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Everyone has Problems,

Everyone has Problems, . but Chemists have Solutions. A solution is defined as a homogeneous mixture of two or more substances. . What you are dissolving into. What you are dissolving. Solubility is a measure of how much solute will dissolve in a solvent at a specific temperature.

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Everyone has Problems,

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  1. Everyone has Problems, but Chemists have Solutions Solutions 2009-2010

  2. A solution is defined as a homogeneous mixture of two or more substances. What you are dissolving into What you are dissolving Solutions 2009-2010

  3. Solubility is a measure of how much solute will dissolve in a solvent at a specific temperature. The saying “like dissolves like” is helpful in predicting the solubility of a substance in a given solvent. What this expression means is that two substances with intermolecular forces of similar type and magnitude are likely to be soluble in each other. Solutions 2009-2010

  4. “Like Dissolves Like” Will bromine be more soluble in water or in carbon tetrachloride? H2O Bromine (Br2) is nonpolar, therefore it will be more soluble in the nonpolar carbon tetrachloride CCl4 Solutions 2009-2010

  5. FYI-When eating hot peppers or hot spicy foods has left you "breathing fire“, drinking water will not relieve you, because the water cannot dissolve the oils which give the spicy taste. A chemist might suggest that the ideal would be to drink a chaser of a non-polar liquid. But most such liquids are toxic, and even gargling with benzene or toluene doesn’t sound very pleasant. A better solution is to eat greasy foods like meats which will dissolve the oils. Alternatively, food like pasta or bread, that can absorb the oils will help "put out the fire." The smell and taste of onions and garlic are also due to oils that are not easily washed away by water and are not absorbed well. Solutions 2009-2010

  6. Two liquids are said to be miscible if they are completely soluble in each other in all proportions. • Oil and water are immiscible. Solutions 2009-2010

  7. Chemists characterize solutions by their capacity to dissolve a solute. • An unsaturated solution contains less solute than it has the capacity to dissolve. • A saturated solution contains the maximum amount of a solute that will dissolve in a given solvent at a specific temperature • A supersaturated solution contains more solute than is present in a saturated solution. The supersaturated solution is not very stable. In time, some of the solute will come out of solution and form crystals. The remaining solution will then be _________. saturated Solutions 2009-2010

  8. Concentration Units Chemists use several different concentration units, each of which has advantages as well as limitations. The four most common units of concentration: percent by mass, mole fraction, molarity and molality. The choice of concentration unit is based on the purpose of the measurement. Solutions 2009-2010

  9. Mole Fraction (X) Moles of A Moles of A + Moles of B + Moles of C … XA = • mole fraction is appropriate for calculating partial pressures of gases and for dealing with vapor pressures of solutions Solutions 2009-2010

  10. Calculate the mol fraction ethanol (C2H5OH) if 25.0 g ethanol is mixed with 50.0 grams water. Solutions 2009-2010

  11. moles of solute liters of solution Molarity = Molarity (M) • the advantage of molarity is that it is generally easier to measure the volume of a solution using precisely calibrated volumetric flasks, than to mass the solvent Solutions 2009-2010

  12. Molarity (M) Calculate the molarity of an aqueous solution containing 34.2 grams of potassium chlorate in 225 mL of solution. Solutions 2009-2010

  13. moles of solute mass of solvent in kg molality = Molality (m) • molality is independent of temperature (the volume of a solution typically increases with increasing temperature, so that a solution that is 1.0 M at 25 oC may become 0.97 M at 45 oC because of the increase in volume) Solutions 2009-2010

  14. Molality (m) What is the molality of a solution containing 14.5 g of ferric nitrate in 285 mL of water? Solutions 2009-2010

  15. Percent by Mass (also called percent by weight or weight percent) Mass of solute Mass of solution X 100% • like molality, percent by mass is independent of temperature • we do not need to know the molar mass of the solute in order to calculate the percent by mass Solutions 2009-2010

  16. Percent by Mass What is the mass percent table salt in a solution containing 25 grams of table salt dissolved in 100 mL of water? Solutions 2009-2010

  17. The effect of temperature on solubility • The solubility of gases in water usually decreases with increasing temperature. • In most, but not all cases, the solubility of a solid substance increases with temperature. Solutions 2009-2010

  18. Solubility curves, which are used to illustrate how the solubility of a solute is affected by temperature, are determined experimentally Solutions 2009-2010

  19. Because the solubility of solids generally decrease with decreasing temperatures fractional crystallization, the process of separating a mixture of substances into pure components on the basis of their differing solubilities, can be used to purify substances. Solutions 2009-2010

  20. Crystallization is the process in which dissolved solute comes out of solution and forms crystals. This occurs because supersaturated solutions are not very stable. In time, some of the solute will come out of a supersaturated solution as crystals. Solutions 2009-2010

  21. A 90.0 g sample of KNO3 is contaminated with a small amount (less than 5.0 g) of NaCl. Explain how you would purify the KNO3. • The goal is not to necessarily get all 90.0 g of KNO3, but to get as much pure KNO3 as possible. Solutions 2009-2010

