UID SOLUTIONS SOLUTION A homogencous mixture of two or more pure substances whose composition may be altered within certain limits is termed as solution. Characteristics of Solution Beds @ _Itishomogencous in nature, yet retaining the properties ofits constituents. Gi) This made of two parts i.e. a solute and a solvent. depends on physical state of the components. (@)__Thecomponent which has the same physical sta in pure form as the solution is. called solvent and the other is called solute. Example, in case of solution of sugar and ‘water, sugar is the solute and water is solvent. Ww Which component to take as solute and which component to take as solvent (iv) _ If both the components have same state as the solution, the one component which is in excess is called solvent and the other is called solute. Example, alcohol in water, benzene in toluene cic, Types of ‘Solution Water vapour in air, mist. Sublimation of a solid into a gas, smoke storms. CO, gas dissolve in water (acrated drink), soda water. Mixture of miscible liquids ¢.g. alcohol in water. Salt in water, sugar in water. Adsorption of gases over metals, hydrogen over palladium.| Mercury in zine, mercury in gold ic. all amalgams. Homogencous mixture of two or more metals alloys) e.g. copper In gold. zinc In copper. Gas Gas Gs Liquid Liquid Liquid Solid Solid Solid Which of the above types can never have a heterogenous mixture. ?METHODS OF EXPRESSING THE CONCENTRATION OF A SOLUTION ‘There are many ways of expressing the concentration of a solution. These methods are as follows- Students should memories all the formulas and should be comfortable in converting one concentration term to another, Comment which of the following concentration terms are temperature dependent and which are temperature independent. ’ Mass percentage : It may be defined as the number of parts by mass of solute per hundred parts by mass of solution. For example. a 5% (by mass) solution of sugar in water means that 100 g of solution contain 5 g of sugar. B® Massof any component x100 Mass Percentage = Totelmase (i) Volume percentage : Itmay be defined as the numberof parts by volume of solute per hundred pars by volume of solution. <> For example, a 25% (by volume) solution of ethyl alcohol means that 100 cm?. of the solution contain 25'¢m> of ethyl alcohol and 75 cm? of water. Volume of component x100 ‘Volume percentage ~ tora] volume of solution (ii) Mass fraction : Be IFW, is the mass of component A and Ws the mass of component B in the solution, then the mass fraction of component A and B is written as MW, Mass fraction of A= Ww, Wy : Mass fraction of B= Wy w, (iv) Mole fraction Mote fraction may be defined as the ratio of the number of moles of one component to the total number ‘of moles of all the components (i.e. solute and solvent) present in the solution. Let us suppose that a sotution contains the components A and B and suppose that a gram of A and b gram of B are present in it. Let the molecular masses of A and B are M,, and Mx respectively. Then number of moles of A are given by my = ig» 4 Bet: ” o) Beh: Bef and number of moles of B are given by ng = ic ‘Total number of moles of A and B= ny +g Mole fraction of A, X_ = =~ A mathe Mole fraction of B, Xp = 58 ‘Sum of mole fractions of all components is always one. a Tatts * tarts ‘So if mole fraction of one component of a binary solution is known say Xg. then the mole fraction of X,=1-Xp. ie. X,+Xpe Tt may be noted that the mole fraction is always independent of the temperature. Mole percent Mole percent is the number of moles of a component in 100 mole of the solute and solvent. Mole percent = Mole fraction x 100 Example. for a solution containing 8 moles NH, and I2 moles of H,0. . Stole 2 Mole fraction of NH. Xyi1y"" [moles + Smokes” § Mole pérezht of NH, = *"100 = 40 mole % Parts per million (ppm) ‘When a solute is present in trace amounts, its concentration is expressed in parts per million. It may be defined as the number of parts by mass of solute per million parts by mass of the solution. Parts per million (ppm) ~ ,ME*2°SSH#S- x 106 Molarity (M) Molarity of a solution is defined as the number of moles of the solute dissolved per litre of the solution. Itis represented by capital M. Mathematically. | Mass of the solution in gram perlitre Molarity (M) = “““Molecularmass of thesolute A solution having molarity “one” is called molar solution. Tt may be remembered that both normality as well as molarity of a solution changes with change in temperature.(viii) 2 Bets ®) Molality (mn) - Molality of a solution may be defined as the number of moles of the solute dissolved in 1000 gm (1 kg) of the solvent. Itis represented by small ‘m*. Mathematically | __Massof thesolutein gram per kg of solvent Modality (m)= Molecular massof thesolute A solution containing one mote of solute per 1000 gm of solvent (1 kg) has molality equal to one and is called molal solution. Molality is expressed in units of moles per kilogram (mol kg“). The molality of a solution does not change with temperature. Normality : Normality ofa solution is defined as the number of gram equivalent of the solute dissolved per litre ‘of the solution. It is represented by N. Mathematically. ___ Massof solutein gram perlitre Normality N = “Eouivalentmass of thesolute A solution having normality equal to one is called "normal solution”. Such a solution contains one gram equivalent of solute perlite of solution. A seminormal solution contains 0.5 gram equivalent of solute. ‘A decinormal solution contains 0.1 gram equivalent and a centinormal solution contains 0.01 gram equivalentof solute per litre of solution. . Mass of the solution x 1000 or Normality = ecivalent mass of the solute x V Where Vis the volume in milliliter. Formality (F): It may be defined as the number of gram formula masses of the ionic solutes dissolved per litre of Mass of the: gram per litre Formality (F) = “Formula mass of the solute ‘Commonly, the term formality is used to express the concentration of the ionic solids which do not exist as molecule but as network of ions.Mlustration 1. A storage battery contains a solution of