2013-02-25 1.1 Analytical Chemistry - I Syllabus Subject Title Prof. Name Analytical Chemistry I 3hrs / week Myeong Hee Moon 2123 - 5634 Text: Quantitative Chemical Analysis 8th ed. Harris. Must Use English Version Textbook Reference: Analytical Chemistry (Christian) 7th Lecture Fundamentals of Analytical Chemistry (Skoog) 8th Info. 1st exam: 25% 2nd exam: 25% Final: 25% Attendance Evaluation (including Quiz) 25 % Lecture note can be obtained from homepage http://chem.yonsei.ac.kr/~mhmoon Total 100 % Anal. Chem. by Prof. Myeong Hee Moon 1 2013-02-25 1.2 Syllabus Week Days CONTENTS 1 3. 4∼3.8 2 3.11∼3.15 3 3.18 ∼3.22 Statistics/Quality Assurance & Calibration 4 3.25∼3.29 5 4.1∼4.5 6 4.8∼4.12 7 4.15∼4.19 Monoprotic Acid-Base Equilibria 8 4.22∼4.26 Midterm Remark Introduction The Analytical Process/chemical measurements Experimental Error/Statistics Quality Assurance & Calibration Chemical Equilibrium 04.02: 1st exam Activity & Systematic treatment of Equilibrium Anal. Chem. by Prof. Myeong Hee Moon 2 2013-02-25 1.3 Syllabus 9 4.29∼5.3 Polyprotic Acid-base Equiilibria 10 5.6∼5.10 Acid-base Titrations 11 5.13∼5.17 EDTA Titrations 12 5.20∼5.24 Advcanced Topics in Equilibrium 13 5.27∼5.31 Fundamentals of Electrochemistry 14 6.3∼6.7 05.7 2nd exam Electrodes and Potentiometry 15 6.10∼6.14 Electrodes and Potentiometry 16 6.17∼6.21 Final Exam 06.11 Anal. Chem. by Prof. Myeong Hee Moon 3 2013-02-25 1.4 Ch 0. Fundamentals in Analytical Chemistry Topics : Stages in Chemical Analysis Concentrations Stoichiometric Calculations Titrations Anal. Chem. by Prof. Myeong Hee Moon 4 2013-02-25 1.5 Analytical Chemistry Applied to: Chemistry, Biology Medicine (hospital), Geology (geological survey) Oceanography, Material Science Forensic Science, Archeology Farming, Food Science Environmental Science, etc (Government regulations on pollution) Anal. Chem. by Prof. Myeong Hee Moon 5 2013-02-25 1.6 ANALYZE ? What is it (chemical elements) ? Qualitative analysis How much is present ? Quantitative analysis Development of New Products ? – want to know composition of mixtures or giving possibility of impurities Anal. Chem. by Prof. Myeong Hee Moon 6 2013-02-25 1.7 0-2. analytical Chemist’s Job analyte : the species being measured in a chemical analysis (chemical substance) * Stages in chemical analysis Decide First Level of Results needed. • Level of accuracy • Economical Aspect Anal. Chem. by Prof. Myeong Hee Moon 7 2013-02-25 1.8 How much caffeine is in a chocolate bar ? 1. Sampling Anal. Chem. by Prof. Myeong Hee Moon 8 2013-02-25 1.9 Sample preparation Anal. Chem. by Prof. Myeong Hee Moon 9 2013-02-25 1.10 Anal. Chem. by Prof. Myeong Hee Moon 10 2013-02-25 1.11 Anal. Chem. by Prof. Myeong Hee Moon 11 2013-02-25 1.12 Anal. Chem. by Prof. Myeong Hee Moon 12 2013-02-25 1.13 Anal. Chem. by Prof. Myeong Hee Moon 13 2013-02-25 1.14 Steps in chemical analysis 1. Formulating the question 2. Selecting analytical procedure: literature survey 3. Sampling 4. Sample Preparation : converting sample into a form suitable for chemical analysis - drying, sample weighing, mixing 3. Chemical Analysis 4. Calibration Curves 5. Interpreting the Results 6. Draw conclusions Anal. Chem. by Prof. Myeong Hee Moon 14 2013-02-25 1.15 Ch 1. Chemical Measurements 1-1 SI Units (Systeme International d'Unites) Anal. Chem. by Prof. Myeong Hee Moon 15 2013-02-25 1.16 Anal. Chem. by Prof. Myeong Hee Moon 16 2013-02-25 1.17 Anal. Chem. by Prof. Myeong Hee Moon 17 2013-02-25 1.18 Conversion between Units Anal. Chem. by Prof. Myeong Hee Moon 18 2013-02-25 1.19 1-2. Chemical Concentrations 1) Molarity (M) # of moles per a liter of solution moles of solute (1 mole = g/fw) Molarity 1 Liter=103cm3 = 1000cc L molecular weight - for moles formula weight - for electrolytes (since no molecule exists in electrolyte sol.) 2) Molality (m) # of moles per a kg of solvent. m temp. independent # of moles kg (solvent ) Anal. Chem. by Prof. Myeong Hee Moon 19 2013-02-25 1.20 3) Percent Composition wt (%) mass of solute 100 mass of total mixtures vol (%) volume of solute 100 volume of total solution 4) ppm & ppb ppm mass of substituent 10 6 mass of sample ppb mass of substituent 10 9 