Chemistry 4631. Instrumental Analysis Lecture 1. Chem 4631

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Chemistry 4631 Instrumental Analysis Lecture 1

Syllabus Chemistry 4631 Spring 2016 Lecture: MWF 9:00 9:50 a.m. Chem 352 Attendance is expected. Instructor: Dr. Teresa D. Golden Chem 279, 565-2888, tgolden@unt.edu. Office hours: TTh 3:30-4:30 p.m. Chem 207B. Course Material: Text: Principles of Instrumental Analysis, 6 th ed.; (Skoog/Holler/Nieman). Prereq: Chem 3451/3452 Quant. Analysis This course covers electronics, spectroscopy, electrochemistry, chromatography, and selected topics.

Syllabus Chemistry 4631 Spring 2016 Homework: 1) Problem sets will be assigned at the end of each chapter. 2) Also spectral interpretations will periodically be assigned. Exams: There will be 4-5 in class exams and a comprehensive ACS final exam. Dates for exams will be announced one week ahead of time. The final is scheduled for 5/11/2016 from 8:00-10:00 a.m. in Room 352. *Absolutely no make-up exams will be given without a signed physician s note. Grading: Exams, quizzes, and assignments will each be given a total point value. The student s final grade will be: (the total number of points received/total number of points possible) x 100.

Syllabus WEEK CLASS ASSIGNMENT TOPICS 1 Ch. 1 & 6 & Appendix Intro, Stats, Data Analysis, Electromagnetic Spectrum, Quantum Theory 2 Ch. 6 & 7 General Components of Optical Instrument and Lasers Lab: Check-in 3 Ch. 7 Optical Instruments and Semiconductors Lab: UV-vis 4 Ch. 13 & 14 UV Theory and Instrumentation Lab: UV-vis 5 Ch. 16 & 17 IR Spectroscopy Theory and Instrumentation, FTIR Lab: FTIR/Fluorescence 6 Ch 15 & 8 Fluorescence Spectroscopy Lab: FTIR/Fluorescence 7 Ch. 9 & 10 & 11 Atomic Emmision/Absorption Spectroscopy and ICP Lab: AAS/ICP 8 Ch. 22 Intro to Electrochemistry Lab: AAS/ICP 9 Spring Break 10 Ch. 23 & 24 Potentiometry, Conductivity Techniques Lab: Potentiometry/Coulometry/Voltammetry 11 Ch. 24 & 25 Voltammetry Techniques Lab: Potentiometry/Coulometry/Voltammetry 12 Ch. 11 & 20 Mass Spectroscopy Instrumentation and Spectra interpretation Lab: GC/Headspace 13 Ch. 26 Intro to Chromatography, Chromatography Theory Lab: GC/Headspace 14 Ch. 27 Gas Chromatography Instrumentation Lab: HPLC/GC/MS 15 Ch. 28 High Performance Liquid Chromatography Instrumentation Lab: HPLC/GC/MS 16 Misc Topics & Review Lab: Check-out 17 Final Exam (ACS) 8:00-10:00 a.m.

Syllabus Chemistry 4632 Spring 2016 Laboratory: M or W 1:30 5:20 p.m. Room 280 and 283 Chemistry Instructor: Dr. Teresa D. Golden (Room 279 Chemistry, 565-2888 tgolden@unt.edu) Teaching Assistants: Ryan Daugherty, Teresa Allen, Katherine Smart and Stephen Sanders (Room 225 and 254 Chemistry) Course Material: Lab Manual (see instructor or TAs). The labs will cover spectroscopy, electrochemistry, chromatography, and selected topics. A pen, calculator, goggles, ruler, and bound lab notebook are required for every lab. All notations, calculations and results are to be included in this lab notebook for each experiment. The TA must sign this book at the end of each lab.

Syllabus Chemistry 4632 Spring 2016 Lab Reports: A formal lab report will be due at the next class period for every lab. This report must include: introduction and theory, experimental section, results, discussion, calculations, graphs, answers to questions, etc. The student will not only be graded on content but also neatness and readability. No late reports will be accepted. Exams: Lab practicums given during lab time. Grading: The final lab grade will be calculated using the following: 10% lab book, 10% lab technique and 80% lab reports.

Syllabus Chemistry 4632 Spring 2016 Week of Lab Assignment * 1/19 No Labs 1/25 Laboratory Practicum: Proper Lab Techniques, Assign Drawers and Glassware 2/1 UV Spectroscopy: Mole-ratio and Slop-ratio Method 2/8 UV Spectroscopy: Electronic Transitions in Organic Molecules 2/15 Infrared Spectroscopy: Spectra of Aldehydes and Ketones 2/22 Fluorescence Spectroscopy: Determination of Fluorescein in Antifreeze 2/29 ICP-MS: Analysis of Metal Contamination in Cigarettes 3/7 Atomic Absorption Spectroscopy: Determination of Fe in Food 3/21 Potentiometry: Ion selective electrode, Fluoride in Water and Toothpaste and Conductivity: Analgesics 3/28 Voltammetry: CV of Vitamin C w/ Graphite Electrodes 4/4 GC/FID: Hydrocarbons & Gasoline 4/11 Headspace GC: Blood Alcohol 4/18 High Performance Liquid Chromatography: Caffeine 4/25 GC/MS: Volatile Organics