  22. Add water to the crystals (100.0 g at least). Heat the solution until all of the crystals dissolve (excess of __ oC). 50 Slowly cool the solution until it reaches 0 oC. At that temperature, about _____ of KNO3 is still soluble and ____ of the NaCl is still soluble. 13 g 5 g That means that ____ of KNO3 will have formed a pure crystal free from NaCl. 77 g Solutions 2009-2010

  23. Mixtures of ions can be separated by precipitation. Precipitation is when an insoluble solid forms and separates from a solution. *Note that both precipitation and crystallization describe the separation of excess solid substance from a supersaturated solution. Solutions 2009-2010

  24. The Effect of Pressure on the Solubility of Gases For all practical purposes, external pressure has no influence on the solubilities of liquids and solids, but it does greatly affect the solubility of gases. The quantitative relationship between gas solubility and pressure is given by Henry’s Law, which states the the solubility of gas in a liquid is proportional to the pressure of the gas over the solution. Solutions 2009-2010

  25. Here c is the molar concentration (mol/L) of the dissolved gas; P is the pressure (in atm) of the gas over the solution (if several gases are present , P is the partial pressure of the specific gas of interest); and k is a constant (for that specific gas) that depends only on temperature. (For example, at a given temperature, CO2 has the same k value, AS LONG AS THE TEMP STAYS CONSTANT.) The constant k has the units mol/L . atm. c = kP Solutions 2009-2010

  26. The solubility of pure nitrogen gas at 25 oC and 1 atm is 6.8 x 10-4 mol/L. What is the concentration of nitrogen dissolved in water under atmospheric conditions? The partial pressure of nitrogen gas in the atmosphere is 0.78 atm. Step 1: Solve for k (which remains constant for this gas at this temp) Step 2: Solve for the solubility of nitrogen gas at 0.78 atm Solutions 2009-2010

  27. Explain how the effervescence of a soft drink when the cap is removed is a demonstration of Henry’s Law. Before the bottle is sealed, it is pressurized with a mixture of air and CO2 and water vapor. Because of the high partial pressure of CO2, the amount dissolved in the soft drink is many times the amount that would dissolve under normal atmospheric conditions. When the cap is removed, the pressurized gases escape, and the excess CO2 comes out of solution causing the effervescence. Solutions 2009-2010

  28. Most gases obey Henry’s law, but there are some important exceptions… • Dissolved gases that react with water have higher solubilities NH3 + H2O  NH4+ + OH- CO2 + H2O  H2CO3 • Normally, oxygen gas is only sparingly soluble in water, however, its solubility in blood is dramatically greater because hemoglobin can bind up to four oxygen molecules Solutions 2009-2010

  29. Colligative Properties Colligative properties (or collective properties) are properties that depend only on the number of solute particles in solution and NOT on the nature of the solute particles. The colligative properties are vapor-pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure. Solutions 2009-2010

  30. Electrolytes and Nonelectrolytes All solutes that dissolve in water fit into one of two categories: electrolytes and nonelectrolytes. • An electrolyte is a substance that, when dissolved in water, results in a solution that can conduct electricity. • A nonelectrolyte does not conduct electricity when dissolved in water Solutions 2009-2010

  31. A solution’s ability to conduct electricity depends on the number of ions it contains. • A nonelectrolyte solution does not contain ions, and the light bulb is not lit. (b) A weak electrolyte solution contains a small number of ions, and the light bulb is dimly lit. (c) A strong electrolyte solution contains a large number of ions, and the light bulb is brightly lit. The molar amounts of the dissolved solutes are equal in all three cases. Solutions 2009-2010

  32. Vapor Pressure When a liquid evaporates, its gaseous molecules exert a vapor pressure. Vapor pressure is defined as the pressure of the vapor of a substance in contact with its liquid or solid phase. Vapor pressure changes with temperature; the higher the temperature, the higher the vapor pressure. Solutions 2009-2010

  33. At the boiling point, bubbles form within a liquid. The pressure inside the bubble is due solely to the vapor pressure of the liquid. The pressure exerted on the bubble is largely atmospheric. When the vapor pressure (internal) equals the external (atmospheric) pressure, the bubble rises to the surface of the liquid and bursts. Solutions 2009-2010

  34. Phase Diagram • A phase diagram shows the conditions at which a substance exists as a solid, liquid or gas. This is a phase diagram for water. • At 1 atm (760 mm Hg) the vapor pressure of water (inside the bubble) is equal to the external atmospheric pressure at 100 oC, the point at which water boils. (See your Water Vapor Reference Sheet to obtain water’s vapor pressure at different temperatures.) Solutions 2009-2010

  35. temperature. What would be true about water’s vapor pressure at the lower temp? higher/lower If you live at higher altitudes, the atmospheric pressure is lower, therefore, the liquid boils at a lower Solutions 2009-2010

  36. Do you need to boil your eggs for less time or more time if you live in Denver, Colorado? Explain. It takes a certain amount of heat (total kinetic energy) to cook a hard-boiled egg. Because water boils at a lower temperature in Denver, (approx 95 oC) it is supplying less heat to the egg, therefore the egg needs to be boiled for longer. *Remember, liquid water in Denver will not get hotter than 95 oC if that is its boiling point!!! Solutions 2009-2010

