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CHEMISTRY The Central Science 8th Edition Chapter 13 Properties of Solutions P. Hatch The Solution Process • Solution: a homogeneous mixture of solute (present in smallest amount) and solvent (present in largest amount). • Solute and solvent are components of the solution. • In the process of making solutions with condensed phases, intermolecular forces become rearranged. Types of Solutions The Solution Process • Consider NaCl (solute) dissolving in water (solvent): – – – – – the water H-bonds have to be interrupted, NaCl dissociates into Na+ and Cl-, ion-dipole forces form: Na+ … -OH2 and Cl- … +H2O. We say the ions are solvated by water. If water is the solvent, we say the ions are hydrated. The Solution Process Ion-dipole Saturated Solutions and Solubility • Dissolve: solute + solvent solution. • Crystallization: solution solute + solvent. • Solubility: maximum amt. of solute dissolved in a given amt. of solvent; amount of solute required to form a saturated solution. • Saturation: maximum amt. of solute dissolved; crystallization and dissolution are in equilibrium. • Supersaturated: a solution formed when more solute is dissolved than in a saturated solution. Solution Composition • Qualitative composition: sol’ns are dilute or concentrated • Quantitative composition: amount of solute per amount of solvent (or sol’n). Mass Percent: percent by mass of solute in a sol’n Mole Fraction (X): ratio of moles of given component to total moles in sol’n Molarity (M): moles of solute per L sol’n Molality (m): moles of solute per kg solvent Ways of Expressing Concentration mass of component in solution mass % of component 100 total mass of solution moles of component in solution Mole fraction of component total moles of solution moles solute Molarity liters of solution moles solute Molality, m kg of solvent Converting between molarity (M) and molality (m) requires density. Solution Composition A solution is prepared by mixing 30.0 mL of butane (C4H4, d = 0.600 g/mL) with 65.0 mL of octane (C8H18, d = 0.700 g/mL). Assuming that the volumes are additive, calculate the following for butane: a. b. c. d. Molarity Mass percent Mole fraction Molality Factors Affecting Solubility Structural effects • Number of carbon atoms in a chain • Number of –OH groups in a molecule • Type of solid Pressure effects Temperature effects The Solution Process Energy Changes and Solution Formation • Step 1: separate solute into individual particles Endothermic, DH > 0 • Step 2: separate solvent’s intermolecular forces Endothermic, DH > 0 • Step 3: solvent-solute interact to form intermolecular forces Mostly Exothermic, DH < 0 When not exothermic, solution forms due to increase in entropy, DS > 0 The Solution Process Energy Changes and Solution Formation • Rule: “like dissolves like” • solubility is favored if solute and solvent have similar properties • polar solvents dissolve polar solutes. • non-polar solvents dissolve non-polar solutes. • Why? Factors Affecting Solubility Solute-Solvent Interaction • Miscible liquids: mix in any proportions. • Immiscible liquids: do not mix. • The number of carbon atoms in a chain affect solubility: the more C atoms the less soluble in water. • The number of -OH groups within a molecule increases solubility in water. Factors Affecting Solubility Solute-Solvent Interaction Factors Affecting Solubility Solute-Solvent Interaction Factors Affecting Solubility Solute-Solvent Interaction Discuss the solubility of each of the following solutes in carbon tetrachloride: a. Ammonium nitrate b. 1-pentanol (CH3CH2CH2CH2CH2OH) c. Pentane (CH3CH2CH2CH2CH3) Factors Affecting Solubility Solute-Solvent Interaction • Covalent-network solids, like sand and diamond, do not dissolve! • Why not? Factors Affecting Solubility Pressure Effects •Solubility of a gas in a liquid is a function of the pressure of the gas. •Higher the P, the greater the solubility. •Lower the P, the lower the solubility. •WHY? Factors Affecting Solubility Pressure Effects • Carbonated beverages are bottled with a partial pressure of CO2 > 1 atm. • As the bottle is opened, the partial pressure of CO2 decreases and the solubility of CO2 decreases. • Therefore, bubbles of CO2 escape from solution. Factors Affecting Solubility Temperature Effects • Experience tells us that sugar dissolves better in warm water than cold. • As temperature increases, solubility of solids generally increases. • Sometimes, solubility decreases as temperature increases (e.g. Ce2(SO4)3). Factors Affecting Solubility Temperature Effects • Experience tells us that carbonated beverages go flat as they get warm. • Therefore, gases get less soluble as temperature increases. • Thermal pollution: if ponds and lakes get too warm, CO2 and O2 become less soluble and are not available for aquatic plants or animals. Colligative Properties • Colligative properties: physical properties of a sol’n that depend on the number of solute particles but NOT the identity of those particles. Vapor pressure lowering Boiling point elevation Freezing point depression Osmotic pressure Colligative Properties Lowering Vapor Pressure • Non-volatile solutes reduce the ability of the surface