Chemistry 102(01) Spring 2013 Instructor: Dr. Upali Siriwardane e-mail: upali@coes.latech.edu Office: CTH 311 Phone 257-4941 Office Hours: M,W 8:00-9:00 & 11:00-12:00 am; Tu,Th,F 9:30 - 11:30 am. Test Dates: September 27, 2013 (Test 1): Chapter 12 & 13 April 24, 2013 (Test 2): Chapter 14 & 15 May13, 2013 (Test 3) Chapter 16 & 17 May 15, 2012 (Make-up test) comprehensive: Chapters 12-17 9:30-10:45:15 AM, CTH 328 CHEM 102, Spring 2013 LA TECH 12-1 Text Book & Resources REQUIRED : Textbook: Principles of Chemistry: A Molecular Approach, 2nd Edition-Nivaldo J. Tro - Pearson Prentice Hall and also purchase the Mastering Chemistry Group Homework, Slides and Exam review guides and sample exam questions are available online: http://moodle.latech.edu/ and follow the course information links. OPTIONAL : Study Guide: Chemistry: A Molecular Approach, 2nd EditionNivaldo J. Tro 2nd Edition Student Solutions Manual: Chemistry: A Molecular Approach, 2nd Edition-Nivaldo J. Tro 2nd CHEM 102, Spring 2013 LA TECH 12-2 Chapter 12. Solutions 12.1 Thirsty Solutions: 12.2 Types of Solutions and Solubility 12.3 Energetics of Solution Formation 12.4 Solubility Equilibrium and Factors Affecting solution Formation 12.5 Expressing Solution Concentration 12.6 Colligative Properties: Vapor Pressure, Freezing Point, Boiling Point, Osmatic Pressure 12.7 Colligative properties of Strong Electrolytes CHEM 102, Spring 2013 LA TECH 12-3 Solution Terminology solute one or more substance(s) dispersed in the solution solvent majority substance in a solution The solubility of a solid in a solvent is typically given in g/100 ml. Types of solutions Mixture of Gases Liquid solutions (L+S,L+L,L+G) Solid solutions (S+S, alloys) Aerosols (L+G) Foam (S+G) CHEM 102, Spring 2013 LA TECH 12-4 Miscible vs. Immiscible CHEM 102, Spring 2013 LA TECH 12-5 “Likes Dissolve Likes” Materials with similar polarity are soluble in each other. Dissimilar ones are not. Polar substances with similar forces are likely to be soluble in each other Non-polar solutes dissolve in non-polar solvents stronger solute-solvent attractions favor solubility, stronger solute-solute or solventsolvent attractions reduce solubility CHEM 102, Spring 2013 LA TECH 12-6 Solubility of Ionic Compounds and Temperature CHEM 102, Spring 2013 LA TECH 12-7 Solution Terminology Miscible - liquids that dissolve in each other Immiscible - liquids that do not dissolve in each other due to differences types of interactions Saturated solution A solution that contains as much it can hold Unsaturated solution A solution that contains less than maximum amount Supersaturated solution A solution that contains more than maximum amount CHEM 102, Spring 2013 LA TECH 12-8 Types of Solutions (Diluted, Saturated, and Supersaturated) CHEM 102, Spring 2013 LA TECH 12-9 Supersaturated Solution CHEM 102, Spring 2013 LA TECH 12-10 Solute - Solvent Interactions CHEM 102, Spring 2013 LA TECH 12-11 The Solution Making Exopthermic Process CHEM 102, Spring 2013 LA TECH 12-12 The Solution Making Endothermic Process CHEM 102, Spring 2013 LA TECH 12-13 Thermodynamic Factors Affecting Solubility 1. Energy: Enthalpy (DH) Lower energy – DH 2. Order: Entropy (DS) Disorder + DS Exothermic –DH favors solubility: product favored Mixing (+DS disorder favors solubility: product favored Gibbs Free Energy: (Chapter 18) DGsoln = DHsoln -TDSsoln, CHEM 102, Spring 2013 LA TECH 12-14 Types of Solute - Solvent Interactions All interactions are electrostatic force ~ Coulombic: proprotional to charge and separation) 1. 2. 3. 4. 