e 2.0 The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile, non-electrolyte solid weighing 0.5 ¢ when added to 39.0 g of benzene (molar mass 78 g mol"), Vapour pressure of the solution, then, is 0.845 bar. What is the molar mass of the solid substance? Solution The various quantities known to us are as follows: P,° = 0.850 bar; p= 0.845 bar; M, = 78 g mol”; w, =0,5 & w, =39g Substituting these values in equation (2.28), we get 0.850 bar - 0.845 bar 0.5 gx 78.g mol" _ ie 0.850 bar ee M, x 39g - Therefore, M, = 170 g molExample 2.7 18 g of glucose, C,H,,0,, is dissolved in 1 kg of water in a saucepan. ‘At what temperature will water boil at 1.013 bar? K, for water is 0.52 K kg mol”. Moles of glucose = 18 g/ 180 g mol = 0.1 mol Solution Number of kilograms of solvent = 1 kg ‘Thus molality of glucose solution = 0.1 mol kg? For water, change in boiling point1 = 0,052 K AT, = K, x m= 0.52 K kg mol! x 0.1 mol KE ee th Since water boils at 373.15 K at 1.013 bar pressure, Sam ors Te boiling point of solution will be 373.15 + 0.052 = 373. 7 Example 2.8 The boiling point of benzene is 353.23 K. When 1.80 g of @ non-volatile solute was dissolved in 90 g of benzene, the boiling point is raised to 354.11 K. Caleulate the molar mass of the solute. K, for benzene is 2.53 K kg molt Solution The elevation (AT,) in the boiling point = 354.11 K- 353. 23 K = 0.88 K Substituting these values in expression (2.33) we get 2.53 K kg mol” x 1.8 g x 1000 g kg* | M, = >. TCS: pt 2 0.88 Kx 90 seemne ‘Therefore, molar mass of the solute, M, = 58 g mot”i < €,) is mixed wi Couple 20 45 4 of etytene glyeo! (C3103) 8 MS {a) the freezing point depress! Jated to thie mol Solution Depression in freezing point ts relat freezing point of the solutig,, n GOO ¢ of water. Caleua,, lality, therefore, the molality moles of ethylene glyco} ofthe solution with respect to ethylene glycol = Tass of water in Kilo, fram es 458 7g Moles of ethylene glycol = § g mol = 600g Mass of water in kg = To00g kg” = 0.6 kg 0.73 mol Hence molality of ethylene glycol = 0.60 kg Therefore freezing point depression, mol = 1.2 mol kg? AT, = 1.86 K kg mol x 1.2 mol kg"! = 2.2 K Freezing point of the aqueous solution = 273, Example_20 1.00 gofa non-electrolyte solute dissolved in Thus, molar mass of the solute = 256 g mol! .15 K- 2,2 K = 270.95 K 50 g of benzene lowered the freezing point of benzene by 0.40 K. The freezing point depression constant of benzene is 5.12 K kg mol", Find the molar mass of the solute. Solution Substituting the values of various terms involved in equation (2.36) we get, 5.12 K kg mol x 1.00 g x 1000 g kg-! M, = 040x580 g = 256 g mol?uy Example 211 200 om? of an aqueous solution of a protein contains 1.26 g of the Protein. The osmotic pressure of such a solution at 300 K is found to be 2.57 x 10° bar. Calculate the molar mass of the protein. Solution The various quantities known to us are as follows: II = 2.57 x 10° bar, V= 200 cm* = 0,200 litre T= 300K R= 0.088 L bar mol K? Substituting these values in equation (2.42) we get 1.26 g x 0.083 L bar K™ mot" x 309 K Me 2.57x10“bar x 0.200 L = 61,022 g mol!ees ut _t LL + represent 1 values for incomplete dissociation. 2g of benzoic acid (C,H,COOH) dissolved in 25 g of benzene shows a Cxample 2.12 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 fit forms dimer in solution? ‘The given quantities are: w, = 2 g; K,= 4.9 K kg mol"; w, = 25g, Solution AT,= 1.62 K substituting these values in equation (2.36) we get: 4.9 K kg mol" x 2 g x 1000 g kg“ 7 25 gx 1.62K ‘Thus, experimental molar mass of benzoic acid in benzene is = 241.98 g mol Now consider the following equilibrium for the acid: 2.C,H,COOH == (C,H,COOH), 241.98 g mol? Ifxrepresents the degree of association of the solute then we would have (1 - x) mol of benzoic acid left in unassociated form and x correspondingly > as associated moles of benzoic acid at equilibrium. ‘Therefore, total number of moles of particles at equilibrium is: x x l-x+>=s1-= 2 2 Thus, total number of moles of particles at equilibrium equals van't Hoff factor Normal molar mass But ¢ = —————____ Abnormal molar mass maize: Solt- 122 pmol" = 241.98gmol! x 122 2°” 241.98 or =. x_- = 2x 0.496 = 0.992 Therefore, degree of association of benzole acid in benzene Is 94 2 1-0.504 = 0.496 or le_213 0.6 mL of acetic acid (CH,COOH). having density 1.06 ¢ m1," , dissolved in 1 litre of water. The depression in freezin, ig Point : observed for this strength of aed was 0.0205°C. Calculate thevy |} Hoff factor and the dissociation constant of acid. | 0.6 mL x 1.06 ¢m1,' | Solution Number of moles of acetic acid = 60g mor | = 0.0106 mol = n | 0.0106 mol i | Molality = 3059 mb oT g mT 7 0-0106 mol kg" Using equation (2.35) AT,= 1.86 K kg mol" x 0.0106 mol kg" = 0.0197 K Observed freezing point 09,0205 K Calculated freezing point = 9.0197 K = 1-041 Acetic acid is a weak electrolyte and will dissociate into two tons: acetate and hydrogen ions per molecule of acetic acid. If xis the degree of dissociation of acetic acid, then we would haven(1-xj | moles of undissociated acetic acid, nx moles of CH,COO™ and nx moles of H* ions, van't Hoff Factor () = CH,COOHD HY + CH,Coo- I nmol 0 0 n(x) nxmol nx mol Thus total moles of particles are: n(1 - RO+x) x+x+M=n(1 4+) =1+x=1.041 Thus degree of dissociation of acetic acid = x= 1.041- 1,000 = 0.041 Then [CH,COOH] = n{1 -.9 = 0.0106 (1 - 0.041), ICH,COO)] = nx = 0.0106 x 0.041, [H"] = nx= ).0106 x 0.041. [CH,COO"IH"] 0.0106 x 0.041 x 0.0106 x 0.041 ““|CH,COOH] = 0.0106 (1.00 —0.041) = 1.86 x 10°