You are on page 1of 5

Chemical Bonding Part-3

(3) Solubility. Alcohols, glycol, glycerol and sugars are soluble in water due to the formation of hydrogen bond with water molecules. Dimethylether, (CH3)2O, is miscible in water as it can form hydrogen bond with water molecule but dimethyl sul hide, (CH 3)2!, is immiscible as it cannot form hydrogen bond with water molecules since the electronegati"ity

of sul hur is less.

(4) Viscosity. #iscosity increases with the e$tent of hydrogen bonding in molecules. %he "iscosity of water is &'.'( milli oise, methanol ) milli oise and dimethyl ether 2.3 milli oise. !ince both H2O and CH3OH are hydrogen bonded the "iscosities are high, but when there is substitution of second methyl grou to roduce the non*hydrogen*bonded dimethyl*ether, (CH3)2O, the "iscosity dro s to a low "alue. +olyhydro$y alcohols such as ethylene glycol, CH2OH.CH2OH and glycerol, CH2OH.CHOH.CH2OH which ha"e e$tensi"e hydrogen bonding e$hibit much higher "iscosities.

(5) Molecular weights. %he association of two or more molecules by intermolecular hydrogen bonding affect the a arent molecular weight. ,n case of carbo$ylic acids (-COOH) it is obser"ed that the a arent molecular weights are

higher than the formula weights. %he a arent molecular weight decreases with increasing tem erature due to dissociation of dimer into monomer.

A monomer*dimer hydrogen*bonded e.uilibrium is the sim lest e$ lanation of these results. ,ncrease in tem erature increases the a"erage /inetic energy of the molecules, brea/ing more hydrogen bonds and shifting the e.uilibrium to left.

(6) Dielectric constants and Dipole moments

%he formation of hydrogen*bond, A ** H...0 leads to an increased olarity of the bond A ** H, and hence, to a larger dielectric constant and greater di ole moment.

( ) !ow density o" ice than water ,n the crystal structure of ice the o$ygen atom of water is surrounded by four hydrogen atoms, two attached with co"alent bonds and two with hydrogen bonds. %hus in ice e"ery water molecule is associated with four other water molecules in tetrahedral attern. ,ce has an o en structure with large em ty s ace due to e$istence of hydrogen*bonds. 1hen ice melts a number of hydrogen bonds are bro/en and the s ace between water molecules decreases and the density of water increases, therefore from '2 to 32C, it is ma$imum. Abo"e 32C the increase in /inetic energy of the molecules dis erse them and the result is that the density now decreases with increasing tem erature.

(#) Stability o" unusual structures 4enerally, the organic com ounds with two ** OH grou s on the same carbon atom are unstable and soon liberate water molecule. 5or e$am le 6

%he stability of com ounds li/e chloral hydrate, CCl 3 ** CH(OH)2 can be e$ lained on the basis of intramolecular hydrogen*bonding.

($) %hain& Sheet and 'hree dimensional structures Hydrogen bonding leads to the formation of chains (HC7, H5, HCOOH), sheet (orthoboric acid, o$yde acid) and three dimensional networ/ (water, 8H2+O3) structures.

(()) Dissociation constants o" carbo*ylic acids %he dissociation constant of an acid de ends on the stability of its ion. ,f the stability of anion of an acid is increased due to intramolecular hydrogen*bonding, the acid strength is greatly enhanced i.e., p8a "alue decreases. %he carbo$ylate ion of o*hydro$y ben9oic acid is stabilised by intermolecular hydrogen*bonding, thus o*salicylic acid is more stronger ( 8a : 2.;<) than ben9oic acid ( 8a : 3.&=).

,t can be seen that two hydrogen*bonds would be e$ ected to bring more stabili9ation than one hydrogen bond, and 2,)*dihydro$y ben9oic acid is much more stronger ( 8a : 2.3') than o* salicylic acid. !imilarly, o*salicylic acid ( 8a : 2.<;) is much stronger due to intramolecular hydrogen bonding than its meta ( 8a : 3.';) and ara ( 8a : 3.(;) isomers.

+a,an-s .ule ,t is generally assumed that co"alent and ionic bonds are entirely distinct but this is robably not a totally "alid assum tion. 0onds intermediate between ionic and co"alent do occur through a rocess of de"ormation or polari/ation.

0onic polari/ation is "a1oured by a number o" "actors which are summari/ed in the "our +a,an-s rules.

(&) Small cation > ,n a small cation there is greater concentration of ositi"e charge o"er a small surface area so it will cause greater de"ormation o" an anion than would he caused by a large cation. %hus small cations ha"e high polari/ing power.

%he effect of cationic si9e u on co"alent character is shown in table below. ,t is clear from the table that with the increase in the si9e of the cation the co"alent character decreases.

%his is ?ustified by the low melting oint of beryllium chloride which is more co"alent than the chlorides of the al/aline earth metals.

2""ect o" cationic si/e upon co1alent character

(2) !arge anion 3 %he large anion has polari/ability. %he outermost orbitals of the anions are shielded from the nucleus by a number of com letely occu ied orbitals hence they are readily polari/ed by a small cation. ,f the si9e of the cation and the charge on both the ions is /e t constant and only the si9e of the anion is increased, more co"alency will be noticed. %his is shown in table from the decrease in the melting oints of calcium halides.

2""ect o" anion si/e upon co1alent character

(3) !arge charge on either o" the ions> ,t is understandable that the electrostatic forces which cause olari9ation will be considerably increased if the ions are highly charged. 'he increased nuclear charge will attract the ions to a greater e*tent causing greater de"ormation and hence co1alent character. %he decrease in melting oints with the increase of charge of the ions is shown in table to ?ustify this generali9ation.

2""ect o" cationic charge upon co1alent character