SOLUTIONS 1.) The molarity of the solution containing 7.1 g of NazSOs in 100 ml of aqueous solution is (a)2M (1M (4) 0.05 M ‘Ans: Molarity=[Link] = given mass x 1000 x1000 =05M Vol. of solution(L) molar mass x vol.(ml) 142 x 100 2.) Which of the following statements is incorrect? (a) A solution in which no more solute can be dissolved at the same temperature and pressure Is called a saturated solution. (b) An unsaturated solution is one in which more solute can be dissolved at the same ‘temperature. (c) The solution which is in dynamic equilibrium with undissolved solute is the saturated solution. Ans: The maximum amount of solute dissolved in a given amount of solvent is its solubility. 3.) Which is an application of Henry’s law? (a) Spray paint (b) Bottled water (c) Filling up a tyre ( Ans: To increase the solubility of CO: in soft drinks and soda water, the bottle is sealed under high pressure 4.) Which of the following liquid pairs shows a positive deviation from Raoult’s law? (a) Water - Nitric aci (c) Water - Hydrochloric acid (d) Acetone ~ Chloroform ‘Ans: Positive deviations are shown by such solutions in which solvent-solvent and solute-solute interactions are stronger than the solute-solvent interactions. In such solution, the interactions among molecules becomes weaker. Therefore, their escaping tendency increases which results in the increase in their partial vapour pressures. In pure methanol there exists intermolecular H-bonding. On adding benzene, its molecules come between ethanol molecules there by breaking H-bonds which weaken intermolecular forces. This results in increase in vapour pressure. 5.) The relative lowering of the vapour pressure is equal to the ratio between the number of (a) solute molecules to the solvent molecules (c) solvent molecules to the total molecules in the solution (d) solvent molecules to the total number of ions of the solute.‘Ans: According to Raoult's law, the relative lowering in vapour pressure of a dilute solution is equal to the mole fraction of the solute present in the solution. Directions: Each of these questions contain two statements, Assertion and reason. Each of these questions also has four alternative choices, only one of which is the correct answer. You have to select one of the codes (a), (b), (c) and (d) given below. (a) Assertion is correct, reason Is correct; reason is a correct explanation for assertion. (b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion {c) Assertion is correct, reason is incorrect (d) Assertion is incorrect, reason is correct. 1.) Assertion: Molarity of a solution in liquid state changes with temperature. Reason: The volume of a solution changes with change in temperature. 2.) Assertion: If a liquid solute more volatile than the solvent is added to the solvent, the vapour pressure of the solution may increase l.e., Ps > Po. Reason: In the presence of a more volatile liquid solute, only the solute will form the vapours and solvent will not. 3.) Assertion: If one component of a solution obeys Raoult’s law over a certain range of composition, the other component will not obey Henry's law in that range. Reason: Raoult’s law is a special case of Henry's law 4.) Assertion: When methyl alcohol is added to water, boiling point of water increases. Reason: When a volatile solute is added to a volatile solvent elevation in boiling point is observed. 5.) Assertion: When NaCl is added to water a depression in freezing point is observed. Reason: The lowering of vapour pressure of a solution causes depression in the freezing point Read the following passage and answer the questions that follow: Solutions are homogeneous mixture of two or more substances. Ideal solution follow Raoult’s law. The vapour pressure of each component is directly proportional to their mole fraction if both solute and solvent are volatile. The relative lowering of vapour pressure is equal to mole fraction of solute if only solvent is volatile. Non-ideal solution form azeotropes