H,SO, 30% by weight. Find out (Molality (i) Molarity (ii) Normality (iv) Mole fraction of H,SO, (Given density of solution = 1.2 grv/em') Sol, 30% by weight => W_._ =30 gm, W___ = 100.gm, WL, =70 gm ra 2 -0306 ‘ates Og Patven ~ TR = 3.889 Paster *1000 _ 0,306%1000 © Motality= “Yr 7 437m Pyne *1000 0.306%1000 @ Molarity= “y= 199 =3.67M 12 Wares 1000 _ 30%1000 wo Normality = 5S = 100 =7-34N setae Vedteion = 4D 12 Alematively Normality = n-factor x Molaity =2x3.67= 734 - 0306 & ow, Mag” )0306+3.889 "097 Exercise Ll Ina solution mole fraction of solute is 0.2. Find out molality of solution. (Given molar mass of sobute 40 gmmole') Ans. 13.89m 2 14.2. gmNa,SO, is dissolved in 400 mL water. Find out (i) formality (ii) Normality of solution. Ans. 0.25, 0.75 SOLUBILITY OF GASES Weare familiar that gases are completely miscible with each other. Gases also dissolve in liquids and. solids. For example, soda-water contains carbon dioxide dissolved in water under high pressure. Oxy- ‘genis sufficiently soluble in water to allow survival of aquatic life in lakes, rivers and oceans. An example of dissolution of a gas in a solids the solubility ofhydrogen gas in palladium.7 ‘The solubility ofa gas in a liquid is determined by several factors. In addition to the nature ofthe gas and the liquid, solubility of the pas depends on the temperature and pressure ofthe system. The solubility of a gas ina liquidis governed by Henry's Law which states that the solubility ofa gas in a liquids directly proportional tothe pressure ofthe gas. Dalton, a contemporary of Henry, also concluded independently that the solubility ofa gas ina liquid solution sa function of the partial pressure of the gas. If we use the moke fraction of the gas in the solution sameasure ofits solubility, then: Mole fraction of the gas in a solution is proportional to the partial pressure of the gos. Or, partial pressure of the gas in solution = K, x mole fraction of the gas in solution. Here K, is Henry's law constant or p = K, x". If we draw a graph between partial pressure of the gas versus mole fraction ofthe gas in solution, then we should get aplot of the type as shown in figure. Piva pesmue oC err $ oie 00x Mode traction of HCI in te ton in orbhexane Figure : Experimental results for the solubility of HCl gas in cyclohexane at 293 K. The slope of the line is the Henry's Law constant (K,) Different gases have different k,, values at the same temperature. This suggests that K, isa function of the nature of the gas. Tt is obvious that the higher the value of K,, at a given pressure, the lower is the solubility of the gas in the liquid. It has been observed that K,, value for both N,, and O, increases with increase of temperature indicating that solubility of gases de- creases with increase of temperature. It is due to this reason that aquatic species are more comfortable in cold waters rather than warm waters. Henry's law finds several applications in industry and explains some biological phenomena. Notable among these are: To increase the solubility of CO, in soft drinks and soda water, the botle is sealed under high pressure. ‘Tominimize the painful effects accompanying the decompression of dcep sca divers, oxygen diluted with less soluble helium gas is used as breathing gas. In lungs, where oxygens present in air with high partial pressure, haemoglobin combines with oxygen to form oxyhaemoglobin. In tissues where partial pressure of oxygen is low, oxyhaemoglobin releases ‘oxygen for utilization in cellular activities.Limitations of Henry's Law : For Henry's law to be applicable (Gas should not react with solvent. (ii) Gas should not associate or dissociate in solution. (Gil) This laws not applicable for highly concentrated solutions. Mustration 1, LEN, gasis bubbled through water at 293K, how many millimoles of N, gas would dissolve in | litre of water, Assume that N, exerts a partial pressure of 0.987 bar. Given that Henry’s law constant for N, at 293 K is 76.48 k bar. Sol. _Thesolubilty of gasis related to its mole fraction in the aqueous solution. The mole fraction ofthe gas in the solution is calculated by applying Henry's law. Thus, Ky, = Pe me ET “2 Ky 76480bar {As 1 litre water contains 55.5 mol oft, therefore, ifn represents number of moles of N, in solution, nmol a s =——_—__s—__8}.29: *s " Finale 55.5mal "555 71 29*10 ‘Thus, n= 1.29 « 10** 55.5 mol = 7.16 « 10“mol 29x10 4 1000m mol =7.16« 104 mol x 9) = 0.716 mmol Exercise 1. Henry's law constant for oxygen and nitrogen dissolved in water at 298K are 2.0 10" Pa and 5.0 «10° Pa, respectively. A sample of water at a temperature just above 273 K was equilibrated with air (20% oxygen and 80% nitrogen) at 1 atm. The dissolved gas separated from a sample of this water and then dried. Determine the composition of this gas. ‘Ans. Amount percent of O, = 38.27%, Amount percent of N, = 61.73% Phase Diagram of water The lines represent simultancous valucs of pressure and temperature at which two phases may be present at equilibrium. At the temperatures and pressures that lic on the line OA, liquid water and its. ‘vapor are at equilibrium. Along the line OB, ice and its vapor are at equilibrium, while the sets of temperature and pressure at which both ice and liquid water are in equilibrium lie along OC. Only at the pressure and temperature corresponding to the triple point (0.01°C, 4.588 torr) are ice, water and ‘Water vapor simultaneously present at equilibrium. The areas between the curves represent temperanures. and pressures at which only one phase can exist.VAPOUR PRESSURE OF SOLUTION AND RAOULTS LAW o Vapour Pressure Ifa sample of water in its liquid phase is placed in an empty container, some of it will vaporize to form gaseous of water. This change is called evaporation. We can write an equation for evaporation ‘occurring spontancously as if it were as chemical equation : H,0() > H,0(8) Kp = Puo where Kp =cquilibrium constant Pye ™ vapour pressiire of H,OXg) ‘The pressure exerted by the vapour (molecules in the | vapour phase) over the surface of the liquid at the i } equilibrium at given temperature is called the vapour pressure ofthe liquid. Praga ee was se Is vapour pressure dependent on surface area and shape of the container? ? Factors affecting vapour pressure (a) Ternperature : Vapour pressure «x Temperature + ‘The temperature at which the vapour pressure of the i liquid becomes cqual to the atmospheric pressure is called its boiling point. i Tepe Con you guess what will be the equation relating vapour pressure and ‘temperature.