Practical Instrumental Analysis: Methods, Quality Assurance, and Laboratory Management

This practical book in instrumental analytics conveys an overview of important methods of analysis and enables the reader to realistically learn the (principally technology-independent) working techniques the analytical chemist uses to develop methods and conduct validation. What is to be conveyed to the student is the fact that analysts in their capacity as problem-solvers perform services for certain groups of customers, i.e., the solution to the problem should in any case be processed in such a way as to be "fit for purpose". The book presents sixteen experiments in analytical chemistry laboratory courses. They consist of the classical curriculum used at universities and universities of applied sciences with chromatographic procedures, atom spectrometric methods, sensors and special methods (e.g. field flow fractionation , flow injection analysis and N-determination according to Kjeldahl). The carefully chosen combination of theoretical description of the methods of analysis and the detailed instructions given are what characterizes this book. The instructions to the experiments are so detailed that the measurements can, for the most part, be taken without the help of additional literature. The book is complemented with tips for effective literature and database research on the topics of organisation and the practical workflow of experiments in analytical laboratory, on the topic of the use of laboratory logs as well as on writing technical reports and grading them (Evaluation Guidelines for Laboratory Experiments). A small introduction to Quality Management, a brief glance at the history of analytical chemistry as well as a detailed appendix on the topic of safety in analytical laboratories and a short introduction to the new system of grading and marking chemicals using the "Globally Harmonized System of Classification and Labelling of Chemicals (GHS)", round off this book. This book is therefore an indispensable workbook for students, internship assistants and lecturers (in the area of chemistry, biotechnology, food technology and environmental technology) in the basic training programme of analytics at universities and universities of applied sciences.

Table of Contents:
Preface to the German Edition XV Preface to the English Edition XIX Dedication XXI Foreword XXIII 1 Introduction 1 1.1 Analytical Chemistry - The History 1 1.2 Analytical Chemistry and Its Role in Today's Society 2 2 Introduction to Quality Management 5 2.1 Historical Background 5 2.2 Variability 6 2.3 The Four Pillars of Wisdom (from Shewhart to Deming) 10 2.4 Zero-Defect Tolerance 10 2.5 Why Standards? 11 2.6 The Controlled Process 11 2.7 ISO Guidelines 9004 12 2.8 Quality Management System (QMS) Requirements 15 3 Fundamentals of Statistics 17 3.1 Basic Concepts 17 3.1.1 Population and Sample 19 3.1.2 Distribution of Values 20 3.2 Important Terms 22 3.2.1 Mean, Arithmetic Mean, Average (x) 22 3.2.2 Standard Deviation (sigma, s) 22 3.2.3 Variance (Var,V) 23 3.2.4 Standard Deviation of Mean Values (S) 24 3.2.5 Relative Standard Deviation (RSD) and Coefficient of Variation (CV) 24 3.2.6 Confi dence Interval (CI), Confi dence Limits 25 3.3 Quality of