which cannot be separated by fractional distillation. Henry's law is special case of Raoult’s law applicable togases dissolved in liquids. Colligative properties depend upon number of particles of solute. Relative lowering of vapour pressure, elevation in boiling point, depression in freezing point and osmotic pressure are colligative properties which depend upon mole fraction of solute, molality and molarity of solutions. (2) 50 mi of an aqueous solution of glucose (Molar mass 180 g/mol) contains 6,02 x 10” molecules. What is its molarity? Ans. 6.02 x 10% molecules > 1 mole of glucose 6.02 x 10”? molecules > 0.1 moles Molarity = 0.1/0.05 = 2M (2) Identify which liquid has lower vapour pressure at 90°C if boiling point of liquid ‘A’ and are 140°C and 180° respectively. Ans. ‘B’ will have lower vapour pressure because its boiling point is higher. (3) What type of azeotropes are formed by non-ideal solution showing negative deviation from Raoult’s law? Ans. Maximum boiling azeotropes. (4) Why meat is preserved for longer time by salting? Ans. Salt inhibits the growth of microorganisms by drawing out water from microbial cells ‘through osmosis 20% salt is needed to kill most species of unwanted bacteria, (5) For a 5% solution of area (molar mass 60 g/mol), calculate the osmotic pressure at 300 K (R 0821 L atm k%), Ans. TIv = nRT TIx 0.1 L = (5/60) x 0.0821 x 300 = 20.52 atm 1, State Henry's law, Ans: Henry's law states that “The partial pressure of the gas in vapour phase is proportional to ‘the mole fraction of the gas in the solution” 2. Define an ideal solution and write one of its characteristics. ‘Ans: Those solutions which obey Raoult’s law at all concentrations are called ideal solutions. Characteristic of an ideal solution: ‘There will be no change in enthalpy AHmx and volume change on mixing AVmx= 0, 3. Define osmotic pressure of a solution. ‘Ans: It is the external pressure which is applied on the solution side which is sufficient to prevent the entry of the solvent through semi-permeable membrane. 4, Define Colligative properties, ‘Ans: All those properties which depend on the number of solute particles in solution Irrespective of the nature of solute are called as colligative properties.mass of solvent (NHaCONH2) = 60 g mol? ’.0.25 mole of urea = 0.25 x 60=15g Mass of solution = 1000+15 = 1015g = 1.015 kg 1.015 kg of urea solution contains 15g of urea ’. 2.5 kg of solution contains urea =15/1.015 x2.5 = 37g 3.) Calculate the mass percentage of benzene (CcHs) and carbon tetrachloride (CCle) if 22 g of benzene is dissolved in 122 g of carbon tetrachloride, ‘Ans: Mass of solution = Mass of CeHs + Mass of CCls 12 g#122 g= 144g Mass % of benzene = 22/144 x 100 =15.28 % Mass % of CCle = 122/144 x 100 = 84.72 % 4,) Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride, a 1 1 i 1 1 ! 5. Give an example of gaseous solution and liquid solution each. ! 1 ‘Ans: Gaseous solution- Water vapour (Liquid in gas) 1 ' Liquld solution- ethanol dlssolved in water (Lqul ' 1 1 i ‘TWO MARKS QUESTIONS { 1 1 i ' 1 1.) H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the 1 1 solubility of H.S in water at STP is 0.195 m, calculate Henry's law constant. 1 1 ‘Ans: Solubility of H2S gas = 0.195 m 1 { 0.195 mole in 1 kg of solvent | ! 1kg of solvent = 100g ! 1000 H = =55.55 moles i ' 18 ' 1 1 1 0.195 ! 1 fgg 1 ' HS "0.1954 55.55 ! 1 1 H 0.195 1 = = 0.0035 i 55.745 | H ~ Pressure at STP = 0.987 bar I 1 Applying Henry's law, i ' Pas ~ Kus ! 