Chem 200

Dr. Saidane Lecture Notes Chapter 13 Properties of Solutions

SOLUTIONS A solution is a homogeneous mixture of two or more substances in a single phase. In a solution, atoms, molecules, or ions are thoroughly mixed, resulting in a mixture that has the same composition and properties throughout. Components of Solutions The dissolving medium in a solution is called a solvent and the substance dissolved in a solution is called the solute. Types of Solutions Solutions can be solids, liquids, or gases. Examples of solid solutions are alloys. Any mixture of gas is a gaseous solution. Liquid solutions can be aqueous or organic. An example of aqueous solution is

salt-water; an example of organic solution is gasoline, which is a mixture of hydrocarbons. In this chapter, we will focus largely on aqueous solutions, but must of this material apply to non-aqueous solutions. Molecular Nature of Dissolving Solids dissolve in water when individual molecules or ions are attracted to water When dissolved, the molecules are surrounded by water and held in suspension by molecules and break away from the solid. dipole-dipole interactions, whereas the ions are held by ion-dipole interactions. Solubility A given quantity of solvent can dissolve only so much solute. A solution is saturated when the solvent has dissolved all the solute it can and some undissolved solute remains.

The concentration of solid solute in a saturated solution has reached its greatest

value and no more can dissolve. In other words, a saturated solution represents the limit of a solutes ability to dissolve in a given quantity of solvent. The molar solubility of a substance is its molar concentration in a saturated solution. A saturated solution is one in which the dissolved and undissolved solute are in A solution that contains less solute than a saturated solution under the existing A supersaturated solution is a solution that contains more dissolved solute than dynamic equilibrium with one another. conditions is an unsaturated solution. a saturated solution under the same conditions. A supersaturated solution may remain unchanged for a long time if it is not disturbed, but once it is disturbed, crystals start to form until the solution becomes saturated. WHY DOES ANYTHING DISSOLVE? Heats of Solutions The formation of a solution is accompanied by an energy change. Solvent and The amount of heat energy change when a specific amount of solute dissolves in a solute particles experience changes in their intermolecular interactions. solvent is the enthalpy of solution. Depending on the solute, the enthalpy of solution can be exothermic or endothermic. The enthalpy of solution, Hsol, is the sum of the enthalpy changes required to separate the molecules or ions of the solute (the lattice enthalpy, HL) and the enthalpy change accompanying their hydration, Hhyd Hsol = HL + Hhyd. In some cases Hsol is exothermic, and in others it is endothermic. In the gaseous state, molecules are so far apart that there are virtually no intermolecular forces between molecules. Therefore, the solute-solute interaction has little effect on the enthalpy of a solution of gases Hsol = 0. Hsol < 0 when a gas dissolves in a liquid because the interaction between gas solute and solvent molecules outweighs the energy needed to separate solvent molecules.

Solubility and Disorder Energy and matter tend to disperse. Matter has a natural tendency to disperse in a disorderly way. The reverse process in unnatural and has no tendency to occur. The dispersal of matter accounts for the expansion of gases and the spreading of matter through the environment, and contributes to the tendency of solids to dissolve. Many substances dissolve to give a system with more disorder than was present When a polar solute is dissolved in water, the water molecules may become initially. organized around it. As a result, the disorder of the solvent is reduced when the solution is formed. The solution is more stable and therefore loses some of its energy to the surroundings, which now becomes less organized because it gained energy. In this process the overall disorder of the solute, solvent and their surrounding must increase. Dissolving depends on the balance between the dispersal of matter in the solution and the dispersal of energy in the surroundings. FACTORS AFFECTING SOLUBILITY The solubility of a substance in a given solvent depends on a number of factors. The solubility of a gas depends on its partial pressure, and the solubilities of all substances, including gases, vary with temperature. Solute-Solvent Interactions The solubility of a substance depends on the choice of solvent as well as on the The interactions between solute molecules and the interactions substance itself.

