1 Solutions POINTS TO 1, Solution: A solution is a homogeneous mixture of two or more pare substances, the relative ratio of which can be changed within certain limits, ‘When the constituents of the solution are two itis called binary, if three then ternary, if four then quaternary and s0 on, The two constituents ofthe solution are solvent and solute. Solvent (A); It is the component of the solution: (0 which is present in a relatively large proportion in the solution, and Gio, whose physical state is same as that of the resulting solution. Solute (B): Its the component of @ solution whieh is present in relatively small proportion. 2. Types of Solutions ‘Table 1.1 ‘Mixture of oxygen and nitrogen gases | Gaseous Solutions Liquid Gas Chloroform mixed with nitrogen gas Solid Gas Camphor in aitrogen gas Gas Liguid ‘Oxygen dissolved in water | Liquid Stations Liquid Liquid Ethanol dissolved in water Solid Liquid Glucose dissolved in water Gas ‘Solution of hydrogen in palladium | | sat ston Liu sai sol sali ‘Amalgam of mercury with sodium Copper dissolved in gold 5 = ma | wn 4 S) D ima ms = = fee) ae ze, Amongst the nine types of solutions, the widely studied ones are: (a) Solid-liquid (6) Liquidliquid and (c) Gas-tiquid solutions, (@) Solid-tiquid solutions: A small amount of solute (usually ionie solids) is dissolved in a large quantity of solvent. If the amount of solvent is large as compared to the solute, the solution is referred to as a dilute solution. If the amount of solvent is small as compared to the solute, the solution is referred to asa concentrated solution Saturated solution: A solution is said to be saturated if it holds the maximum amount of solute at @ given temperature in a given quantity of the solvent. Solubility: It may be defined as the maximum amount of solute that can be dissolved in 100 g of solvent at a specified temperature. The solubility of solid into liquid depends upon the following factors: () Nature of solute (i) Nature of solvent (ti) Temperaturece Ww a] = Lu a paul ce [e) oa wn | z le) a Causes of solubilit with a solvent: (@ Inter-ionie attraction in the solute molecules: Ions are held together in the lattice due to electrostatic forces. Due to these forces molecules are stabilised and the energy released is called lattice energy. This is defined as the energy released when 1 g mole of the compound is formed due to electrostatic attraction between the ions. (i Inter-molecular attraction between solvent molecules: Water is a polar solvent because of the difference in electronegativity between hydrogen and oxygen atoms constituting water molecule. This difference gives rise to the development of a slight negative charge on oxygen and equal positive charge on hydrogen. A dipole is thus ereated giving rise to dipole-dipole attraction between water molecules. (iid) Solvation: It represents force of attraction between solute and solvent molecules, Ifthe solvent is Water then the energy released is called hydration energy. IF hydration energy > lattice energy, then solution is easily formed. Both the ions of the solute get hydrated to overcome the Lattice energy of the solute. (i) Temperature: Saturated solution represents equilibrium between undissolved solute and dissolved solute, ‘he following types of forces of attraction are operated when a solute is mixed Undissolved solute + Solvent — Solution A,,W=+x If A.) H <0, Le., (-ve), the dissolution is exothermic. In this ease, as the temperature increases, solubility decreases (Le Chatelier’s principle). If A, H > 0, ie. (+ve), there is endothermic dissolution. In this case, increase in temperature jnereases the solubility (Le Chatelier’s principle). (6) Liquid-liquid solutions: When two liquids are mixed, three different situations result: (@ Miscible liquids: The two components are completely soluble. They are miscible only when they have similar nature or belong to the same homologous series. Example: water and alcohol (both polar), benzene -toluene (both belong to the same homologous series). There is a rule: Like dissolves like ~ Polar solute is soluble in polar solvent and a non-polar one in @ non-polar solvent. (i Partially miscible liquids: This happens only when the intermolecular forces of one liquid is greater than that of the other is. Solubility, however, increases with increasing temperature. Examples: aniline-water, phenol-water. (ii) Immiscible liquids: Two components are completely insoluble. This happens when one Tiquid is polar and the other is non-polar. Examples: carbon tetrachloride-water, chloroform-water. (6) Gas-tiquid solutions: The gases are generally soluble in water and to a limited extent in other solvents ‘too. Solubility, however, depends on the following factors: (@ Nature of gus: Easily liquefiable gases are generally more soluble in common solvents. (ii) Nature of liquid: Those gases which easily form ions in solution are more soluble in water than in other solvents. lon formation in other solvents is not an easy process. HCIg) + H,0() == H,0%ag) + Cr(aq) (iii) Temperature: With ise in temperature, the solubility generally decreases because gas is expelled, Some gases, however, find their solubility increased at a higher temperature. (») Pressure: Pressure is an important factor affecting the solubility of gas in liquids. This is governed by Henry’s law. == Henry's law: It states that at a constant temperature, the solubility of a gas in a liquid is directly proportional to the pressure of the gas ‘The most commonly used form of Henry’s law states that the partial pressure (p) of @ gas in vapour pphase is proportional to the mole fraction of the gos (x) inthe solution and is expressed as pa Ky Here x is the mole fraction of the gas and Ki; is the Henry's law constant. Its value depends on the nature of solute, nature of solvent and temperature. Note: Mole fraction is discussed in detail further in this chapter.Limitations of Heney’s La Henry's law is applicable only when © The pressure of the gas is not foo high and temperature is not too low. @ The gas should not undergo any chemical change. @ The gas should not undergo association or dissociation in the solution, Applications of Henry's Law: ‘© To increase the solubility of CO, in soda water and soft drinks, the bottle is sealed under high pressure. © Toavoid the toxic effects of high concentration 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). © thigh altinudes, low blood oxygen causes climbers to become weak and make them unable to think clearly, which are symptoms of a condition known as anoxia Methods of Expressing Concentration of Solutior ‘The concentration of solution is the amount of the solute present inthe given quantity of solution or solvent. Itcan be expressed in any of the following ways: (@) Mass percentage (w/w): It may be defined as mass of solute per 100 g of solution. Mass fsolute 99 Total mass of the solution Mass% of solute = (6) Volume percentage (V/V): It may be defined as volume of solute per 100 mL of solution. Volume of solute Volume % of solute= — Volume of solute, Total volume of solution a (©) Mass by volume percentage (w/V): It may be defined as the mass of solute per 100 mL. of the solution. Mass by volume % = —Msss of solute _,. 199 ‘Volume of solution (d) Parts per million (ppm): It is the parts of a component per million (10°) parts of the solution. Number of parts of the component ——————evvsaemee oi oO? Total number of parts of all components of the solution ppm = It is convenient to express concentration in ppm when a solute is present in trace quantities (6) Mole fraction (x): It may be defined as the ratio of the number of moles of one component (solute or solvent) to the total number of moles of all the components present in the solution. fin a solution, n, and ng are the number of moles of solvent and solute, respectively, then Mole fraction of solvent inthe solution, Po +My ‘Mole fraction of solute in the solution, 7,7 My ee In a solution, sum of the mole fractions ofall the components is unity. For example, in a binary solution (having two components), 24+ X= (P Molarity (MD: Its defined as number of moles of solute dissolved in one lite of solution. Moles of solute Molarty = ——— Moles of solute —__ clarity = Yotume of solution (in ite) Unit of molarity is mol L~! or M (molar). Molarity changes with change in temperature as volume ‘changes with change in temperature. vu = a = Va) =) e) v2) a < ua < wo a A(@) Molality (m): Ibis defined as the number of moles of the solute dissolved in one kilogram (kg) of the solvent and is expressed as: Motality = Moles ofsolute __ Number of moles of solute ‘Mass of solvent (in kg) Mass of solvent (in grams) ‘Unit of molality is mol kg“ or molal (m). Molality is independent of temperature 4. Vapour Pressure of Pure Liquid and Solution ‘Vapour pressure: When a liquid is taken in a closed vessel, a part of the liquid evaporates and its vapours ‘occupy the available empty space. These vapours cannot escape as the vessel is closed. They would rather have a tendency to condense into liquid form. In fact an equilibrium is established between vapour phase and liquid phase and the pressure that its vapour exert is termed as vapour pressure. Thus, vapour pressure of @ liquid may be defined as the pressure exerted by the vapours above the liquid surface in equilibrium ‘with the liquid phase at given tensperature. ‘The vapour pressure of aliquid depends on the following factors: Nature of the liquid: Liquids having weak intermolecular forces are volatile and therefore have greater ‘vapour pressure Temperature: Vapour pressure of a liquid increases with increase in temperature. This is because with jnrease in temperature, the kinetic eneray of the molecules increases and therefore lange number of molecules are available for escaping from the surface of the liquid. (@) Vapour pressure of liquid-liquid solution: Raoult’s Law for solutions of volatile liquids: It states that for a solution of volatile liquids the partial pressure of each component of the solution is directly proportional to its mole fraction present ina solution. Mathematically, Prey Pate Pa= Paka Pa= Pars where p, and py are partial vapour pressures, x, and xp are mole fractions, p% and pp are the vapour pressure of pure components A and B respectively. If p is total vapour pressure then according to Dalton’s law of partial pressure, P=Pa*Ps = Pata t Pete = PA (1-49) + Pinks = PA + 05—Pa) Xe As p' and p'y are constants ata given temperature, itis evident from the above equations that the total ‘vapour pressure varies linearly with the mole fraction xp (or x, since x, = 1 — %). ‘The composition of the vapour phase in equilibrium with the solution can be determined from the Partial pressure of the two components. If y, and yg are the mole fractions of components A and B respectively in the vapour phase, then 1000 ce Ww re] a Lu a WwW rae e) F wn eR z le) a In general, = Raoult’s law as a special case of Henry's law. In the solution of a gas ina liquid, if one of the components is so volatile that it exists as a gas, then it ‘can be said that Raoult’s law becomes a special case of Henry’s law in which K,, becomes equal top. (®) Vapour pressure of solutions of solids in liquids Raoult’s law for a solution containing a non-volatile