2/27/2012 Two Ways to Form Solutions Role of Disorder in Solutions • Disorder (Entropy) is a factor • Solutions mix to form maximum disorder 1. Physical Dissolving (Solvation) • NaCl(s) Na+(aq) + Cl-(aq) • C12H22O11(s) C12H22O11(aq) • Particles are surrounded by solvent molecules • Can evaporate water/solvent to get original compound back Types of Reactions 2. Chemical reaction • Ni(s) + 2HCl(aq) NiCl2(aq) + H2(g) • Evaporating solvent gives the products Solubility – Maximum amount of a solute that can dissolve in 100 mL of a solution Ex: NaCl 35.7 g/100mL – Saturated solution – Contains the max. amount of solute with some undissolved solid, – Unsaturated – more solute will dissolve. 1 2/27/2012 – Supersaturated – More than the max is dissolved by heating and slowly cooling. Like Dissolves Like: Miscibility • Polar dissolves polar (dipole-dipole Forces) and ionic (ion:dipole) – Water and Ammonia • Non-Polar dissolves non-polar (London Forces) – Soap and grease Would acetone (shown below) dissolve in water? :O: || CH3CCH3 Acetone Using you knowledge of “like dissolves like”, explain the following trends in solubility. Alcohol CH3OH Solubility in H2O (mol/100 g H2O at 20oC) ∞ CH3CH2OH ∞ CH3CH2CH2OH ∞ CH3CH2CH2CH2OH 0.11 CH3CH2CH2CH2CH2OH 0.030 CH3CH2CH2CH2CH2CH2OH 0.0058 CH3CH2CH2CH2CH2CH2CH2OH 0.0008 Pressure Effects • Solubilty of a gas increases with pressure of gas over the liquid (soda bottle) • Henry’s Law Sgas = kPgas 2 2/27/2012 Henry’s Law Temperature Effects The Henry’s law constant for CO2 is 0.031 mol/Latm. a. Calculate the concentration of CO2 in a soda bottle pressurized to 4.00 atm of CO2. b. After the bottle has been opened, the concentration drops to 9.3 X 10-6 M. Calculate the partial pressure of CO2 over the soda. Ways of Expressing Concentration Mass % = mass of compound in soln X total mass of soln 100 Parts Per Million • Solubility of most solids increases with temperature • Solubility of most gases decreases with temperature (warm soda) – Warm water is deoxygenated – Problem with thermal pollution of lakes Concentration: Ex 1 13.5 g of C6H12O6 is dissolved in 0.100 kg of water. Calculate the mass percentage. mass % = 13.5 g X 100 = 11.9% (100 g + 13.5 g) ppm = mass of component X 106 total mass of soln Concentration: Ex 2 A 2.5 g sample of groundwater is found to contain 5.4 g of Zn2+. What is the concentration of the Zn2+ ion in ppm. Concentration: Ex 2 A 2.5 g sample of groundwater is found to contain 5.4 g of Zn2+. What is the concentration of the Zn2+ ion in ppm. 5.4 g | 1X10-6g = 5.4 X 10-6 g | 1 g ppm = mass of component X 106 total mass of soln ppm = 5.4 X 10-6 g X 106 = 2.2 ppm 2.5g 3 2/27/2012 Concentration: Ex 3 Concentration: Ex 4 Calculate the mass percentage of NaCl in a solution containing 1.50 g of NaCl in 50.0 g of water. Bleach is 3.62 % NaOCl. What mass of NaOCl is contained in 2500 g of bleach? ANS: 2.91 % ANS: 90.5 g NaOCl Mole Fraction Mole Fraction X = moles of component total moles of all components What is the mole fraction of HCl if 36.5 grams is dissolved in 144 grams of water? Molality Molality = moles of solute kilograms of solvent Why not use Molarity? • Molarity varies with temperature • Total volume of a solution changes with temperature (liquid expands) • Mass does not change with temperature ANS: 0.111 Molality: Ex 1 A solution is made by dissolving 4.35 grams of C6H12O6 in 25.0 mL of water. Calculate the molality of the glucose. 