between solvent molecules must be replaced by solute-solvent interactions when a solution forms. If the new interactions are similar to those replaced, very little energy is required for the solution to form and the dissolution is favorable. When the main cohesive forces in a solute are hydrogen bonds, the solute is more likely to dissolve in a hydrogen-bonded solvent than in other solvent, because the new

interactions solute-solvent have similar energies than solute-solute or solvent-solvent interactions. If the principal cohesive forces between solute molecules are London forces, than Soaps and detergents are a practical application of the like-dissolves-like rule. the best solvent is likely to be one held together by the same kind of forces. Soaps are the sodium salts with anions of a carboxylic acid. Soaps have a polar carboxylate (-CO2) group, called the head group, at one end of a long nonpolar hydrocarbon chain. Because of its polar character, the head group is hydrophilic, or water attracting, whereas the nonpolar hydrocarbon tail is hydrophobic, or water repelling. The hydrophobic tails dissolve in grease (London forces), leaving the hydrophilic head dissolved in water (dipole-dipole or hydrogen bonds). As a result, the whole soap with the grease trapped in it dissolves in water and is washed away when rinsed. Solubility of Ionic Compounds We can predict whether a given ionic solid is likely to dissolve in water by using In order to dissolve an ionic compound, the ion-dipole interaction must be greater Ionic compounds with large anions with low the solubility rules (Chapter 4, table 4.1, p. 11). than the ion-ion interaction. This happens when ionic compounds are formed from large anions with low charges. charges are often soluble. Pressure and Solubility: Henrys Law The solubility of a gas is directly proportional to its partial pressure, because an increase in pressure corresponds to an increase in the rate at which gas molecules strike the surface of the solvent. The molar solubility of a gas is denoted by Cg, and Henrys law is written: Cg =
kH x P, where kH, which is called Henrys constant, depends on the gas, the solvent,

and the temperature. The law implies that at constant temperature, doubling the partial pressure of a gas doubles its solubility. Temperature and Solubility The variation of solubility with temperature is difficult to predict, except in the case of gases, where raising the temperature nearly always lowers the solubility. 4

Most ionic and molecular compounds are more soluble in hot water than in cold.

However, a few solids, such as lithium sulfate, are less soluble at high temperatures than at low. A smaller number of compounds show a mixed behavior. EXPRESSING CONCENTRATION The amount of solute in a solvent, also called concentration, can be expressed in different ways as shown in the following table: Concentration Molarity Molality Volume percentage Mass percentage Mole Fraction (X) Definition Moles of solutes per liter of solution Moles of solute per kilograms of solvent Volume of solute expressed as a percentage of the total volume Mass of solute expressed as a percentage of a total mass Number of moles of solute expressed as a fraction of the total number of moles in the Parts per million Parts per billion solution. Volume of solute in mL per kL of solution. Mass of solute in mg per kg of solution Volume of solute in L per kL of solution. Mass of solute in g per kg of solution Solution Stoichiometry Molarity The molarity, M, of a solution is the number of moles of solute molecules or formula units divided by the volume of the solution (in liters). Molarity = number of moles of solute / volume of solution (liters) Molarity can be used to calculate the number of moles, n, of a solute in a solution or the volume, V, of a solution. Dilution Diluting a solution is the reduction of the molarity from an initial value by adding more solvent. When a solution is diluted, the same number of solute molecules occupies a larger volume. n=MxV or V=n/M ppm (by volume) ppm (by mass) ppb (by volume) ppb (by mass) Units mol/L or M mol/kg, or m % % -

The amount of solute in the final solution is the same as the amount of solute in the initial volume of solution. Titrations Titrations are used to determine the amount of an acid or base, or the amount of oxidizing or reducing agent is a solution. The solution being titrated is called the analyte. A known volume of the analyte is transferred into a flask to which an indicator was added. Then a solution called titrant is added to the analyte until the indicator change color. The change of color of the indicator corresponds to the stoichiometric point. At the stoichiometric point the solution contains an equal amount of titrant and analyte. n titrant = nanalyte Mtitrant x Vtitrant = Manalyte x V analyte This allows to determine the stoichiometric relation between analyte and titrant species. COLLIGATIVE PROPERTIES The presence of a solute affects the physical properties of the solvent. Four physical properties are affected in the same way by solutes regardless of the identity of the solute. Properties that depend on the number of solute molecules and not on their chemical identity are called colligative properties. Vapor-Pressure Lowering The vapor pressure of a solvent is lowered by a nonvolatile solute. For example, ninitial = nfinal Minitial x Vinitial = Mfinal x V final

the vapor pressure of pure water at 40C is 55 Torr but that of 0.1 m NaCl(aq) solution is only 44 Torr at the same temperature. A nonvolatile solute particle can block the escape of solvent molecule but has no effect on the rate of return of the solvent particles from the vapor to the solution. Raoults Law: The vapor pressure of a solvent in the presence of a nonvolatile solute is proportional to the mole fraction. P = Xsolvent Ppure. Where Ppure is the vapor pressure of the pure solvent, Xsolvent is the mole fraction of the solvent in the solution. Freezing Point Depression The freezing point of the solvent is lowered by the presence of a solute.