solute and volatile solvent: It states thatthe relative lowering of vapour pressure is equal to mole fraction of solute which is non-volatile. Mathematically, P=Pa*Pa or, P =p, (Since solute B is non-volatile) PHPatyP= Pi (l 9) =P Phite Pate =Pa-P Pane or er! a ‘or Relative lowering of vapour pressure = Mole fraction of solute 5. Ideal and Non-Ideal Solutions (@) Ideal solution: A solution is called an ideal solution ifit ‘obeys Raoult’s law over a wide range of concentration (Fig. 1) at a specified temperature. For an ideal solution, P=PatPa=PaXat Pade Liquids having similar nature and structure are likely to form ideal solutions. Examples are: ‘© Mixture of methanol and ethanol © Mixture of n-hexane and n-heptane ‘© Mixture of benzene and toluene. Reasons for formation of ideal solutions: A solution ‘of two miscible liquids A and B will be ideal if two ‘essential conditions are fulfilled. (@ IEF,_j isthe force of attraction between molecules of A and Fp_ is that of molecules of B, then 4 and B will form an ideal solution only if, Fug Fy-an Fenn (i The solution of A and B liquids will be ideal if A and B have similar structures and polarity Methanol and ethanol have the same functional group and almost same polarity and therefore, form ideal solutions. Vapour pressure —> 2 vu = a = Va) =) e) v2) a < ua < wo a az For an ideal solution (@ Raoult’ law is obeyed, ie., py =p", and pp =p'pXy (if) Agig H= Oand (id) gig V=0. (@) Non-ideal solution: solution which does not obey Raoult’s law for all concentrations is called a non-ideal solution. For a non-ideal solution (@ Raoult’ law is not obeyed, 1.0. Pg # PX, and Py # PgXy (ii) Aue H #0 and (id) gig V0. ‘[Link]-ideal solution can show either positive or negative ‘deviation from Raoult’s Taw. (A) Positive Deviation: The deviation will be called positive when the partial pressure of each component and the resultant total pressure are greater than the pressure expected on the basis of Raoult’s law (Fig, 1.2). In such cases, the intermolecular forces between solvent-solute molecules (F_») are weaker than those between solvent-solvent (F,_4) and solute-solute (Fg) molecules. That is, Fug PoXe © Sng H> 0, he, + ve, © nix V>0, hea +¥e, ‘Some examples of the solution exhibiting positive deviations are: (i Ethyl alcohol and water (dé) Acetone and carbon disulphide (iti) Carbon tetrachloride and benzene (iv) Acetone and benzene (B) Negative Deviation: The deviation is called negative deviation, if the partial pressure of each component (4 and B) and resultant total vapour pressure are less than the pressure expected on the basis of Raoult’s law. (Fig. 1.3) This type of deviation is shown by the solutions in which Fug? Fag and Fog Due to this, thete is decrease in the escaping tendency of 4 or B molecules from the surface of solution. Consequently, the vapour pressure of the solution = et will be lower. a lu ia e) F wn eR < le) io Characteristics of a Solution Showing Negative Deviation © PAX Paes Pe DBs: a> D's Mii Ain H > 0, ie, +¥E Agix <0, be, ve (iy) gin V> 0, Le., #ve Apix Va lu ia e) a v eR < le) io KW, x 1000, ‘Therefore Sh= aa K, XW, 1000 AT, xW, (©) Depression of freezing point: Freezing point is defined as the temperature at which the vapour pressure of a substance {nits liquid phase is equal to its vapour pressure in the solid ‘phase. A solution freezes when its vapour pressure equals the vapour pressure of the pure solid solvent. Whenever 2 non-volatile solute is added to the volatile solvent, its ‘Vapour pressure decreases and it would become equal to ‘that of solid solvent ata lower temperature. The difference in the freezing point of pure solvent (7) and that of the solution (7;) is known as depression of freezing. point (GT). Thus, Depression of freezing point = AT, = 17 ~ Tp. | solution is the excess pressure that must be applied. to a solution to prevent osmosis, ie, to stop the passage of solvent molecules into it through Lk savent semipermeable membrane (Fig. 1.6). Osmotic pressure (r) is proportional to molarity (C) of the solution at a given temperature 7, Thus, j Sener n=CRT W,XRXT E zl MXP XRXT or, a m= Reverse osmosis: If a pressure larger than the ‘osmotic pressure is applied to the solution side, the pare solvent (or water) flows out of the solution ‘through the semipermeable membrane, In tis aye decton af smo eee seamen YH" and so the process is called reverse osmosis oe emmeei ‘Thus, we can say that reverse osmosis is just opposite to the osmosis when an extra ‘i 4 Water ’ pressure is applied. Reverse osmosis is used fuatst Pm in desalination to get pure water from sea water. ‘= Isotonic solutions: Two solutions are said to ‘beisotonic when they exert the same osmotic pressure because they have the same molar concentration. All intravenous injections must be isotonic with body fluids. vu = a = Va) =) e) v2) a < m < wo a A = _Isosmotic solutions: When two isotonic solutions are separated by a semipermeable membrane, no ‘osmosis occurs. The solutions are called isosmotic solutions. = Hypotonic solutions: A sotution having lower osmotic pressure than the other solution is said to be hypotonic with respect to the other solution = Hypertonic solution: solution having higher osmotic pressure than the other solution is said to be hypertonic with respect to other solution. == Plasmolysis: When the cell is placed in 2 hypertonic solution, the fd comes out of the cell due to ‘osmosis and as a result cell material shrinks gradually. This process is called plasmolysis. 