Results (Accuracy and Precision) 25 3.3.1 Measurement Deviations 28 3.3.2 Random Deviations - Influence on Precision 30 3.3.2.1 Precision 30 3.3.2.2 Determination of Random Deviations 30 3.3.2.3 Causes of Random Deviations 31 3.3.3 Systematic Deviations - Influence on Accuracy 31 3.3.3.1 Accuracy/Trueness 31 3.3.3.2 Bias 31 3.3.3.3 Causes of Systematic Deviations 32 3.3.3.4 Effects on the Measurement 32 3.3.3.5 Determination of Systematic Deviations 32 3.3.3.6 Recovery Experiments 33 3.3.4 Gross Errors 33 3.3.4.1 Causes of Gross Errors 34 3.3.5 Uncertainty of Measurement Results 34 3.3.5.1 Standard Uncertainty of Single Measurements 34 3.3.5.2 Combined Uncertainty 35 3.3.5.3 Procedure for Determining the Combined Uncertainty 35 3.3.5.4 Rules for Uncertainty Propagation 37 3.3.5.5 Extended Uncertainty 38 3.3.6 Non-statistical Methods of Estimation 38 3.3.6.1 Tolerance 38 3.3.7 Expressing Analytical Results 39 3.3.7.1 Expressing the Measurement Uncertainty in the Value of a Quantity 39 3.3.7.2 Accordance with the National Institute of Standards and Technology, U.S. Department of Commerce (NIST) 39 3.3.8 Signifi cant Figures - "Box-and-Dot" Method 40 3.3.9 Outlier Tests 42 3.3.9.1 The 2.5 s Barrier 42 3.3.9.2 Test according to Grubbs 42 3.4 Regression 43 3.4.1 Regression Analysis 43 3.4.2 Calibration Function 43 3.4.3 The "Optimal" Trend Line 44 3.4.4 Linear Regression 45 3.4.4.1 Linearity 45 3.4.4.2 Statistical Information from Linear Regression 46 3.4.4.3 Analytical Sensitivity 46 3.4.4.4 Correlation Coeffi cient (R) 46 3.4.4.5 Coeffi cient of Determination (R2) 47 3.4.4.6 Regression Equation 47 4 The Analytical Process 53 4.1 The Analytical Process in the Overall Context 53 4.2 Planning Phase 55 4.2.1 Analytical Problem 55 4.2.2 Object of Investigation 56 4.2.3 Sample 56 4.2.4 Sampling 57 4.2.4.1 Types of Sampling 58 4.2.4.2 Sampling Errors 59 4.2.4.3 Sample Handling 60 4.2.4.4 Diffi culties of Sample Processing 60 4.2.5 Examination Procedures 61 4.2.6 Analyte 62 4.2.7 Literature and Database Research 62 4.2.7.1 Types of Chemical Literature 63 4.2.7.2 From the Question to the Document 63 4.2.7.3 From the Quotation to the Document 63 4.2.7.4 The Question of Topic 65 4.2.7.5 Science Citation Index Expanded 66 4.2.7.6 Scopus 66 4.2.7.7 Medline 66 4.2.7.8 Current Information 67 4.2.7.9 Specific Types of Documents Such As Norms and Patents 67 4.3 Analysis 67 4.3.1 Measurement 67 4.3.2 Method Optimization 68 4.3.3 Calibration 69 4.3.3.1 External Calibration 70 4.3.3.2 Internal Standard (IStd) 71 4.3.3.3 Standard Addition Method (Spiking Method) 71 4.3.3.4 One-Time Addition 71 4.3.3.5 Multiple Additions 72 4.3.3.6 Recovery Standard (RStd) 73 4.4 Assessment 74 4.4.1 Quantification 74 4.4.1.1 Traceability 74 4.4.2 ("True") Content 74 4.4.2.1 Terminology 75 4.5 Validation 75 4.5.1 Validation Elements 77 4.5.1.1 Selectivity/Specifi city 77 4.5.1.2 Working Range 78 4.5.1.3 Detection, Determination and Quantitation Limit 78 4.5.1.4 German Standard DIN 32645 78 4.5.1.5 Calculations 81 4.5.1.6 Limit of Detection according to Kaiser 84 4.5.1.7 Robustness 86 4.5.2 Using the Computer 86 4.6 Final Documentation 87 4.6.1 Review 88 5 Example of a Validation Strategy 89 5.1 Determination of Phenol in Industrial Waste Water 90 5.1.1 