2 Outline 9.1 Mixtures and Solutions 9.2 The Solution Process 9.3 Solid Hydrates [skip]9.4 Solubility9.5 The Effect of Temperature on Solubility9.6 The Effect of Pressure on Solubility: Henry’s Law9.7 Units of Concentration9.8 Dilution9.9 Ions in Solution: Electrolytes9.10 Electrolytes in Body Fluids: Equivalents and Milliequivalents9.11 Properties of Solutions [skip]9.12 Osmosis and Osmotic Pressure9.13 Dialysis [skip]
3 1. What are solutions, and what factors affect solubility 1. What are solutions, and what factors affect solubility? Be able to define the different kinds of mixtures and explain the influence on solubility of solvent and solute structure, temperature, and pressure. 2. How is the concentration of a solution expressed? Be able to define, use, and convert between the most common ways of expressing solution concentrations. 3. How are dilutions carried out? Be able to calculate the concentration of a solution prepared by dilution and explain how to make a desired dilution.
4 What is an electrolyte?Be able to recognize strong and weak electrolytes and nonelectrolytes, and express electrolyte concentrations.How do solutions differ from pure solvents in their behavior?Be able to explain vapor-pressure lowering, boiling-point elevation, and freezing-point depression for solutions.6. What is osmosis?Be able to describe osmosis and some of its applications.
6 Heterogeneous mixtures are those in which the mixing is not uniform and have regions of different compositionHomogeneous mixtures are those in which the mixing is uniform and have the same composition throughoutSolutions are homogeneous mixtures that contain particles the size of a typical ion or small moleculeColloids are homogeneous mixtures that contain particles ranging in diameter from 2 to 500 nmso they scatter (reflect) light
15 “Oil and water don’t mix” “Like dissolves like”Polar solvents dissolve polar and ionic solutesNonpolar solvents dissolve nonpolar solutes“Oil and water don’t mix”Intermolecular forces between water molecules = strongIntermolecular forces between oil molecules = weak
16 NaCl doesdissolve in waterPositively charged Na+ ions are attracted to the negatively polarized oxygen of waterNegatively charged Cl− ions are attracted to the positively polarized hydrogens of waterThe forces of attraction between ions and water molecules pulls the ions away from the crystal and into solution
17 NaCl doesdissolve in waterOnce in solution, water molecules form a large electrostatic shell around each iona phenomenon called solvation or hydrationThe size of this shell prevents NaCl traveling through an osmotic membranethus allowing the desalination of sea water by reverse osmosis
19 which is used in making ‘heat packs’ The dissolution (dissolving) of a solute in a solvent is a physical change since the solution components retain their chemical identitiesThe dissolution of a substance in a solvent always has some enthalpy change associated with itwhich is used in making ‘heat packs’Some substances dissolve exothermicallyreleasing heatCaCl2 in waterOther substances dissolve endothermicallyabsorbing heat and cooling the resultant solutionNH4NO3 in water (remember entropy)
23 Some ionic compounds attract water strongly enough to hold onto water molecules even when crystallineforming solid hydratesIn the formula of a hydrate, CaSO4• ½ H2O for example, the dot between the compound and the water indicates that there is one water for every two units of the ionic compoundIonic compounds that attract water so strongly that they pull water vapor from humid air to become hydrated are called hygroscopic
27 9.4 Solubility Very little theory Mostly observation (phenomenology) We measure and build tables of dataWe define helpful terms
28 Miscible: Mutually soluble in all proportions Ethyl and methyl alcohols will continue to dissolve in water no matter how much are addedBut most substances reach a solubility limit beyond which no more will dissolve in waterSolubility: The maximum amount of a substance that will dissolve in a given amount of solvent at a specified temperatureOnly 9.6 g of sodium hydrogen carbonate (baking soda) will dissolve in 100 mL of water at 20 °C, for instancebut 204 g of sucrose will dissolve under the same conditions
29 Saturated solution: Contains the maximum amount of dissolved solute at equilibrium No more than 35.8 g of NaCl will dissolve in 100 mL of water at 20 °CAny amount above this limit sinks to the bottom of the container as a solidA saturated solution is in a state of dynamic equilibrium:
30 9.5 The Effect of Temperature on Solubility More phenomenology
31 Temperature often has a dramatic effect on solubility, but is very unpredictable In Intro, most solids become more soluble as temperature rises, while the solubility of gases always decreasesbut check out NaCl and Ce2(SO4)3
32 Those solids that are more soluble at high temperature than at low temperature can form supersaturated solutionsOnce cooled, these solutions are unstableand precipitate dramatically when disturbed
33 Addition of heat always decreases the solubility of gases in Intro Chem So as water temperature increasesthe concentration of gases like oxygen decreasekilling fish that cannot tolerate low oxygen levels
34 Pop quiz Heating a can of pop before opening will reduce fizzing: T or F
35 Worked example 9.2From the following graph of solubility versus temperature for O2:Estimate the concentrations of oxygen dissolved in water at 25°C and at 35°C
