INTRODUCTION TO ANALYTICAL CHEMISTRY FOUNDATIONS OF ANALYTICAL CHEMISTRY BLOCK I INTRODUCTION TO ANALYTICAL CHEMISTRY Chapter 1. Chapter 2. Chapter 3. Principles of Analytical Chemistry Analytical properties Traceability. Reference materials BLOCK II. THE ANALYTICAL PROCESS BLOCK III. SOCIO–ECONOMIC PROJECTION OF ANALYTICAL CHEMISTRY ANNEX 1. GLOSSARY OF TERMS ANNEX 2. ANSWERS TO THE QUESTIONS 1-1

INTRODUCTION TO ANALYTICAL CHEMISTRY BLOCK I INTRODUCTION TO ANALYTICAL CHEMISTRY Chapter 1. Principles of Analytical Chemistry Contents 1.1.1. Introduction to Block I 1.1.2. Definitions 1.1.3. Aims and objectives of Analytical Chemistry 1.1.4. Analytical Chemical references 1.1.5. (Bio)chemical information 1.1.6. Conceptual and technical hierarchies 1.1.7. Classifications 1.1.8. New paradigms of Analytical Chemistry 1.1.9. Research and transfer in Analytical Chemistry Teaching objectives To introduce students to analysis, the third essential component of Chemistry To define Analytical Chemistry To establish the landmarks of the discipline To state key definitions in a hierarchical manner 1-2

1 2 3 1.1.1. Introduction to Block I BLOCK I Chapter 1. Principles of Analytical Chemistry 1.1.1. Introduction to Block I BLOCK I INTRODUCTION TO ANALYTICAL CHEMISTRY CHAPTER 1 PRINCIPLES OF ANALYTICAL CHEMISTRY 1 2 CHAPTER 2 CHAPTER 3 ANALYTICAL PROPERTIES TRACEABILITY. REFERENCE MATERIALS 3 1-3

ANALYTICAL CHEMISTRY 1.1.2. Definition (I): Straightforward approaches Chapter 1. Principles of Analytical Chemistry 1.1.2. Definition (I): Straightforward approaches The discipline of “Analysis”, the third basic component of Chemistry The discipline of (bio)chemical measurements A C ANALYTICAL CHEMISTRY The discipline producing (bio)chemical information The (bio)chemical metrological discipline B D 1-4

Chapter 1. Principles of Analytical Chemistry 1.1.2. Definition (II): Straightforward approaches Placement of Analytical Chemistry in the Chemistry domain Synthesis Applications Triangle of Chemistry Theory Analysis Analytical Chemistry 1-5

Q 1.1.2. Definition (III): Straightforward approaches Chapter 1. Principles of Analytical Chemistry 1.1.2. Definition (III): Straightforward approaches Analytical Chemistry in the context of interdisciplinarity Q SYNTHESIS THEORY APPLICATIONS ANALYSIS OTHER SCIENTIFIC AND TECHNICAL AREAS 1-6

Chapter 1. Principles of Analytical Chemistry 1.1.2. Definition (IV): Formal/comprehensive ANALYTICAL CHEMISTRY IS A METROLOGICAL DISCIPLINE AIMED AT DEVELOPING, OPTIMIZING AND APPLYING (R&D&T)* MEASUREMENT PROCESSES IN ORDER TO OBTAIN QUALITY (BIO)CHEMICAL INFORMATION FROM NATURAL AND/OR ARTIFICIAL SYSTEMS WITH A VIEW TO FULFILLING INFORMATION REQUIREMENTS AND FACILITATING WELL-FOUNDED, TIMELY DECISION-MAKING IN THE SCIENTIFIC, TECHNICAL, ECONOMIC AND SOCIAL REALMS. * Research, Development, and Transfer of Knowledge and Technology 1-7

