Solutions Chapter 14 Hein and Arena Version 1.1 Eugene Passer Chemistry Department 1 College Bronx Community © John Wiley and Sons, Inc Chapter Outline 14.1 General Properties of Solutions 14.2 Solubility 14.3 Factors Related to Solubility 14.4 Rate of Dissolving Solids 14.5 Solutions: A reaction medium 14.6 Concentration of Solutions 14.7 Colligative Properties of Solutions 14.8 Osmosis and Osmotic Pressure 2 General Properties of Solutions • A solution is a system in which one or more substances are homogeneously mixed or dissolved in another substance. • The solute is the component that is dissolved or is the least abundant component of the solution. • The solvent is the dissolving agent or the most abundant component in the solution. 3 4 Properties of True Solutions • The mixture of two or more components– solute and solvent –is homogeneous and has a variable composition. – This means that the ratio of solvent to solute can be varied. • The dissolved solute is molecular or ionic in size. • It is either colored or colorless and is usually transparent. 5 • The solute remains uniformly distributed throughout the solution and will not settle out with time. • The solute can generally be separated from the solvent by purely physical means such as evaporation. • The solute particles of a true solution are molecular or ionic in size. – The particle size range is 0.1 nm to 1 nm (10-8 cm to10-7cm). 6 Formation of a Solution solute solvent solution 7 Solubility Solubility describes the amount of solute that will dissolve in a specified amount of solvent. 8 Solubilities of substances vary widely. 9 • Terms that describe the extent of solubility of a solute in a solvent: – very soluble – soluble – moderately soluble – slightly soluble – insoluble 10 • Terms that describe the solubility of liquids: – miscible: liquids that are capable of mixing and forming solutions. methyl alcohol and water – immiscible: liquids that are insoluble in each other. oil and water 11 Solubility of Various Common Ions in Cold Water 12 14.2 Factors Related to Solubility • Factors that affect solubility are – ion size – interactions between solute and solvent – temperature 13 The Nature of the Solute and Solvent • The general rule for predicting solubility is “like dissolves like”. 14 • Polar compounds tend to be more soluble in polar solvents than nonpolar solvents. Solvent Polarity – NaCl (sodium chloride) is • soluble in water • slightly soluble in ethyl alcohol • insoluble in ether and benzene 15 Dissolution of sodium chloride in water. The hydrated ions slowly diffuse away from the crystal to dissolved in Asbecome the attraction between Polar water molecules are solution. the ions weakens, the ions + attracted to Na and Clmove apart and become ions in the salt or crystal, surrounded by water weakening the attraction dipoles. between the ions. 16 14.3 • Nonpolar compounds tend to be more soluble in nonpolar solvents than in polar solvents. Solvent Polarity – benzene is • insoluble in water • soluble in ether. 17 The Effect of Temperature on Solubility Most solutes have a limited solubility in a specific solvent at a fixed temperature. 18 Effect of Temperature on the Solubility of a Solid in a Liquid • For most solids dissolved in a liquid, an increase in temperature results in increased solubility. – Some solids increase in solubility only slightly with increasing temperature. – Some solids decrease in solubility with increasing in temperature. 19 large increase in solubility with temperature decrease in solubility with increasing temperature slight increase in solubility with temperature 20 21 Effect of Temperature on the Solubility of a Gas in Water • The solubility of a gas in water usually decreases with temperature. – Kinetic molecular theory accounts for this decreased solubility. – For the gas to dissolve it must form bonds of some sort with the molecules of the liquid. – At higher temperatures the kinetic energy of the gas molecules is sufficient to break 22 the gas water bond. large decrease in solubility with increasing temperature 23 The Effect of Pressure