4.35 g 1 mol 180.2 g Molality = 0.0241 mol 0.0250 kg = Molality: Ex 2 Calculate the molality of a solution made by dissolving 36.5g C10H8 in 425 grams of toluene (solvent). 0.0241 mol = 0.964 m ANS: 0.671 m 4 2/27/2012 Molality: Ex 3 A solution of HCl contains 36 percent HCl by mass. Calculate the mole fraction and molality of HCl. Pretend 100 g 36 g HCl 64 g H2O 36 g HCl 1 mol HCl = 36.5 g HCl 64 g H2O 1 mol H2O = 18 g H2O 0.99 mol HCl XHCl = 0.99 mol HCl 0.99 mol + 3.6mol = 0.22 Molality = 0.99 mol HCl 0.064 kg H2O = 15 m Molality: Ex 4 A commercial bleach solution contains 3.62 percent NaOCl by mass. Calculate the mole fraction and molality of NaOCl. 3.6 mol HCl Molality: Ex 5 The density of a solution of 5.0 g of toluene (C7H8) and 225 g of benzene (C6H6) is 0.876 g/mL. Calculate the molality and molarity of the toluene. ANS: XNaOCl = 0.00900, 0.505 m Molality: Ex 5 The density of a solution of 5.0 g of toluene (C7H8) and 225 g of benzene (C6H6) is 0.876 g/mL. Calculate the molality and molarity of the solution. Molality 5.0 g 1 mol = 0.054 mol 92.0 g Molarity D = mass/V V = mass/D V = 230 g = 263 mL 0.876 g/ml M = 0.054 mol = 0.21 M 0.263 L m = 0.054 mol/ 0.225 kg = 0.24 m 5 2/27/2012 Molality: Ex 6 A solution containing equal masses of glycerol (C3H8O3) and water has a density of 1.10 g/mL. Calculate a) molality (10.9 m) b) mole fraction (XC3H8O3 = 0.163) c) molarity of glycerol in the solution (5.97 M) Colligative Properties: Vapor Pressure Lowering Non-volatile solutes lower the vapor pressure of the solvent Raoult’s law PA = XAPoA PA = Vapor pressure XA = Mole fraction of solvent PoA = Pressure of pure solvent Raoult’s Law: Ex 1 What is the vapor pressure of a solution made by adding 50.0 mL of glycerin (C3H8O3) to 500.0 mL of water? The density of glycerin is 1.26 g/mL and the vapor pressure of pure water is 23.8 torr. XH2O = 27.8 mol = 0.976 (27.8 mol + 0.684 mol) PA = XAPoA PA = (0.976)(23.8 torr) = 23.2 torr MassC3H8O3 = (50.0 mL)(1.26 g/mL ) = 63.0 g MolesC3H8O3 = 63.0 g/92.1 g/mol = 0.684 mol MolesH2O = 500.0 g/18 g/mol = 27.8 mol Raoult’s Law: Ex 2 The vapor pressure of water at 110oC is 1070 torr. A solution of ethylene glycol and water has a vapor pressure of 1 atm at 110oC. What is the mole fraction of ethylene glycol in the solution? ANS: 0.290 Colligative Properties: Boiling Point Elevation • Non-volatile solute raises the boiling point of a solution • Shifts the phase diagram • The pressure of the solution reaches atmospheric pressure at a higher temp. Tb = iKbm 6 2/27/2012 Colligative Properties: Freezing Point Depression • Solutions freeze at a lower temperature than pure solvent • Salt water freezes lower (-2oC) than distilled water (0oC) Tf = iKfm • The more ions produced, the greater the freezing point depression or boiling