5. London Dispersion Forces: (O2 dissolved in Liq. N2) Ion-Ion Interaction: (Ionic liquids in batteries) Ion-Dipole Interaction (hydrated ions Na+(aq)) Dipole-Dipole Interaction (CCl4 in benzene (C6H6) Hydrogen Bonding. (water and éthanol) CHEM 102, Spring 2013 LA TECH 12-15 1) What are the main factors affecting a solubility of a solute in a solvent? CHEM 102, Spring 2013 LA TECH 12-16 The Solution Making Exopthermic Process CHEM 102, Spring 2013 LA TECH 12-17 The Solution Making Endothermic Process CHEM 102, Spring 2013 LA TECH 12-18 2) Arrange the following inter-particles forces in liquids and solids in the order of increasing strength: ion-ion, ion-dipole, hydrogen bond, dipole-dipole and London dispersion CHEM 102, Spring 2013 LA TECH 12-19 3) Identify the most important type of inter-particle force for each of the following compounds: a) NaCl(s) or NaCl(l) b) N2(l) or N2(s) c) N2(g) d) Na(s) and Na(l) e) H2O(l) or H2O(s) f) CH3CH2OH(l) or CH3CH2OH(s) CHEM 102, Spring 2013 LA TECH 12-20 4) Which of the above inter-particle force could be named as intermolecular force? a) NaCl(s) or NaCl(l) b) N2(l) or N2(s) c) N2(g) d) Na(s) and Na(l) e) H2O(l) or H2O(s) f) CH3CH2OH(l) or CH3CH2OH(s) CHEM 102, Spring 2013 LA TECH 12-21 Identify Hydrogen Bonding, Polar and Non-polar groups in Covalent Molecules Acetic acid HC2H3O2 CH3COOH Hexanol C6H13OH Hexane C6H14 Propanoic acid C2H5COOH “Like Dissolves Like” CHEM 102, Spring 2013 LA TECH 12-22 5) What types of inter-particle forces solute-solute:DH1, solvent-solvent: DH2, solvent-solute:DH3) are involved when a) CH3CH2OH(l): dissolved in water,H2O: DH1 = ; DH2 = ; DH3= For covalent compounds: DHsoln= DH1+ DH2+ DH3 CHEM 102, Spring 2013 LA TECH 12-23 Water Dissolving An Ionic Solute CHEM 102, Spring 2013 LA TECH 12-24 Solution Process of Ionic Compounds CHEM 102, Spring 2013 LA TECH 12-25 Hydration of a Sodium Ion CHEM 102, Spring 2013 LA TECH 12-26 Heats of Solution CHEM 102, Spring 2013 LA TECH 12-27 5) b) Na2SO4(s) dissolved in water: DH1 = ; DH2 = ; DH3 = Ion-ion inter-particle forces in solids are called Lattice Energy. ( this is related to DH1) Ion-water inter-particle forces are called Hydration Energy (this is related to DH2 and DH3) For ionic compounds; DHsoln = DHlattice + DHhyd Qualitatively speaking which of the above a) or b) would have a more exothermic DHsoln? CHEM 102, Spring 2013 LA TECH 12-28 6) Assign the entropy (most +, medium + or least +) for i) S1 –solute: ii) S2-solvent: iii) S3, solution (solvent-solute): For the following: (Indicate which one is highest, intermediate and lowest order) For a) CH3CH2OH(l): dissolved in water: S1 = ; S2 = ;S3= Na2SO4(s) dissolved in water: S1 = ; S2 = CHEM 102, Spring 2013 LA TECH ;S3 = 12-29 5) Qualitatively speaking which of the above a) or b) would have a more positive DSsoln? a) CH3CH2OH(l): dissolved in water: S1 = ; S2 = ;S3= b) For Na2SO4(s) dissolved in water: S1 = CHEM 102, Spring 2013 LA TECH ; S2 = ;S3 = 12-30 7) Why sand is insoluble in both polar and nonpolar solvents? CHEM 102, Spring 2013 LA TECH 12-31 8) How does temperature and pressure affect the solubility of following? a) NH4NO3(solid) in water with +(positive) DHsoln: b) CO2 gas in water: CHEM 102, Spring 2013 LA TECH 12-32 Solubility of Oxygen in Water CHEM 102, Spring 2013 LA TECH 12-33 Henry’s Law CHEM 102, Spring 2013 LA TECH 12-34 Henry’s Law Solubility of Gases in Solvents Sg = kHPg where Sg solubility kH Henry’s Law constant Pg partial pressure of gas Increasing the pressure of a gas above a liquid increases its solubility CHEM 102, Spring 2013 LA TECH 12-35 9) Deep sea divers may experience a condition called the "bends" if they do not readjust slowly to the lower pressure at the surface. Using the diagram on pressure dependence solubility of gases on water explain this phenomenon. CHEM 102, Spring 2013 LA TECH 12-36 Solution Concentration Units a) Molarity (M) b) Molality (m) c) Mole fraction (Ca) d) Mass percent (% weight) e) Volume percent (% volume) f) "Proof" g) ppm and ppb CHEM 102, Spring 2013 LA TECH 12-37 Molarity The number of moles of solute per liter of solution. molarity M moles of solute M= liter of solution units molar = moles/liter = M CHEM 102, Spring 2013 LA TECH 12-38 Molarity Calculation An aqueous solution 58.5 g of NaCl and 2206g water has a density of 1.108 g/cm3. Calculate the Molarity of the solution. 