Chapter 1. Principles of Analytical Chemistry 1.1.3. Aims and objectives of Analytical Chemistry (I) METROLOGICAL QUALITY SOLVING INFORMATION-RELATED PROBLEMS FULFILLING THE CLIENT’S INFORMATION REQUIREMENTS AIMS THEORETICAL PRACTICAL CONTRADICTION ANALYTICAL CHEMISTRY OBJECTIVES AUGMENTATION DIMINUTION LESS MATERIALS TIME EFFORT COSTS HAZARDS MORE BETTER (BIO)CHEMICAL INFORMATION CONTRADICTION 1-8

Chapter 1. Principles of Analytical Chemistry 1.1.3. Aims and objectives of Analytical Chemistry (II) CONTRADICTION IN AIMS OBJECTIVES Quality trade-off Quality trade-off Metrological quality Problem solving Augmentation objectives Diminution objectives 1-9

Chapter 1. Principles of Analytical Chemistry 1.1.3. Aims and objectives of Analytical Chemistry (III) ANALYTICAL CHEMISTRY METROLOGY APPLIED FACETS AIMS HIGH ACCURACY LOWEST UNCERTAINTY AUGMENTATION (more, better information) SOLVING INFORMATION-RELATED PROBLEMS DIMINUTION (less materials, effort, time, etc.) OBJECTIVES 1-10

Chapter 1. Principles of Analytical Chemistry 1.1.4. Analytical chemical references (I) Analytical Chemistry, as a metrological science, aims at measuring (bio)chemical parameters Measuring is comparing comparing requires using references/standards Analytical Chemistry makes no sense in the absence of appropriate standards for each information-related aim EXAMPLES Qualitative analysis Quantitative analysis 1-11

Chapter 1. Principles of Analytical Chemistry 1.1.4. Analytical chemical references (II) Basic Analytical Chemical references CLASSICAL CHARACTERISTICS OF USER’S REQUIRED INFORMATION MEASUREMENT STANDARDS WRITTEN STANDARDS (norms, methods) PRACTICAL QUALITY (problem solving) METROLOGICAL QUALITY ANALYTICAL QUALITY 1-12

1.1.4. Analytical chemical references (III) Chapter 1. Principles of Analytical Chemistry 1.1.4. Analytical chemical references (III) WRITTEN STANDARDS IN ANALYTICAL CHEMISTRY 4 1 NORMS AND GUIDES STANDARD ANALYTICAL METHODS 2 OFFICIAL METHODS 3 LEGISLATION (directives, regulations) 1-13

1.1.4. Analytical chemical references (IV) Chapter 1. Principles of Analytical Chemistry 1.1.4. Analytical chemical references (IV) CEN-CWA 14924 (2004) European guide to good practice in knowledge management ISO 26000:2010 Guidance on SOCIAL RESPONSIBILITY WRITTEN STANDARDS OSHAS 180001:2007 Requirements for establishing an occupational risk prevention system ISO 9001:2008 Requirements for establishing a quality assurance system ANALYTICAL CHEMISTRY ISO 17025:2005 General requirements for the competence of testing calibration laboratories ISO 14001:2004 Requirements for establishing environmental management systems 1-14

Chapter 1. Principles of Analytical Chemistry 1.1.5. (Bio)chemical information (I) Main “product” (output) of Analytical Chemistry LEGISLATIVE POWER Significance EXECUTIVE POWER SOCIETY JUDICIAL POWER SCIENCE AND TECHNOLOGY INFORMATION C A P I T A L LABOUR RAW MATERIALS ECONOMY (BIO)CHEMICAL INFORMATION 1-15

ANALYTICAL CHEMISTRY 1.1.5. (Bio)chemical information (II) Need to use Chapter 1. Principles of Analytical Chemistry 1.1.5. (Bio)chemical information (II) NUTRITION HEALTH HYGIENE SUSTAINABLE DEVELOPMENT TRANSPORTATION ANALYTICAL CHEMISTRY SPORTS BUILDING DRESSING HOUSEHOLD TECHNOLOGIES NEW CULTURE Need to use reliable (bio)chemical information 1-16