solvent molecules to escape the liquid. • Therefore, vapor pressure is lowered. • The amount of vapor pressure lowering depends on the amount of solute. • The more solute particles present, the greater the vapor pressure lowering. Colligative Properties Lowering Vapor Pressure Raoult’s Law: the vapor pressure of a sol’n (PA) is directly proportional to the mole fraction of the solvent (XA) present. PA A P A • PA = vapor pressure of sol’n • PA = vapor pressure of pure solvent • A = the mole fraction of solvent. Colligative Properties Lowering Vapor Pressure The vapor pressure of a sol’n containing 53.6 g of glycerin, C3H8O3, in 133.7 g of ethanol, CH3CH2OH, is 113 torr at 40oC. Calculate the vapor pressure of the pure ethanol at 40oC assuming that glycerin is a nonvolatile solute in ethanol. PA A P A Colligative Properties Lowering Vapor Pressure • Ideal solution: one that obeys Raoult’s law. • Raoult’s law breaks down when the solvent-solvent and solute-solute intermolecular forces are greater than solute-solvent intermolecular forces. Colligative Properties Boiling-Point Elevation • A non-volatile solute increases the boiling point of a solvent. • At 1 atm (normal boiling point of pure liquid) there is a lower vapor pressure of the solution. Therefore, a higher temperature is required to reach a vapor pressure of 1 atm for the solution (DTb). • Molal boiling-point-elevation constant, Kb, expresses how much DTb changes with molality, m: DTb Kb m Colligative Properties Freezing Point Depression • A non-volatile solute decreases the freezing point of a solvent. • Decrease in freezing point (DTf) is directly proportional to molality (Kf is the molal freezing-point-depression constant): DT f K f m Colligative Properties Colligative Properties How does the presence of a non-volatile solute affect the phase diagram for a solvent? a. b. c. d. Vapor pressure curve is lowered Melting curve is lowered Boiling Point is increased (Temp of VP curve at 1 atm) Melting Point is decreased (Temp of MP curve at 1 atm) Colligative Properties Osmosis • Osmosis: the flow of a pure solvent into a sol’n through a semipermeable memebrane. • Semipermeable membrane: permits passage of some components of a solution. Example: cell membranes and cellophane. • There is movement in both directions across a semipermeable membrane. Colligative Properties Osmosis • As solvent moves across the membrane, the fluid levels in the arms becomes uneven. Eventually the pressure difference between the arms stops osmosis. Colligative Properties Osmosis Osmotic pressure, : the pressure required to stop osmosis: V nRT n RT V MRT • • • • = osmotic pressure in atm M = molarity of sol’n, mol/L R = gas law constant, 0.0821 L.atm/mol.K T = temperature in Kelvin Colligative Properties Osmosis • An aqueous solution of 10.00 g of catalase, an enzyme found in liver, has a volume of 1.00 L at 27oC. The solution’s osmotic pressure at 27oC is 0.745 torr. Calculate the molar mass of the catalase. = MRT; M = molarity Colligative Properties • • • • Osmosis Isotonic solutions: two solutions with the same separated by a semipermeable membrane. Hypotonic solutions: a solution of lower than a hypertonic solution. Osmosis is spontaneous. Red blood cells are surrounded by semipermeable membranes. Colligative Properties Osmosis • Crenation: – red blood cells placed in hypertonic solution (relative to intracellular solution); – there is a lower solute concentration in the cell than the surrounding tissue; – osmosis occurs and water passes through the membrane out of the cell. – The cell shrivels up. Colligative Properties Osmosis Colligative Properties Osmosis • Hemolysis: – – – – red blood cells placed in a hypotonic solution; there is a higher solute concentration in the cell; osmosis occurs and water moves into the cell. The cell bursts. • To prevent crenation or hemolysis, IV (intravenous) solutions must be isotonic. Colligative Properties Osmosis – Cucumber placed in NaCl solution loses water to shrivel up and become a pickle. – Limp carrot placed in water becomes firm because water enters via osmosis. – Salty food causes retention of water and swelling of tissues (edema). – Water moves into plants through osmosis. – Salt added to meat or sugar to fruit prevents bacterial infection (a bacterium placed on the salt will lose water through osmosis and die). Colligative Properties Osmosis • Active transport is the movement of nutrients and waste material through a biological system. • Active transport is not spontaneous. Colloids • Colloids are suspensions in which the suspended particles are larger than molecules but too small to drop out of the suspension due to gravity. • Particle size: 10 to 2000 Å. • There are several types of colloid: – – – – aerosol (gas + liquid or solid, e.g. fog and smoke), foam (liquid + gas, e.g. whipped cream), emulsion (liquid + liquid, e.g. milk), sol (liquid + solid, e.g. paint), Colloids – solid foam (solid + gas, e.g. marshmallow), – solid emulsion (solid + liquid, e.g. butter), – solid sol (solid + solid, e.g. ruby glass). • Tyndall effect: ability of a Colloid to scatter light. The beam of light can be seen through the colloid. Colloids End of Chapter 13 Properties of Solutions