After studying this Unit, you will be able to describe the formation of different types of solutions; express concentration of solution in different units state and explain Henry's law and Raoult’s law; distinguish between ideal and non-ldeal solutions; explain deviations of real solutions from Raoult’s law; describe colligative properties of solutions and correlate these with molar masses of the solutes; explain abnormal colligative properties exhibited by some solutes'in solutions. Almost all processes in body occur in some kind of liquid solutions. In normal life we rarely come across pure substances. Most ofthese re mises confaing tvo.or more pury Substances Their utility or importance in life depends on their composition. For example, the properties of ‘(BrASS{ (mixture of, fare quite different from those of (mixture of, coppers zanay and or (mixture of 7 (ppm) of, in water while ‘auses the tooth to become mottled and high concentrations of fluoride (for crample, MGR used in intravenous injections are always dissolved in water containing salts at. particular ionic concentrations that match with blood plasma concentrations and so on. In this Unit, we will consider mostly liquid solutions and their formation. This will be followed by studying the properties of the solutions, like vapour pressure and colligative properties. We will begin with types of solutions and then various alternatives in which concentrations of a solute can be expressed in liquid solution. 1.1 Types of Solutions are homogeneous mixtures of two or more than two components. By homogenous mixture we mean that its composition Solutions and properties are uniform throughout the mixture. Generally, the component that is present in the 7 One or more components present in the solution other than solvent are called solutes. In this Unit we shall consider only binary solutions (i.c.,| Gaseous Solutions | Liquid Solutions Solid Solutions 14.2 Expressing Concentration of Solutions Consisting of two components). Here each component may be solid. liquid or in gaseous state and are summarised in Table 1-1 Table 1.1: Types of Solutions Gas Mosture of oxygen and nitrogen gases Liquid Chloroform mixed with nitrogen gas Solid Solid Solid Gas Camphor in nitrogen gas Gas Liquid | Oren dissolved im water Liquid Liquid | Ethanol dissolved in water Solid Liquid | Glucose dissolved in water Liquia Solid | Amalgam of mercury with sodium Copper dissolved in gold Composition of a solution can be described by expressing its concentration. The latter can be expressed either qualitatively or quantitatively. For example, qualitatively we can say that the solution Is dilute (Le., relatively very small quantity of solute) or it is concentrated (Le., relatively very large quantity of solute). But in real life these kinds of description can add to lot of confusion and thus the need for. quantitative description of the solution. There are several ways by which we can describe the concentration of the solution quantitatively. Mass percentage (w/w): The mass percentage of a component of a solution is defined as: Mass % of a component = Mass of the component in the solution - Total mass of the solution For example, if a solution is described by 10% glucose in water by mass, it means that 10g of glucose is dissolved in 90 goof water resulting in a 100 g solution. Concentration described by mass percentage {s coinmonly used in industrial chemicat applications. For example. tains (ii) Volume percentage (V/V): The volume Percentage is defined as: Volume of the component Total volume of solution «100 ay Volume % of a component = a2——_ For example, 10% ethanol solution in water means that 10 rl, of ethanol is dissolved in water such that the total volunic of the solution ts 100 mL, Solutions containing liquids are commonly expressed in this unit. For example, « 1/0) solution of (tii) Mass by volume percentage (w/V): Another unit whieh is commonly used in medicine and pharmacy is mass by volume percentage. It is the mass of solute dissolved in 100 mL, of (he solution, (tv) Parts per million: When a solute is present in trace quantities, it 1s convenient to express concentration in parts per million (ppm) and is defined as: Parts per million = | Number of parts of the component _ Total number of parts of all components of the solution 10" (1.3) | As in the case of percentage, concentration in parts per million can also be expressed as mass to mass, volume to volume and mass to volume. A litre of sea water (which weighs 1030 g) contains about 6 x 10° g of dissolved oxygen (O,). Such a small concentration is also expressed as 5.8 g per 10” g (5.8 ppm) of sea j water. The concentration of pollutants in water or atmosphere is j often expressed in terms of jigiml™orippmy | (¥) Mole fraction: Commonly used symbol for mole fraction is x and subscript used on the right hand side of x denotes the component. It ts defined as: j | | Mole fraction of a component = j Number of moles of the component __ | Total number of moles of all the components (4) | For example, in a binary mixture, if the number of moles of A and Bare n, and ry respectively, the mole fraction of A will be | n A (15) For a solution containing { number of components, we have: | n, n » én RAG feaatn San eS It can be shown that in a given solution sum of all the mote fractions ts unity, 1.e. Wy PF tncsersiereersten PSL a7 Mole fraction unit {s very usefull in relating some physical properties of solutions, say vapour pressure with the concentration of the solution and quite useful in describing the calculations involving gas mixtures. | | |Eo ? i (vii) Molality: Molality (m) is defined as the number of moles of the | solute per kilogram (kg) of the solvent and is expressed as: Moles of solute Molality (m) =~ °©S © SOUNe_ 9) fy (Om) - ras of solvent in kg For example, 1.00 mol kg" (or 1.00 m) solution of KC! means that 1 mol (74.5 g) of KCI is dissolved in 1 kg of water. Each method of expressing concentration of the solutions has its | | own merits and demerits. | are independentiofemperaturt. wherea a function of | a | Calculate molality of 2.5 g of ethanoic acid (CH,COOH) in 75 g of benzene f Molar mass of C,H,O,: 12*2+14+ 16x 2= 60g mol" Solution 25¢ Moles of CyH,O2 = Ge gesagt 7 0-0417 mol Mass of benzene in kg = 75 g/1000 g kg! = 75 x 10° kg Moles of C,H,O, _ 0.0417 mol x 1000 g kg Molality of CH,O.