36 From the graph we estimate that the solubility of O2 at 25 °C is approximately 8.3 mg/Lat 35 °C is 7.0 mg/L
37 By what percentage does the concentration of O2 change as the temperature rises to 35oC?
38 From the graph we estimate that the solubility of O2 at 25 °C is approximately 8.3 mg/Lat 35 °C is 7.0 mg/L
39 9.6 The Effect of Pressure on Solubility: Henry’s Law Increasing pressure increases concentration of a gas
40 Pressure has no effect on the solubility of solids or liquids in water – because they are not compressibleBut pressure has a powerful effect on the solubility of gasesHenry’s law: The solubility of a gas is directly proportional to the partial pressure of the gas if the temperature is held constant
42 An exercise for the student Henry’s law can also be explained using Le Châtelier’s principleWhen the system is stressed by increasing the pressure of the gas, more gas molecules go into solution to relieve the increased pressureWhen the pressure of the gas is decreased, more gas molecules come out of solution to relieve the decrease
44 So partial pressure can be used to express the concentration of gas in a solution If the partial pressure of a gas over a solution changes while the temperature is constant, the new solubility of the gas can be found easily:
47 Worked example 9.3At a partial pressure of oxygen in the atmosphere of 159 mmHg, the solubility of oxygen in blood is 0.44 g/100 mL.What is the solubility of oxygen in blood at 11,000 ft, where the partial pressure of O2 is 56 mmHg?According to Henry’s law, the solubility of the gas divided by its pressure is constant:Of the four variables in this equation, we know P1, C1, and P2, so we need to find C2
50 Percent Concentrations 1) For solid solutions (eg, brass) concentrations are typically expressed as mass/mass percent concentration, (m/m)%:2) For liquid solutions, concentrations are expressed as volume/volume percent concentration, (v/v)%:
56 Percent Concentrations 3) A third ‘percent’ method is to give the number of grams of solute as a percentage of the number of millilitersThis is mass/volume percent concentration, (m/v)%:
57 mass/volume percent concentration 12.0 grams of sucrose are added to a volumetric flask.Enough water is added to bring the final dissolved volume to 500 mL.What is the mass/volume percent concentration?
