Chapter 12 Solutions Solutions solute is the dissolved substance ◦ seems to “disappear” ◦ “takes on the state” of the solvent solvent is the substance solute dissolves in ◦ does not appear to change state when both solute and solvent have the same state, the solvent is the component present in the highest percentage solutions in which the solvent is water are called aqueous solutions 2 Solution Concentration Molarity moles of solute per 1 liter of solution used because it describes how many molecules of solute in each liter of solution if a sugar solution concentration is 2.0 M, 1 liter of solution contains 2.0 moles of sugar, 2 liters = 4.0 moles sugar, 0.5 liters = 1.0 mole sugar moles of solute molarity = liters of solution 3 Molarity and Dissociation the molarity of the ionic compound allows you to determine the molarity of the dissolved ions CaCl2(aq) = Ca+2(aq) + 2 Cl-1(aq) A 1.0 M CaCl2(aq) solution contains 1.0 moles of CaCl2 in each liter of solution ◦ 1 L = 1.0 moles CaCl2, 2 L = 2.0 moles CaCl2 Because each CaCl2 dissociates to give one Ca+2 = 1.0 M Ca+2 ◦ 1 L = 1.0 moles Ca+2, 2 L = 2.0 moles Ca+2 Because each CaCl2 dissociates to give 2 Cl-1 = 2.0 M Cl-1 ◦ 1 L = 2.0 moles Cl-1, 2 L = 4.0 moles Cl-1 4 Solution ConcentrationMolality, m moles of solute per 1 kilogram of solvent ◦ defined in terms of amount of solvent, not solution like the others does not vary with temperature ◦ because based on masses, not volumes moles of solute molality, m kg of solvent 5 Percent parts of solute in every 100 parts solution mass percent = mass of solute in 100 parts solution by mass ◦ if a solution is 0.9% by mass, then there are 0.9 grams of solute in every 100 grams of solution or 0.9 kg solute in every 100 kg solution Mass of Solute, g Mass Percent 100% Mass of Solution, g Mass of Solute Mass of Solvent Mass of Solution 6 Using Concentrations as Conversion Factors concentrations show the relationship between the amount of solute and the amount of solvent ◦ 12%(m/m) sugar(aq) means ◦ 5.5%(m/v) Ag in Hg means ◦ 22%(v/v) alcohol(aq) means 7 Preparing a Solution need to know amount of solution and concentration of solution calculate the mass of solute needed ◦ start with amount of solution ◦ use concentration as a conversion factor 5% by mass 5 g solute 100 g solution ◦ “Dissolve the grams of solute in enough solvent to total the total amount of solution.” 8 Example A solution is prepared by mixing 15.0 g of Na2CO3 and 235 g of H2O. Calculate the mass percent (% m/m) of the solution. What volume of 10.5% by mass soda contains 78.5 g of sugar? Density of solution is 1.04 g/ml Solution Concentration PPM grams of solute per 1,000,000 g of solution mg of solute per 1 kg of solution 1 liter of water = 1 kg of water ◦ for water solutions we often approximate the kg of the solution as the kg or L of water grams solute x 106 mg solute mg solute L solution kg solution grams solution 10 Solution Concentrations Mole Fraction, XA the mole fraction is the fraction of the moles of one component in the total moles of all the components of the solution total of all the mole fractions in a solution = 1 unitless the mole percentage is the percentage of the moles of one component in the total moles of all the components of the solution = mole fraction x 100% mole fraction of A = XA = moles of components A total moles in the solution 11 Example What is the molarity of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? What is the percent by mass of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? Example What is the mole fraction of a solution prepared by mixing 17.2 g of C2H6O2 with 0.500 kg of H2O to make 515 mL of solution? A water sample is found to contain the pollutant chlorobenzene with a concentration of 15 ppb (by mass). What volume of this water contains 5.00 x 102 mg of chlorobenzene? Assume density of 1.00 g/ml Spontaneous Mixing When the barrier is removed, spontaneous mixing occurs, producing a solution of uniform concentration. 14 Mixing and the Solution Process Entropy formation of a solution does not necessarily lower the potential energy of the system ◦ the difference in attractive forces between atoms of two separate ideal gases vs. two mixed ideal gases is negligible ◦ yet the gases mix spontaneously the gases mix because the energy of the system is lowered through the release of entropy entropy is the measure of energy dispersal throughout the system energy has a spontaneous drive to spread out over as large a volume as it is allowed 15 Energy changes and the solution process Simply put, three processes affect the energetics of the process: _ Separation of solute particles ΔH1( this is always endothermic) _ Separation of solvent particles ΔH2 ( this too is always endothermic) _ New interactions between solute and solvent ΔH3 ( this is always exothermic) The overall enthalpy change associated with these three processes : ΔHsoln = ΔH1 + ΔH2+ ΔH3 (Hess’s Law) Intermolecular Forces and the Solution Process Enthalpy of Solution The solute-solvent interactions are greater than the sum of the solute-solute and solventsolvent interactions. The solute-solvent interactions are less than the sum of