Chapter 1. Principles of Analytical Chemistry 1.1.5. (Bio)chemical information (III) General types according to quality QUALITY INTRINSIC INFORMATION IDEAL TRUENESS INFORMATION HELD AS TRUE (e.g., CRMs) REFERENTIAL A C U R Y U N C E R T A I Y PRACTICAL ROUTINE ANALYTICAL INFORMATION 1-17

Chapter 1. Principles of Analytical Chemistry 1.1.5. (Bio)chemical information (IV) Information-related key words of Analytical Chemistry Chapter 3 Chapter 7 METROLOGY SOCIO–ECONOMIC INFORMATION REQUIRED Chapter 3 TRACEABILITY (BIO)CHEMICAL INFORMATION ANALYTICAL PROBLEM Chapter 2 ANALYTICAL PROPERTIES Chapter 7 Chapter 9 RESPONSIBILITY SOCIAL ANALYTICAL PROCESS QUALITY Chapter 8 Chapters 4–6 1-18

Chapter 1. Principles of Analytical Chemistry Significance hierarchies 1.1.6. Conceptual and technical hierarchies (I) An approach intended to facilitate a friendly definition of key words for the discipline by grouping them in a hierachical manner Types 1 2 Significance hierarchies Scope hierarchies A > B > C A 3 B C Mixed hierarchies 1-19

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (II) Information (I) GENERAL MEANING (BIO)CHEMICAL CONTEXT DIRECT INFORMATION-RELATED COMPONENTS OF REALITY PRIMARY DATA SIGNALS FROM MEASURING INSTRUMENTS collection computation DESCRIBING REALITY INFORMATION RESULTS OF (BIO)CHEMICAL PROCESSED EXPRESSED AS REQUIRED interpretation processing UNDERSTANDING AND INTERPRETING REAILITY. DECISION-MAKING KNOWLEDGE REPORTS CONTEXTUAL- IZING INFORMATION, SUPPORTING DECISIONS, STATING HYPOTHESES AND ESTABLISHING MECHANISMS creating new paradigms CRISIS breaking boundaries IMAGINATION (Einstein) 1-20

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (III) Information (II) Analytical information level Reports To analyse Results To characterize Primary data To detect To sense Non-analytical information Secondary data 1-21

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (IV) Technique – Process – Method – Procedure (A) Technique Sample Results Measurement and transducing of analytical signal Data handling and processing Preliminary operations Increasing concreteness Analytical process Method Procedure 1-22

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (V) Technique – Process – Method – Procedure (B) Technique A general principle used to derive information that involves using and instrument in the second step of the analytical process. Analytical process The body of operations separating the uncollected, unmeasured, untreated sample from the results expressed as required. Method The specific manner of implementing an analytical technique to determine one or more analytes in a given sample. The materialization of an analytical process. Procedure A detailed description of an analytical method. 1-23

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (VI) Analyser – Instrument – Apparatus – Device (A) Process Analyser Instrument Apparatus Device Technique 1-24

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (VII) Analyser – Instrument – Apparatus – Device (B) Analyser A system performing (nearly) the whole analytical process (and hence the method and the procedure). Instrument The materialization of an analytical technique providing analyte-related data. Apparatus A system performing an operation in the analytical process but producing no analytical information. Device A part of an apparatus. 1-25

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (VIII) Analyser – Instrument – Apparatus – Device (C) Examples Type of information Ranked elements Examples Analyser for gases (O2, CO2) in blood Autoanalyser for C and H in steel Balance Polarograph Mass spectrometer Chromatograph (GC, LC, SFC) Microwave digester Extractor (L–L, S–L) Centrifuge Pressure and temperature sensors Electronic interfaces Analyser Analytical Instrument Apparatus Performance- related Device 1-26

Chapter 1. Principles of Analytical Chemistry ANALYTE OR A DERIVATIVE 1.1.6. Conceptual and technical hierarchies (IX) Problem – Object – Sample – Measurand – Analyte (A.1) Analysis – Determination – Measurement (B.1) PROBLEM OBJECT SAMPLE ANALYSIS MEASURAND DETERMINATION ANALYTE MEASUREMENT PROPERTIES OF THE ANALYTE OR A DERIVATIVE 1-27