7. Abnormal Molar Masses = Association: Association of molecules leads to decrease in the number of particles in the solution resulting in a decrease in the value of colligative property. As colligative property is inversely related to the molecular mass. Therefore, higher value is obtained for molecular mass than normal values.For example, when ethanoic acid is dissolved in benzene it undergoes dimerisation and shows a molecular mass of 120 (normal molecular mass is 60). Ht 2cH,—coon S=Es HAC. CH; HO = Dissociation: Dissociation leads to increase in the number of solute particles in the solution resulting in an increase in the value of colligaive property. Since coligative property is inversely related to the molecular mass, therefore, molecular mass of such a substance as calculated from colligative property will be less than its normal value. For example, KCl is an elecwolyte. When itis dissolved in water it issociates into K* and Cr ions and there would be double the number of particles if complete 745 dissociation takes place. Hence, it is expected to have molecular mass 37.25 g or ) |e. Kel —- kK’ + cr => van't Hoff Factor (i: It may be defined as the ratio of normal molecular mass to the observed molecular mass of the solute. ‘Normal molecular mass ‘Observed molecular mass Observed colligative property Calculated value of colligative property = Total number of moles of panicles after association/dissociation ‘Number of particles before association/dissociation vvan’t Hoff factor (i) expresses the extent of association or dissociation of the solute particles in the solutions. or, or, foe lu co =a peu) >a lu ia e) F wn eR < le) io In case of association, i <1 In case of dissociation, i> 1 ‘When there is neither association nor dissociation, 8. Modified Form of Colligative Properties Inclusion of “" modifies the equation for colligative properties as follows: = Relative lowering of vapour pressure of solvent Pa Pa te Pa i ‘= Elevation of boiling point, AT, =i K, m = Depression of freezing point, ATy= i Kym = Osmotic pressure, x =i CRT Important Formulae {In the formulae given below, A represents solvent and B represents solute, also M, = Molar mass of solvent ‘My = Molar mass of solute 1, = Mass of solvent Wg = Mass of solute ¥ = Volume of solution d= Density of solution GEM = Gram Equivalent Mass GMM = Gram Moleculat MassMs 1. Mass pereniage (ww) = a gz * 100 ¥, Volume percentage (FIP) = 5 p- * 100 W100 Val) Mass by volume percentage (*) Parts per million (ppm) = 2. Mole fraction of 4, x, Mole fraction of B, x watt Moles of solute ny Volume of solution in litre (nL) M,XV GaL) Moles of solute W100: ‘Mass of solvent in kg Mg *W, (ing) Gram equivalents of solute _ W, ‘Volume of solution in litre GEM of solute * V (in L) ‘6 Relationship between Molarity and Normality ‘The normality (V) and molarity (I) of a Solution are related as follows: ‘Normality * Equivalent mass (solute) = Molarity x Molar mass (solute) 7. Relationship between Molarity and Normality with Mass percentage (p) Ifpis the mass percentage and dis the density ofthe solution then 3. Molarity (Mf) = 4, Molality (mi) = vu ©) a = Va) =) e) v2) a < a < wo a az 5. Normality (¥) = sie Xd X10 folarity = “folecular mass (eolute) * xd%10 Normality = ——?- ‘Equivalent mass (solute) 8. Relationship between Molarity (A) and Metality (m) . 1000 M (1000 xa ) = (x GME) Relationship between Molality (m) and Mole fraction of solute (xp) mxGMM, m *8 = 1000+ m= GMM, 1000 x, iy ™" TOM, 10. Dilution formula: Ifthe solution of some substance is diluted by adding solvent from volume F to volume V, then MF, = MP Similarly, NK, = NPsja lu faa) = pea) 7 lu a) [e) ad Va) — 2 (2) (ey 2 13. Ta 15, 16. 17, ‘Molarity of « mixture: If ¥, mL of @ solution of molarity Af, is mixed with another solution of same substance with volume V, and molarity M, then molarity of the resulting mixture of solution (§M) can be obtained as: MRM jae ur, Relationship between molarity (M) and mole fraction of solute (xq) MxGMM, *8 * SA(GMM, -GMM,)=1000d 1000 xx, A M~ > XGMM, + x,* GMM, Raoult’s law for volatile solute Par Pit, and Pa Party where p, and py are partial vapour pressures of component *4” and component ‘Bin the solution. p? and _@ are Vapour pressures of pure components “4° and “B’ respectively. Total vapour pressure, p= Pat Po = PAX«t Paks Raoult’s law for non-volatile solute i : SE ag HE TE WE Fore slation ny 2NaCI+H,0 + CO, NaHCO; + HCl —» NaCl +H,0 + CO. I mole of Na,CO, requires HCI = 2 moles *. 0,00526 mole of NayCOs requires HCI = 0,00526 x 2 moles = 0.01052 moles | mol of NaHCO, requires HCI = 1 mol 0.00526 motes of NaHCO, requires HCI = 0.00526 moles Total HCI required = 0.01052 moles + 0.00526 moles = 0.01578 moles To ealeulate volume of 0.1 M HCL 0.1 moles of 0.1 M HCI are present in 1000 ml. of HCI 0.01578 moles of 0.1 M HC! will be present in HCI or x 558 2 Thus, Moles of Na,CO; = 00526 1 0.00526 1000 - Dy * 0.01578 = 187.8 mL Q.7. A solution is obtained by mixing 300 g of 25% and 400 g of 40% solution by mass. Calculate the mas percentage of the resulting solution. 