on Solubility • Small pressure changes have little effect on the solubility of – solids in liquids – liquids in liquids • Small pressure changes have a great effect on the solubility of gases in liquids. – The solubility of a gas in a liquid is directly proportional to the pressure of 24 that gas above the liquid. Effect of Pressure on the Solubility of a Gas number of gas particles doubles solubility of gas doubles liquid 25 Saturated, Unsaturated and Supersaturated Solutions • At a specific temperature there is a limit to the amount of solvent that will dissolve in a given amount of solute. • When this condition occurs the solution is said to be saturated. 26 • In a saturated solution two processes are occurring simultaneously – The solute is crystallizing out of solution. – The solid is dissolving into the solution. solute (dissolved) solute (undissolved) 27 Dissolving a Solid in a Liquid A saturated solution may Solution is is be Solution either dilute or unsaturated. saturated. depending concentrated, Solute dissolves KCl of the on No themore solubility can dissolve. solute. 35 34 KCl 10 15 20 25 30 5 ggKCl 100 g H2O 20oC 28 Dissolving a Solid in a Liquid A solution that is saturated at one temperature may not be saturated at another temperature. Raise temperature 35 g KCl It may increase or decrease depending on the Solubility of a solute solute-solvent in a solvent changes system. with temperature. Solute dissolves The solution is unsaturated 100 g H2O A saturated solution may be either dilute or concentrated. 50oC 20 C 29 Dissolving a Solid in a Liquid A stress to the system will cause the solute in Whenever a solution contains solute in excess of solution excessA supersaturated of the saturation limit istounstable. come out of its solubility limit the solution is supersaturated. solution. Cool Solution to 20oC 35 g KCl At 20oC the solubility of KCl in water is 34 g/100 g H2O. 100 g H2O 20oC 50 The Nosolution KCl precipitates. contains 1 gram of KCl in excess of the solubility limit. 30 Rate of Dissolving Solids • Particle Size – A solid can dissolve only at the surface that is in contact with the solvent. – Smaller crystals have a larger surface to volume ratio than large crystals. – Smaller crystals dissolve faster than larger crystals. 31 32 14.5 • Temperature – In most cases, the rate of dissolving of a solid increases with temperature. – This occurs because solvent molecules strike the surface of the solid more frequently and harder, causing the solid to dissolve more rapidly. 33 • Concentration of the Solution Δc Δt Δc Δt As solution concentration increases, the rate of dissolving decreases. The rate of dissolving is at a maximum when solute and solvent are first mixed. 34 • Agitation or stirring. – When a solid is first put into water, it comes in contact only with water. The rate of dissolving is a maximum. 35 • Agitation or stirring. – When a solid is first put into water, it comes in contact only with water. The rate of dissolving is a maximum. – As the solid dissolves, the amount of dissolved solute around the solid increases and the rate of dissolving decreases. 36 • Agitation or stirring. – When a solid is first put into water, it comes in contact only with water. The rate of dissolving is then a maximum. – Stirring As the solid distributes dissolves, thethedissolved amount ofsolute dissolved solute throughout the water; around more the solid water is in increaseswith contact and the theratesolid of dissolving causing it to decreases. dissolve more rapidly. 37 Solutions: A Reaction Medium Many solids must be put into solution to undergo appreciable chemical reactions. sodium chloride reacts with silver nitrate 38 Ag+ NO-3 Na+ Cl- NaCl(s) + AgNO3(s) → no reaction If the reactants are in the solid phase, no 39 reaction occurs. Ag+ NO-3 Na+ Cl- NaCl(s) + AgNO3(s) → no reaction NaCl(s) and AgNO3(s) do not react because their 40 ions are securely locked in their crystal lattices. NO-3 Na+ Cl- Ag+ If the reactants are dissolved in water, an 41 immediate reaction occurs. NO-3 Na+ ClAg+ NaCl(s) + AgNO3(s) → AgCl(s) +NaNO3(aq) Mobile Ag+ and Cl- ions come into contact and 42 form insoluble AgCl which precipitates. NO-3 Na+ ClAg+ NaCl(s) + AgNO3(s) → AgCl(s) +NaNO3(aq) Na+ 3 and NO remain in solution. 