(b) Nature of liquid: 1 ‘The strength of imermolecular forces acting between molecules Forexample, CCI, has higher vapour pressure because of the weak intermolecular forees acting between its molecules than water which has stronger intermolecular forces acting between water molecules of volatile iquid has lower boiling point than a non-volatile liquid. ‘Vapour pressure of liquid a (i) Raoult’s Law for volatile solute : For a two component solution A (volatile) and B (volatile) the ‘vapour pressure of solution is given by Vapour pressure of solution = Vapour pressure of solvent in solution + Vapour pressure of solute. According to Raoult's Law partial pressure of a component is equal to its mole fraction in solution multiplied with partial pressure in pure state Thus P, = PY,X, P*,= vapour pressure in pure state of A X,=Mole fraction of A in solution P, = Partial pressure of A in solution Beh: Total vapour pressure of solution P= /P*,X, + P*pX, XT X20 Wn ee X20 Xt Htustration ON 1, A125°C;'the vapour pressure of methyl alcohol is 96.0 torr. What is the mole fraction of CH,OH ina solution in which the (partial) vapor pressure of CH,OH is 23.0 torr at 25°C? P. Xen = pet Be Sol. on = Bo 5g 7024 Pcuon — ee Exercise ea 1. The vapour pressure of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal solution is prepared at the same temperature by mixing 60 g of ethanol with 40 g of methanol. Calculate total vapour pressure of the solution. Ans, 66.13mmHg 5 i i ! | | i to the liquid (solvent). It is found that the vapour pressure of the solution is less than that of the pure solvent. This is due to the fact that the solute particles occupy a certain surface area and evaporation takes place from the surface only. The particles ofthe solvent will have a less tendency to change is place from the surface only. The particles of the solvent will have a less tendency to change& (P*,-P,)isthe lowering of vapour pressure whereas into vapour i.e. the vapour pressure of the solution will be less than that of the pure solvent and it is termed as lowering of vapour pressure. Fora solution of non-volatile solute with volatile solvent. P=P, X, P= vapour pressure of solution Pa Py Xy P, = vapour pressure of solvent If mole fraction of solute is Xp, then X,, = mole fraction of solvent and P® = vapour pressure of pure solvent. X,y+Xpol Pa = PP, (I-Xp) = Pty — PyXp RP, Xp> ye is called relative lowering of vapour pressure. ‘Vapour pressure of pure solvent ~ Vapour pressure of solution Mole fraction of solate = ‘vapour pressure of solvent Mlustration : Ba ‘The vapour pressure of pure liquid solvent A is 0.80atm: When a nonvolatile substance B is added to the solvent its vapour pressure drops to 0.60 atm. What is the mole fraction of component B in the solution? 025 " § "¢ Ans. ‘Two liquids A and B form an ideal solution at temperature T. When the total vapour pressure above the solution is 400 tor, the mole fraction ofA in the vapour phase is 0.40 and in the liquid phase 0.75. What are the vapour pressure of pure A and pure B at temperature T? Pj, = 213.33 torr, P= 960.0 torr ‘The vapour pressure of pure water at 25°C is 23.76 torr. The vapour pressure of a solution containing 5.40 g of a nonvolatile substance in 90.0 g water is 23.32 torr. Compute the molecular weight of the sohue, 57.24 g/mol ‘What weight of the non-volatile solute, urea needs to be dissolved in 100 g of water, in order to decrease the vapour pressure of water by 25%? What will be the molality ofthe solution? 111.1g, 18.52molal<> & @) ‘So Raoult's law can also be defined as “For a solution containing non-volatile solute, at a particular temperature. The relative lowering of vapour pressure is equal to mole fraction of the solute”. pressure of solutions having non volatile solute will always be less Vopour than that of solvent, however pressure of solutions with volatile Solute may be more or less than hat of pure solvent ‘Types of Solutions (a) Ideal Solution : An ideal solution may be defined as the one which obeys Raoult’s law over all ‘concentration ranges ata given temperature. The total vapour pressure of an ideal solution containing. liquids A and Bis given by the following equation. PHP, +Py =PIX, + PX In an ideal solution of two components A and B, all attractive forces betwees!A and B molecules or ‘between A and A molecules or between B and B molecules (A-B, A~Aand B=B) must be identical so that the escaping tendency of an A or B molecule is independent of whether itis surrounded by A. molecules, B, molecules of varying proportions of A and B molecules. The escaping tendency of pure liquid Ain solution remains the same: Similarly the escaping tendency of B remains the same. Liquids {form ideal solution only when they have nearly same molecular size and related constitution so that they have simitar molecular environmentin the pure state as well 2s in solution. A perfect ideal solution is rare ‘but many liquids form nearly ideal solution. Liquid heptane and hexane form an ideal solution because the interaction between a hexane molecule and another heptane molecule is the same 2s the interaction between two heptane molecules other examples of ideal solutions are: > benzene + toluene, chlorobenzene + bromobenzene: hy cit bromide» ethy iodide: n-butyl chloride + n-butyl bromide ethyl alcohol + methyl alcohol Conditions for forming ideal solution: 1 2 3 ‘Two liquids on mixing form an ideal solution only when both have similar structures and polarity so that they have similar molecular environment. both have similar molecular sizes, both have identical intermolecular forces. (®) Non-tdeal solutions : Solutions which do not obey Raoult’s law over all concentration ranges at ‘constant temperature are called