300x258 _ ‘Ans. 300 g of 25% solution contains solute = "55" = 752 400 x 40 100 400 g of 40% solution contains solute 1608Ans, Qo Ans. Q.10. Ans, Qu. Ans, ‘Total mass of solute = 160 g +75 g= 235 g ‘Total mass of solution = 300 g-+ 400 g = 700 g 4 ofsouein eal soon = 22 160 = 348% 4% of solvent in the final solution = 100~33.5 = 66.8% ‘An antifreeze solution is prepared from 222.6 ¢ of ethylene glycol, CHO), and 200 g of water. Calculate the molality ofthe solution. Ifthe density ofthe solution is 1.072 g mi“, then what shall be the molarity of the solution? Mass of ethylene glycol = 222.6 g Molar mass of ethylene glycol, C,H,(OH), = 62 g mo! 2268 emo" Mass of water = 200 g = 0.20 ke Moles of ethylene glycol _ 3,59 mol ‘Mass of solvent in kg) ~ 0.20kg Total mass of the solution = 222.6 g + 200 ¢= 422.6 g Mass of solution _ 422.6 Density of solution 1,072 g mL" 3.59 mol Number of moles of ethylene glycol ‘Molality of solution = 7.95 mol ke Volume of solution = 904.2 mL = 03942 L. Moles of ethylene glycol 3.59 mol Mioletofedylens geal. c “1 Volume of solution (in Ly 0.30421 = 9-1 molt Molarity of solution = A sample of drinking water was found to be severely contaminated with chloroform, CHI, which is supposed to be a carcinogen. The level of contamination was 15 ppm (by mass). () Express this in percent by mass. (ii) Determine the molality of chloroform in the water sample. Let the mass of sotution be 10° ‘Mass of solute, chloroform = 15 g Mass of chloroform (i) % by mass of chloroform = A SS atigg * 100 E5100 = 15 x 10 % 10° g Gi) Mass of solvent, water = 10° 2-15 g~ 10°2= 107 kg 15, Number of moles of chloroform _ 0.126 mol ‘Mass of water (in kg) 10° ke = 1.26 x 10 mol kg ‘What role molecular interaction play in the solution of alcohol and water? ‘There is intermolecular hydrogen bonding in alcohol as well as in water. On mixing, the magnitude of attractive forces tends to decrease, Due to decrease in attractive forces, the solution shows positive deviations from ideal behaviour. As a result, the solution will have higher vapour pressure and lower boiling point as compared to that of pure water and pure alcohol separately. ‘Why do gases always tend to be less soluble in liquid as the temperature is raised? Gas + Liquid <> Dissolved gas: AH =—ve Dissolution of gas in liquid is an exothermic process. As the temperature is increased, according to the Le Chateliers principle the equilibrium will shift backward, This results in decrease of solubility of gases in Liquid. Molality of solutionQ.12. State Henry’s law and mention some important applications. Ans. Refer to Points to remember 2(c). Q.13. The partial pressure of ethane over a solution containing 6.56 x 10" g of ethane is 1 bar. If the solution contains 5.00 x10 g of ethane, then what shall be the partial pressure of the gas Ans. According to Henry's law, m= Ky xp Case L 6.56 x 10g = Ky x bar or, Ky = 6.56% 10° g bar" Case I. 5.00 x 107 g = (6.56 x 107 g bat) xp. 500x107 g or P = 7.62 bar © 656% 107 g bar? Q.14. What is meant by positive and negative deviations from Raoult’s law and how is the sign of Ayia related to positive and negative deviations from Raoult’s law? ‘Ans. Refer to Points to remember 5(b). Q.15. An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the normal boiling point of the solvent. What is the molar mass of the solute? ‘Ans. Vapour pressure of pure water atthe boiling point (p®) = 1 atm ‘Vapour pressure of solution (p,) = 1.004 bar Mass of solute, Wy =? g Mass of solution = 100 g Mass of solvent, W, = 100 g—2.¢=98 g Applying Raoult’s law for dilute solution (being 2%) Pa Pe 013 bar mye nt (1.013 bar- 1,004 bar) _ 2gX18.g mol! 1.013 bar = My X98 2gX18gmol™ x 1.013 bar z * Me= “og ¢x0.009 bar = 41'S emo!” Q.16. 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 0f 26.0 g of heptane and 35.0 g of octane? Ans. Molar mass of heptane, C7H,s = 100 mol ‘Molar mass of octane, CgHyg = 114 g mol 26.0e 0.26 mol ge Da ce" Toone 35.0. eee “= 114 mol 0.26 0.26+0.31 =D 105.2 kPa x 0.456 =47.97 kPa Prqtiy = 46.8 KPa x 0.544 = 25.46 kPa Praat = Posy, + Pests = 47.97 + 25.46 PoitteQ.17. The vapour pressure of water is 12.3 kPa at 300 K. Caleulate the vapour pressure of 1 molal solution of a non-volatile solute init. Ans. | molal sotution means 1 mol of the sotute is present in 1000 g of the solvent, HO (assuming the solution to be dilute). 1000 nyo = “yg = 55:5 moles i Nome = [FF 700177 PP, 123-p, Also, Sanse® Sy 00177 = 55 or p, = 12.08 kPa Q.18. Calculate the mass of a non-volatile solute (moar mass 40 g mot") which should be dissolved in 114 octane to reduce its vapour pressure to 80%. Wy 30% of p”= = 0.80 p°sng= gq mol 100 14g 1 mol (Molar if CgH yg = 114, ry tegiy = PAE | = 1 mol (Molar mass of Cy = 114 g mol ca” Tag mort Hye dg Now, =% 1, /40 ,/40*1 or Wy=108 Q.19. A solution containing 30 g of a non-volatile solute exactly in 90 g of water has a vapour pressure of 2.8 kPa at 298 K. Further 18 g of water is then added fo the solution, the new vapour pressure becomes 2.9 kPa at 298 K. Calculate () molar mass of the solute (i) vapour pressure of water at 298 K. ‘Ans. (i) Suppose the molar mass of the solute = Mg g mol” Number of moles of solute, ny = 32- mot 908 Number of solvent (water) 4 = =; =5 mol 18 mol According to Raoult’ law, PA-Ps Pa or 12 30M, 5+30M,-30M, or 1 ~3+G0M) ~ 3+G0My) ~3+G0/M,) 5+ GM) = ro) After adding 18 g of water, Number of moles of water (14) = “ =6 molAccording to Raoult’s law, Pu-29 30M, Pa 6+G0M,) 129, 30M py 6+ G0M,) 29 30/M, —_ 6+ (30/M,) - (30/M,) 6 = P| 6+ GOM,) 6+G0/M,) 6+G0MM,) Py 6+G0M,) = 29 6 Pa a aes di) Dividing equation (i) by equation (ii), we get 29 _ L*@iM,) 2.8 ~ 1+G/M,) 5 6 or 2a(i+gr) My HS 5g, 18 23, eonetear or 2947 a28+ OF ay HOLL oF Mp=23 gmol Gi) Putting the value of Mg in equation (), we get Pi or Q.20, A 3% solution (by mass) of eane sugar in water has a freezing point of 271 K. Calculate the freezing, point of a 5% glucose in water if the freezing point of pure water is 273.15 K. ‘Ans. Let the mass of solution = 100 Mass of the cane sugar = 5 g Mass of solvent, water = 100 g-5 = 958 AT,= 273.15 K-271 Ks 215K K,*W, X1000 AT, x M,xW, iii os Ree XW, 1 W100 2.15342 95 1 = dy = 13.97 K kg mol” For 5% sotution of glucose in water K,*Wy*1000 _ 13.075 1000 T80x95 Freezing point of glicose solution, Tj= AT ~ AT;= 273.15 K ~4.08 K = 269.07 K