SUBJECTIVE Problem 1: Calculate the molecular weight of cellulose acetate if its 0.5% (wt./vol) solution in acetone (sp. gr. = 0.9) shows an osmotic rise of 23 mm against pure acetone at 27°C. Solution: 0.5% (wt. / vol) solution means 0.5 gm of cellulose acetate is dissolved in 100 ml solution. Osmotic pressure = 23 mm of pure acetone 2.3 0.9 = 2.3 Cm of pure acetone = cm of Hg = 0.1522 cm of Hg 13.6 0.1522 = atm = 0.002 atm 76 0.5 Let the molecular weight of the cellulose acetate be M ncellulose acetate = M Volume = v = 100 ml = 0.1 lit R = 0.082 lit atm mol–1 K–1, T = ( 27 + 273) = 300 K n 0.5 1 = RT 0.002 = 0.0821 300 M = 61575 v M 0.1
Problem 2: 1kg of an aqueous solution of Sucrose is cooled and maintained at –4°C. How much ice will be separated out if the molality of the solution is 0.75? Kf (H2O) = 1.86 Kg mol–1K. Solution: Since molality of solution is .75 , hence .75 moles of sucrose are present in 1000 g of solvent (i.e. water) msolution = mwater + msucrose = 1000 + .75 × 342 = 1256.5 gm 256.5 msucrose (in kg) = × 1000 = 204.14 gm ,. mwatrer = 1000 – 204.14 = 795.86 gm 1256.5 204.14 / 342 Tf = Kf × m 4 = 1.86 × w = 277.15 W / 1000 amount of ice = 795.86 – 277.15 = 518.31 gm
Problem 3: River water is found to contain 11.7% NaCl, 9.5% MgCl2, and 8.4%. NaHCO3 by weight of solution. Calculate its normal boiling point assuming 90% ionization of NaCl, 70% ionization of MgCl2 and 50% ionization of NaHCO3 (Kb for water = 0.52) 11.7 9.5 8.4 Solution: nNaCl = = 0.2, n MgCl2 = = 0.1, n NaHCO3 = = 0.1 58.5 95 84 iNaCl = 1+ = 1+ 0.9 = 1.9, i MgCl2 = 1 + 2 = 1+ 0.7 2 = 2.4 , i NaHCO3 = 1+ 2 = 1+ 0.5 2 = 2.0 Weight of solvent = 100 – (11.7 + 9.5 + 8.4) = 70.4 g (i NaCl n NaCl i MgCl2 n MgCl2 i NaHCO3 n NaHCO3 ) K b 1000 Tb = Weight of solvent
(1.9 0.2 2.4 0.1 2 0.1) 0.52 1000
= = 5.94°C 70.4 Boiling point of solution = 100 + 5.94 = 105.95°C Problem 4: An aqueous solution containing 288 gm of a non–volalite compound having the stochiometric composition CxH2xOx in 90 gm water boils at 101.24°C at 1.00 atmospheric pressure . What is the molecular formula? Kb(H2O) = 0.512 K mol–1 kg Tb (H2O) = 100°C Solution: Elevation in B.P. = 101.24 – 100 = 1.24°C 288 1000 Tb = Kb i molality 1.24 = 0.512 ( i = 1) m 90 m = 1321.2 gm mol–1 molar mass of CxH2xOx = 12x + 1 2x + 16x = 30x 30x = 1321.2 x = 44 Hence the molecular formula is = C44H88O44
Problem 5: 30 ml of CH 3OH (d = 0.7980 gm Cm –3 ) and 70 ml of H 2 O (d = 0.9984 gm
cm–3) are mixed at 25°C to form a solution of density 0.9575 gm cm–3. Calculate the freezing point of the solution. Kf (H2O) is 1.86 Kg mol–1 K. Also calculate its molarity Solution: Weight of CH3OH (w1) = 30cm3 0.7980 gm/cm3 = 23.94 gm Weight of solvent (H2O) (w2) = 70 cm3 0.9984 gm cm3 = 69.888 gm 23.94 1000 m= = 10.7046 molal 32 69.88 Tf = Kf i molality, (for CH3OH, i = 1) Tf = 1.86 10.7046°C = 19.91°C Freezing point of the solution = 0– 19.91°C = –19.91°C Weight of solution = weight of solute + weight of solvent = 23.94 + 69.888 = 93.828 gm wt. of the solution 93.828 volume of the solution = density of the solution = = 97.99 ml 0.95751 23.94 1000 M (molarity) = mol lit–1 = 7.63 M 32 97.99