the solute-solute and solventsolvent interactions. Intermolecular Attractions 18 Relative Interactions and Solution Formation Solute-to-Solvent Solute-to-Solvent Solute-to-Solvent Solute-to-Solute + > Solvent-to-Solvent Solute-to-Solute + = Solvent-to-Solvent Solute-to-Solute + < Solvent-to-Solvent Solution Forms Solution Forms Solution May or May Not Form when the solute-to-solvent attractions are weaker than the sum of the solute-to-solute and solvent-to-solvent attractions, the solution will only form if the energy difference is small enough to be overcome by the entropy 19 Will It Dissolve? Chemist’s Rule of Thumb – Like Dissolves Like a chemical will dissolve in a solvent if it has a similar structure to the solvent when the solvent and solute structures are similar, the solvent molecules will attract the solute particles at least as well as the solute particles to each other 20 Classifying Solvents Solvent Class Structural Feature Water, H2O polar O-H Methyl Alcohol, CH3OH Ethyl Alcohol, C2H5OH Acetone, C3H6O polar polar polar O-H O-H C=O Toluene, C7H8 Hexane, C6H14 Diethyl Ether, C4H10O nonpolar nonpolar nonpolar C-C & C-H C-C & C-H C-C, C-H & C-O, (nonpolar > polar) Carbon Tetrachloride nonpolar C-Cl, but symmetrical Tro, Chemistry: A Molecular Approach 21 Example 12.1a predict whether the following vitamin is soluble in fat or water OH The 4 OH groups make the molecule highly polar and it will also H-bond to water. Vitamin C is water soluble OH H 2C C H H C O C C O C HO OH Vitamin C 22 Example 12.1b predict whether the following vitamin is soluble in fat or water The 2 C=O groups are polar, but their geometric symmetry suggests their pulls will cancel and the molecule will be nonpolar. Vitamin K3 is fat soluble O H C C CH3 HC C C HC C CH C H C O Vitamin K3 Tro, Chemistry: A Molecular Approach 23 Heats of Hydration for aqueous ionic solutions, the energy added to overcome the attractions between water molecules and the energy released in forming attractions between the water molecules and ions is combined into a term called the heat of hydration ◦ attractive forces in water = H-bonds ◦ attractive forces between ion and water = iondipole ◦ DHhydration = heat released when 1 mole of gaseous ions dissolves in water Tro, Chemistry: A Molecular Approach 24 Ion-Dipole Interactions when ions dissolve in water they become hydrated each ion is surrounded by water molecules 25 Solution Equilibrium 26 Solubility Limit a solution that has the maximum amount of solute dissolved in it is said to be saturated ◦ depends on the amount of solvent ◦ depends on the temperature and pressure of gases a solution that has less solute than saturation is said to be unsaturated a solution that has more solute than saturation is said to be supersaturated 27 Example Example: The solubility of NaNO3 in water at 50oC is 110g/100g of water. In a laboratory, a student use 50.0 g of NaNO3 with 200 g of water at the same temperature ◦ How many grams of NaNO3 will dissovle? ◦ Is the solution saturated or unsaturated? ◦ What is the mass, in grams, of any solid NaNO3 on the bottom of the container? Temperature Dependence of Solubility of Solids in Water Solubility depends on temperature most solids increases as temperature increases. ◦ Hot tea dissolves more sugar than does cold tea because the solubility of sugar is much greater in higher temperature When a saturated solution is carefully cooled, it becomes a supersaturated solution because it contains more solute than the solubility allowssolubility is generally given in grams of solute that will dissolve in 100 g of water for most solids, the solubility of the solid increases as the temperature increases ◦ when DHsolution is endothermic 29 Solubility Curve solubility curves can be used to predict whether a solution with a particular amount of solute dissolved in water is saturated (on the line), unsaturated (below the line), or supersaturated (above the line) Temperature Dependence of Solubility of Gases in Water solubility is generally given in moles of solute that will dissolve in 1 Liter of solution generally lower solubility than ionic or polar covalent solids because most are nonpolar molecules for all gases, the solubility of the gas decreases as the temperature increases ◦ the DHsolution is exothermic because you do not need to overcome solute-solute attractions the solubility of gases in water increases with increasing mass as the attraction between the gas and the solvent molecule is mainly dispersion forces ◦ Larger molecules have stronger dispersion forces. 31 Henry’s Law the solubility of a gas in a liquid is directly related to the pressure of that gas above the liquid. at higher pressures, more gas molecules dissolve in the liquid. Soap Action most dirt and grease is made of nonpolar molecules – making it hard for water to remove it from the surface soap molecules form micelles around the small oil particles with the polar/ionic heads pointing out this allows the micelle to be attracted to water and stay suspended The polar heads of the micelles attract them to the water, and simultaneously repel other micelles so they will not coalesce and settle out. 33 34