43 Concentration of Solutions The concentration of a solution expresses the amount of solute dissolved in a given quantity of solvent or solution. 44 Dilute and Concentrated Solutions • The terms dilute and concentrated are qualitative expressions of the amount of solute present in a solute. • A dilute solution contains a relatively small amount of dissolved solute. • A concentrated solution contains a relatively large amount of solute. 45 • Concentrated HCl contains 12 mol of HCl per liter of solution. • In some laboratories a dilute solution might be 6 mol of HCl per liter of solution. • In another laboratory dilute HCl might be 4 mol of HCl per liter of solution. 46 Mass Percent Solution Mass percent expresses the concentration of solution as the percent of solute in a given mass of solution. g solute g solute mass percent = x 100 = x 100 g solute + g solvent g solution 47 What is the mass percent of sodium hydroxide in a solution that is made by dissolving 8.00 g NaOH in 50.0 g H2O? grams of solute (NaOH) = 8.0 g grams of solvent (H2O) = 50.0 g g solute mass percent = x 100 g solute + g solvent 8.00 g NaOH 8.00 g NaOH + 50.0 g H O x 100 = 13.8% NaOH solution 2 48 What masses of potassium chloride and water are needed to 250. g of 5.00% solution? The percent expresses the mass of the solute. Dissolving 12.5 g 250.g = total mass of solution KCl in 238 g H O 2 g solute mass percent = x 100 gives a 5.00% KCl g solution solution. mass percent x g solution = g solute 100 5.00 x 250. g = 12.5 KCl solute 100 250.g – 12.5 g = 238 g H2O 49 A 34.0% sulfuric-acid solution has a density of 1.25 g/mL. How many grams of H2SO4 are contained in 1.00 L of this solution? Step 1. Determine grams of solution. Mass Density = Volume Grams of solution are determined from the solution density. Density x Volume = Mass 1.00 L = 1.00 x 103 mL 1.25 g (1.00 x 103 mL) = 1250 g (mass of solution) 1 mL 50 A 34.0% sulfuric-acid solution has a density of 1.25 g/mL. How many grams of H2SO4 are contained in 1.00 L of this solution? Solve the mass percent equation for grams of solute. g solute mass percent = x 100 g solution mass percent x g solution g solute = 100 mass of solution = 1250 g 34.0 g H 2SO4 1250 g = g H 2SO 4 = 425 g H 2SO4 100 g 51 Mass/Volume Percent (m/v) Mass /volume percent expresses the concentration as grams of solute of solute per 100 ml solution. g solute mass/volume percent = x 100 mL solution 52 A 3.0% H2O2 solution is commonly used as a topical antiseptic to prevent infection. What volume of this solution will contain 10. g of H2O2? Solve the mass/volume equation for grams of solute. g solute mass/volume percent = x 100 mL solution g solute mL solution = x 100 m/v percent mL solution = 10 g H 2O2 3.0 m/v percent x 100 = 330 mL 53 Volume Percent Solutions that are formulated from The liquids volumearepercent oftenis the expressed volume of as a liquid volume in 100 percent ml of solution. with respect to the solute. volume of liquid in question volume percent = x 100 total volume of solution 54 Volumes are not necessarily additive. • A bottle of rubbing alcohol reads 70% by volume. • The alcohol solution could be prepared by mixing 70 mL of alcohol with water to make a total volume of 100 mL of solution. • 30 m L of water could not be added to 70 mL of alcohol because the volumes are not necessarily additive. 