14 Solutions Brass, a solid solution of Zn and Cu, is used to make musical instruments and many other objects. Foundations of College Chemistry, 14th Ed. Morris Hein and Susan Arena © 2014 John Wiley & Sons, Inc. All rights reserved. Chapter Outline 14.1 General Properties of Solutions 14.2 Solubility 14.3 Rate of Dissolving Solids 14.4 Concentration of Solutions 14.5 Colligative Properties of Solutions 14.6 Osmosis and Osmotic Pressure © 2014 John Wiley & Sons, Inc. All rights reserved. General Properties of Solutions Solution: a homogeneous mixture of one or more solutes and a solvent. Solute: substance being dissolved. Solvent: dissolving agent that is usually the most abundant substance in the mixture. Note: a solution does not always just refer to liquids. Example: Air is a solution composed of N2, O2, Ar and CO2 N2 is the solvent as it composes 78% of air. © 2014 John Wiley & Sons, Inc. All rights reserved. Solutions Practice Soda is a mixture of sugar in water. Which substance is the solute? a. sugar b. water c. soda A solution is prepared by adding 25 mL of ethyl alcohol to 75 mL of water. Which substance is the solvent? a. ethyl alcohol b. water © 2014 John Wiley & Sons, Inc. All rights reserved. Common Types of Solutions © 2014 John Wiley & Sons, Inc. All rights reserved. Properties of a True Solution 1. A homogeneous mixture of two or more components whose ratio can be varied. 2. The dissolved solute is molecule or ionic in size (< 1 nm). 3. Can be colored or colorless, though solutions are usually transparent. 4. The solute remains dissolved and does not settle (precipitate) out of solution over time. 5. The solute can be separated from solvent by physical means (usually evaporation). © 2014 John Wiley & Sons, Inc. All rights reserved. Solubility Solubility: the amount of a substance that will dissolve in a specific amount of solvent at a given temperature. Example 27 g KBr/100g H2O at 23 ºC Miscible: when two liquids dissolve in each other. Immiscible: when two liquids do not dissolve one another. A mixture of oil and water is immiscible. © 2014 John Wiley & Sons, Inc. All rights reserved. Solubility Rules Insoluble Soluble Na+, K+, NH4+ Nitrates (NO3-) Acetates, (C2H3O2-) Cl-, Br-, I- Except Ag+, Hg22+, Pb2+ Sulfates (SO42-), Ag+, Ca2+ (slightly) Except Ba2+, Sr2+, Pb2+ NH4+, Group I Except © 2014 John Wiley & Sons, Inc. All rights reserved. Carbonates (CO32-) Phosphates (PO43-) OH-, Sulfides (S2-) Solutions Practice Predict the solubility of barium sulfate. a. soluble b. insoluble Most sulfates are soluble, except Ba2+. Predict the solubility of NaCl. a. soluble b. insoluble All Na+ salts are soluble. © 2014 John Wiley & Sons, Inc. All rights reserved. Solutions Practice Predict the solubility of silver nitrate. a. soluble b. insoluble All NO3- salts are soluble. Predict the solubility of silver hydroxide. a. soluble b. insoluble Most hydroxides are insoluble. Predict the solubility of ammonium carbonate. a. soluble b. insoluble All NH4+ salts are soluble. © 2014 John Wiley & Sons, Inc. All rights reserved. Factors Affecting Solubility “Like Dissolves Like” Polar compounds dissolve in polar solvents. Ethanol (CH3OH) dissolves in water (HOH). Nonpolar compounds dissolve in nonpolar solvents. Carbon tetrachloride (CCl4) dissolves in hexanes (CH3(CH2)4CH3). © 2014 John Wiley & Sons, Inc. All rights reserved. Factors Affecting Solubility Ionic Compound Solubility in Polar Solvents Several ionic compounds dissolve in water, due to strong ion-dipole forces. The individual cations and anions are surrounded by H2O molecules (i.e., hydrated). The cation is attracted to the partially negative O atom. The anion is attracted to the partially positive H atoms. © 2014 John Wiley & Sons, Inc. All rights reserved. Temperature and Solubility Solubility increases with temperature for most solids (red lines) Solubility decreases with temperature for all gases (blue lines). As a gas increases in temperature, the kinetic energy