non-ideal solutions,Distinction between ideal & non ideal solutions Ideal solution ‘Non Ideal solution They obcy Raoult’s Law They donot obey Raoult’s Law AH, ay =0= noheatis AH any # 0 = heat is absorbed absorbed or released during or released during dissolution dissolution AV amg =0=> the total volume AV cane #0 => the total volume of the solution is equal tothe sum of the | of the solution is not equal to the sum of the volume of the pure liquids mixedtoform | volume of the pure liquids mixed to the solution formthe solution. Inideal solution P,=P,°X,, In non ideal solution P, # P,'X,. ‘Components of ideal solution can be separated in pure form by fractional ésillation ‘Types of non-ideal solutions (1) Nonideal solutions showing positive deviation (ll) Nonideal solutions showing negative deviation, © —_Nom ideal solutions showing pesitive deviation Condition for forming non-ideal solution showing positive deviation from Raoult’s law. ‘Two liquids A and B on mixing form this type of solution when 1.“ A—Batractive force should be weaker than A—A and B—B attractive forces. 2. *A’and“B*have different shape, size and charater. 3. ‘A’and “B*escape easily showing higher vapour pressure than the expected value. Example: “2h acetone + ethanol acetone + C5, water + methanol: water + ethanol: CCI, + toluene: CCl, + CHCI,: ‘acetone + benzene: Ci, + CH,OH: cyclohexane’ ethanol Graphical representation of vapour pressure of non-idcal solution showing positive deviation(1) Non ideal solutions showing negative deviation. Condition for forming non-ideal solution showing negative deviation from Raoult’s law. ‘Two liquids A and Bon mixing form this type of solution when 1, A—Bamtractive force should be greater than A—A and B—B attractive forces. 2. ‘A’and BY have different shape, size and character, 3. Escaping tendency of both components ‘A’ and ‘B"is lowered showing lower vapour pressure than expected ideally. Example: Zp acetone + aniline: CH,OH + CH,COOH: chloroform + diethyl ether, acetic acid + pyridine: a chloroform + benzene H,O + HNO,: water + HCl e an, acetone + chloroform: cl —c—n O=C. 4 ‘en, Graphical representation of vapour of non-ideal solution showing negative deviation Vapour pressure Pa < Pa’ Xq3 Px + Pat Pa_ vapours (Dalton's law) EOE@POPMOG) yom mole fraction oA i vapour phase ¥,~ mole fraction of B in Vapour phase Wy solution (Raoukt's law) X, = mole fraction of A in liquid phase X= mole fraction of B in liquid phase (%+%=) FromRaoult’slaw P=P2X,+PzX, =PX,and Py From Dalion's aw, Partial pressure = Mole fraction x Total pressure ForA P,=y,*P =PiX, PRX = y,- Xa oll) ‘Similarly PBX, ae 2) Above formula is used for calculation of mole fraction of B in vapour phase i = Peya , Pxyp _ onadting X,+X,= “HA + az ' ae + Rist‘Above formula is used to calculate total vapour pressure when mole fractions are given in vapoure phase fraction are given in liquid phase Pp P=PsX, + PgX, => This formula is used to calculate total pressure when mole <> & to uA pum fraction are given in vapour phase ‘Thus, in case of ideal solution the vapour phase is phase is richer with more volatile component ie., the one having relatively greater vopour pressure. + * = This formula is used to calculate total pressure when mole Mlustration £ ‘The vapour pressures of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal solution is formed at the same temperature by mixing 60 g of ethanol with 40 g of methanol. Calculate the tale presar ote seiton andes acon of meting No. of moles of ,H,0H = 2 Fa 71.304, No. of moles of CH, ou- 2 =125 *X,' of ethyl alcohol = =0.5107 Taos 1.25 °X,' of methylalcohol= 7554 7 95 70.4893 Partial pressure of ethyl alcobol=X,.P°=0.5107 x 44.5 =22.73 mm Hg Partial pressure of methy! alcohol = X, P,' = 0.4893 * 88.7= 43.40 mm Hg ‘Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg Partial pressure of CHj0H — 43.40 Mole fraction of methyl alcohol in the vapour = Fo .3p eB =0.6563 Exercise i R Ans. ‘At 90°C, the vapour pressure of toluene is 400 torr and that of o-xylene is 150 torr, What is the ‘composition ofthe liquid mixture that boils at 90°C, when the pressures 0.50 atm? What isthe composition of vapour produced? 92 mol% toluene; 96.8 mol % toluene For an ideal binary liquid solution with P; > Pj, which relation between X,, (mole fraction of A in liquid. phase) and Y (mole fraction of A in vapour phase) is correct? XX, WY, %p oy xs aa oysx oOCOLLIGATIVE PROPERTIES >The properties of dilute solutions containing nonvolatile solute, which depends upon relative number of solute and solvent particles but do not depend upon their nature are called colligative properties. Some of the colligative properties are (i) Relative lowering of vapour pressure i) Elevation in boiling point (ii) Depression in freezing point; and” (Gv) Osmotic pressure. Factors that Affect the Colligative Property : The number of solute particles in solution. To be more ‘accurate, the colligative property depends upon the fraction of solute and solvent particles in solution. ay ‘Nature of the solvent (2) _ Independent of the nature of the solute e) Extent of association and dissociation of solute particles in solution. @ Relative Lowering of Vapour Pressure ‘As shown earlier the mathematical expression for relative lowering of vapour pressures as follows ar . 