Syllabus Chemistry 4631 Spring 2016 California State University Study Multitasking take notes Purdue University Study - Spacing Effect restudy previous material Washington University Self-testing (Active testing) study groups Harvard Study Memory and fine motor skill take notes Study Tips: 1. Attend Class 2. Reread/Rewrite Notes Each Week 3. Write and Draw to Study (Practice Test)

Introduction Instrumentation - used by chemist to solve analytical problems. Measurement of physical properties Identification of unknowns Preparation of components

insert

Instruments All instruments have the same basic components:

The response is almost always represented by peaks, But can also be color or a number (i.e. temperature, ph, etc )

Chemist choose the correct analytical method or instrument to solve a problem. In order to do this, the chemist must understand a wide variety of instruments and the limitations of each one.

To correctly select the instrument, the problem must be clearly defined. 1. What accuracy is required? 2. How much sample is available? 3. What is the concentration range of the analyte? 4. What components of the sample will cause interference? 5. What are the physical and chemical properties of the sample matrix? 6. How many samples are to be analyzed?

Precision

Bias Bias = x t population mean x t true concentration

Bias Sample finite number of experimental observations (all the replicate). The sample is a fraction of the infinite number of observations possible. (i.e. 50 measurements). This infinite number of observations (measurements) is called the population or universe of data.

Sensitivity Instruments or methods ability to discriminate between small differences in analyte concentration.

Selectivity Degree to which the method is free from interference by other species contained in the sample matrix.

Detection Limit Minimum concentration or mass of analyte that can be detected at a known confidence level.

Dynamic Range

Applications of UV/vis Spectrometry Calibration curve Calibration standards need to approximate the composition of sample to be analyzed If cannot match the matrix best to use the standard addition method (Chapter 1).

Calibration Standard Addition Method Internal Standard

Data Analysis Standard addition method Add one or more increments of a standard solution to sample aliquots of the same size. Each solution is diluted to a fixed volume and absorbance is measured. Plot Absorbance versus Volume Standard Solution, ml.

Data Analysis Determination of Stoichiometry of Complex Ions Mole-ratio method Method of continuous variation

Data Analysis Mole-ratio Procedure A known concentration of central atom is prepared A known concentration of ligand is prepared at the same concentration Add complexing ligand in increments and measure absorbance after each addition Plot absorbance versus mole ratio (ligand:metal)

Data Analysis Determination of Stoichiometry of Complex Ions Mole-ratio procedure Example: What is the number of CN- ions attached to Cd 3+ in basic solution? Absorbance Mole ratio 0.210 0.75 0.425 1.50 0.645 2.25 0.852 3.00 1.00 3.75 1.12 4.50 1.14 5.25 1.15 6.00

Data Analysis Determination of Stoichiometry of Complex Ions 1.2 1.0 Absorbance 0.8 0.6 0.4 0.2 0 1 2 3 4 5 6 mole ratio

Data Analysis Determination of Stoichiometry of Complex Ions Mole-ratio procedure There are four ligands to one metal ion [Cd(CN) 4 ] 2-

Data Analysis Determination of Stoichiometry of Complex Ions Method of Continuous Variation Total number of moles of ligands + moles of M n+ is constant.

Data Analysis Determination of Stoichiometry of Complex Ions Method of continuous variation Procedure: Mix 2.0 ml of one solution (0.01 M) and 8.0 ml of the other (0.01 M) (must use 10 ml for all other measurements) Measure absorbance of each mixture Plot absorbance versus mole fraction of ligand (moles of ligand/moles of ligand + moles of metal)

Data Analysis Determination of Stoichiometry of Complex Ions Method of Continuous variation Example: Determine the ratio of ligand to metal for the Fe 2+ - phenanthroline system, if a continuous variation gave the following: Absorbance Mole fraction 0.10 0.1 0.22 0.2 0.33 0.3 0.45 0.4 0.56 0.5 0.67 0.6 0.76 0.7 0.65 0.8 0.33 0.9

Data Analysis Determination of Stoichiometry of Complex Ions Method of continuous variation 0.8 0.7 0.6 Absorbance 0.5 0.4 0.3 0.2 0.1 0.0 0.0 0.2 0.4 0.6 0.8 1.0 mole fraction of chelate

Data Analysis Determination of Stoichiometry of Complex Ions Method of continuous variation 0.75 = (0.75)/(0.75 +0.25) 0.75 mole fraction of chelate 0.25 mole fraction of metal 3 times as much ligand as metal ion

Data Analysis Determination of Stoichiometry of Complex Ions Method of continuous variation Very low ligand concentrations give low absorbance on the first side of the curve. On the second side you have high ligand concentrations but low Fe 2+

Data Analysis Determination of Stoichiometry of Complex Ions Method of continuous variation Coordination number = 6 (ligand binds twice to Fe 2+, bidentate ligand)

Assignment Read Chapter 1 Read Appendix 1 Homework: Ch. 1: 11 and Appendix 1: 1, 2, 10, and 12 (extra credit)