Confi rmation of Identity 92 5.1.1.1 Selectivity 92 5.1.1.2 Precision 92 5.1.2 Sample Content Determination 93 5.1.2.1 Accuracy 93 5.1.2.2 Calibration Function - Calibration, Linearity, Working Range 94 5.1.2.3 Determination of the Detection, Determination and Quantitation Limits according to DIN 32645 - Direct and Indirect Method 96 5.1.2.4 Measurement Uncertainty 99 5.1.2.5 Robustness 101 5.1.3 Selection 102 5.1.3.1 Final Documentation 102 6 Organizational and Practical Procedures in the Teaching Laboratory Program 103 6.1 Goals 103 6.2 Safety in the Laboratory Class 104 6.3 Experimental Project Workflow 104 6.3.1 Preparation 104 6.3.2 Laboratory Notebook 105 6.4 Reports 110 References 114 7 Literature 115 7.1 Cited Literature 115 7.2 Recommended Norms (Selection) 116 7.2.1 Calibration 116 7.2.2 Inter-laboratory Tests 116 7.2.3 Quality Management 117 7.3 Suggested Books (Selection) 117 8 Projects 119 8.1 Chromatography 121 8.1.1 Gas Chromatography - GC, Project: Tanker Accident 121 8.1.1.1 Analytical Problem 121 8.1.1.2 Introduction 123 8.1.1.3 Material and Methods 135 8.1.1.4 Questions 139 References 139 8.1.2 Gas Chromatography Coupled with Mass Selective Detection - GC/MS, Project: "Circumvention of the Formerly Mandatory Declaration of Fragrances in Perfumes?" 139 8.1.2.1 Analytical Problem 139 8.1.2.2 Introduction 141 8.1.2.3 Material and Methods 155 8.1.2.4 Questions 158 References 159 8.1.3 High-Performance Liquid Chromatography - HPLC, Project: "Stricter Control of Drugs" 159 8.1.3.1 Analytical Problem 159 8.1.3.2 Introduction 161 8.1.3.3 Material and Methods 170 8.1.3.4 Questions 173 References 173 8.1.4 High-Performance Liquid Chromatography Coupled with Mass-Selective Detection - LC/MS, Project "Cocaine Scandal: Hair Sample with Consequences" 173 8.1.4.1 Analytical Problem 173 8.1.4.2 Introduction 175 8.1.4.3 Material and Methods 189 8.1.4.4 Questions 193 References 194 8.1.5 Ion Chromatography (IC), Project: "Water Is Life" 194 8.1.5.1 Analytical Problem 194 8.1.5.2 Introduction 196 8.1.5.3 Material and Methods 215 8.1.5.4 Questions 220 References 220 8.1.6 High-Performance Thin-Layer Chromatography (HPTLC), Project: "Ensuring Regulatory Compliance by Quantification of Lead Compounds (Markers) in Herbal Combination Products" 221 8.1.6.1 Analytical Problem 221 8.1.6.2 Introduction 223 8.1.6.3 Material and Methods 232 8.1.6.4 Questions 236 References 236 8.2 Spectroscopy 236 8.2.1 UV-VIS Spectroscopy, Project: "Evaluation of Potential Saving through Use of Optimized Alloys" 236 8.2.1.1 Analytical Problem 236 8.2.1.2 Introduction 238 8.2.1.3 Bandwidth 242 8.2.1.4 Material and Methods 243 8.2.1.5 Questions 246 References 247 8.2.2 Fourier-Transform Infrared Spectroscopy (FTIR), Project: "Benchmarking with a New Competitive Japanese Product" 247 8.2.2.1 Analytical Problem 247 8.2.2.2 Introduction 249 8.2.2.3 Material and Methods 259 8.2.2.4 Questions 263 References 264 8.2.3 Near-Infrared (NIR) Spectrometry, Project: "Accelerated Raw Material Intake Control" 264 8.2.3.1 Analytical Problem 264 8.2.3.2 Introduction 266 8.2.3.3 Material and Methods 282 8.2.3.4 Questions 286 Reference 286 8.2.4 Atomic Absorption Spectroscopy (AAS), Project: "Recycling of Sewage Sludge in Agriculture" 286 8.2.4.1 Analytical