a To avoid bends, as well as, the toxic effects of high concentrations of nitrogen in the blood, the tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen) * At high altitudes the partial pressure of oxygen is 4ess than that at the ground level, This leads to low concentrations of oxygen in the blood and tissues of people living at high altitades or climbers. Low blood oxygen causes climbers to become weak and unable to think clearly. symptoms of a condition known as anoxia. Effect of Temperature 7 Solubility of gases in liquids decreases with rise in temperature. When dissolved, the gas molecules are present in liquid phase and the process of dissolution can be considered similar to condensation and heat is evolved in this process. We have learnt in the last Section that dissolution process involves dynamic equilibrium and thus must follow Le Chatelier’s Principle. As dissolution is an exothermic process, the solubility should decrease with increase of temperature. Intext_ Questions 16 1S. a toxic gas with rotten egg like smell. is used for the qualitative analysis. If the sohability of H,S in water at STP is 0.195 m, calculate Henry's law constant. 1.7 Henry's law constant for CO, in water is 1.67x10* Pa at 298 K. Calculate the quantity of CO, in 500 mL of soda water when packed under 2.5 atm CO, pressure at 298 K. Liquid solutions are formed when solventis a liquid. The solute can be a gas. a liquid or a solid. Solutions of gases in liquids have already been discussed in Section 2.3.2. In this Section, we shall discuss the 1s of liquids and solids in a liquid. Such solutions may contain xe oF more volatile components. Generally, the liquid solvent is volatile. ‘The solute may or may not be volatile. We shall discuss the properties only binary solutions, that gs, the solutions containing two ats, namely, the solutions of (i) liquids int liquids and (if) solids solutio componés in liquids. Let us consider a binary solution of two volatile liquids and denote the feo components as | and 2. When taken in a closed vessel, both the components would evaporate and eventually an equilibrium would be established between vapour phase and the liquid phase. Let the total vapour pressure at this stage be p,,.. and p, and p, be the partial pour pressures of the two components 1 and 2 respectively. These partial pressures are related to the mole fractions x, and x, of the two components I and 2 respectively. The French chemist, Francois Marte Raoult (1886) gave the quantitative relationship between them. The relationship is known as the Raoult’s law which states that for a solution of volatile liquids, en Solutionspressure the parte ort onal to kts mole fract is directly proporti Thus, for component | ren and PE PL wher remperattire, Similarly, for component 2 oy. P,* Pa % where p,” represent According to Dalton’s (Pau) over the solution phase in tial pressures of the components of part Prot = Pi * Pa Substituting the values of Py Prat 2% Pi *% Pa" =(-x) PPP = pot: - PS Following conclusions can ( Total vapour pressure over fraction of any one component. (a) Total vapour pressure over the solution ep) ts the vapour press ‘3 the vapour pres: 1aw of partial pressu of the solution ment of each contPimpresent In solution. tion prose! (1.12) ure of pure component 1 at the same (1.13) the pure component 2. res, the total pressure he sum of the n asi (1.14) gure of the container will be 1 the solution and 1s give and p,, we get (1.15) (1.16) be drawn from equation (1.16). the solution can be related to the mole varies linearly with the mole fraction of component 2. Mole fraction x | 1.3: The plot of vapour pressure and mole fraction of an ideal solution at constant temperature, The dashed lines land If represent the partial pressure of the components. (lt can be seen from the plot that p, and p; are directly ‘proportional to x, and x, respectively). The total vapour pressure is given by line marked ii in the figure. i ‘9 (ui) Depending on the vapour pressures of the pure components 1 and 2, total vapour pressure over the solution decreases or increases with the increase of the mole fraction of component 1. ‘A plot of p, or p, versus the mole fractions x, and x for a solution gives a linear plot as shown in Fig. 1.3. These lines (I and Il) pass through the points for which x, and x, are equal to unity. Similarly the plot (Line I11) of pra: Versus % 4s also linear (Fig. 1.3). The minimum male of Proua 8 p,° and the maximum value px’, assuming that component volale than component 2, Les Dive Pe The composition of vapour phase in equilibrium with the solution is determined by the partial pressures of the components. If y, and y, are the mole fractions of thecomponents 1 and 2 respectively in the vapour phase then, using Dalton's law of partial pressures: P= Ui Prost a7 Pa = Us Poss (1.18) In general PLE Y Posat (1.19) Vapour pressure of chloroform (CHCI,) and dichloromethane (CH,CL,) at 298 K are 200 mm Hg and 415 mm Hg respectively. (i) Calculate the vapour pressure of the solution prepared by mixing 25.5 g of. CHCL, and 40 g of CH,Cl, at 298 K and, ii) mole fractions of each component in vapour phase. : 7 @ Molar mass of CH,Cl, = 12x 1+1%*2+35.5%2=85 g mol Molar mass of CHCL, = 12% 1+1%1+35.5%3= 119.5 g mol! 40g Moles of CH,Cl, = Bema = 0-47'mol 25.56 Moles of CHCl, = [795 qmoil = 0213 mol Total number of moles = 0.47 + 0.213 = 0.683 mol a 0.47 mol = 0.688 0.683 mol Xcucly = 1.00 - 0.688 0.312 Using equation (1.16). : Prost = Px? + (2° — P,°) %,= 200 + (415 - 300) x 0.688 = 200 + 147.9 = 347.9 mm Hg zi (i) Using the relation (1.19), y, = P/Pioar We ean calculate the mole fraction of the components in gas phase (y). Porc = 0.688 * 415 mm Hg = 285.5 mm Hg Pena = 0.312 x 200 mm Hg = 62.4 mm Hg Vorych = 285.5 mm Hg/347.9 mm Hg = 0.82 Yeucy = 62.4 mm Hg/347.9 mm Hg = 0.18 Note: Since, CH,Cl, is a more volatile component than CHCl, | PSujci, = 415 mm Hg and Pfjjciy = 200 mm Hg] and the vapour phase is also richer in CH,Cl, [Yeryc, = 0.82 and Ycucig = 0.18), It may thus be concluded that at equilibrium, vapour phase will be always rich in the component which is more volatile. eT Te tehdq, Solutions1.4.2 Raoult's According to Raoult’s law, the vapour pre aauire of ctr component in a given solution is given by P= % Pi Int a Tr ae LS liquid, one of the components Is 8° volatile that i cla us 8 we have already seen that tts solubility Is given by Henry's law which states that p= Ky If we compare the equations / a ieiaseeaure oft can be seen that the partial pressure of is directly proportional to its mole fraction in solution, Only the proportionality constant Ky differs from p,". Thus, Raoult’s law becomes a special case of Henry's law in which Ky becomes equal to p; or Raoult’s law and Henry's Jaw, it 1e volatile component oF gas 1.4.3 Vapour Another important class of solutions consists of solids dissolved In Paegaure of * Uquid, for example, sodium chloride, glucose, urea and cane sugar in Solutions of water and fodine and sulphur dissolved in carbon disulphide Some Solids in physical properties of these solutions are quite different from those of Liquids pure solvents, For example, vapour pressure. We have learnt tn Unit 5 Class XI. that liquids at a given temperature vapourise and under quilibrium conditions the pressure exerted by the vapours of the liquid over the liquid phase is called vapour pressure [Fig. 1.4 (a)] In a pure liquid the entire surface is occupled by the molecules of the liquid. Ifa non-volatile solute is added to a solvent to uive a solution [Fig 1.4.(b)], the vapour pressure of the solution is solely from the solvent alone. This vapour pressure of the solution at a given temperature is found to be lower than the vapour pressure of the pure solvent at the same temperature. In Fig. 1.4: Decrease in the vapour pressure of the the solution, the surface has both solute and solvent on account of the presence of solvent molecules: thereby the fraction of the agus mie poor fal ore athe surface covered by the solvent molecules gets ae nan fon anoiee: Xluced. Consequently, the number of Sree tentenoted bye and hey Solvent molecules eseaping from the surface Te cateajenvaiihe suchen ate is correspondingly reduced, thus, the vapour pressure is also reduced. ‘The decrease in the vapour pressure of solvent depends on the quantity of non-volatile solute present in the solution, irrespective of its nature. For example, decrease in the vapour pressure of water by adding 1.0 mol of sucrose to one kg of water is nearly similar to that produced by adding 1.0 mol of urea to the same quantity of water al the same temperature aoe Raoult's law in its general form can be stated as, for any solution the partial vapour pressure of each volatile component in the solution is directly proportional to its mole fraction. Ina binary solution, let us denote the solve 3 2, When the solute is non volatile, only the solvent molecclee are present in vapour phase and contribute to vapour pressure. Let p, be @the vapour pressure of the solvent, x, be Us mole fraction, p)” be tts concentrartons, tts | vapour pressure | would vary linearly from zero to the ‘vapour pressure of the pure solvent. The proportionality constant Is equal to the vapour pressure of pure #olvent, 7? | A plot between the vapour pressure and Mole fraction ofsdvem! the mole fraction of the solvent is linear Nt > (Fig. 1.5) | apour pressure | t in the pure state, Then according to | we us § Raoult’s law | Ya solution obeys : Pix | Raouilt’s law for all & and p, = x, p® (1.20) 3 : $ | 13 Ideal and Hon- Liquid-liquid solutions can be classified into ideal and non-sdeal ideal Solutions Solutions on the basis of Raoult’s law. 5.1 ideal The solutions which obey Raoult's law over the entire range of | Sebutions = c&acentration are known as ideal solutions. The ideal #lutions have two other important properties. ‘The enthalpy of mixing of the pure components to form the solution is zero and the volume of mixing, is | also zero, i.e. Anat = 0, AnyV = 0 . (21) It means that no heat is absotbed or evolved when the components are mixed. Also, the volume of solution would be equal to the sum of volumes of the two components. At molecular level, ideal behaviour of the solutions can be explained by considering (wo components A and B. In pure components, the intermolecular attractive interactions will be of types A-A and B-B, whereas in the binary solutions in addition to these two interactions, A-B type of interactions will also be present. If this leads to.the.formationof ideal} |. A perfectly ideal solution is rare but some solutions are nearly: ideal in behaviour. Solution of fall into this category. 1.5.2 Non-ideal When a solution does not obey Raoult’s law over the entire range of Solutions concentration, then it {s called non-ideal solution. The the solution ER exhibits ‘The plots of vapour pressure as a function of mole fractions for such solutions are shown In Fig. 1.6, ‘The cause for these deviations lic in the nature of interactions at the molecular level. rom Raoult’s law, AY e., in this case the intermolecular attractive forces between the solute-solvent molecules are weaker than those between the solute-solute and solvent-solvent molecules. This means that in such solutions, molecules of A (or B) will find {t easier to escape than in pure state, This will increase the vapour