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Introduction to Chem II. Instructors Course Objectives Course Topics Laboratory Exercises Course Website Today’s Agenda Syllabus. Course Objectives. Review some familiar topics Investigate some of these topics at a more in-depth level Model sound pedagogy
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Introduction to Chem II • Instructors • Course Objectives • Course Topics • Laboratory Exercises • Course Website • Today’s Agenda • Syllabus
Course Objectives • Review some familiar topics • Investigate some of these topics at a more in-depth level • Model sound pedagogy • Obtain hand-on practice with Venier Data Collection • Show some effective demonstrations
Course Topics • Stoichiometry • Calorimetry • Equilibrium • Solubility • Acid-base chemistry • Redox chemistry • Thermochemistry
5 Lab Exercises • A calorimetry experiment using a temperature probe • Solubility using a Ca ion selective electrode • Equilibrium constant using a Colorimeter • Acid-base titration • Ag Ion Indicator electrode
Course website http://alpha.chem.umb.edu/chemistry/bpschemII/ Syllabus Lab experiments Course notes Homework solutions
Today’s Agenda • Take a 2 hr exam • Paperwork, surveys • Lunch • Lecture; g/mol, Classification of reactions, Stoichiometry, LR, Energetics of Reactions • Lab Lecture; Calorimetry • Lab Experiment 1 • Early start on HW
Investigating Stoichiometry using Calorimetry Experiment 1
Heat of Reaction - DH • At constant pressure – most lab experiments • aA + bB → products DH/mol A • . DH = q (heat produced or absorbed)
Calorimetry • Method of measuring the heat of reaction • Calorimeter-coffee cup • q = cmDT • c is the specific heat [J/(g ºC)] of solution • m = mass of solution • .DT is change in temperature • .DT is directly proportional to the heat of reaction
The experiment • Mix reactants in different molar ratios • Predict the stoichiometry of the reaction from the ratio that gives the maximum temperature increase
Example of the Experiment • 1 to 1, A + B → products • Mixing molar ratios • Constant total volume - cmDT
Example 2 • 2 to 1, 2A + B → products
Example 3 • 3 to 1, 3A + B → products
Determining the DHm • . DH = cmDT = (4.4 J/gC)*(50 g)*(36) = 7920 J • mol A reacted = 18.8 mmol A • .DHm = DH/(mol A reacted) = (7920)/(.0188 mol) = 421276 J/mol = 421 kJ/mol
Products • Thiosulfate is a classic reducing agent • 2S2O32-↔ S4O62- + 2e- • Cl- is the product of the reduction of OCl- • Write a balanced redox equation • Step 1: determine half reactions. • Step 2 Make the reduction half reaction and oxidation half reaction have the same number of electrons by multiply reactions by common denominator • Step 3: Add reactions
OCl- + H2O + 2 e- ↔ Cl- + 2OH- • 2S2O32-↔ S4O62-+ 2e- • ________________________ • OCl- + H2O + 2S2O32-→ Cl- + 2OH- + S4O62-
Solubility of CaSO4 Experiment 2
Goals • Determine the solubility of CaSO4 in three different solution • Saturated CaSO4 in H2O • Saturated CaSO4 in 0.10 M KNO3 • Saturated CaSO4 in 0.10 M Na2SO4 • Compare and rationalize the results
Major concepts • Solubility Product Constants and saturated solution • LeChatlier’s principle and the common ion effect • Effect of ionic strength and ion activities on Ksp • Ion Selective Electrodes
Ksp of CaSO4 • CaSO4(s)↔ Ca2+ + SO42- • Ksp(CaSO4) = [Ca2+][SO42-] = 2.4∙10-5
Saturated solution in water • Add several grams of CaSO4 to 1 L of water • Shake and mix for weeks • Allow CaSO4 that did not dissociate to settle to bottom • Ksp(CaSO4) = [Ca2+][SO42-] = 2.4∙10-5 = x2 [Ca2+] = 5.0∙10-3 M
Saturated solution in 0.10 M Na2SO4 • Add several grams of CaSO4 to 1 L of 0.10 M Na2SO4 • Common Ion effect • Ksp(CaSO4) = [Ca2+][SO42-] = 2.4∙10-5 = x(x+0.10) Assume x <<< 0.10 x = 2.4∙10-4 M [Ca2+] = 2.4∙10-4 M
Saturated solution in 0.10 M KNO3 • Activities • Ksp(CaSO4) = ACa2+ASO42- = [Ca2+]gCa2+[SO42-]gSO42- = 2.4∙10-5 • Activity coefficient (g) is dependent on the ionic strength of the solution, and the size and charge of the ion. It is a number between 0 and 1. At very low ionic strength, g approaches 1
Ionic strength • A measure of the concentration of ions in solution m = ½ ∑ cizi2 Sat. solution in 0.10 M KNO3 m = ½ ([K+](+1)2 + [NO3-](-1)2 + [Ca2+](2+)2 + [SO42-](-2)2) = 0.12 M gCa2+@m=0.12 =
Take home message • The common ion effect decreases the solubility by over an order of magnitude • At high ionic strengths, solubility increases slightly ( by a factor of 1.5 -5).
Ion Selective Electrode • A probe that consists of two reference electrodes connected electrically through a specific type of salt bridge through the solution being measured. • The salt bridge is a membrane that specifically binds the ion of interest • A junction potential develops at this membrane that is proportional to the concentration of the ion of interest
voltmeter Cathode Reference electrode Ag/AgCl, sat. KCl Anode Reference electrode Ag/AgCl, sat. KCl solution Ion selective membrane Engineer this whole set-up in one probe pH meter Ca2+ selective electrode
Response of Ca2+ Selective Electrode • Ecell = constant + 29.58 logACa2+