point elevation • C12H22O11 (i=1) • NaCl = Produces two ions (i=2) • CaCl2 = Produces three ions (i=3) i = Van’t Hoff factor m = molality of the nonvolatile solute Pure Solvent Solution Boiling Point Boiling Point Freezing Point Freezing Point Colligative: Ex 1 Ethylene Glycol, C2H6O2, is used in antifreeze. What will be the freezing and boiling point of a 25.0 mass percent solution of ethylene glycol and water? Pretend 100 grams of solution 25 grams of C2H6O2 75 grams of H2O (0.075 kg) Colligative: Ex 2 25 grams of C2H6O2 = 0.403 moles m = 0.403 moles 0.075 kg H2O = 5.37 m o Calculate the freezing point of a solution containing 0.600 kg of CHCl3 and 42.0 g of C10H18O. Kf for CHCl3 is 4.68oC/m and the normal freezing point is -63.5 oC. Tb = iKbm = (1)(0.52oC/m)(5.37 m) = 2.8oC Tf = iKfm = (1)( 1.86oC/m)(5.37 m) =10.0oC Boiling Point = 102.8oC Freezing Point = -10.0oC ANS: -65.6oC 7 2/27/2012 Colligative: Ex 3 Rank the following aqueous solutions in order of their expected freezing points: 0.050 m CaCl2 0.15 m NaCl 0.10 m HCl 0.050 m HC2H3O2 (acetic acid) 0.10 m C12H22O11 (sugar) Colligative: Ex 4 Rank the following in order of the increase in boiling point that they will produce in 1 kg of water 1 mol Co(NO3)2 2 mol KCl 3 mol C2H6O2 (a very, very weak electrolyte(acidic)) 0.050 m CaCl2 0.15 m NaCl 0.10 m HCl 0.050 m HC2H3O2 0.10 m C12H22O11 (0.15 m in particles) (0.30 m in particles) (0.20 m in particles) (just above 0.05 m) (0.10 m in particles) Lowest FP Highest FP NaCl < HCl < CaCl2 < C12H22O11 < HC2H3O2 1 mol Co(NO3)2 2 mol KCl 3 mol C2H6O2 (3 mol particles) (4 mol of particles) (3+ mol of particles) Lowest BP Highest BP Co(NO3)2 < C2H6O2 < KCl Freezing Pt Depression: Ex 5 Colligative Properties: Osmotic Pressure What would be the molality of salt water if it freezes at 0 oF? Kf = 1.86 oC/m. • Osmosis – movement of solvent from high concentration to low concentration • semipermeable membrane – allows to passage of some particles but not others Cucumber Skin cell after in salt water soaking in a tub ANS: 4.78 m 8 2/27/2012 • Note that solvent moves both ways • Solute too large to pass through membrane • Net movement is to try to dilute the side with solutes • Osmotic Pressure ( ) – pressure required to prevent osmosis PV = inRT V = inRT = inRT V = iMRT M = molarity Osmotic Pressure: Ex 1 Osmotic Pressure: Ex 2 The average osmotic pressure of blood is 7.7 atm at 25oC. What concentration of glucose will be isotonic with blood? What is the osmotic pressure at 20oC of a 0.0020 M sucrose, C12H22O11, solution? Express your answer both in atmosphere and in torr. (0.31 M) ANS; 0.048 atm, 37 torr Molar Mass: Ex 1 A solution of an unknown nonelectrolyte was prepared by dissolving 0.250 g in 40.0 g of CCl4. The boiling point of the resulting solution was 0.357oC higher than that of the pure solvent. Kb for CCl4 is 5.02 oC/m. Calculate the molar mass of the unknown. Tb = iKbm m = Tb /iKb m = (0.357oC)/(1 X 5.02 oC/m) = 0.0711 m m = mol of solute kilograms of solvent molsolute = (m)(kg of solvent) molsolute = (0.0711 m)(0.0400 kg) = 0.00284 mol Molar Mass = 0.250 g 0.00284 mol = 88.0 g/mol 9 2/27/2012 Molar Mass: Ex 2 Camphor, C10H16O, melts at 179.8oC and has a Kf of 40.0 oC/m. When 0.186 g of an unknown substance is dissolved in 22.01 g of liquid camphor, the freezing point is 176.7oC. What is the molar mass of the solute? Molar Mass: Ex 3 A solution contains 3.50 mg of protein dissolved in water to form 5.00 mL of a solution. The osmotic pressure at 25oC was found to be 1.54 torr. Calculate the molar mass of the protein. 