  37. Vapor-pressure Lowering If a solute is nonvolatile (therefore the solute does not have a measurable vapor pressure), the vapor pressure of the solution will always be less than that of the pure solvent. Thus, the relationship between solution vapor pressure and solvent vapor pressure depends on the concentration of the solute in the solution. This relationship is expressed by Raoult’s law P1 = X1 .P01 , where P1 = partial pressure of the solvent over a solution P01 = vapor pressure of the pure solvent (torr, mm Hg, atm or kPa) X1 = mole fraction of the solvent in the solution Solutions 2009-2010

  38. Calculate the new vapor pressure when 10.0 mL glycerol (C3H8O3), a nonvolatile solute, is added to 500.0 mL water at 50 oC. At this temperature, the vapor pressure of pure water is 92.5 torr and its density is 0.988 g/mL. The density of glycerol is 1.26 g/mL. Solutions 2009-2010

  39. In a solution containing only one solute, X1 = 1 – X2, where X1 is the mole fraction of the solvent, and X2 is the mole fraction of the solute. The previous equation can therefore be rewritten substituting 1 – X2 for X1 P1 = (1 – X2) . P01 P1 = P01 – X2P01 -P01 + P1 = - X2P01 P01 - P1 = X2P01 Using this formula will give you the CHANGE in vapor pressure. DP = X2P01 Solutions 2009-2010

  40. Let’s solve the previous problem again, this time solving for change (decrease) in vapor pressure using this derived formula. Calculate the vapor pressure lowering when 10.0 mL glycerol (0.137 mol) is added to 500.0 mL (27.4 mol) water at 50 oC. At this temperature, the vapor pressure of pure water is 92.5 torr Now we can use Raoult’s law to calculate how much the vapor pressure was lowered by the addition of the glycerol Solutions 2009-2010

  41. Why is the vapor pressure of a solution less than that of the pure solvent? One of the driving forces in physical and chemical processes is an increase in disorder – the greater the disorder, the more favorable the process. Vaporization increases the disorder of a system because molecules in a vapor are not as closely packed and therefore have less order than those in a liquid. Because a solution is more disordered that a pure solvent, the difference in disorder between a solution and a vapor is less than that between a pure solvent and a vapor. Thus solvent molecules in a solution have less of a tendency to leave the solution than to leave the pure solvent to become vapor, and the vapor pressure of a solution is less than that of the pure solvent. Solutions 2009-2010

  42. Nature tends towards disorder (entropy) The pure solvent is highly ordered, therefore many of the particles will leave the solvent because it GREATLY increases disorder, this results in high vapor pressure. Nonvolatile solute This solution is already somewhat disordered, therefore less of the solvent particles will leave the solvent, this results in lower vapor pressure. Pure solvent Solutions 2009-2010

  43. If both components of a solution are volatile (that means they both have measurable vapor pressure), the vapor pressure of the solution is the sum of the individual partial pressures. Raoult’s law holds equally well in this case. PT = XAP0A + XBP0B Where PT is equal to the total pressure (PA + PB) Solutions 2009-2010

  44. Fractional Distillation Solution vapor pressure has a direct bearing on fractional distillation, a procedure for separating liquid components of a mixture based on their different boiling points. Solutions 2009-2010

  45. Fractional distillation is somewhat analogous to fractional crystallization. When you boil a mixture containing two substances with appreciably different boiling points (80.1 oC and 110.6 oC), the vapor formed will be somewhat richer in the more volatile compound (the one that vaporizes/boils at the lower temp). If the vapor is condensed in a separate container and that liquid is boiled again, a still higher concentration of the more volatile substance will be obtained in the vapor phase. By repeating this process many times, it is possible to obtain a pure sample of the more volatile substance. Solutions 2009-2010

  46. Boiling-point elevation Because the presence of a nonvolatile solute lowers the vapor pressure of a solution, it must also affect the boiling point of the solution. Solutions 2009-2010

  47. Phase Diagram of a pure substance. “Normal” boiling and freezing points are indicated. Solutions 2009-2010

  48. Phase diagram of a pure substance and curves representing the effect of adding a solute. For each temperature the solute decreases the vapor pressure of the solution. Notice that the solution boils at a higher temperature than the pure substance (boiling occurs when the vapor pressure is equal to atmospheric pressure – in this case 1 atm - so now the solution needs to be hotter to reach a vapor pressure of 1 atm.) Solutions 2009-2010

  49. Boiling-point elevation (DTb) is defined as the CHANGE in the boiling point (boiling point of the solution minus the boiling point of the pure solvent). The value of DTb is proportional to the concentration (molality) of the solution. That is, DTb = kbm where kb is the molal boiling point elevation constant. The units of kb are oC/m. (You can find a table of molal boiling-point elevation and freezing-point depression constants of several common liquids on your reference sheet.) Solutions 2009-2010

  50. Boiling-point elevation (DTb) What is the new boiling point when 175 grams of sucrose, C12H22O11, are added to 285 mL of water? Solutions 2009-2010

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