77 Xp™ mole fraction of solute AP = P*, — P, = lowering of vapour pressure. P, = vapour pressure of pure solvent Molecular mass of non-volatile Substance can be determined from relative lowering of vapour pressure RP Wa My Pe WaT My + Wye For dilute solution Wp/Mg We ”- Mlustration 1. Onemole of anon-volatile solute is dissolved in two moles of water. The vapour pressure ofthe solution relative to that of water is «23 @yu3 @12 32 Pp -P, P, Sol. Fist —Frctoee =| (mole fraction of solute in solution) Or ry, Pann 2S abetAns. ‘The vapour pressure of water is 17.54 mm Hg at 293 K. Calculate vapour pressure of 0.5 molal solution of a solute init. 1738 Pressure over ideal binary liquid mixture containing 1O moles each of liquid A and Bis gradually decreased isothermally. If P2 =200 mm Hg and Pg =100 mm Hg. find the pressure at which half ofthe liquid is converted into vapour. (A)1SOmmHg —(B)166Smmiig —(C)133mmHHg —(D) 141.4 mmilg @ Elevation in Boiling Point ‘The boiling points clevates when a non-volatile solute is added to a volatile solvent. Which occurs duc to lowering of vapour pressure. The boiling point of a liquid may be defined as the temperature at which its vapour pressure becomes equal to atmospheric pressure. ‘So when a non-volatile solute is added to a volatile solvent results lowering Of vapour pressure and consequent elevation of boiling point where Ty = boiling point of solution Elevation in boiling point Itis found that elevation of boiling point is directly proportional to the number of moles of the solute in given amount of the solvent(m). aT, =m aT, = Kym ‘Where ‘mis the molality of solution. ‘Where K, is ebullioscopic or boiling point elevation constant. When molality ofthe solution is equal to one. Then at, = K, Hence mola! elevation constant ofthe solvent may be defined as the elevation in its boiling point when ‘one mole of non-volatile solute is dissolved per kg (1000 gm) of solvent. The unit of K, are K kg. mot! We 1000 Because molality of solution m= yt. wy,1000 x Wa - 1000 - So at, =k, We ow, Mg~ “at, «Wy Where W, = mass of solvent, We = mass of solute, M, = Molar mass of solvent, Mp = Molar mass of solute. _ Ky= aS » ie ssseee3), where R is molar gas constant, , is the boiling point of the solvent on Kelvin scale and L, the latent heat of vaporization of solvent in calories per gram. 2x(3737° 1000%540 If energy is taken in joule then use R = 8.314 JK+ mole* Energy is taken in calorie then use R= 2 cal K* mole Forwater y= =0515 K-kg/mol Mlustration 1, An aqueous solution of glucose boils at 100.01°C. The molal elevation constant for water is 0.5K mot! Kg. The number of molecules of glucose in the Solution containing 100 g of water is (A) 6.023 x 10 (B)6.023 x 107 (C) 12.046 x 10 (D) 12.046 x 10 Ans. (C) AT, _ 0.01 Sol AT,=K,.m Or m= —*=—— = 02moleKg" of water K, 05 So, the number of mokes of glucose in 100 g of water = oe =0,002 moles of glucose = 0,002 x 6.023 x 10° = 2 x 6.023 x 10° Exercise 1. Estimate the boiling point ofa solution of 25.0g of urea NH CONH, phis 25.0g of thiourea NH,CSNH, in 500g of chloroform, CHCI,, The boiling point of pure chloroform is 61.2°C, K, of chloroform = 3.63 Km. Ans. 66.645°C 2. Calculate the molal elevation constant, K, for water and the boiling point of 0.1 molal urea solution. Latent heat of vaporisation of water is 9.72 kcal mol"! at 373.15 K. Ams. K,= 0.512 kg mol K", T, = 373.20KDepression in Freezing Point ‘The freezing point of a pure liquid is fixed. Ifa non-volatile solute is dissolved in a liquid the freezing point of the solution is lowered. The freezing point is that temperature at which the solvent has the ‘same vapour pressure in two phases liquid solution and solid solvent. Since the solvent vapour pressure in solution is depressed. Its vapour pressure will become equal to that of the solid solvent at lower temperature \T, = Tp Ty Itis (ound that depression in freezing point s directly proportional to the number of moles ofthe solute iven amount of the solvent(m). Hence ATyam AT, = Kym Where m = molality of the solution. K,= molal depression constant ‘When molarity (m) ofthe solution is one. then ATr= Ky Hence molal depression constant or molal cryoscopic constant may be defined as “the depression in froezing point when one mole of non-volatile solute is dissolved per kilogram (1000 gm) of solvent” and molar depression constant is defined as “the depression in freezing point when one mole of non- volatile solute is dissolved per litre (1000 ml) of solvent.” ‘The molecular mass of the non-volatile solute may be calculated by the use of following mathematical equation 2g 1000 xa ‘Where W,=mass of solvent, Wy = mass of solute, M, = Molar mass of solvent, My = Molar mass of solute. Determination of K, of solvent K, ischaracteristic ofa particular solvent andcan be calculated from the thermodynamical relationship. -Ae Ks" Feo, wne3) ‘where T, is the freezing point of solvent in absolute scale and L, the latent heat of fusion in calories per ‘gram of the solvent. For water, k= 0.002 (273)" 80 1.86 K-kg/mole Tf energy is taken in joule then use R = 8.314 JK mole" Energy is taken in calorie then use R= 2 cal K' mole?K, . Ky for various Solvents Antifreeze solutions - Water is used in radiators of vehicles as cooling liquid. If the vehicle is to be used at high altitudes where temperature is sub-zero, water would freeze in radiators. To avoid this problem. a solution of ethylene glycol in water is used in radiators which will lower the freezing point lower than zero. Mlustration ‘Whats the percent by mass of iodine needed to reduce the freezing point of benzene 10 3.5°C? The freezing point and cryoscopic constant of pure benzene are 5.5°C and 5. 2 Kimrapecely. Sol AT,=T$-1,-K,.m 55°C -3.5°C =5.12%m 2 = <7. =0.39mobl m= 59 7039ma + Mass of iodine needed for 100g f benzene = m x molecular mass of iodine |, =0.39 molcg « 254 g/mol = 99.06 pkg + 1000g +.99.06g solition contains 99.06 1, “ 99.062 x100 100g soluti 2D6Ex10° 9.01% 0g solution conins Exercise 1. Theclemenss X and ¥ form compounds having molecular formula XY , and XY,,, When dissolved in 20 gm of benzene, | gm XY, lowers the freezing point by 2.3°, whereas | gm of XY , lowers the freezing point by 1.3°C. The molal depression constant for benzene is 5.1. Calculate the atomic masses of X and Y. Ans x=256,y=426 2. Calculate the amount of ie that will separate out of cooling a solution containing 50g of ethylene glycol in 200 g water to -9.3°C. (K, for water = 1.86 K mol“! kg) Ans. 38.71g (iv) Osmotic Pressure (2) Osmesis : Spontancous flow of solvent molecules through a semipermeable membrane from a pure solvent to the solution (or from a dilute solution to a concentrated solution) is termed as osmosis.