Problem 286 8.2.4.2 Introduction 288 8.2.4.3 Material and Methods 296 8.2.4.4 Questions 299 References 299 8.3 Electrophoretic Separation Methods 299 8.3.1 Capillary Electrophoresis, Project: "Preservatives in Cosmetics: Friend or Foe" 299 8.3.1.1 Analytical Problem 299 8.3.1.2 Introduction 301 8.3.1.3 Material and Methods 313 8.3.1.4 Questions 316 References 316 8.4 Automation 316 8.4.1 Flow Injection Analysis (FIA), Project: "Phenol-like Flavor in Beer: a Quality Parameter to be Mastered" 316 8.4.1.1 Analytical Problem 316 8.4.1.2 Introduction 319 8.4.1.3 Material and Methods 324 8.4.1.4 Questions 327 References 328 8.5 Mass Analytical Determination Methods 328 8.5.1 Karl Fischer Water Determination, Project: "Water Content as a Quality Parameter" 328 8.5.1.1 Analytical Problem 328 8.5.1.2 Introduction 330 8.5.1.3 Material and Methods 344 8.5.1.4 Questions 347 References 347 8.6 General Analytical Methods 348 8.6.1 Nitrogen and Protein Determination according to Kjeldahl, Project: "Offi cial Control at the Swiss Alps Dairy Ltd" 348 8.6.1.1 Analytical Problem 348 8.6.1.2 Introduction 350 8.6.1.3 Material and Methods 355 8.6.1.4 Questions 359 References 359 8.6.2 Determination of Dissolved Oxygen (DO), Project: "Monitoring the Efficiency of the Biological Stage in a Sewage Treatment Plant" 359 8.6.2.1 Analytical Problem 359 8.6.2.2 Introduction 361 8.6.2.3 Material and Methods 366 8.6.2.4 Questions 369 References 369 8.7 Universal Separation Methods 370 8.7.1 Field Flow Fractionation (FFF), Project: "Characterization of Nanoparticles" 370 8.7.1.1 Analytical Problem 370 8.7.1.2 Introduction 372 8.7.1.3 Material and Methods 384 8.7.1.4 Questions 387 References 387 Appendix A Selection of Recommended Sources by Subject Area 389 A.1 General Sources 389 A.1.1 Rompp 389 A.1.2 Wikipedia 389 A.1.3 CRC Handbook of Chemistry and Physics, David R. Lide (Ed.) 389 A.1.4 Merck Index: Encyclopedia of Chemicals, Drugs and Biologicals 390 A.1.5 ChemSpider 390 A.2 Analytical Chemistry 390 A.2.1 Encyclopedia of Analytical Chemistry, RA Meyers (Ed.), John Wiley & Sons Ltd, Chichester (2000) 390 A.2.2 Official Methods of Analysis, Association of the Official Analytical Chemists (1990) 390 A.3 Inorganic and Organometallic Chemistry 390 A.3.1 Gmelin Handbook of Inorganic Chemistry 390 A.3.2 Dictionary of Inorganic (Metals and Organic) Compounds 391 A.4 Chemical Engineering/Technical Chemistry/Process Engineering 391 A.4.1 Ullmann's Encyclopedia of Industrial Chemistry 391 A.4.2 Kirk-Othmer Encyclopedia of Chemical Technology 391 A.5 Chemicals: Directory of Suppliers 391 A.5.1 Databases Subject to Charge 391 A.5.2 Free Access (Selection) 391 A.6 Organic Chemistry 392 A.6.1 Science of Synthesis ("Houben-Weyl Methods of Molecular Transformations, Methods of Organic Chemistry") 392 A.7 Physico-chemical Data 392 A.7.1 CRC Handbook of Chemistry and Physics 392 A.7.2 Landolt-Bornstein Numerical Data and Functional Relationships in Science and Technology 392 A.7.3 TRC Thermodynamic Tables 393 A.8 Polymers and Materials 393 A.8.1 DECHEMA Materials Table 393 A.8.2 Polymer Handbook 393 A.9 Spectra 393 A.9.1 Printed Data Collections 393 A.9.2 Online Products Requiring a License 394 A.9.3 Free Access Online Products 394 A.10 Toxicology and