dissoci that the mass of 2 mol particles ion, we could be led to conclude : 2 is 74. are the mass of one mole of KCL would be 37.25 g. This brings into light the rule that, \ i id) dimerise in thanoie acid (acetic act a ee aes pda bonding. This normally happens d se the number Canis solvents of low dielectric constant. In this ca A So Gey Of particles is reduced due to dimerisation. Association of * molecules is depicted as follows: N G ecules of ethanoic ‘0 —H--O" ited here that if all the mol ble id apnea 'N7, for ethanoic acid will be half in benzene, then AT, oF aie se pal value. The molar mass calculated on the basis of this 47, or AT, will, therefore, be twice the expected value, Such & molar mass that is either lower or higher than the expected or normal value is called as abnormal molar mass. In 1880 van't Hoff introduced a factor £ known as the van't Hoff factor, to account for the extent of dissociation or association. This factor iis defined as: H,C-C Normal molar mass ‘Abnormal molar mass _ Observed colligative property Calculated colligative property ‘Total number of moles of particles after association/dissociation Number of moles of particles before association/dissociation Here abnormal molar mass is the experimentally determined molar mass and calculated colligative properties are obtained by assuming that the non-volatile solute is neither associated nor dissociated. In it ‘or example, the value of i for aqueous KCI solution is close to 2, while the value for ethanoie acid in benzene is nearly 0.5. Inclusion of van't Hoff factor modifies the equations for colligative properties as follows: Relative lowering of vapour pressure of solvent, PL-Pr _; % Pp ny Elevation of Boiling point, AT, Depression of Freezing point. AT, Osmotic pressure of solution, I iK,meae ee oe values of the factor, i for several strong electrolytes. ed sek MgSO,, ivalues approach 2 as the solution becomes . As expected, the value of i gets close to 3 for K,SO, Table 1.4: Values of van't Hoff factor, i, at Various Concentrations for NaCl, KCI, MgSO, and K,SO,. | NaCl ‘Kel | MgSO, | K,S0, * represent {values for incomplete dissociation. 2 g of benzoic acid (C;H,COOH) dissolved in 25 g of benzene shows a depression in freezing point equal to 1.62 K. Molal depression constant for benzene is 4.9 K kg mol". What is the percentage association of acid ifit forms dimer in solution? = 258, ‘The given quantities are: w, = 2g AT, = 1.62 K Substituting these values in equation (2.36) we get: 4.9 K kg mol" 2 g x 1000 g kg" _ , M, 95 gx 1.62 K = 241.98 g mol ‘Thus, experimental molar mass of benzoic acid in benzene is = 241.98 g mol” Now consider the following equilibrium for the acid: 2C,H,cCOOH = (C,H,COOH), association of the solute then we would If x represents the degree of ot in unassociated form and have (1 - x) mol of benzoic acid left i correspondingly a as associated moles of b ‘Therefore, total number of moles of particles at equilibrium is: x enzoic acid at equilibrium. a daxtGrhg ‘Thus, total number of moles of, particles at equilibrium equals van't Hoff factor i. Normal molar mass But (= 7p normal molar mass122 ¢mol | “241.984 mol | or we yy. 504% 0.406 2 241.98 or x @2*0 496 = 0.99% Therefore, degree of association of benzole acid in benzene i¢ 99.2. %, 0.6 mL of acetic acid (CH,COOH). having density 1.06 g mL * dissolved in 1 Hire of water, The depression ir freezing 1 observed for this strength of acid was 0,0208°C. Calculate th Hoff factor and the dissoctation constant of acid 0.6 mL 7 1.06 ¢ mL 60 ¢ mol ' = 0.0106 mol = n Number of moles of acetic acid = 0.0106 mol Molal = = 0.0106 9) gt ety 00 mL vi git OF I0E ined ig Using equation (1.35) AT, = 1.86 K kg mol! «0.0106 mol kg! = 0.0197 K Observed freezing point 0.0205 K Calculated freezing point * 6.9197 K Acetic acid ts a weak electrolyte and will dissociate into two lone acetate and hydrogen Jona per molecule of acetic acid van't Hoff Factor ()) = = 1.04) If x ts the degree of dissociation of acetic acid, then we would have n (i =x moles of undissociated acetic acid, nx moles of CH.COO and ax moles of H’ ions, CH,COOH =H! + CH,COO. nmol oO 0 nlx) rocmol re mol ‘Thus total moles of particles are; n(l~ x + x + x © nf} + x” po MOLD n l+x ©1041 Thus degree of dissociation of aceuc acid = «= | G4} 1.606 = 0,041 Then [CH,COOH] = Ui — x) = 0.0106 (1 0.041), ICH, COO | = 1x = 0.0106 * 0.041, [H"} = x= 0.0106 x 0.041 [CH,COO JIE] _ 0.0106 * 0.041 * 0.0106 % 0.041 ‘a ICH,COOH| — 0.0106 (1.00 ~0.041) = 1.86 * 10%Summary @ homogeneous mixture of two or more substances. Solutions are Solid, Uquid and gaseous solutions. The concentration of a solution is “vin terms of mole fraction, molarity, molality and in percentages. The dissolution of a gas In a liquid is governed by Henry's law, according to which. at a given temperature, the solubility of a gas in a liquid is directly proportional to ‘he partial pressure of the gas. The vapour pressure of the