(b) Osmotic Pressure : ‘When a solution is separated from the pure solvent with the help of a semipermeable membrane. There ‘occurs the flow of solvent molecules from the pure solvent to the solution side. The flow of solvent ‘molecules from a region of highcr concentration of solvent to the region of lower concentration of solvent és termed as the phenomenon of osmosis. This also happens when two solution of different concentra- tions are separated by a semipermeable membrane. Asa result of osmosis a pressurc is developed which is termed as osmotic pressure. It is defined in various methods. (1) The excess hydrostatic pressure which builds up as a result of osmosis is called osmotic pressure. (2) Theexcess pressure that must be applied to the solutio Side to prevent the passage of solvent into it through a semipermeable membrane. GB) Osmotic pressure of a solution is equal 10 the negative pressure which must be applied to the solvent in order to just stop the osmosis. (4) The osmotic pressure of d S6lution may be defined as the extra pressure which should be applied 16 the solution to increase the “chemical potential of solvent in solution equal tothe chemical [potential ofthe pure solvent at the same temperature. (©) Theory of Dilute Solutions : The osmotic pressure of a dilute solution was the same as the solute ‘would have exerted if it were a gas at the same temperature as of the solution and occupied a volume ‘equal to that of the solution. This generalization is known as Van"t Hoff theory of dilute solutions. ‘The osmotic pressure is a colligative property. So the osmotic pressure is related to the number of moles of the solute by the following relation xV= aRT a x= GRT (. R= CRT Here C = concentration of solution in moles per litre; R= solution constant; ‘T= temperature in Kelvin degree; = number of moles of solute; and ‘V=volume of solution. ‘This equation is called Van't HofT’s equation. QO 1 (If solute particles undergo Dissociation in the solution) <1 (If solute patticles undergo Association in the solution) (i) Application of Van't Hoff Factor: (a) Caletilation of Degree of Dissociation of solute particles: A =m No. of moles dissolved I mol oo No. of moles after dissociation I-a Total number of moles present insolation = (1 —a)+na , - Moles of solute actually present in solution Ven 1 Hof factor, | Moles of solute dissolved = CoO (a1) of a= int 1 m1 (b) Calculation of Degree of Association of solute particles: Letn moles of the solute, A, associate to form (A), If a is the degree of association. mw = A No. of moles dissolved I mol 0 No ofmolesafterdissociation Ia an ‘Total number of moles present in solution = (l-a)+a/nMlustration L ‘Molal clevation constant K, for water is 0.52 K/m. 0.1 molal solution of NaCI will boil at (A) 100.52°C (B) 100.052°C (C) 101.04°C (D) 100.104°C Ans. (D) Sol Ifvant off factors, then AT, =iK,.m (forNaCli=2) =2« 0.52. 0.1 =0.104. And, so the boiling point of solution will be 100.104°C. 2. Assohution is prepared by dissolving 26.3g of CdSO, in 1000g water. The depression in freezing point of solution was found to be 0.284K. Calculate the Van't Hoff factor. The cryoscopic constant of water is 1.86K kg solvent mot - solute. 1.21 Molecular mass CdSO, = 112.4 +32 +4 x 16 = 208.4 g/mol ee . Mass CdSO, Molality CdSO, = ‘ojecular mass CdSO, x Mass solvent in kg 263g = =0216m (208-4¢/moty>{ 1000}, 0.284K 86K /mx0.126m “121 1. A decimolar solution of potassium ferrocyanide is 50% dissociated at 300K. Calculate the osmotic pressure of the solution. (R=8.314 JK-! mol!) 7.482 10° Nm? Ans. 2. 1.2% solution (w/v) of NaC is isotonic with 7.2% solution (w/v) of glucose. Calculate degree of ionization and Van't Hoff factor of NaCl. Ans. 0: 9S 3. ‘0.001 molal solution of a complex [MA,] in water has the freezing point of -0.0054°C. Assuming 100% ionization of the complex salt and K, for H,O= 1.86 k.m"', write the correct representation for the: ‘complex. (IMA) (B)[MA,JA (CIMAJA, —-(D)[MAJA,Solubility of gases (i) Effect of temperature (ii) Effect of pressure THE ATLAS Liquid Solutions 1, Vapour Pressure 2. Raoult’s law (i) When volatile solute is added (a) When solute and solvent; both are miscible (b) When both are immiscible (ii) When non-volatile solute is added. 3. Condensation of vapours of solution 4, Ideal and non-ideal solutions 5. Azeotropic mixtures Colligative propertics (C.P.) 1. Introduction 2. The various CP. (i) Lowering of VP. (2) Determination of molar masses (b) It's measurement i) Boiling point elevation (iii) Depression in freezing point (iv) Osmotic pressure (a) Osmosis (b) Reverse osmosis {€) Isotonic solution 3.Van't Haff factor, Where the solute associates or dissociates in solution.SOLVED EXAMPLES OBJECTIVE Q.1 214.2 gramof sugar syrup contains 34.2 gram of sugar. Calculate (i) molality of the solution and (ii) mole fraction ofthe sugar inthe syrup ~ (A)0.55Sm, 0.0099 (B)0.455m,0.0110 (C)0.355m,0.0199 (D)None ofthese ‘Ams. (A) M2 wz Sol @) — Massof sugar=34.2 gram. Number of moles of sugar ot mass "agg 70.1 Mass of water = (214.2 34.2) = 180 gram or 1 kg — 1000 Number of moles of water = “2° = 10 | Naof moles of 1 Molality= “\ices cf waler mie 7 S35 X 1000=0.555 m @ Total no. of moles = 10.0 + 0.1 = 10.1 . No.of moles of sugar _» lt Mole fraction of sugat = Tota number of moles, 10,1 9-099 Q2 Calculate the amount of oxalic acid (H,C;0,, 2H,0) required to obtain 250 ml of semimolar solution. (A) 15.75, (B)1 S75 (C) 157.5 (D) None Am. (A) Sol. Molarityof solution =0.5 M Volume of solution = 250 ml J+ milli mole oxalic acid = Mx Vml)= 3 x250 or ¥ x 1000=0.5x250 250 «126 w= Fya999 1576 g Q3 _15gramof methyl alcohols dissolved in 3S gram of water. Whats the mass percentage of methyl alcobol insolation? (A) 30% (B) 50% (C) 70% (D)7S% Ans. (A) Sol. Total mass of solution = (15 +35) gram=$0 gram Mass of methy! alcohol mass percentage of methyl alcohol = “SEL TETMBEONM 199 = 35 x 100" 30% QA 1.82ametal required 32.5 mL of N HCIto dissolve it. What is equivalent weight for metal? (A) 65, (B)75 (©)56 (D) 90 As ©Ans Qs F £ Meq. of metal = Meg. of HCI. or 122 x 1000=325x1 E=56 ‘The vapour pressure of pure liquid ‘A’ at 310°C is 1201orr. The vapour pressure of this liquid in solution with liquid B is 72 tort. Calculate the mole fraction of ‘A’ in solution if the mixture obeys Raoult’ law. (A)0.06 (B)09 (C03 (D)06 @) Given is vapour pressure of