Q.21, Two elements 4 and B form compounds having molecular formula 4B and AB,, When dissolved in 20g, of benzene (C,H) 1 g of AB, lowers the freezing point by 2.3 K whereas 1.0 g of AB, lowersiit by 1.3 K. The molal depression constant for benzene is $.1 K kg mol" Calculate atomic masses of 4 and B. Ans. We know, K, 1000 M, ATW,a2. Ans, Q2. Q24. Ans. = 5X1 1000 Tien sig, = SELL 10572 Sina, iy, = SERED gg mor! ‘Suppose atomic masses of 4 and B are ‘a’ and ‘b’ respectively. Then ‘Molar mass of AB, = a + 2b = 110.87 g mol” Molar mass of AB, = a +4b = 196.15 g mol" Subtracting equation (i) from equation (i), we get 2b = 85.28 or b = 42.64 ‘Substituting the value of 6 in equation (), we get a+ 2x42.64= 110.87 or a Thus, Atomic mass of A= 25.59 0 Atomic mass of B= 42.64 0 At 300 K, 36 g of glucose present in a litre of its solution has an osmotic pressure of 4.98 bar. If the ‘osmotic pressure of the solution is 1.52 bar at the same temperature, what would be its concentration? Osmotic pressure, = CRT ) 5.59 First ease: 368 Number of moles of glucose, C,Hj,0, = ——"—> = 0.2 mol 180 2 mot ji , 0.2 mol 4, Molar concentration of solution, C= 957°" = 0.2 mol L i 4.98 bar= 0.2 mol L“! x Rx 300 K i) Second case: 152=CxRx300K Ai) Dividing equation (i) by equation (), we get 1.52 bar Cx Rx300K }98bar 0.2 mol Lx RX 300K 0305 = —___ 0.2 mol E or (C= 0.0610 mol L"* ‘Suggest the most important type of intermolecular interaction in the following pairs: @ n-hexane and n-octane (i) T, and CCl, ii) NaClO, and water (ir) methanol and acetone (») acetonitrile (CHyCN) and acetone (C3H,0). (@ Dispersion or London forces as both are non-polar. (ii) Dispersion or London forces as both are non-polar. (i) Lon—dipote interactions as sodium chlorate gives Na* and C10, iv) Dipole-dipole interactions as both are polar molecules. (0) Dipole-dipole interactions as both are polar molecules. Based on solute-solvent interactions, arrange the following in order of increasing solubility in n-octane and explain. Cyclohexane, KCI, CH,OH, CH,CN (8 Cyclohexane and n-octane both are non-polar. Hence, they will mix completely in all proportions. Gi KC1 is an ionic compound whereas n-octane is non-polar. Hence, KCI will not dissolve at all in nsoctane, (did) CH,OH and CH,CN both are polar but CH,CN is less polar than CH,OH. As n-octane is non-polar, CHCN will dissolve more than CH;OH in n-octane. ‘Therefore, the order of solubility in n-octane will be KCI < CH,OH < CH,CN < Cyclohexane. jons and water is a polar molecule.Q.28, Ans. Q27. Ans. Q.28. Ans. Q.29. Ans, Amongst the following compounds, identify which are insoluble, partially soluble and highly soluble {in water: (@ phenol, (i) toluene, (if) formic acid, (ir) ethylene glycol, (») chloroform, (vi) pentanol. () Partially soluble as it has non-polar C,H group and polar —OH group which can form hydrogen bond with water. (ii) Insoluble as toluene is non-polar while water is polar. (id) Highly soluble as formic acid can form hydrogen bonds with water. (iv) Highly soluble as ethylene glycol can form hydrogen bonds with water. () Insoluble as chloroform despite its polarity, cannot form hydrogen bonds with water. (v2) Panially soluble as OH group is polar but the bulky CH, , partis non-polar. If the density of some lake water is 1.25 g ml.“ and contains 92 g of Na’ ions per kg of water, calculate the molality of Na* ions in the lake, 23. gmoft Number of moles of Na* ions Mass of water in kg Amol * Tk If the solubility product of CuS is 6 x 10", calculate the maximum molarity of CuS in aqueous solution. ‘Maximum molarity of CuS in aqueous solution = Solubility of Cus in mol L~'. Af Sis the solubility of CuS in mol L“! then Cus = Cu +S Molality of Na" ions = = =4m mol kg” soos Kg =(Cu™] [S*]=Sx5=2 S$ a6x 10" or S= Vox10" = 2.45 x 10% mol Lt Maximum molarity of CuS in aqueous solution = 2.45 x 10" mol L~ Calculate the mass percentage of aspirin (C;H,0,) in acetonitrile (CHyCN) when 6.5 g of CsH,Og is dissolved in 450 g of CH,CN. Mass of solution = 6.5 2 + 450 g = 456.5 g Mass of aspirin 65 3 Mas orectaion 1) ase5 "00 A Nalorphene (C gH;,NO3) similar to morphine, is used to combat withdrawal symptoms in narcotic users. Dose of nalorphene generally given is 1.5 mg, Calculate the mass of 1.5 x 10° m aqueous solution required for the above dose. 1.5 x 10 m solution means that 1.5 x 107 mole of nalorphene is dissolved in 1kg of water. Molar mass of C pHa NO, = 19 x 12 +21 + 14+48=311 g mor 1.5 x 10° mole of C,H,iNO, = 1.5 x 107 x 311 Mass of sotution = 1000 + 0.467 g = 1000.467 g ‘Thus, for 0.467 g of nalorphene, solution required = Mass % of aspiti 1000.467g 3 Hence, for 1.5 x 10 g of nalorphene, solution requited = 5 geq-— X 1.5 X 10 B= 3s g Calculate the amount of benzoic acid (C,H,COOH) required for preparing 250 mI. of 0.15 mol L™ solution in methanol. sqy = Mass of solute/Molar mass, Molarity = Sass of solute’ Molar mass _ ‘Volume of solution (in litres) ‘Mass of benzoic acid = Molarity x Volume of solution x Molar massQ.32. Ans, Q33. 