58 mass/volume percent concentration The appropriate amount of solute is weighed and placed in a volumetric flaskEnough solvent is then added to dissolve the soluteAdditional solvent is then added to reach final volume
59 An exercise for the student Parts per Million (ppm) or Parts per Billion (ppb)When concentrations are very small, as often occurs in dealing with trace amounts of pollutants or contaminants, it is more convenient to use parts per million (ppm) or parts per billion (ppb)The “parts” can be in any unit of either mass or volume as long as the units of both solute and solvent are the same:
60 Mole/Volume Concentration: The most generally useful way of expressing concentration in the laboratory is molarity (M), the number of moles of solute dissolved per liter of solution
61 Definition: A solution of a given molarity is prepared by dissolving the solute in enough solvent to give a final solution volume of 1.00 Lnot by dissolving it in an initial volume of 1.00 LImportant: Molarity can be used as a conversion factor to relate the volume of a solution to the moles of solute it contains – we will do a couple of these
62 Here, the weighed solute is added to a 1 liter volumetric fyiMoles of solute needed for a one liter solution are converted into gramsHere, the weighed solute is added to a 1 liter volumetricEnough solvent is added to dissolve with swirlingThe volumetric is carefully diluted to 1 liter with solvent
65 Worked Example 9.10 Molarity as Conversion Factor: Molarity to Mass A blood concentration of M ethyl alcohol (EtOH) is sufficient to induce comawhat would be the total mass of alcohol (grams) in 5.6 L of blood (male adult)?The molar mass of ethyl alcohol is 46.0 g/mol
67 Worked Example 9.11 Molarity as Conversion Factor: Molarity to Volume Gastric juice that is about 0.1 M in HClHow many mLs of gastric juice will react completely with an antacid containing 500 mg of magnesium hydroxide?The molar mass of Mg(OH)2 is 58.3 g/mol, and the balanced equation is
70 Many solutions are stored in high concentrations and then prepared for later use by dilution The amount of solute remains constant; only the volume is changed by adding more solventBecause the number of moles remains constant, we can set up the following equation for Molarity:
71 This equation can be rewritten to solve for the concentration of the solution after dilution: Dilution factor is the ratio of the initial and final solution volumes Vc / VdThe dilution equation can be generalized to all other concentration units: CcVc = CdVd
78 An electric current results because Ionic compounds, such as NaCl, in aqueous solution conduct electricity when they dissolveAn electric current results becausenegatively charged Cl– anions can migrate through the solution toward the positive terminal of the power sourcewhereas Na+ cations migrate toward the negative terminal
79 Weak electrolytes are substances that are only partly ionized in water Strong electrolytes are substances that ionize completely when dissolved in waterNaCl, HClWeak electrolytes are substances that are only partly ionized in waterCH3CO2H (acetic acid)Nonelectrolytes are substances that do not produce ions when dissolved in waterC6H12O6 (Glucose)
84 A mélange of electrolytes Since the body contains these electrolytes in solution all at once …it makes no sense to talk of NaCl as if it maintained its identity isolated from K2SO4So clinical chemists focus on individual ions (as opposed to compounds of ions)especially their contribution to the total positive and/or negative charges in solution
85 The definition of ‘Equivalent’ They utilize the concept ‘Equivalents of ions’One equivalent (Eq) is equal to the number of ions that carry one mole of chargeFor Na+ that would be x 1023 ionsFor Ca2+ that would be x 1023 ionsWe can calculate the number of equivalents of a particular ion per liter, simply by multiplying the molarity (M) of the particular ion by its charge
86 gram-equivalents Equivalents is a vital concept it often appears in multiple choice questionsIn practice chemists use the more practical unit gram-equivalent (g-Eq)The amount of ions (in grams) that actually contains that one mole of charge
87 Examples Ion(s) that have a +1 or −1 charge so 1 gram-equivalent of Na+ is simply 23.0 gso 1 gram-equivalent of Cl− is simply 35.4 gIon(s) that have a +2 or −2 chargeso 1 gram-equivalent of Mg2+ is (24.2/2) = 12.2 gso 1 gram-equivalent of S2− is (32.1/2) = 16.0 g
88 Because ion concentrations are so low in the body, clinical chemists use milli-equivalents So Na+ in blood is 0.14 Eq/L or 140 mEq/LThe gram-equivalent (or milligram-milliequivalent) is a useful conversion factorwhen converting from volume of solution to the mass of its ionsNote:
89 Worked Example 9.14The normal concentration of Ca2+ in blood is 5.0 mEq/LHow many milligrams of Ca2+ are in 1.00 L of blood?