58.5 g 1 mole Solution volume 58.5 g + 2206 g in L 2264.5 g solution 1 cm3 solution 1 L solution 1.108 g solution 1000 cm3 solution = 2.044 L solution 1.00 mole NaCl Molarity of NaCl solution = ------------------------- = 0.489 M 2.044 L solution CHEM 102, Spring 2013 LA TECH 12-39 Molality number of moles of solute particles (ions or molecules) per kilogram of solvent #moles solute m= #kilograms of solvent Calculate the molality of C2H5OH in water solution which is prepared by mixing 75.0 mL of C2H5OH and 125 g of H2O at 20oC. The density of C2H5OH is 0.789 g/mL. CHEM 102, Spring 2013 LA TECH 12-40 Molarity Calculation 75.0 mL C2H5OH 0.789 g C2H5OH 1 mole C2H5OH 1 mL 46.08 g C2H5OH = 1.284 C2H5OH 125 g of H2O = 0.125 kg H2O 1.284 mole C2H5OH Molality(m) = ------------------------ = 10.27 m 0.125 kg H2O CHEM 102, Spring 2013 LA TECH 12-41 Mole Fraction Xi = #moles of component i total number of moles Calculate the mole fraction of benzene in a benzene(C6H6)-chloroform(CHCl3) solution which contains 60 g of benzene and 30 g of chloroform. M.W. = 78.12 (C6H6) M.W. = 119.37 (CHCl3) CHEM 102, Spring 2013 LA TECH 12-42 Mole Fraction Calculation moles of a na Mola Fraction(ca) = ------------------- = -------------moles of na + moles nb na + nb a = C6H6 b = CHCl3 nC6H6 Mola Fraction(ca) = -----------------nC6H6 + nCHCl3 m.w (C6H6) = 78.12 g/mole m.w (CHCl3) = 119.37 g/mole 60/78.12 = 0.768 mole C6H6 30/119.37 = 0.251 mole CHCl3 ca(C6H6) = 0.768/ 0.786+ 0.251 =0.754 Ca(CHCl3) = 0.0.251/ 0.786+ 0.251 = 0.246 1.000 CHEM 102, Spring 2013 LA TECH 12-43 Weight Percent wt % = #g of solute #g of solution 102 Volume Percent Vol % = #L of solute #L of solution 102 Proof proof = Vol % x 2 CHEM 102, Spring 2013 LA TECH 12-44 Problem What is the mole fraction of ethanol, C2H5OH, in ethanol solution that is 40.%(w/w) ethanol, C2H5OH, by mass? a. 0.40 b. 0.46 c. 0.21 d. 0.54 CHEM 102, Spring 2013 LA TECH 12-45 Parts per Million #g of solute #mg of solute 106 = ppm = #g of solution #kg of solution #mL solute ppm = #L of solution Parts per Billion #g of solute ppb = #g of solution CHEM 102, Spring 2013 LA TECH 109 = #micro-g of solute #kg of solution 12-46 ppm and ppb conversions 1 ppm = (1g/ 1x 106g) 1x 106 = (1/1000 g) x 1x 106 1x 106 / 1000g = mg/ 1x 103 g = mg/ L 1 ppb = (1g/ 1x 109g) 1x 109 = (1/1000000 g) 1x 109/1000000g = mg/ 1x 103 g = mg/ L CHEM 102, Spring 2013 LA TECH 12-47 Problem A solution of hydrogen peroxide is 30.0% H2O2 by mass and has a density of 1.11 g/cm3. The MOLARITY of the solution is: a) 7.94 M b) 8.82 M e) none of these c) 9.79 M d) 0.980 M.W. = 34.02 (H2O2) CHEM 102, Spring 2013 LA TECH 12-48 10) Define following solution concentration units: a) Molarity (M) b) Molality (m) c) Mole fraction (Ca) weight) d) Mass percent (% e) Volume percent (% volume) f) "Proof" g) ppm and ppb CHEM 102, Spring 2013 LA TECH 12-49 Comparison of Concentration Terms CHEM 102, Spring 2013 LA TECH 12-50 11) Compare the advantages and disadvantages of these solution concentration parameters. CHEM 102, Spring 2013 LA TECH 12-51 12) Determine the number of moles of solute present in 416 mL of 3.75 M HBr solution. (Atomic weights: Br = 79.9, H = 1.008). CHEM 102, Spring 2013 LA TECH 12-52 13) Determine the mass (g) of solute required to form 25 mL of a 0.1881 M H2O2 solution. (Atomic weight O = 16.00, H = 1.008). CHEM 102, Spring 2013 LA TECH 12-53 14) A concentrated solution of AgNO3 is 21.9% by weight and the density is 1.220 g/cm3. How many grams of the solution are required to prepare 150.0 mL of a 0.200M solution? (Atomic weights: Ag = 107.87, N = 14.01, O = 16.00). CHEM 102, Spring 2013 LA TECH 12-54 15) A solution of carbon tetrachloride, CCl4, in benzene (C6H6) is 0.010 m. What mass (g) of CCl4 is in 50.0 g of benzene? (Atomic weights: C = 12.01, H = 1.008, Cl = 35.45). CHEM 102, Spring 2013 LA TECH 12-55