increases, which means it interacts less with the liquid, making it less easy to solvate. © 2014 John Wiley & Sons, Inc. All rights reserved. Pressure and Solubility Pressure does not affect solubility of liquids or solids. Gas solubility in a liquid is proportional to the gas pressure over the liquid. Example: A bottle of root beer is under high pressure. As the bottle opens, the pressure decreases, and the bubbles formed indicate gas loss from the liquid. © 2014 John Wiley & Sons, Inc. All rights reserved. Saturated and Unsaturated Solutions There are limits to the solubility of a compound at a given temperature. Saturated solutions: contain the maximum amount of dissolved solute in a solvent. Saturated solutions are still dynamic; dissolved solute is in equilibrium with undissolved solute. undissolved solute dissolved solute Unsaturated solutions: contain less than the maximum amount of possible dissolved solute in a solvent. © 2014 John Wiley & Sons, Inc. All rights reserved. Supersaturated Solutions Supersaturated solutions: contain more solute than needed to saturate a solution at a given temperature. How is this possible? Heating a solution can allow more to dissolve. Upon cooling to ambient temperature, the solution is supersaturated. These solutions are unstable -- disturbing the solutions can cause precipitation of solute. Some hotpacks release heat by crystallization of a supersaturated solution of sodium acetate. © 2014 John Wiley & Sons, Inc. All rights reserved. Solubility Practice Will a solution prepared by adding 9.0 g of KCl to 20.0 g of H2O be saturated or unsaturated at 20 ºC? Using Table 14.3, 34.0 g of KCl will dissolve in 100.0 g of H2O at 20 ºC. 6.8 g of KCl will then dissolve in 20.0 g of water at that temperature. The KCl solution should be saturated. © 2014 John Wiley & Sons, Inc. All rights reserved. Rate of Dissolving Solids Effect of Particle Size A solid can only dissolve at a surface that is in contact with the solvent. Since smaller crystals have a higher surface to volume area, smaller crystals dissolve faster than larger ones. © 2014 John Wiley & Sons, Inc. All rights reserved. Rate of Dissolving Solids Effect of Temperature Increasing the temperature normally increases the rate of dissolution of most compounds. Solvent molecules strike the solid surface more often, causing the solid to dissolve more rapidly. The solute molecules are more easily separate from the solid due to a higher kinetic energy. © 2014 John Wiley & Sons, Inc. All rights reserved. Rate of Dissolving Solids Effect of Solute Concentration Rate is highest at higher concentration and decreases at lower concentration. As the solution approaches the saturation point, the rate of solute dissolving decreases. © 2014 John Wiley & Sons, Inc. All rights reserved. Rate of Dissolving Solids Effect of Agitation/Stirring Stirring a solution briskly breaks up a solid into smaller pieces, increasing surface area, thereby increasing the rate of dissolution. © 2014 John Wiley & Sons, Inc. All rights reserved. Surface Area Surface Area of Two Crystals Surface area = 6(side)2 = 6(0.1)2 = 0.06 cm2 1000 cubes have a total surface area of 1000 x 0.06 cm2 = 60 cm2 What is the surface area of a 1 cm square crystal? Surface area = 6(side)2 = 6(1)2 = 6 cm2 © 2014 John Wiley & Sons, Inc. All rights reserved. Solutions: A Reaction Medium The purpose of dissolving reactants in a solution is often to allow them to come in close contact to react. Example: Solid-solid reactions are generally very slow at ambient temperature KCl (s) + AgNO3 (s) No Reaction By dissolving both compounds in water, the ions can collide with one another and react to form an insoluble compound. KCl (aq) + AgNO3 (aq) K+(aq) + Cl-(aq) + Ag+(aq) + NO3-(aq) AgCl (s) + KNO3 (aq) AgCl(s) + K+(aq) + NO3-(aq) © 2014 John Wiley & Sons, Inc. All rights reserved. Concentration of Solutions Qualitative Expressions of Concentrations Dilute: a solution that contains a relatively small amount