pure component ‘A’, P*, = 120torr Partial pressure of A, P, = 72 torr ‘Suppose its mole fraction is solution is X ,, then according to Raoult’s law. PA=P*A.xA m 72=120xxA or XA= 355 70.6 ‘The degree of dissociation of Ca{NO, ), in dilute aqueous solution containing 7.0 g of saltper 100.0 g of water at 100°C is 70%. Ifthe vapour pressure of water at 100°C is 760 mm Hg. the vapour pressure of the solution is (A)748.3 mmHg (B)1492.6mmHg _(C)373.2mmHg_ > (D)74.03 mmHg @) Moles of Ca(NO. “3 prestitin 100.0 g of water ‘Since dissociation is 70%, the total number of particles - Gro =00875=n 100 Also, moles of solvent = 5° =5.55=N ‘Applying Raouks lew PP Pras po a+N 70 - 08" Or 160-p 0.087 760 ~ 0.087+555 Or OrQ7 ee ee ‘The vapour pressure of a solvent is 20 torr whereas that ofits dilute solution is 17 torr. The mole fraction ofthe solventis (A)06 (B04 (C)0.85 (D)0.7 © ‘Vapour pressure of solvent p° = 20 torr and vapour pressure of solution p, = 17 torr. Pe-P, Therefore, 5 = mole fraction of solute 20-17 , Or Zp 70-15 = mole fraction of solute Mole fraction of solvent = 1 -0.15= 0.85 Methyt alcohol and ethy1 alcohol have vapour pressure equal 10 88.5 mm and 42.0 mm respectively at 45°C. 116.0 g of methanol and 46.0 g of ethanol are mixed at 45°C, the mole fraction of methanol in the vapour is....(the mixture may be taken as ideal solution). (A)0.467 (B)0.502 (C)0.513 (D)0.556 © For an ideal solution, obeying Raoult’s law, the vapour pressure of mixture Prraare ™ we ct’ dima * oP od rixae ~ macthanol metharel cthuaol ethanol 16/32 46/46 Or Ppesare = 88.5% +42.0x 16 46 + 32 46 7.4mm os Paisare = 88.5475 + 42.0% ‘The mole fraction of any constituent ‘i’ in vapour phase is Ps arig NAPPressurcof the constituent in solution Pr ts Total vap. pressure of solution na -s5 _ 12 |p © [Pu 116/32+46/46 }/ >” Or the mole fraction of methanol in vapour phase = 29.47 /$7.44= 0.5130Qs Ans. Sol Qu ‘The vapour pressure of benzene at 80°C is lowered by 10mm when 2.0 of anon-volatile substance is dissolved in 78 g of benzene. The vapour pressure of pure benzene at 80°C is 750 mm. The molar mass of the non-volatile substance is. (ayiso (8) 1050 (c) 1500 (D) 1550 “a If P° is the vapour pressure of pure benzene and P the vapour pressure of solution, w the weight of non- ‘volatile substance of molecular mass “m’ and w the weight of solvent benzene with molecular mass M, = 150.37 ~150 Calculate the molal elevation constant of water evaporates at 100°C with the absorption of 536 calories pergm (R= 2cals) (A)0.519°C (B)0.0519C (C)1.sivc (D)2.51°C “” ‘Molal clevation constant of the solvent. RY _ 2373x373 PRE 3732973 ce Ky = 7 x1000 = “5361000 = 9-5! 0.15gofa substance dissolved in | 5g of solvent boiled ata temperature highcr by 0.216°C than that of the pure solvent. Calculate the molecular weight of the substance. Molal elevation constant for the solventiis2.16°C. (A216 (B) 100 (cy 178 (D)Nonc of these @) Here itis given that w=0.15g AT, =0.216C W= 15 gk, =216C nf a . . 1000% Ky xw 1000«2.16x0.15 ‘Substituting values inthe expression,m= srw ™= gates If latent heat of fusion of ice is 80 cals per g at 0°C, calculate molal depression constant for water. (A) 18.63, (B) 186.3 (C) 1.863 (D)0.1863 oOSol. ee Qu4 RE Quis Ans, Sol. RT? K,= Too0, Here R = 2 cals, T,= 0 + 273 = 273 K, ,= 80 cals 2273x273 Ke= “Fo00.80 = 1-863 ‘Osmotic pressure of a sugar solution at 24°C is 2.5 atmospheres. Determine the concentration of the solution in gm mote per bite. (A)0.0821 molesitre (B) 1.082moles/lite (C)0.1025moles/litre (D)0.0827 molesilitre oO Hereitis given that R=25 atm, T= 24 +273 = 297A", S= 0.0821 lit. atm. deg"! mot, C=? 25 We know that x= CST or C= 35 = apazis a7 ~ 0.1025 molesiiitre ‘Twenty grams ofa substance were dissolved in 500 mil. of water and the osmotic préssure ofthe solution was found to be 600 mm of mercury at 15°C. Determine the molecular weight of the substance. (ayo (@)1198 (©) 1200 (D) None of these ® Here itis given that w=20 gm; V=$00ml.= 22 505 lee = 600 mm = $0 sum; T=15+273= 288A m=? ‘According to Van"t Hoffequation, w rVenST =oxV= ST ‘What weight of NaCI is added to one litre of water so that AT/K,= *’ (A)5.858 (B)0.585 g (C)0.0585 g (D) 0.0855 g oO For NaCli=2 Or AT p=i.K,.m AT(K,=2.m =2xm1 1 1 ity = —K op i 1 imately —— Or molality 7555 ©F jopg Moles are dissolved Kg” of water or approximately To, moles are present in 1.0 litre of water (considering molarity and molality to be the same) . 1 Weight of NaCl= 7555 «58.5 gof NaCI = 0.0585 g of NaCl. SUBJECTIVE Q.16 The addition of 3 gm of substance to 100 gm CC1,(M = 154 gm mot) raises the boiling point of CCl, Ans. Sol. by 0.60°C. K, of CCI, 5.03 kg mol’ K. Calculate (a) the freezing point depression (b) the relative lowering of vapour pressure (©) the osmotic pressure at 298 K (Gd) the molar mass of the substance Given K(CCI,)= 31.8 kg mot“"K and p (density) of solution = 1.64 gmc’, (a) 3.79°C, (b) 0.018, (c) 4.65 atm, (d) 251.5 @ 0.60=K,xm AT,=K,xm AT, Ke 318 0.60 ~ K, > 5.03 AT,~3:79°C Ans. 0.60 o) S03 = 0.12 Pas = O12, Mairene = ve =6.49 O12 oo1sans. linen 6.49 Relative lowering of VP. (© Amountof solutein 100 gm of solvent =3 gm Amount of solute in 1000 gm of solvent = 30 gm 1030 _ 1030 1030 Wotan = 1030 EM, Vissaion™ 5 164 cm? = ien0 Vite PeseRT BO Vie 0,120,082 298 = T9765 (ate) Ans, 1640Qi7 fF Quis (a) (©) d) © 3000 Monee” O12, = 250 (app) Ans. ‘Vapour pressure of CH, and C,H, mixture at SO°C is given by P (mm Hg)™ 180 X, +90, where X, is the mole fraction of C,H, A solution i prepared by mixing 936 g benzene and 736 g toluene and ifthe vapours over this solution are removed and condensed into liquid and again brought to the temperature of SO°C, what would be the new mote fraction of C,H, in the vapour state? 