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Chapter 13 Properties of Solutions. Consider KCl (solute) dissolving in water (solvent): H-bonds in water have to be interrupted, KCl dissociates into K + and Cl - , ion-dipole forces form: K + … -OH 2 and Cl - … +H 2 O. ions are solvated by water.
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Consider KCl (solute) dissolving in water (solvent): • H-bonds in water have to be interrupted, • KCl dissociates into K+ and Cl-, • ion-dipole forces form: K+…-OH2 and Cl- …+H2O. • ions are solvated by water.
Energy Changes and Solution Formation • There are three enthalpy steps in forming a solution: • separation of solute molecules (H1), • separation of solvent molecules (H2), andformation of solute-solvent interactions (H3). • The enthalpy change in the solution process is • Hsoln = H1 + H2 + H3. • Hsoln can either exothermic or endothermic depending on the intermolecular forces.
Energy Changes and Solution Formation • To determine whether Hsoln is positive or negative, consider the strengths of all solute-solute and solute-solvent interactions: • H1 and H2 are both positive. • H3 is always negative. • It is possible to have either H3 > (H1 + H2) or H3 < (H1 + H2).
Energy Changes and Solution Formation • Examples: • NaOH added to water has Hsoln = -44.48 kJ/mol. • NH4NO3 added to water has Hsoln = + 26.4 kJ/mol. • “Rule”: polar solvents dissolve polar solutes. Non-polar solvents dissolve non-polar solutes. • If Hsoln is too endothermic a solution will not form. • NaCl in gasoline: the ion-dipole forces are weak because gasoline is non-polar. Therefore, the ion-dipole forces do not compensate for the separation of ions.
Saturated Solutions and Solubility • Saturation: crystallization and dissolution of a solute are in equilibrium. • Solubility: amount of solute required to form a saturated solution. • Supersaturated: a solution formed when more solute is dissolved than in a saturated solution.
Factors Affecting Solubility • Polar liquids tend to dissolve in polar solvents. • 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. • Generalization: “like dissolves like”. • The more polar bonds in the molecule, the better it dissolves in a polar solvent. • The less polar the molecule the less it dissolves in a polar solvent and the better is dissolves in a non-polar solvent.
Solute-Solvent Interaction • Network solids do not dissolve because the strong intermolecular forces in the solid are not re-established in any solution. • Pressure Effects • Solubility of a gas in a liquid is a function of the pressure of the gas.
Pressure Effects • The higher the pressure, the more molecules of gas are close to the solvent and the greater the chance of a gas molecule striking the surface and entering the solution. • Therefore, the higher the pressure, the greater the solubility. • The lower the pressure, the fewer molecules of gas are close to the solvent and the lower the solubility. • 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.
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).
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 lakes get too warm, CO2 and O2 become less soluble and are not available for plants or animals.
Colligative Properties • Colligative properties depend on quantity of solute molecules. (E.g. freezing point depression and melting point elevation.)
Lowering Vapor Pressure • Non-volatile solvents 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.
Lowering Vapor Pressure • Raoult’s Law: The vapor pressure of an ideal solution (PA) is a fraction of the vapor pressure of the pure solvent (PA).
Boiling-Point Elevation • 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 teach a vapor pressure of 1 atm for the solution (Tb). • Molal boiling-point-elevation constant, Kb, expresses how much Tb changes with solute molality, m:
Freezing Point Depression • The solution freezes at a lower temperature (Tf) than the pure solvent. • Decrease in freezing point (Tf) is directly proportional to solute molality (Kfis the molal freezing-point-depression constant):