Problem 6: A complex is represented as CoCl3.xNH3. Its 0.1 m solution in aqueous solution shows Tf = 0.558° Kf(H2O) = 1.86 mol–1 K and assume 100% ionization and co–ordination number of Co(III) is six . What is the complex? Solution: Tf = i Kf m, 0.558 = 1.86 0.1 i 0.558 i= =3 0.186 or, i 3 indicates that complex ionize to form three ions since coordination number is 6 hence x=5 i.e., CoCl3.5NH3 [Co(NH3)5Cl]++ + 2Cl– 1 Cation 2 anions So, the complex is [Co(NH3)5Cl]Cl2
Problem 7: A solution comprising 0.1 mol of naphthalene and 0.9 mol of benzene is cooled until some benzene freezes out. The solution is then decanted off from the solid and warmed to 353 K, where its vapour pressure is found to be 670 torr. The freezing and normal boiling point of benzene are 278.5 K and 353 K, respectively. Calculate the temperature to which the solution was cooled originally and the amount of benzene that must have frozen out. Assume conditions of ideal solution. Kf for benzene = 5K kg mole–1. Solution: Molality of the resulting solution (i.e. after the benzene freezes out) can be determined on the basis Raoult’s law. (760 670) X naph 1000 760 m = 1.72 mol kg–1. X benzene 78 0.88 78
1000 Weight of benzene in the resulting solution = 0.1 = 58.1 g 1.72 Amount of benzene frozen = 0.9 78 – 58.1 = 12.1 g Tf = Kfm = 5 1.72 = 8.60 K Hence the temp to which the solution was cooled = 278.5 – 8.60 = 269.9 K
Problem 8: Find Ka, the ionization constant of tartaric acid if a 0.100 molal aqueous solution of tartaric acid freezes at –0.205°C. Assume that only the first ionization is of importance and that 0.1 m = 0.1M. Kf = 1.86 kg mol–1 K. Solution: Assuming that the tartaric acid be a monobasic as AH. It ionizes as AH A + H+ Initially conc. C 0 0 Conc. after dissociation C(1–) C C, C(1 ) C C C(1 ) Here, i = , where = degree of dissociation = = 1+ C C Molal concentration = 0.1 Tf = Kf Cm i 0.205 = 1.86 0.1 (1+) = 0.1 C C 2 C 0.1 2 [A ][H ] 0.1 Ka = = C(1 ) 1 Ka = = 1.11 10–3 [AH] 1 0.1 Ka = 1.11 10–3
Problem 9: The freezing point depression of a 0.109 M aq. solution of formic acid is –0.21°C. Calculate the equilibrium constant for the reaction, HCOOH (aq) H+ (aq) + HCOO– (aq) Kf for water = 1.86 kg mol–1 K Solution: HCOOH (aq) H+(aq) + HCOO– (aq) Initially moles C 0 0 Moles after dissociation (1–) C C C (1 ) C C C i = 1 + , 1 C Tf = Kf i Cm 0.21 = 1.86 (1+) 0.109 ( for dilute solution molality molarity) 0.21 1+ = = 1.0358 = 0.0358 = 0.036 1.86 0.109 2 [H ][HCOO ] C 0.109 (0.036) 2 Ka = = = = 1.41 × 10–5 [HCOOH] 1 0.964 Problem 10: The freezing point of a solution of acetic acid (mole fraction is 0.02) in benzene 277.4 K. Acetic acid exists partly as a dimer 2A A2. Calculate equilibrium constant for dimerisation. Freezing point of benzene is 278.4 k and (Kf for benzene is 5) Solution: 2A A2 1 0 initially moles 1– /2 moles after dimer is formed 1 2 i= = 1 – /2 1 XA = 0.02, XB = 0.98 xA 1000 0.02 1000 Molality of A in B = m X = = 0.262 mol kg–1 of Benzene B B 78 0.98 Since, Tf = Kf i molality 278.4–277.4 = 5 i 0.262 1 or, 1 = 5 i 0.262 , i = = 0.763, 1– /2 = 0.763 = 0.47 5 0.262 Hence the molality of A after dimer is formed = (1–) initial molality = (1 – 0.48) initial molality = 0.52 0.262 Molality of A2 after dimer is formed 0.48 = molality = 0.262 = 0.24 0.26 = 0.06288 2 2
A 2 0.06288 The equilibrium constant Keq = A 2 = (0.13624)2 = 3.39 kg mol–1