of dissolved solute. Example: A 0.1 M HCl solution is dilute acid. Concentrated: a solution that contains a relatively large amount of dissolved solute. Example: A 12 M HCl solution is concentrated acid. © 2014 John Wiley & Sons, Inc. All rights reserved. Concentration of Solutions Quantitative Expressions of Concentrations: Units Symbol Mass percent % m/m Part per million ppm Mass/Volume percent % m/v Volume percent % v/v Molarity M Molality m Definition mass solute x 100 mass solution mass solute x 1,000,000 mass solution mass solute x 100 mL solution mL solute x 100 mL solution mol solute L solution mol solute kg solvent © 2014 John Wiley & Sons, Inc. All rights reserved. Mass Percent Calculate the mass % of NaCl in a solution prepared by dissolving 50.0 g of NaCl in 150.0 g of H2O. Knowns Formula Calculate 50.0 g NaCl (solute mass) 150.0 g H2O (solvent mass) 200.0 g solution (solute + solvent mass) mass % = mass solute x 100 mass solution mass % = 50 g NaCl 200 g soln x 100 = 25% NaCl © 2014 John Wiley & Sons, Inc. All rights reserved. Mass Percent Practice What is the mass of Na2CO3 needed to make 350.0 g of a 12.3% aqueous solution? Knowns 12.3% solution (mass %) 350.0 g solution (solute + solvent mass) Solve for mass of solute (Na2CO3) Formula mass % x mass soln mass solute mass % = x 100 mass solute = 100 mass solution Calculate 12.3 x 350.0 g = 43.1 g Na2CO3 mass solute = 100 © 2014 John Wiley & Sons, Inc. All rights reserved. Mass-Volume Percent Saline is a 0.9 m/v % NaCl solution. What mass of sodium chloride is needed to make 50 mL of saline? Knowns 50.0 mL solution (solution volume) 0.90 m/v% (mass/volume %) Solve for mass of solute (NaCl) Formula g solute m/v % = x 100 mL solution Calculate m/v % x mL soln mass solute = 100 mass solute = 50.0 x 0.90 = 0.45 g NaCl 100 © 2014 John Wiley & Sons, Inc. All rights reserved. Mass-Volume Percent Practice What volume of a 3.0% H2O2 solution will contain 10.0 g of H2O2? a. 33.0 mL soln b. 330. mL soln Knowns 10.0 g H2O2 (desired solute mass) c. 3.00 L soln 3.0 m/v% d. 165 mL soln Solve for volume of solution Formula m/v % = g solute x 100 mL solution Calculate mass solute = mL solution = 10.0 g 3.0 g solute m/v % x 100 = 330. mL sln © 2014 John Wiley & Sons, Inc. All rights reserved. x 100 Volume Percent What volume of soda that is 6.0 % by volume alcohol contains 200.0 mL of ethanol (CH3CH2OH)? 20.0 mL ethanol (solute volume) 6.0 volume % Solve for volume of solution Knowns Formula volume solute volume % = x 100 volume solution volume soln = volume solute x 100 volume % Calculate volume soln = 200.0 x 100 = 3300 mL soda 6.0 © 2014 John Wiley & Sons, Inc. All rights reserved. Volume Percent Practice A solution is prepared by mixing 20.0 mL of propanol with enough water to produce 400.0 mL of solution. What is the volume percent of propanol? a. 20.0 % b. 2.00 % c. 5.00 % d. 10.0 % Knowns 20.0 mL propanol (solute volume) 400.0 mL solution (solution volume) Solve for volume percent Formula volume % = Calculate volume solute x 100 volume solution 20.0 x 100 volume % = = 5.00% propanol 400.0 © 2014 John Wiley & Sons, Inc. All rights reserved. Molarity A common unit for solution concentration due to convenience. mol solute molarity = L solution Example: To prepare a 1.0 M KCl solution, 1.0 mol of KCl is dissolved in enough water to make 1.0 L of solution. © 2014 John Wiley & Sons, Inc. All rights reserved. Molarity Practice Calculate the molarity of a solution prepared by dissolving 9.35 g of KCl in enough water to prepare a 250.0 mL solution. Knowns Formula Calculate 9.35 g KCl (solute mass) 250.0 mL solution (solution volume) Solve for molarity mol solute molarity = L solution 1 mol KCl = 0.125 mol KCl 9.35 g KCl x 74.551 g KCl molarity = 0.125 mol KCl = 0.502 M KCl 0.250 L solution © 2014 John Wiley & Sons, Inc. All rights reserved. Molarity Practice How many grams of KOH are required to prepare 600.0 mL of a 0.450 M KOH solution? a. 0.270 g KOH Knowns 600 mL (solution