91 Colligative property: A property of a solution that depends only on the number of dissolved particles, not on their identityVapor pressure is lower for a solution than for a pure solventBoiling point is higher for a solution than for a pure solventFreezing point is lower for a solution than for a pure solventOsmosis occurs when a solution is separated from a pure solvent by a semipermeable membrane
92 Vapor Pressure Lowering in Solutions Vapor pressure depends on the equilibrium between molecules entering and leaving the liquid surfaceIf some solvent molecules are replaced by solute particles, the rate of evaporation decreasesThe vapor pressure of a solution is lower than that of the pure solventThe identity of the solute particles is irrelevantonly their concentration matters
97 Boiling Point Elevation in Solutions The boiling point of the solution is higher than that of the pure solventThe solution must be heated to a higher temperature for its vapor pressure to reach atmospheric pressureEach mole of solute particles raises the boiling point of 1 kg of water by 0.51 °C1 mol of glucose raises the temperature by 0.51 °Cglucose is one particle1 mol of NaCl by 1.02 °C.NaCl dissociates into two particles
99 Freezing-Point Depression of Solutions The freezing point of a solution is lower than that of the pure solventSolute molecules are dispersed between solvent molecules, making it more difficult for solvent molecules to organize into ordered crystals
100 Freezing-Point Depression of Solutions The freezing point of a solution is lower than that of the pure solventSolute molecules are dispersed between solvent molecules, making it more difficult for solvent molecules to organize into ordered crystalsFor each mole of nonvolatile solute particles, the freezing point of 1 kg of water is lowered by 1.86 °C1 mole of glucose lowers the freezing point 1.86oC1 mole of NaCl lowers the freezing point 3.72oC
104 Worked Example 9.15 Properties of Solutions: Boiling Point Elevation What is the boiling point of a solution of 0.75 mol of KBr in 1.0 kg of water?AnalysisThe boiling point increases 0.51 °C for each mole of solute per kilogram of water. Since KBr is a strong electrolyte, there are 2 moles of ions (K+ and Br–) for every 1 mole of KBr that dissolves.Ballpark EstimateThe boiling point will increase about 0.5 °C for every 1 mol of ions in 1 kg of water. Since 0.75 mol of KBr produce1.5 mol of ions, the boiling point should increase by (1.5 mol ions) (0.5 °C/mol ions) = 0.75 °C.SolutionThe normal boiling point of pure water is 100 °C, so the boiling point of the solution increases to °C.Ballpark CheckThe 0.77 °C increase is consistent with our estimate of 0.75 °C.
108 As the liquid in the tube rises, its gravitational weight creates a pressure that pushes solvent back through the membrane until the rates of forward and reverse passage become equal and the liquid level stops risingOsmotic pressure is the amount of external pressure that must be applied to a solution to prevent the net movement of solvent molecules across a semipermeable membrane
110 Notice that a ‘bare’ Na+ (purple) would probably fit through the pores But Na+ surrounded (hydrated) by six water molecules does not fit through
111 The osmotic pressure of a 0.15 M NaCl solution at 25 °C is 7.3 atm Osmotic pressure depends only on the concentration of solute particlesOsmolarity (osmol) is the sum of the molarities of all dissolved particles in a solution
112 Osmosis is particularly important in living organisms because the membranes around cells are semipermeable.Isotonic: Having the same osmolarityHypotonic: Having an osmolarity less than the surrounding blood plasma or cells.Hypertonic: Having an osmolarity greater than the surrounding blood plasma or cells.
116 The pores in a dialysis membrane allow both solvent molecules and small solute particles to pass throughHemodialysis is used to cleanse the blood of patients whose kidneys malfunctionBlood is diverted from the body and pumped through a long cellophane dialysis tube suspended in an isotonic solutionSmall waste materials such as urea pass through the dialysis membrane and are washed away
117 Hemodialysis is used to cleanse the blood of patients whose kidneys malfunction Figure 9.13 Operation of a hemodialysis unit used for purifying blood.
118 Protein molecules do not cross semipermeable membranes and thus play an essential role in determining the osmolarity of body fluidsThe pressure of blood inside the capillary tends to push water out of the plasma (filtration)The osmotic pressure of colloidal protein molecules tends to draw water into the plasma (reabsorption)
119 At the arterial end of a capillary, filtration is favored At the venous end, where blood pressure is lower, reabsorption is favored, and waste products from metabolism enter the bloodstream
120 Time released medication Chapter 9, Unnumbered Figure 2, Page 284