1 1 ' > Ky Aas _ 0987 «op 7bar i H Xu,s 0.0035 i 1 1 1 1 4 2.) Calculate the mass of urea (NH2CONH,) required in making 2.5 kg of 0.25 molal aqueous 1 ! solution. ' 1 ‘Ans: 0.25 Molal aqueous solution to urea means that moles of urea = 0.25 1 t mole t 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 i 1 1 1 1 1 1 1 t 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ‘ :‘Ans: 30% by mass of Cts in CCla => 30 g CeHs in 100 g solution .1:10. of moles of CsHo("Cshe) = 30/78 = 0.385 (molar mass of CgH,~ 78g) no. of moles of CCI, (ecy,) = 2 = 0.455 a eye Celle Beg, + Nccy, 0.385 _ 0.385 0385+0.455 oa 458 Xocy™ | ~0.458=0.542 5.) Calculate the mass of ascorbic acid (vitamin C, CcHsOs) to be dissolved in 75 g of acetic acid to lower its melting point by 1:5°C, (Ks for CHsCOOH) = 3-9 K kg mot) Ans: Mass of acetic acid (Wa) = 75 g = 0-075 kg. Depression in freeing point (AT;) = 1-5°C = 15K Molar mass of ascorbic acid (Mp) = 6 x 12 + 8 x 1 +6 x 16 = 176 g mot Molal depression constant (K) = 3-9 K kg mol"! _ {176g mol“) x (15K) x (0-075 kg) _ (3-9K kg mol!) Ws 08 1) Calculate the mass of a non-volatile solute(molecular mass 40 g mol") that should be dissolved in 114 g of octane to reduce its pressure to 80%. ‘Ans: According to Raoult’s Law, Pa PS _ fa Ps mm Let Py = 1 atm, Ps = 0°8 atm ; P, - Ps = 0:2 atm ; Mg = 40 g mol!; Wy = i4g; Ma (Celis) = 114g mol = a= Ps) Mp x W, : Ps My = (O-2atm) , (40g mol) x (114g) _ “(0-8am) ~~ (i4gmor!) = 10082.) Two elements A and B form compounds having formula AB, and ABs. When dissolved in 20g of benzene (Cats), 1 g of ABs lowers the freezing point by 2.3 K whereas 1.0 g of ABs lowers it by 1.3 K. The molar depression constant for benzene is 5.1 K kg mol”, Calculate atomic masses of A and B, Ans: : 1 Using the relation, af, = 100% Ay *™2 wx AT, 1000 x 5-11 M, = * 2x23 M,. -1000x51x1 AM = S013 7 19615 gmor! Let the atomic masses of A and B are ‘p’ and ‘q’ respectively, Then molar mass of AB,=p+2q=110-87g mol" ...() And molar mass of AB,=p+4q= 196-15 g mol" ...(ii) Substracting equation (if) from equation (i), we get 2q =85.28 => q= 42.64 Putting q= 42.64 in equ. (i), we get P= 110.87-85.28 p=25.59 Thus, atomic mass of A=25.59 g mol! and atomic mass of B= 42.64 gmol! = 110-87 g mol 3) Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure of a mixture of 26.0 g of heptane and 35.0 g of octane?Ans: Molar mass of heptane (C,H,,) =7%12+16=100 gmol! Molar mass of octane (C,H,,) =8%12+18=114 gmol! Moles of heptane present in mixture 226-0 , 100 Moles of octane present in mixture 26 mol Mole fraction of heptane xj, ____026 0.26 + 0307 Mole fraction of octane, x, = (1 -0-458)= 0-542 Vapour pressure of heptane = xj x P® =0.458 « 105.2 kPa=48.18kPa Vapour pressure of octane = x)% P® = 0-542 « 46-8 kPa =25-36 kPa Vapour pressure of mixture =48-18+25-36=73-54 kPa 1) (i) State Kohlrausch law. (ii) Calculate the emf of the following cell at 298 K: ‘Al(s)/AV* (0.15M)//Cu?*(0.025M) /Cu(s) (Given E%(AP*/Al) = -1.66 V, Eo(Cu?*/Cu)=0.34V, log0.15=- 0.8239, log 0.025 = -1.6020) ‘Ans: (i) limiting molar conductivity of an electrolyte can be represented as the sum of the individual contributions of the anion and cation of the electrolyte. (ii) E°cell = E°cathode -E°anode = 0.34-(-1.66) = 2,00 V ocell ~0.059/n (log [Al3+]?/[Cu2+]") Heren=6 = 0.059/6 (log [0.15]? /[0.025]*) 2-0.059/6 ( 2log 0.15 ~ 3 log 0.025) 2~0.059/6 (-1.6478 +4.8062) = 2- 0.0311 = 1.9689V =0458 2.) On the basis of Eovalues identify which amongst the following is the strongest oxidising agent Ch(g) + 2e- > 2Cr E°= +1.36V, MnO. + 8H" + Se" > Mn?*+4H.0 €°= +151 V CrO7? + 14H" + Ge" > 2Cr* + 7H2O E? = +1.33 V(ii) The following figure, represents variation of (Am ) vs Vc for an electrolyte. Here Am is the molar conductivity and c is the concentration of the electrolyte. 300 194 1486 1482 1470 0 005 010 015 020.025 030 035 nett) a) Define molar conductivity b) Identify the nature of electrolyte on the basis of the above plot. Justify your answer. ¢) Determine the value of An° for the electrolyte. d) Show how to calculate the value of A for the electrolyte using the above graph. Ans: (i) MnO (ii) (2) Molar conductivity of a solution at a given concentration is the conductance of the volume V of solution containing one mole of electrolyte kept between two electrodes with area of cross section A and distance of unit length. (b)Strong electrolyte, For strong electrolytes, /m increases slowly with dilution = 150 Scmmol (d) A= slope (149 - 147.8/ 0.010-0.022) = 100 Sem’mot?