volume) b. 4.81 g KOH 0.450 M (solution molarity) c. 1.52 x 104 g KOH d. 15.1 g KOH Plan Solve for moles, then grams using molarity and molar mass as conversion factors mol solute Formula molarity = mol solute = molarity x L soln L solution Calculate moles solute = 0.450 M KOH x 0.600 L = 0.270 mol KOH 0.270 mol KOH x 56.11 g KOH = 15.1 g KOH 1 mol KOH © 2014 John Wiley & Sons, Inc. All rights reserved. Solution Stoichiometry Similar to previous stoichiometry problems, but we can now use molarity as an additional conversion factor. How many mL of 0.175 M Hg(NO3)2 are needed to precipitate 2.50 g of KI? Hg(NO3)2 (aq) + 2 KI (aq) Plan g KI mol KI 2 KNO3 (aq) + HgI2 (s) mol Hg(NO3)2 mL soln Calculate 1 mol Hg(NO3)2 1 mol KI 1000 mL soln × × 2.50 g KI × 166.00 g KI 0.175 mol Hg(NO3)2 2 mol KI = 43.0 mL Hg(NO3)2 © 2014 John Wiley & Sons, Inc. All rights reserved. Solution Stoichiometry Practice How many grams of AgCl will form by adding enough AgNO3 to react fully with 1500. mL of 0.400 M BaCl2 solution? 2 AgNO3 (aq) + BaCl2(aq) 2 AgCl (s) + Ba(NO3)2 (aq) a. 172 g AgCl b. 86.0 g AgCl c. 8.37 x 10-3 g AgCl d. 36.0 g AgCl Plan Volume BaCl2 mol BaCl2 mol AgCl g AgCl Calculate 0.400 mol BaCl2 2 mol AgCl × 143.4 g AgCl 1500. mL × × 1000 mL 1 mol BaCl2 1 mol AgCl = 172 g AgCl © 2014 John Wiley & Sons, Inc. All rights reserved. Dilution Dilution: Adding a solvent to a concentrated solution to make the solution less concentrated (i.e. dilute). When a solution is diluted, only the volume changes. The number of moles of solute remains constant. moles before dilution = moles after dilution Molarity1 x Volume1 = Molarity2 x Volume2 M1 × V1 = M2 × V2 © 2014 John Wiley & Sons, Inc. All rights reserved. Dilution Practice What volume of 12 M HCl is needed to make 500.0 mL of a 0.10 M HCl? 12 M HCl M1 0.10 M HCl M2 500.0 mL V2 Knowns Solving for: volume of 12 M HCl V1 M1 × V1 = M2 × V2 Calculate V1 = V2M2 M1 = 500 mL x 0.10 M 12 M © 2014 John Wiley & Sons, Inc. All rights reserved. = 4.2 mL Dilution Practice Calculate the molarity of a NaOH solution prepared by mixing 100. mL of 0.20 M NaOH with 150 mL of H2O. a. 2.0 M NaOH Knowns 0.20 M NaOH M1 100 mL sln V1 100 + 150 = 250 mL V2 Solving for: molarity NaOH M2 b. 0.050 M NaOH c. 0.080 M NaOH d. 12.5 M NaOH M1 × V1 = M2 × V2 Calculate M2 = M1V1 V2 = 0.20 M x 100 mL 250 mL = 0.080 M NaOH © 2014 John Wiley & Sons, Inc. All rights reserved. Colligative Properties of Solutions Colligative Property: A solution property that depends only on the number of solute particles not the nature of the particles. Common Colligative Properties: 1. Vapor Pressure Lowering Solutions have lower vapor pressures than pure solvent. 2. Boiling Point Elevation Solutions have higher boiling points than pure solvent. 3. Freezing Point Depression Solutions have lower freezing points than pure solvent. 4. Osmosis and Osmotic Pressure © 2014 John Wiley & Sons, Inc. All rights reserved. Vapor Pressure Lowering Dissolving a solute in a solvent lowers the vapor pressure of the solvent. As a result, the solvent’s boiling point is increased (a) while the freezing point of the solvent is lowered (b). © 2014 John Wiley & Sons, Inc. All rights reserved. 14-42 Molality Since colligative properties depend on the number of particles in the solvent and not the identity, a new concentration unit is used when discussing colligative properties. mol solute molality = kg solvent Example: What is the molality of a solution prepared by dissolving 0.10 mol of starch in 0.50 kg of water? 