Safety 394 Appendix B Statistical Tables 395 Appendix C Obligatory Declaration for Students 399 Appendix D The International System of Units (SI) - and the "New SI" 401 Appendix E Evaluation Guide for Formal Reports 413 Appendix F Safety in the Analytical Laboratory 415 F.1 General Precautionary Measures 415 F.1.1 Measures for Personal Protection 415 F.1.2 Eye Protection 415 F.1.3 Skin Protection 416 F.1.4 Protective Clothing 416 F.1.5 Hearing Protection 416 F.1.6 Respiratory Protection 416 F.2 First Aid 417 F.2.1 Rescue 417 F.2.2 Alerting Emergency Personnel 418 F.2.3 Treatment of Unconscious Victim 418 F.2.4 Bleeding Wounds 418 F.2.5 Shock 419 F.2.6 Eye Injuries 419 F.2.7 Burns 420 F.2.8 Caustic Burns 420 F.2.9 Poisoning 420 F.3 Working with Chemicals 421 F.3.1 Chemicals 421 F.3.2 Solvents 422 F.3.3 Handling of Glass and Glass Equipment 423 F.3.4 Electrical Apparatus, Heating Sources 423 F.3.5 Fire Prevention 424 F.3.6 Sources 424 F.3.7 Fume Hood 424 F.4 Chemical Reactions under Increased Pressure 424 F.4.1 Chemicals 425 F.4.2 Apparatus 425 F.4.3 Working in Clean Rooms 425 F.4.3.1 General Conduct 426 F.4.3.2 Handling of Chemicals 426 F.4.3.3 Devices 426 F.5 Disposal of Chemicals 427 F.5.1 Organic Chemicals 427 F.5.2 Inorganic Chemicals 428 F.6 Gases 430 F.6.1 Compressed Gas Bottles with Small Leak 430 F.6.2 Compressed Gas Bottle with Large Leak 430 F.6.3 Explosive, Flammable or Oxidizing Materials That Develop Flammable Gas When Combined with Water 430 F.7 Liquids 431 F.7.1 Aqueous 431 F.7.2 Organic 431 F.7.3 Mercury 431 F.8 Working with Electricity 431 F.8.1 General Conduct 432 F.9 Working with High Voltage 433 F.9.1 General Facts 434 F.9.2 Experimental Setup 434 F.9.3 Operation 434 F.10 Handling of Compressed Gas Bottles and Gas 435 F.10.1 General Facts 435 F.10.2 Transport 435 F.10.3 Storage 435 F.10.4 Valves and Fittings 435 F.10.5 At the Place of Use 436 F.11 Risk and Safety Phrases (R/S Phrases) 436 F.12 GHS (Globally Harmonized System of Classification and Labeling of Chemicals) 443 F.12.1 Principles of the GHS 443 F.13 GHS Pictograms 444 F.13.1 Precautionary Statements 451 Index 457

About the Author :
After his apprentiship, Sergio Petrozzi worked as a chemical lab technician at the Laboratory of Physical Chemistry ETHZ (Swiss Federal Institute of Technology) and at the Swiss Federal Institute of Aquatic Sciences and Technology (EAWAG), Switzerland. After acquiring his federal diploma (Diplom Hohere Fachprufung), he joined the Institute of Chemical Engineering ETHZ where he gained great experience as teaching assistant in laboratory courses. His daily routine focused among other topics,on the following topics at the ETHZ in Zurich: Development, optimisation and validation of analytical methods. He subsequently worked as an application chemist at Buchi Labortechnik AG, Flawil (Switzerland) with a focus on the validation of applications for environmental determinations. He has authored numerous publications in international journals and is presently employed as a Scientific Associate at the Zurich University of Applied Sciences ZHAW, Wadenswil (Switzerland), where, among other things, he is teaching adviser in analytical chemistry laboratory at the Institute for Chemistry and Biological Chemistry (ICBC).