= “7 of benzene ~ 75g Intext Questions 1.1 Calculate the mass percentage of benzene (CgH,) and carbon tetrachloride (CCl,) if 22 g of benzene is dissolved in 122 g of carbon tetrachloride. mass in carbon tetrachloride. 1.2 Calculate the mole fraction of benzene in solution containing 30% by 1.3 Calculate the molarity of each of the following solutions: (a) 30 g of Co(NOs)». 6H,0 in 4.3 L of solution (b) 30 mL of 0.5 M H,SO, diluted to 500 mL. 1.4 Calculate the mass of urea (NH,CONH,) required in making 2.5 kg of 0.25 molal aqueous solution. “Z.8) Calculate (a) molality (b) molarity and (c) mole fraction of KI if the density of 20% (mass/mass) aqueous KI is 1.202 g mL’. Solubility of a substance is its It depends upon the in as well a and Let us consider the effect of these factors in solution of a solid or a gas in a liquid. iimm_Solutions ___1.3.1 Solubility of a Solid in a Liquid 1.3.2 Solubility of aGasina Liquid Chemistry selaam Every solid does not dissolve in a given liquid. While sodium chloride and sugar dissolve readily in water. On the other hand, It is observed that in the two or we may say like dissolves like. When a solid solute is added to the-solvent, some solute dissolves i res 7 cess is known as and its concentration increases in solution. This process is kn ‘Some solute particles in solution collide with the solid solute Particles and get separated out of solution, This process is known as ‘A stage is reached when the two processes occur at the same rate. Under such conditions, number of solute particles going into solution will be equal to the solute particles separating out and a state of, jis reached. Solute + Solvent = Solution (1.10) At this stage the concentration of solute in solution will remain constant under the given conditions, i.e., temperature and pressure. Similar process is followed when gases are dissolved in liquid solvents. Such a solution in which no more solute can be dissolved at the same temperature and pressure is called a Sattiratedysolmtiey. An unsaturated solution is one in which more solute can be dissolved at the same temperature. The solution which is in dynamic equilibrium with undissolved solute is the saturated solution and contains the maximum amount of solute dissolved in a given amount of solvent. Thus, the Earlier we have observed that solubility of one.substance into another depends on the nature of the substances. In addition to these variables, two other parameters, {.e., temperature and pressure also control this phenomenon. Effect of temperature ‘The solubility of a solid in a liquid is significantly affected by temperature changes. Consider the equilibrium represented by equation 1.10. This being dynamic equilibrium. must follow Le Chateliers Principle. In general. if in a nearly saturated solution, the dissolution process is endothermic (4,4 H > 0), the solubility should increase with rise in temperature and if it is. exothermic (A, H<0) the solubility should decrease. These trends are also observed experimentally. Effect of pressure Pressure does not have any significant effect on solubility of solid: liquids. It is so because, eee se and Many gases dissolve in water. Oxygen dissolves only to a small ly extent in water. It is this dissolved oxygen which sustains all aquatic life. on the other hand, hydrogen chloride &as (HCI is highly soluble in water. Solubility of gases in liquids is Greatly affected by pressure and Fig Partial pressure of HCI /torr1000 500} Partial pressure of HCI /torr Mole fraction of HCI in its solution in cyclohexane Fig. 1.2: Experimental results for the solubility of HCL gas in cyclohexane at 293 K. The 0.010 pee et ke temperature, The solubility of gases increase with Increase of pressure For solution of gases in a solvent, consider a system as shown in Fig. 1.1 a). The lower part Is solution and the upper part ts gaseous system at pressure p and temperature 7. Assume (his system to be tn 4 state of dynamic equilibrium, t.¢., under these conditions rate of gaseous particles entering and leaving the solution phase fs the same Now ine the pressure over the solution phase by compressing (he gas to a smaller volume [Fig, 1.1 (b)}. This will inerease the number of cous particles per unit volume over the solution and also the rate at which the gaseous particles are striking the surface of solution to enter it, The solubility of the gas will increase until a new equilibrium: \s reached resulting in an increase in the pressure of a gas above the solution and thus its solubility increases. Henry was the first to give a quantitative relation between pressure and solubility of a gas in a solvent which is known as Henry's law. The law states that at a constant (temperature, the solubility of a gas in a liquid is directly proportional to the partial pressure of the gi present above the surface of liquid or solution. Dalton, a contemporary of Henry, also Fe eee a istad Galubilty ofa gas. The concluded independently that the concentration of dissolved gas is proportional to the ae Preature Gh tha gas tikes solution solubility of a gas in a liqui solution is a function of partial pressure of the gas. If we use the mole fraction of a gas in the solution as a measure of its solubility, then it can be said that the mole fraction of gas in the solution is proportional to the partial pressure of the gas over the solution. The most commonly used form of Henry's law states that “the partial pressure of the gas in vapour phase (p) is proportional to the mole fraction of the gas (x) in the solution” and is expressed as: P=Kyx aay Here K,, 1s the Henry's law constant. If we draw a graph between partial pressure of the gas versus mole fraction of the gas in solution, then we should get a plot of the type as shown in Fig. 1.2. 0.020 Different gases have different K,, values at the same temperature (Table 1.2). This suggests that /KWUSTa’ It s obvious from It can be seen from Table 1.2 slope of the line ls the that K,, values for both N, and O, increase with increase Henry's Law constant, K,, of temperature indicating that the solubility of gases lag, Solutions Senin