0.10 mol = 0.20 m m = 0.50 kg H2O © 2014 John Wiley & Sons, Inc. All rights reserved. Molality Practice What is the molality (m) of a solution prepared by dissolving 2.70 g of methanol (CH3OH) in 25.0 g of water? a. 0.812 m b. 6.74 m c. 3.37 m d. 1.69 m 2.70 g CH3OH × 1 mol CH3OH 32.04 g CH3OH = 0.0843 mol CH3OH 0.0843 mol m = = 3.37 m 0.0250 kg H2O © 2014 John Wiley & Sons, Inc. All rights reserved. Colligative Properties Calculating the change in boiling/freezing point of a solution: molality Change in temperature ΔT = m x K Freezing (Kf) or boiling (Kb) point constants Freezing/Boiling Points and the Related K Constants © 2014 John Wiley & Sons, Inc. All rights reserved. Boiling Point Elevation What is the boiling point of a solution prepared by dissolving 0.10 mol of sugar in 0.50 kg of water? (Boiling point of water is 100.0 ºC and Kb = 0.512 ºC/m) 0.10 mol = 0.20 m 0.50 kg H2O ΔTb = 0.20 m x 0.512 ºC/m = 0.10 ºC Boiling point is always elevated by added solute, so the change in temperature is added to the boiling point of pure water. Tb = 100.0 ºC + 0.10 ºC = 100.1 ºC © 2014 John Wiley & Sons, Inc. All rights reserved. Boiling Point Elevation Practice What is the boiling point of an aqueous solution that is 4.00 m in solute? Tb(pure water) = 100.0 ºC and Kb = 0.512 ºC/m a. 100.00 ºC b. 102.05 ºC c. 97.95 ºC ΔTb = 4.00 m x 0.512 ºC/m = 2.05 ºC d. 2.05 ºC Boiling point is always elevated by added solute, so the change in temperature is added to the boiling point of pure water. Tb = 100.0 ºC + 2.05 ºC = 102.05 ºC © 2014 John Wiley & Sons, Inc. All rights reserved. Freezing Point Depression What is the freezing point of a solution prepared by dissolving 0.10 mol of sugar in 0.50 kg of water? (Freezing point of water is 0.0 ºC and Kf = 1.86 ºC/m) Molality = 0.10 mol 0.50 kg H2O = 0.20 m ΔTf = 0.20 m x 1.86 ºC/m = 0.37 ºC Freezing point is always depressed by added solute, so the change in temperature is subtracted from the freezing point of pure water. Tb = 0.0 ºC – 0.37 ºC = -0.37 ºC © 2014 John Wiley & Sons, Inc. All rights reserved. Freezing Point Depression Practice What is the freezing point of 100. g of C2H6O2 dissolved in 200 g of H2O? Tf(pure water) = 0.0 ºC and Kf = 1.86 ºC/m) a. -15.0 ºC b. 15.0 ºC c. -0.015 ºC d. -7.35 ºC 2.70 g C2H6O2 × 1 mol C2H6O2 62.07 g C2H6O2 = 1.61 mol C2H6O2 1.61 mol Molality = = 8.05 m 0.20 kg H2O ΔTf = 8.05 m x 1.86 ºC/m = 15.0 ºC Freezing point is always depressed by added solute, so the change in temperature is subtracted from the freezing point of pure water. Tf = 0.0 ºC – 15.0 ºC = -15.0 ºC © 2014 John Wiley & Sons, Inc. All rights reserved. Osmosis Osmosis: diffusion of water from a dilute solution or pure water, through a semipermeable membrane into a solution of higher solute concentration. © 2014 John Wiley & Sons, Inc. All rights reserved. Osmotic Pressure Osmotic Pressure: difference in the amount of pressure necessary to apply to a solution to stop the flow of water due to osmosis and the atmospheric pressure. Demonstrating Osmotic Pressure Water flows through the membrane into the more concentrated sugar solution, causing the solution to rise in the tube. © 2014 John Wiley & Sons, Inc. All rights reserved. Blood and Osmosis Isotonic: same concentration of dissolved solute as a cell. (0.9% saline) Hypertonic: higher concentration of dissolved particles relative to cellular levels. (1.6% saline) Hypotonic: lower concentration of dissolved particles relative to cellular levels. (0.2% saline) Effect of Different Concentrations on Red Blood Cells isotonic hypertonic hypotonic © 2014 John Wiley & Sons, Inc. All rights reserved. Learning Objectives 14.1 General Properties of Solutions List the properties of a true solution 14.2 Solubility Define solubility and the factors that affect it. 14.3 Rate of Dissolving Solids Describe the factors that affect the rate at which a solid dissolves. © 2014 John Wiley & Sons, Inc. All rights reserved. Learning Objectives 14.4 Concentrations of Solutions Solve problems involving mass percent, volume percent, molarity, and dilution. 14.5 Colligative Properties of Solutions Use the concept of colligative properties to calculate molality, freezing point, boiling point, freezing point depression, boiling point elevation of various solutions. 14.6 Osmosis and Osmotic Pressure Discuss osmosis and osmotic pressure and their importance in biological systems. © 2014 John Wiley & Sons, Inc. All rights reserved.