093 C\H,-B, CH,-T 936 16 Ee B= gp 78 Dy 12 Xo" nyem, ~ i268 P=180X,+90 Now P= (Pf —pt) X, + Pf P2=90mm, P,°=270mm P, = 0.6 x 270, P= 180 x 0.6 +90 =162mm =198mm 9 7 x20 97 900 29 =0.93 Ans ‘The vapour pressure of two pure liquids, A and B that form an ideal solution are 300 and 800 torr respectively, al temperature T. A mixture of the vapour of A and B for which the mole fraction of Ais 0.25 is slowly compressed at temperature T. Calculate the composition ofthe first drop of the condensate, the total pressure when this drop is formed, the composition of the solution whose normal boiling point i T, the pressure when only the last bubble of vapour remains, and the composition of the last bubble.Ans, ‘Sol. Qs (3) 0.47, (b) $65 torr, (c) x,=0.08, x,= 0.92, (4) 675 torr, (€) x',= 0.11, x= 0.89 @) P,=X,xP! me ea CPP PS o (©) __Atboiling temp vapour pressure = 760 torr 300 X, + 800 X, = 760 X,, (300 - 800) + 800 = 760 X,= 0.08 x, 70.92 (@)_ Whenonly the last bubble of vapour remains, we can assume that the composition of vapours ow he composition of he condensation X,=0.25, X,=0.75 P+ XP? ='0.28'x'300 +'0.75 « 800 = 675 tor (©) Composition of last bubble =X, x, F Ye Xp Pe 7s, X,2 Gg tll, X 0.11 = 0.89 ‘When the mixture of two immicible liquids (water and nitrobenzene) boils at 372 K and the vapour pressure at this temperature are 97.7 kPa (H,O)and 3.6 kPa (C,H,NO,). Calculate the weight % of nitrobenzene in the vapour. 20.11% Let vapour contains W, gm of C,H,NO, and W, gmofH,O wy ms = S723 TR for gases Ratio of moles = Ratio of pressure 1:0, =3.6:97.7 Mi, 18 _ 36 123 °w, 97.7 wy 3.6123 ws | 18x97,7 = 0-252Q20 Qu fF w, = w (le), w, = 0.252 w 0.252w 1252w * 100 = 20.11 % Ans. %w,= A very dilute saturated solution ofa sparingly soluble salt ,B, hasa vapour pressure of 20 mm of Hg at temperature T, while pure water exerts a pressure of 20,0126 mm Hig at the same temperature. Calculate the solubility product constant of A,B, at the same temperature. 54x10 Letthe solubility of A,B,=S AB, ——> 3A*+ 4B s o 0 o 3s 4s Solubility product of A, B, (k,,) = (3S) (4S)'= 6912S? For A, Byi=7 To solve this problem we will assume Malarity = Molality and w= Waa Molality of A,B,=S => n= S.w = 1000 gm 1000 Magen Tg 7 55-56, Nate Pon Paseo jy Tate Phe Pen 20.0126=20 _ 5x7 20.0126 55.56 S=5*10°M Solubility product of A, B, (K,,)= 6912S" = 6912 x 57 x 10t= 34x10" Ifthe apparent degree of ionization of KCI in water at 290 K is 0.86. Calculate the mass of KCI which must be made up to I dm? of aqueous solution to the same osmotic pressure as the 4.0% solution of glucose at that temperature. 89 gm Glucose (C,1,,0,), . 4.0x1000 _ 2 Molar concentration of glucose solution.(C\)" 30, 199" 9‘w = amount of KCI present in | dm’ solution. x, Osmotic pressure of KCI solution wRT 186% TAS am 9 2 t= 1.86w RT “4S 274.0 9x186 w=89 gm £; Mass of KCI present in 1 dmv’ of aq, solution =8.9 gm Q.22 The specific conductivity ofa 0.5 M aq. solution of monobasic acid HA at 27°C is 0.006 Sc". It's ‘molar conductivity at infinite dilution is 200 S cm? mot"'. Calculate osmotic pressure (in atm)of 0.5 M HA (aq) solution at 27°C. Given R = 0.08 L-anvK-mol Ans 12.72 Kx1000 _ 0.006x1000 co ore 1 Soh AQ Cc 0.500 12 Sm? mot! AY, =200scm’mol K =e am Ae = 0.06 focHA, n=2 s1+@-Na +(2=1)* 06 i= 1.06 x=ixCRT = 1.06 x 0.5 « 0,082 x 300 x= 12.72 atm Q.23 The freezing point of 0.02 mol fraction solution of acetic acid (A) in benzene (B)is 277.4K. Acetic acid exists partly asa dimer 2A =A. Calculate equilibrium constant for the dimerisation. Freezing point of benzene is 278.4 K and its heat of fusion is 10.042 kJ mot. K=322 X, =0.02—>n, = 0.02 and n, = 0.98 W, =0.98 « 78 gm ; 4 x1000 0.021000 Molality (0) = "W = “Dog 7a be = 0.2616 _ Rim, 8.314x (278.4) 78 Ks" 75,1000 ~ “100421000 =5.00K/mKm Tix 50.2616 1 5x0.2616 = 0.7645 (ta As acetic acid dimerise, n= 2 a 0.7645 = 1-5 a= 0.4710 ‘Weassume : Motarity = Motality + Molarity (C)= 0.2616 A A, i 0 Atequi. —_C(I-a) s hy Ca a 0.471 [AF 2C%(1-a} 2C(-a} ~ 2x02616 (05297 “322 Q.24 _Ikgofan aqucous 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? K, (H,O)= 1.86 Kg mol 'K. Sol. Since molality of solutionis.75, hence.75 moles of sucrose are present in 1000 g of solvent (ie. water) Fm." M+ M,_, = 1000 +.75 x 342 = 1256.5 gm acme (iN KB) = 1956.5 2565 7g * 1000= 204.14 gm,.. m,__, = 1000 - 204.14 = 795.86 gm 1s AT,=K,x 41,86 x MBE =27115 VAT;SK,xm — >4= 1.86% Soop >w=271 . amount of ice = 795.86 - 277.15 = 518.31 gmQus Q.26 Q27 Sol River wateris found to contain 11.7% NaCl, 9.5% MgCl, and 8.4%. NaHCO, by weight of solution. Calculate its normal boiling point assuming 90% ionization of NaCl, 70% ionization of MgCl, and $0% ionization of NaHCO, (K, for water = 0.52) at a =02, Maen Fe = OL, Moco Ge = OL ig a= 1409-19, iggy t+ 20= 140.7 2=24, inno, = 14 20= 140.5 x2=2.0 Weight of solvent = 100~-(11.7+9.5+8.4)= 70.48 2% + hy Pang, tina, Maaco, *Ky 1000 Weight of solvent - (.9n02024n0.1 2x 0.080.5271000 “sore +. Boiling point of solution = 100 + 5.94 = 105.95°C An aqueous solution containing 288 gm of anon-volalite compound having the stochiontetric composition C,H,,O, in 90 gm water boils at 101.24°C at 1.00 atmospheric pressure What is the molecular formula? K\(H,0) = 0.512 K mol" kg T, (H,0) = 100°C Elevation in B.P. = 101.24~ 100=1.24°C 4T,=K, xi xmolality= 1.24 = 0512 x a x - 2 m= 1321.2gmmobt molarmiss of CH,,O, = [2x #1'x 2x + 16x= 30x 2 30x 9321.2 Peer Hence the molecular formula is = C,H,,0,, 30 ml of CH,OH (d= 0.7980 gm Cm) and 70 ml of H,O (d= 0.9984 gm cm) are mixed at 25°C to form a solution of density 0.9575 gm em, Calculate the freezing point of the solution. K,(H,O)is 1.86 Kgmol'K. Alsocalculate its molarity Weight of CH,OH (w,)=30cm' x 0.7980 gm/em’ = 23.94 gm ‘Weight of solvent (11,0) (w,) = 70cm’ x 0.9984 gmem? = 69.888 gm 1000 32“ goag = 10.7046 molal 2. A1,=K, xixmolality, (forCH,OH, AT, = 1.86 x 10.7046° 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 density of the solution ~ 0.95751 1000 ‘9795 Molli ‘volume of the solution = 97.99 ml =7.63MQ.28 Find K,, the ionization constant of tartaric acid if a 0.100 molal aqueous solution of tartaric acid freezes Sol. at ~0.205°C. Assume that only the first ionization is of importance and that 0. m=0.1M. K,= 1.86 kgmot K. Assuming that the tartaric acid be a monobasic as AH. It ionizes as AHO ee A” + H Initially conc. c 0 0 ‘Conc. after dissociation C(1-a) Ca Ca, CUl-a)+Ca+Ca c Here, i= lta where a.= degree of dissociation = ae. Molal concentration = 0.1 AT=K,xC,xi => 0.205 = 1.86x0.1x(I4a) a= 0.1 k= (04x08 no?