having largest dipole moment among the following is (A) CH4 (C) CCl4 (B) CHCl3 (D) CHI3

Solution: (B)

Example. Compare the dipole moment of cis 1, 2 dichloroethylene and trans 1, 2 dichloroethylene.

Solution:

In the trans compound the C-Cl bond dipoles are equal and at the same time acting in opposition cancel each other while in cis compound the dipoles do not cancel each other resulting in a higher value.

Generally all Trans compounds have a lower dipole moment corresponding to Cis isomer, when both the substituents attached to carbon atom are either electron releasing or electron withdrawing.

PERCENTAGE OF IONIC CHARACTER

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

= 4.8 0.83 1018 esu cm = 3.984 D

% ionic character = 1.82/3.984 100 = 45.68

The example given above is of a very familiar compound called HF. The % ionic character is nearly 43.25%, so the % covalent character is (100 43.25) = 56.75%. But from the octet rule HF should have been a purely covalent compound but actually it has some amount of ionic character in it, which is due to the electronegativity difference of H and F. Similarly knowing the bond length and observed dipole moment of HCl, the % ionic character can be known. It was found that HCl has 17% ionic character. Thus it can be clearly seen that although we call HCl and HF as covalent compounds but it has got appreciable amount of ionic character. So from now onwards we should call a compound having more of ionic less of covalent and vice versa rather than fully ionic or covalent.