1.54 torr 1 atm 760 torr = 0.00203 atm ANS: 110 g/mol = iMRT M = /iRT M = 0.00203 atm = 8.28X10-5 M (1)(0.0821 L-atm/mol-K)(298) M = moles liter moles = (M)(liters) = (8.28X10-5 M)(0.00500L) moles = 4.14 X 10-7 mol Molar mass = 3.50 X 10-3 g = 8454 g/mol 4.14 X 10-7 mol Molar Mass: Ex 4 A 2.05 g sample of a plastic was dissolved in enough toluene to form 100 mL of solution. The osmotic pressure of this solution is 1.21 kPa at 25oC. Calculate the molar mass of the plastic. (1 atm = 101.325 kPa). ANS: 42,000 g/mol Colloids Solutions/ Homogeneous Ions/Molecular size solute particles Never separate Colloids Suspensions/ Heterogeneous Mixture Medium particles (10 to 2000 Å) Larger particles (like dirt in water) 2 or more separate phases Separates quickly • Examples – Fog – Smoke – Whipped Cream – Milk • Tyndall effect – scattering of light 10 2/27/2012 Stabilization of Colloids • Hydrophobic/hydrophilic imf – Biomolecules Emulsifying agents – Soap – Sodium stearate(used to digest fats) 6. Larger Noble gases have greater London Forces (greater dipole: induced dipole forces) 16.a) Ion:Dipole b) Dipole: induced dipole c) Hydrogen bonding (weakest) b < c < a (strongest) 30.a) glucose (OH’s allow h-bonding) b) sodium propionate (has an ion) c) HCl (small and polar) 34.S = kP k = S/P = 1.38 X 10-3M/0.21 atm -3 k =6.57 X 10 M/atm Partial Pressure of O2 at the higher elevation: 650 torr = 0.855 atm PO2 = (0.855 atm)(0.21) PO2 = 0.180 atm S = kP S=(6.57 X 10-3 )(0.180 atm) -3 S = 1.18 X 10 M 36a) 7.2% I2 b) 7.9 ppm Sr2+ 38a) 0.0285 b) 5.66% c) 0.638 m 40a) 0.125 M b) 0.140 M c) 0.630 M 42a) 4.34 m b) 3.1 g S8 44a) 27.7% b) 0.0377 c) 2.18 m d) 1.92 M 46a) 0.0439 b) 0.498 m c) 0.417 M 48a) 0.278 mol b) 6.25X10-5 mol c) 0.00329 mol 50a) 21.8 g b) 7.7 g/112.3g c) 209 g d) 11 mL of 6.0 M HCl 52) 15 M NH3 11 2/27/2012 62.a) 222 torr b) 150 g 64. a) 0.75 b) 0.47 66. 10% sucrose < 10% glucose < 10% NaNO3 68. 0.030 m phenol < KBr = 0.040 m glycerin 70.a) -115.2, 78.8 b) -78, 72.4 c) -9.3, 102.6 72.-18 oC 74.2.8 atm 76.180 g/mol 78. 380 g/mol Write Net Ionic Equations for: MgCO3(s) + HNO3(aq) H2SO4(aq) + 2KOH(aq) NaHCO3(aq) + HCl(aq) A solution of nickel(II)sulfate is stored in a zinc coated bucket. a. Write the net ionic reaction that occurs. b. Suppose the nickel(II)sulfate was stored in a copper bucket. Would this be a better choice? c. Write the net ionic reaction that occurs between nickel(II)sulfate and barium nitrate. 1. 2. 3. 4. 5. Lots of ice, little water Stir and take temperature (~2 min) Add medicine cup of rock salt Stir and take temperature (~2 min) Clean Up 1. Rinse Foam cup, medicine cup, and thermometer 2. Place in drying rack 12