At the freezing point of a solution, the solute particles get in the way of the

solvent and inhibit the solid formation, freezing, (or melting). Only if the temperature is lowered will that flow be stopped and the freezing (melting) will occur. The freezing point of an ideal solution is proportional to the molality of the solute. For a non-electrolyte solution (solute is molecular), Freezing point depression = kf x molality. Where kf is the molal freezing point constant of the solvent (in K.kg/mol). For an electrolyte solution (ionic solution), each formula unit contributes two or more ions. In a dilute solution, the cations and anions move independently and contribute nearly independently in lowering the freezing point. But in more concentrated solutions, the ions do not move independently and the freezing point depression is different from that of a dilute solution. Freezing point depression = i xkf x molality. Where i is the vant Hoff factor. It is determined experimentally and depends on both the concentration and the type ions in the solution. Freezing point depression can be used to measure the molar mass of the solute. The presence of a solute raises the boiling point of the solvent. Thus the boiling For all solutions, we have: Boiling point elevation = kf x molality. where kf The boiling point elevation can be used to determine the molar mass of the solute. Osmosis occurs whenever a semipermeable membrane separates two solutions of Semipermeable membranes allow the movement of some particles while blocking Osmosis is the flow of solvent through a semipermeable membrane from the side Boiling Point Elevation point of a solution is higher than the boiling point of the solvent. is the molal boiling point constant of the solvent (in K.kg/mol). Osmosis different concentrations. the movement of others. of the lower solute concentration to the side of the higher solute concentration. The

presence of solute particles on one side of the membrane hinders solvent molecules from passing into the side containing pure solvent. Osmotic pressure is the external pressure that must be applied to stop the flow of The osmotic pressure is related to the molarity of the solute by the vant Hoff the solvent.

equation: = R T x molarity. Vant Hoff equation is used to determine the molar masses of polymers and Osmosis help the transport the nutrients in living cells. In reverse osmosis, a pressure greater than the osmotic pressure is applied to the natural macromolecules.

solution side of the semipermeable membrane. This application of pressure increases the rate at which solvent molecules leave the solution, and thus reverses the flow of solvent. Reverse osmosis is used to remove salts and other impurities in water. COLLOIDS A colloidal dispersion is formed when large particles are dispersed in a solvent. Many colloids appear homogeneous because their particles cannot be seen. The The distinctive properties of solutions, colloids, and suspensions are summarized Colloids Heterogeneous Particle sizes: 1-1000 nm Do not separate on standing Cannot be separated by Suspensions Heterogeneous Particle sizes: over 1000 nm Particles settle out Can be separated by

particles are, however large enough to scatter light. in the following table. Solutions Homogeneous Particle sizes: 0.01-1 nm Do not separate on standing Cannot be separated by

filtration filtration filtration Do not scatter light Scatter light May scatter light There are several classes of colloids as indicated in the following table: Class of colloid Sol Gel Liquid emulsion Foam Aerosol Smoke Phase Solid dispersed in liquid Solid network extending throughout liquid Liquid dispersed in a liquid Gas dispersed in liquid Solid dispersed in gas Solid dispersed in gas 8

Fog Smog Solid emulsion

Liquid dispersed in gas Solid and liquid dispersed in gas Liquid dispersed in solid

Skills you should have mastered Conceptual 1. Explain the basis for the like-dissolves-like rule. 2. Explain how solutions result from the tendency of matter and energy to disperse. 3. Explain how diluting a solution affects the concentration of a solute. 4. Explain the significance of the stoichiometric point (equivalence) of a titration. 5. Explain how nonvolatile solute lowers the vapor pressure, raises the boiling point, and lowers the freezing point of a solvent. 6. Explain the different properties of solutions and colloids. Problem-solving 1. 2. 3. the reactant concentration. 4. (molarity) of a solute from titration data. 5. given pressure, given its Henrys constant. 6. ions. 7. 8. Calculate the mole fraction and Calculate the amount of solute molality of a solute, given the masses or mass percentages of solute and solvent. present in a given mass of solvent from the molality. Predict the relative enthalpies of two Calculate the solubility of a gas at a Calculate the molar concentration Calculate the molarity of a solute in Determine the volume of solution Calculate the volume of solution a solution, volume of solution, and mass of solute, given the other two quantities. needed to prepare a dilute solution of a given molarity. required for a reaction, given the corresponding balanced chemical equation and

9. fraction or molarity. 10. solvent by using Raoults law. 11. in a solution. Descriptive

Convert between molality and mole Calculate the vapor pressure of a Find the molar mass of a substance

from its freezing point depression, boiling point elevation, or its osmotic pressure

1. Describe the purpose and procedure of a titration.

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