55 Molarity Molarity of a solution is the number of moles of solute per liter of solution. number of moles of solute moles molarity = M = = liter of solution liter 56 Molarity can be expressed in grams of solute rather than moles of solute. number of moles of solute moles molarity = = liter of solution liter g solute moles solute = molar mass g solute moles molar mass molarity = = liter of solution liter g solute moles molarity = = molar mass x liter of solution liter57 Preparation of a 1 molar solution 58 14.7 What is the molarity of a solution containing 1.4 mol of acetic acid (HC2H3O2) in 250. ml of solution? It is necessary to convert 250. mL to L since molarity = mol/L. mol mol The conversion is: =M mL L 1.4 mol 1000 mL = 5.6 mol = 5.6 M L L 250. mL 59 How many grams of potassium hydroxide are required to prepare 600. mL of 0.450 M KOH solution? Convert: mL L mol g The data are: volume = 600 mL 0.450 mol M= L 56.11 g molar mass KOH = mol The calculation is: 1 L 0.450 mol 56.11 g KOH 600 mL = 15.1 g KOH L mol 1000 mL 60 Calculate the number of moles of nitric acid in 325 mL of 16 M HNO3? Use the equation: moles = liters x M Convert: mL L 1L (325 mL) = 0.325 L 1000 mL Substitute the data given in the problem and solve: 16 mol HNO3 moles = 0.325 L = 5.2 mol HNO3 1L 61 What volume of 0.250 M solution can be prepared from 16.0 g of potassium carbonate? Convert: g K 2CO3 mol K 2CO3 L solution The data are: mass K 2CO3 = 16.0 g 0.250 mol M= L 138.2 g molar mass K 2CO3 = mol The conversion is: 1 mol K 2CO3 1L = 0.463 L 16.0 g K2CO3 138.2 g K 2CO3 0.250 mol K 2CO3 62 How many mL of 2.00 M HCL will react with 28.0 g NaOH? Step 1 Write and balance the equation for the reaction. HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(aq) Step 2 Find the number of moles of NaOH in 28.0 g NaOH. Convert: g NaOH mol NaOH 1 mol = 0.700 mol NaOH 28.0 g NaOH 40.0 g 63 How many mL of 2.00 M HCL will react with 28.0 g NaOH? Step 3 Solve for moles and volume of HCl. Convert: mol NaOH mol HCl L HCl mL HCl 1 mol HCl 1 L HCl = 0.700 mol NaOH 0.350 L HCl 1 mol NaOH 2.00 mol HCl 1000 mL = 0.350 L HCl 350 mL HCl 1L 64 65 Dilution Problems • If a solution is diluted by adding pure solvent: – the volume of the solution increases. – the number of moles of solute remain the same. 66 NO-3 Na+ NaNO3 solution 67 NO-3 Na+ Solution volume is doubled. Solution concentration is halved. 68 Moles of solute remain the same. Calculate the molarity of a sodium hydroxide solution that is prepared by mixing 100. mL of 0.20 M NaOH with 150. mL of water. Assume volumes are additive. Step 1 Calculate the moles of NaOH in the original solution. mol M= L mol = L M 0.20 mol NaOH 0.100 L = 0.020 mol NaOH 1L 69 Calculate the molarity of a sodium hydroxide solution that is prepared by mixing 100. mL of 0.20 M NaOH with 150. mL of water. Assume volumes are additive. Step 2 Solve for the new molarity. solution volume = 100. mL + 150. mL = 250. mL 0.020 M NaOH M= = 0.080 M NaOH 0.250 L 70 Alternative Solution When the moles of a solute in a solution before and after dilution are the same, the moles before and after dilution may be set equal to each other. mol1 = mol2 before dilution after dilution mol1 = L1 × M1 mol 2 = L2 × M 2 L1 × M1 = L2 × M 2 V1 and V2 must have the same volume units. V1 × M1 = V2 × M 2 71 Calculate the molarity of a sodium hydroxide solution that is prepared by mixing 100. mL of 0.20 M NaOH with 150. mL of water. Assume volumes are additive. V1 = 100. mL V2 = 250. mL M1 = 0.20 M M2 = unknown V1 × M1 = V2 × M 2 (100. mL)(0.20 M) = (250. mL)M2 (100. mL)(0.20 M) M2 = = 0.080 M NaOH 250 mL 72 How many grams of silver chloride will be precipitated by adding sufficient silver nitrate to react with 1500. mL of 0.400 M barium chloride solution? 2AgNO3(aq) + BaCl2(aq) → 2AgCl(s) + Ba(NO3)2(aq) Step 1 Determine the number of moles of BaCl2 in 1500 mL of 0.400 M solution. mol M= L mol = L M 1500 mL = 1.500 L 0.400 mol BaCl 2 1.500 L = 0.600 mol BaCl 2 L 73 How many grams of silver chloride will be precipitated by adding sufficient silver nitrate to react with 1500. mL of 0.400 M barium chloride solution? 2AgNO3(aq) + BaCl2(aq) → 2AgCl(s) + Ba(NO3)2(aq) Step 2 Use the mole-ratio method to calculate the moles and grams of AgCl. Convert: mol BaCl 2 mol AgCl g AgCl 2 mol AgCl 143.4 g AgCl = 172 g AgCl 0.600 mol BaCl2 1 mol BaCl 2 mol AgCl 74 Colligative Properties of Solutions When a nonvolatile solute is added to a solvent, three physical properties of the solvent will change: Boiling point elevation. Colligative Freezing point depression. Properties Vapor pressure. 