solvent {s lowered by the presence of a non-volatile solute in the solution and this lowering of vapour pressure of the solvent is governed by Raoult’s law, according to which the relative lowering of vapour pressure of the solvent over a solution is equal to the mole fraction of a non-volatile solute present in the solution. However, in a binary ‘iquld solution, if both the components of the solution are volatile then another form of Raoult’s law is used, Mathematically, this form of the Raoult's law is stated 88! Pou = Pi + P2X2 . Solutions which obey Raoult’s law over the entire range of concentration are. called ideal solutions. Two types of deviations from Raoult’s law, called positive and negative deviations are observed. Azeotropes arise due to ery large deviations from Raoult’s law. The properties of solutions which depend on the number of solute particles and are independent of their chemical identity are called colligative properties. These are lowering of-vapour pressure, elevation of bolling point, depression of freezing point and osmotic: pressure. The process of osmosis can be reversed if a pressure higher than the osmotic pressure is applied to the solution. Colligative properties have been used to determine the molar mass of solutes. Solutes which dissociate in solution exhibit molar mass lower than the actual molar mass and those which associate show higher molar mass than their actual values. Quantitatively, the extent to which a solute is dissociated or associated can be expressed by van't Hoff factor i This factor has been defined as ratio of normal molar mass to experimentally determined molar mass or as the ratio of observed olligative property to the calculated colligative property. A solution 1s classifi expres! ne the term solution. How many types of solutions are formed? Write briefly ul each type with an example. le of a solid solution in which the solute is a gas. 2 Give an.examplk 1.8 Define the following terms: (i) Mole fraction (i) Molality (i) Molarity (tv) Mass percentage. 1-4 Concentrated nitric acid used in laboratory work is 68% nitric acid by mass in aqueous solution, What should be the molarity of such a sample of the acid if density of the solution fs 1.504 g mL"? the Bie Solutionsen sen senenininsiionsacnstinets, Summary \ solution 18 @ homogeneous mixture of two or more substances. Solutions are ified as solid, Liquid and gaseous solutions. The concentration of a solution 1s expressed in terms of mole fraction, molarity, molality and in percentages. The dissolution of a gas in a Liquid ts governed by Henry's law, according to which, at a given temperature, the solubility of a gas in a liquid is directly proportional to he partial pressure of the gas. The vapour pressure of the solvent is lowered by pe presence of a non-volatile solute in the solution and this lowering of vapour I pressure of the solvent fs governed by Raoult’s law, according to which the relative Jomering of vapour pressure of the solvent over a solution is equal to the mole fraction of @ non-volatile solute present in the solution. However, in a binary liquid solution, if both the components of the solution are volatile then another form of Raouit's law is ‘used, Mathematically, this form of the Raoult's law is stated a8: Piva = P)X\ + P2Xy. Solutions which obey Raoult’s law over the entire range of concentratioin are called ideal solutions. Two types of deviations from Raoult’s Inw, called positive and negative deviations are observed. Azeotropes arise due to very large deviations from Raoult's law. The properties of solutions which depend on the number of solute particles and are independent of thelr chemical identity are called colligative properties. These are lowering of: vapour pressure, elevation of boiling point, depression of freezing point and osmotic pressure. The process of osmosis can be reversed if a pressure higher than the osmotic pressure Is applied to the solution. Colligative properties have been used to determine the molar mass of solutes. Solutes which dissociate in solution exhibit molar mass lower than the actual molar mass and those which associate show higher molar mass than their actual values. Quantitatively, the extent to which a solute is dissociated or associated can be expressed by van't Hoff factor i, This factor has been defined as ratio of normal lar mass (o' experimtentally determined molar mass or as the ratio of observed olligative property to the 1.1 Define the ferm solution. How many types of solutions are formed? Write briefly about each type with an example. 1.2 Give an.example of a solid solution in which the solute is a gas. 1.8 Vefine the following terms: (i) Mole fraction (ii) Molality (ii), Molarity iv) Mass percentage. La Concentrated nitric afd used in laboratory work is 68% nitric acid by mass in aqueous solution. What should be the molarity of such a sample of the acid if the density of the solution is 1.504 g mL-'2 Bi Solutions