mass of sample Anal. Chem. by Prof. Myeong Hee Moon 20 2013-02-25 1.21 1-3. Preparing Solutions Dilution Mconc Vconc = Mdil Vdil ex) A solution of ammonia in water is called "ammonium hydroxide" because of the equilibrium : NH3 + H2O NH4+ + OHThe density of concentrated ammonium hydroxide, which contains 28.0 wt% NH3, is 0.899 g/mL. What volume of this reagent should be diluted to make 500 mL of 0.250 M NH3 ? (Ans: 8.45mL) Anal. Chem. by Prof. Myeong Hee Moon 21 2013-02-25 1.22 1-4. solutions & Stoichiometry 1) Volumetric calculation a A + b B products mol A = a mol b B ex) In acid solution, potassium permanganate reacts with H2O2 to form Mn2+: 5H2O2 + 2 MnO4- + 6 H+ 5O2 + 2Mn2+ + 8 H2O In neutral solution, it reacts with MnSO4 to form MnO2: 3Mn2+ + 2 MnO4- + 4 OH- 5 MnO2 + 2 H2O Calculate the number of milliliters of 0.100 M KMnO4 that will react with 50.0 mL of 0.200 M H2O2 and 50.0 ml of 0.200 M MnSO4. Anal. Chem. by Prof. Myeong Hee Moon 22 2013-02-25 1.23 2) gravimetric calculation Cl2 2 AgCl (s) mol cl2 = 1 mol AgCl 2 g cl 2 Gravimetric factor Anal. Chem. by Prof. Myeong Hee Moon 23 2013-02-25 1.24 Additional Exercise in Stoichiometric Calculations 1. A 0.2638-g soda ash sample is analyzed by titrating the sodium carbonate with the standard 0.1288 M hydrochloric acid solution, requiring 38.27 mL. Calculate the percent sodium carbonate in the sample. Anal. Chem. by Prof. Myeong Hee Moon 24 2013-02-25 1.25 2. A 0.200-g sample of pyrolusite is analyzed for manganese content as follows. Add 50.0 mL of a 0.100 M solution of ferrous ammonium sulfate to reduce the MnO2 to Mn2+. After reduction is complete, the excess ferrous ion is titrated in acid solution with 0.0200 M KMnO4, requiring 15.0 mL. Calculate the percent manganese in the sample as Mn3O4 (only part or none of the manganese may exist in this form, but we can make calculations on the assumption that it does). (Ans: 66.7%) 2 Fe2+ + MnO2 + 4 H+ 2 Fe3+ + Mn2+ + 2 H2O 5 Fe2+ + MnO4- + 8 H+ 5 Fe3+ + Mn2+ + 4 H2O Anal. Chem. by Prof. Myeong Hee Moon 25 2013-02-25 1.26 1.5 Titrations titration acid-base redox precipitation Spectrophotometric biochemistry : Addition of titrant to analyte for calculation of conc. Calculate conc. of analyte from how much it is consumed. Anal. Chem. by Prof. Myeong Hee Moon 26 2013-02-25 1.27 1.5 Titrations Calculation of analyte conc. from how much titrant is consumed. By HOW to DETECT ? 1. detecting sudden change in V or I 2. color change (indicator) 3. change in Absorbance * Equivalence Point : ideal, stoichiometric. : occurs when the quantity of titrant added is the exact amount necessary for stoichiometric rxn with analyte. * End Point : actually observable point. Sudden change in color or voltage. Anal. Chem. by Prof. Myeong Hee Moon 27 2013-02-25 1.28 1.5 Titrations In case of titration, conc. of titrant should be known first. Is it accurate ? Use primary standard. 99.9 % or better in purity. Stable when dried by heating or vacuum * In case of titrant which is not primary std. Use standardization titrate a proper primary std with the titrant. Then calculate the conc. of titrant. Anal. Chem. by Prof. Myeong Hee Moon 28 2013-02-25 1.29 1-6. Titration Calculations key step : molestitrant = molesanalyte ex) standardization of titrant - analysis of unknown - Determination of Ca content in Urine oxalate 1. Ca+2 + C2O42- Ca(C2O4)H2O (s) 2. precipitate in ice-cold water and wash (to remove free oxalate) then redissolve in acid 3. heat to 600C, and titrate with standardized KMnO4 until purple end. Anal. Chem. by Prof. Myeong Hee Moon 29 2013-02-25 1.30 1-6. Titration Calculations Q1: standardization ? Suppose 0.3562 g Na2C2O4 (fw=134.00) in 250.0 mL flask. Calculate molarity of KMnO4 when 10.0 mL of the sol. consumes 48.36 mL of KMnO4. 5 C2O4-2 + 2 MnO4- + 16 H+ 10 CO2 + 2 Mn+2 + 8 H2O Anal. Chem. by Prof. Myeong Hee Moon 30 2013-02-25 1.31 Q2: Analysis of unknown. Suppose Ca in 5.00 mL urine is precipitated and it requires 16.17mL of std. MnO4- solution. [Ca+] in urine ??? Anal. Chem. by Prof. Myeong Hee Moon 31 2013-02-25 1.32 Homework In the Textbook: 1-19, 20, 30, 31, 34, 42, 45 Anal. Chem. by Prof. Myeong Hee Moon 32