75 Colligative properties of a solution depend only on the number of solute particles in a solution and not on the nature of those particles. Boiling point elevation. Colligative Freezing point depression. Properties Vapor pressure. 76 Each solvent shows a characteristic: freezing point depression constant boiling point elevation constant 77 The vapor pressure of a liquid depends on the ease with which its molecules can escape from the liquid’s surface. H2O(l) → H2O(g) 78 If 10% of the molecules in a solution are nonvolatile solute molecules, the vapor pressure of the solution is 10% lower than that of the pure solvent. H2O(l) → H2O(g) 79 A liquid solution boils willwhen haveitsa vapor lower pressure vapor pressure. equals atmospheric and consequently pressure. a higher boiling point. Vapor Pressure Curve of Pure Water and Water Solution: Boiling Point Elevation 80 A solution liquid freezes will have when a lower its vapor pressure. pressure equals and consequently the vapor pressure a lower freezing of its solid. point. Vapor Pressure Curve of Pure Water and Water Solution: Freezing Point Depression water vapor pressure curve solution vapor pressure curve ice vapor pressure curve 81 Molality The freezing point depression and the mol solute boiling point elevation are directly molality = solution proportional to the kg number of moles of solute per kilogram of solvent. 82 • • • • • Symbols used in the calculation of colligative properties m = molality Δtf = freezing point depression: oC Δtb = boiling point elevation: oC Kf = freezing point depression constant Kb = boiling point elevation constant 83 What is the molality (m) of a solution prepared by dissolving 2.70 g CH3OH in 25.0 g H2O? The conversion is: 2.70 g CH 3OH mol CH 3OH mol CH 3OH 25.0 g H 2O 25.0 g H 2O 1 kg H 2O The molar mass of CH3OH 32.04 g/mol 2.70 g CH 3OH 1 mol CH 3OH 25.0 g H O 32.04 g CH 3OH 2 1000 g H 2O 1 kg H O 2 3.37 mol CH 3OH = 1 kg H 2O 84 A solution is made by dissolving 100. g of ethylene glycol (C2H6O2) in 200. g H2O. What is the freezing point of the solution? Calculate moles of C2H6O2: 1 mol C2 H 6O2 = 1.61 mol C2 H 6O2 100 g C2 H 6O2 62.07 g C2 H 6O2 Calculate kilograms of H2O 1 kg 200. g H 2O = 0.200 kg H 2O 1000 g 85 A solution is made by dissolving 100. g of ethylene glycol (C2H6O2) in 200. g H2O. What is the freezing point of the solution? Calculate the freezing point depression. 1.61 mol C2 H 6O2 1.86 C kg H 2O o = 15.0 C Δt f = 0.200 kg H 2O 1 mol C2 H 2O 2 o freezing point solution = freezing point solvent – Δtf. = 0oC – 15oC = – 15oC 86 A solution made by dissolving 4.71 g of a compound of unknown molar mass in 100.0 g of H2O has a freezing point of –1.46oC. What is the molar mass of the compound? Δtf = + 1.46oC Δt f = mK f Δt f m= Kf 1.46oC × mol solute 0.785 mol solute m= = o 1.86 C × kg H 2O kg H 2O 87 Convert 4.71 g solute/100 g H2O to g/mol. 4.71 g solute 1000 g H 2O 1 kg H 2O 100 g H O 1 kg H O 0.785 mol solute 2 2 = 60.0 g mol molar mass of the compound 88 Osmosis and Osmotic Pressure Osmosis is the diffusion of water, either from a dilute solution or from pure water, through a semipermeable membrane into a solution of higher concentration. 89 91 14.9 • A 0.90% solution of sodium chloride in water is known as physiological saline solution. It is isotonic with blood plasma. • Red blood cells do not shrink or swell in an isotonic solution. 92 • Red blood cells swell in a hypotonic solution. • Red blood cells shrink in a hypertonic solution. 93 Osmotic pressure is the pressure that must be exerted to prevent osmosis of solvent particles through a semipermeable membrane that is separating two solutions of different solute concentrations. Osmotic pressure is a colligative property. 97 In osmosis,the net transfer of solvent is always from the less concentrated to the more concentrated solution. water passes through the cellophane 98 14.9 Key Concepts 14.1 General Properties of Solutions 14.2 Solubility 14.3 Factors Related to Solubility 14.4 Rate of Dissolving Solids 14.5 Solutions: A reaction medium 14.6 Concentration of Solutions 14.7 Colligative Properties of Solutions 14.8 Osmosis and Osmotic Pressure 99