250 Volume of solution = 250 mL= =" 1 20.251 solution = 25 i 25 Molar mass of benzoic acid, CH,COOH =7 x 12+6x 142% 16= 122 g mol! Mass of benzoic acid = 0.15 mol L”! x 0.25 Lx 122 g mot"! = 4.875 g The depression in freezing point of water observed for the same amount of acetic acid, tri-chloroacetic acid and trifluoroacetic acid increases in the order as given. Explain briefly. ‘The depression in freezing points are in the order: CH,COOH < C1,CCOOH < F,CCOOH Fluorine, being the most electronegative, has the highest negative inductive effect. As a result of this, trifluoroacetic acid is the strongest acid while acetic acid is the weakest acid. Hence, trifluoroacetic acid ionises to the largest extent while acetic acid ionises to the minimum extent to give ions in their solutions in water. Greater the ions produced, greater is the depression in freezing point. Hence, the depression in freezing point is the maximum for the trifluoroacetic acid and minimum for acetic acid Caleulate the depression in the freezing point of water when 10 g of CH,CH,CHCICOOH is added to 250 g of water; K, = 1.4 x 10%, K,= 1.86 K kg mol, log Ta gmart 715% 107 mot ‘Number of moles of CH,CH,CHCICOOH = Molality of the solution = —No-of moles of solute, 999 Mass of solvent (in grams) *1000 = 0.3264 mol kg"! If exis the degree of dissociation of CH,CH,CHCICOOK, then CH;CH;CHCICOOH = = CH,CH;CHCICOO™ + HY Initial cone. mol L™ 0 0 At equilibrium cua) ca co (Considering (1 - 1 for dilute solution] or 065 Calculation of van't Hoff factor: CH,CH,CHCICOOH =* CH,CH,CHCICOO™ + H Initial motes 1 0 ° Moles at equilibrium Ia « a Total number of mole of particles after dissociation Total number of moles of particles after dissociation ‘Number of particles before dissociation -atata=ite 18 <1 4e= 1 +0065 = 1.065 AT, =i Km = (1.065) (1.86) (0.3264) = 0.65 K 195 g of CH,FCOOH is dissolved in 500 g of water. The depression in the freezing point observed is, 1.0°C. Caleulate the van't Hoff factor and dissociation constant of fluoroacetic acid. OR ‘When 19.5 g of F—CH,—COOH (Molar mass = 78 g mol”) is dissolved in $00 g of water, the depression in freezing point is observed to be 1°C. Calculate the degree of dissociation of F—CH,—COOH. (Given: K, of water = 1.86 K kg mol” [CBSE 2020 (56/3/1))Ans, Ans. Q.36. Ans, Calculation of van’t Hoff factor (: 195 ‘Number of motes of fluoroacetie acid = =~ = 0.25 mol 78g mol" Number of moles of luoroacetic a ‘Mass of water in ke =0.5 mol kg”! Molality, m = 47, Ape RK Xm Re Here, AT)= 1.0 K; Kp= 1.86 K kg mol"; m=0.5 mol kg”! = ss 1.86 K kg mol” x 0.5 mol kg’ Calculation of dissociation constant, FCH,COOH = * FCH;COO" + HT Initial cone. 05 0 0 Atequilibrium — 0.5 (1- a) osa = OSa Total =0.5 (1 +4) os(+a) Serta or asi-1=1.0753- 150.0753 05 k= WSa405a _ 05a? _ 0.5% (0.0753)? ‘@ 05(1-a) 1-@ 10.0753 K, =3.07 x 107 ‘Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure of water at 293 K when 25 g of glucose is dissolved in 450 g of water. pi, = 17.535 mm Hg; Wy = 25 g; W, = 450 g: Mp = 180 g mol"; My = 18 g mot" ‘Substituting the values in the expression Pan Ps _ Wa My ay x WERE Pm MXM, 17535 P, asx 18 2, 17535 180x450 |=! a7335 19 Ray or p,=1744mm Hg Henry's law constant for the molality of methane in benzene at 298 K is 4.27 x 10° mm Hg, Caleulate the solubility of methane in benzene at 298 K under 760 mm Hg. Here, Ky =4.27» 10% mm Hg, p= 760 mm Hg According to Henry's law, p= Ky Xen, _p 760mm Hg eK, 4.2710 mmHg x 78x 107 Mole fraction of methane in benzene, xc, = 1.78 107 100 g of liquid A (molar mass 140 g mol") was dissolved in 1000 g of liquid B (molar mass 180 g mol"). The vapour pressure of pure liquid B was found to be 500 torr. Calculate the vapour pressure of pure liquid A and its vapour pressure in the solution if the total vapour pressure of the solution is 475 torr. 100g 5Q.37. Ans. Ans, pag ang eS eos "4 577+ 5019 ~ 395/63 ~ 7“ 395 ~ 305 xg= 10.114 = 0.886 Also, given P3 = 500 torr According to Raoult’s law, Py HPD ps, Py = XpP9 = 0.886 x 500 = 443 tore P=pa+Po 475 = 0.114 po +443 « _ 475-443, or PAS 01a Substituting this value in equation (?), we get Py = 280.7 x 0.114 = 32 torr 280.7 torr Ai) ‘Vapour pressures of pure acetone and chloroform at 328 K are 741.8 mm Hg and 6328 mm Hg respectively. Assuming that they form ideal solution over the entire range of composition, plot Prot Pettortorn, #4 Pacetgue 88 9 function of X,pqiaqe the experimental data observed for different compositions of mixture is: 100 X Xyectme o | 18 | 24 | 360 | 508 | 582 | 645 | 721 Pecos (mn Hg o | 349 | 1101 | 2024 | 3227 | aos9 | 4541 | S211 Penoroform/ mmHg | 632.8 | 548.1 | 469.4 | 359.7 | 287.7 | 1936 | 161.2 | 120.7 Plot this data also on the same graph paper. Indicate whether it has positive deviation or negative deviation from the ideal solution. g 8 Vapour Pressure (nm) B88 8 D1 02 03 0405 06 07 08 Mole fraction of acetone (Xacti) a 0 | 0118 | 0234 | 0360 | 0.508 | 0582 | 0.645 | 0.721 Paccone/ tm HE o | 549 | 1101 | 2024 | 322.7 | 4059 | 4541 | 5210 |Peatoroform / mn Hg 6328 | 548.1 | 4604 | 359.7 | 257.7 1936 | 1612 | 1207 fo 6328 | 6030 | S795 | 5621 | S804 | 5005 | 6153 | GHB Since the plot for Piya dips downwards, the solution shows negative deviation from the ideal behaviour. Benzene and toluene form ideal solution over the entire range of composition. The vapour pressures of pure benzene and toluene at 300 K are $0.71 mm Hg and 32.06 mm Hg respectively. Caleulate the mole fraction of benzene in the vapour phase if 80 g of benzene is mixed with 100 g of toluene. Molar mass of benzene (C,H) = 78 g mot” ‘Molar mass of toluene (C,H) = 92 g mor808 Regi, = Sy = 1.026 mol ‘He 78.2 mol fog, = oo = 1.087 mot . 1.026 * eat 1026+ 1.087 ep, = 1 0.486 = 0.514 Pbgig = 50.71 mm He, py = 32.06 mm Hg Applying Raoult’s law Poqttg = Xcqitg ¥ Pegg = 0.486 x 50.71 mm Hg = 24.65 mm He Pests = XcitgX Po, = 0.514 x 32.06 mm Hg = 16.48 mm Hg Pox, Peau, * Pet, 24.65 2465+1688 41.13 ‘Mole fraction of benzene in the vapour phase Q.39. The air is a mixture of a number of gases. The major components are oxygen and nitrogen with approximate proportion of 20% is to 79% by volume at 298 K. The water is in equilibrium with air at a pressure of 10 atm. At 298 K, if the Henry’s law constants for oxygen and nitrogen at 298 K are 3.30 x 10” mm and 6.51 x 10” mm respectively, calculate the composition of these gases in water. As. Pail res of oxygen o,= 2 x10 am 2am = 2760 mm Hg = 1520 mn Hg Partial pressure of nitrogen, py, 2 x 10 atm = 7.9 atm = 7.9 x 760 mm Hg = 6004 mm Hg Ky (Oz) = 3.30 x 107 mm, Ky (Nz) = 6.51 x 10" mm Applying Henry's law, Poy = Ku Xo, Po, ___1520mm " = j— on eee eae be “°K,” 330610" mm Py, = KX an, Py 6004 min Ky 6.5110? mm Q.40. Determine the amount of CaCl, (/= 2.47) dissolved in 2.5 litre of water such that its osmotic pressure is 0.78 atm at 27°C. iW, XRXT 1XM, XV oe XV 2° TXRXT Molar mass of CaCl, My = 40 +2x35.5 °. = 9.22 x 10% on XN, Mass of CaCl, We =342g Q.41. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K,SO, in 2 litre of water at 25°C, assuming that it is completely dissociated. ICBSE Dethi 2013, 2019 (56/S/2)) Anns. K3S0, dissolved = 25 mg = 0.025 2 ‘Votume of solution =2 L, T= 25°C = 208 K Molar mass of K,SO, = 2.x 39 +32+4.x 16= 174 g mor Since K,S0, dissociates completely as K,SO, > 2K* + SO,‘Number of moles of particles after dissociation Number of moles of particles before dissociation Applying van't Hoff equation, XW, XRXT M,xV 3 2 30,025 g x 0.0821 L atm K™' mol”! x 298K 174g mol! x2L ae Multiple Choice Questions Choose and write the correct option(s) in the following questions. = 2 Which of the following is an example of a solid solution? ICBSE Sample Paper 2022) (@) Sea water (6) Sugar solution (c) Smoke (d) 2 carat gold ‘One kilogram of sea water sample contains 6 mg of dissolved O,. The concentration of O, in ppm in the sample is (@) 0.06 60 oe @ 06 An azeotropic mixture of two liquids has a boiling point higher than either of the two liquids when it (CBSE 2023(56/3/3)] (@) shows large negative deviation from Raoult’s law. (6) shows no deviation from Raoult’s law. (6) shows large positive deviation from Raoult’s law. (@ obeys Raoult’s law. 50 mI. of an aqueous solution of glucose C,H,,0, (Molar mass : 180 g/mol) contains 6.02 x 10% molecules. The concentration of the solution will be [CBSE 2020 (5672/1) @O01M (02M (10M @ 20M ‘On dissotving sugar in water at room temperature solution feels cool to touch. Under which of the following cases dissolution of sugar will be most rapid? [NCERT Exemplar] (a) Sugar erystals in cold water (6) Sugar erystals in hot water (c) Powdered sugar in cold water (@) Powdered sugar in hot water Solubility of gases in liquids decreases with rise in temperature because dissolution is an [CBSE Sample Paper 2022) (a) endothermic and reversible process. (©) exothermic and reversible process. (©) endothermic and irreversible process. (A) exothermic and irreversible process. ‘Which of the following factor(s) affect the solubility of a gaseous solute in the fixed volume of liquid solvent? INCERT Exemplar] @ nature and solute (i) temperature iii) pressure (@) Gi) and (i at constant T () (@ and Gi at constant P (©) Gi and (ii only @ Gi) only ‘Value of Henry's constant Ky [CBSE 2023 (56/2/1) | (@) increases with decrease in temperature (©) decreases with increase in temperature. (© increases with increase in temperature. (@) remains constant.9. Low concentration of oxygen in the blood and tissues of people living at high altitude is due to ICBSE 2023 (56/1/1)) (a) high atmospheric pressure, (©) low temperature. (0) low atmospheric pressure. (@) both low temperature and high atmospheric pressure. 10. Which one of the following pairs will not form an ideal solution? [CBSE 2023 (56/3/3)) (a) Benzene and Toluene (B) Nitric acid and Water (c) Hexane and Heptane (d) Ethyl chloride and Ethyl bromide 11. Considering the formation, breaking and strength of hydrogen bond, predict which of the following mixtures will show a positive deviation from Raoult’s law? [NCERT Exemplar| (a) Methanol and acetone (6) Chloroform and acetone (0) Nitric acid and water (d) Phenol and aniline 12. Intermolecular forces between two benzene molecules are nearly of same strength as those between {two toluene molecules. For a mixture of benzene and toluene, which of the following is not true? () Agu HT = 7800 ©) Ay P= 220 (©) These will form minimum boiting azeotrope. (d) These will form an ideal solution. 13, When 1 mole of benzene is mixed with 1 mole of toluene, the vapour will contain (Given: vapour pressure of benzene = 12.8 kPa and vapour pressure of toluene = 3.85 kPa). ICBSE Sample Paper 2021] (@) equal amount of benzene and toluene as it forms an ideal solution (®) unequal amount of benzene and toluene as it forms 2 non ideal solution (©) higher percentage of benzene. (@ higher percentage of toluene. 14. In the following diagram point, ‘X’ represents [CBSE 2022 (56/3/4)) Temperature —> (a) boiling point of solution (8) freezing point of solvent (©) boiling point of solvent (@) freezing point of solution ‘An unripe mango placed in a concentrated salt solution to prepare pickle, shrivels because 3 INCERT Exemplar] (G) it gains water due to osmosis. (it loses water due to reverse osmosis. (@ it gains water due to reverse osmosis. @ it loses water due to osmosis. 16. In Which of the following cases blood cells will shrink? (CBSE Sample Paper 2022) (@) when placed in water containing more than 0.9% (mass Volume) NaCI solution. @) when placed in water containing less than 0.9% (mass /volume) NaC solution. (©) when placed in water containing 0.9% (mass/volume) NaCl solution. (@) when placed in distilled water. 17. The colligative property used for the determination of molar mass of polymers and proteins is [CBSE 2023 (56/1/1)) (@) osmotic pressure (©) depression in freezing point. ©) relative lowering in vapour pressure. (@ elevation is boiling point.