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (X) Problem – Object – Sample – Measurand – Analyte (A.2) Analysis – Determination – Measurement (B.2) Problem Description of the information requirement Object System from which the information is to be obtained Sample (A.2) Aliquot of the object in space and time Mesurand Quantity to be measured in the sample Analyte A measurand in the form of a chemical species whose presence and/or concentration is to be established Analysis of the sample (B.2) Determination of the measurand and/or analyte Measurement of a property of the analyte or some reaction product Therefore, a sample is analysed, an analyte is determined and one or several physico–chemical properties of the analyte or some derivative are measured. 1-28

Chapter 1. Principles of Analytical Chemistry 1.1.6. Conceptual and technical hierarchies (XI) Problem – Object – Sample – Measurand – Analyte (A.3) Analysis – Determination – Measurement (B.3) Examples Problem Object Sample(s) Analytes The river, with its geopgraphic and temporal characteristics Aliquots of the object collected at different places and times Example 1 Contamination of a river Organic and inorganic contaminants Drug abuse at the Olympic Games Amphetamins, hormones, Β-blockers, etc. Example 2 Athletes Urine Adulteration of olive oil with extrananeous fat Factory output Aliquots representative of the output Vegetable and animal fat Example 3 Surface scrapings from several toys selected according to a sampling plan Toxicity of yellow-painted toys (cadmium paint) Toys from an imported batch Example 4 Cadmium Economic feasibility of gold recovery from mining waste Samples of the object collected at differents depths at different places The waste dump as a whole Example 5 Gold 1-29

Chapter 1. Principles of Analytical Chemistry proportion of analytes 1.1.7. Classifications (I) AN OVERVIEW OF COMPLEMENTARY CLASSIFICATIONS Analytical separation systems Quantitative analysis Structural analysis Classical analysis Instrumental analysis Qualitative analysis Others According to purpose According to technique 1 2 General classifications of Analytical Chemistry 6 3 According to object availability According to nature of sample/analyte 5 4 According to initial sample size According to relative proportion of analytes 1-30

Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (II): According to purpose QUALITATIVE ANALYSIS DETECTION Identification Result: a YES/NO response QUANTITATIVE ANALYSIS DETERMINATION Structural analysis 3 Quantification Result: 2.30 ± 0.03 µg/L Quantitative analysis 2 STRUCTURAL ANALYSIS Elucidation of the spatial structureof the sample (e.g., spatial arrangement of a protein) an analyte (e.g., a thalidomide enantiomer) 1 Qualitative analysis 1-31

1.1.7. Classifications (III): According to technique (*) Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (III): According to technique (*) Classical analysis “Instruments” used for centuries HUMAN SENSES CLASSICAL BALANCE CLASSICAL BURETTE FLUORIMETER MASS SPECTROMETER SPECTROPHOTOMETER VOLTAMMETER NMR SPECTROMETER POTENTIOMETER IR SPECTROMETER Others. Instrumental analysis Other “instruments” (*) Unscientific, but historically pertinent, classification RIGHT Analytical separation systems Analytical separation techniques Analytical separation methods PARTLY RIGHT WRONG 1-32

1.1.7. Classifications (IV): According to technique and purpose Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (IV): According to technique and purpose Qualitative analysis Classical analysis Quantitative analysis N O Instrumental analysis Structural analysis 1-33

According to nature of sample and analyte (A) Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (V): According to nature of sample and analyte (A) Sample I B O Inorganic Organic Biochemical I-i I-o I-b O-i O-o O-b B-i B-o B-b Inorganic Organic Biochemical o i b Analyte 1-34

According to nature of sample and analyte (B) Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (V): According to nature of sample and analyte (B) Examples Sample Analyte Example I O B i o b Determination of the gold content of a mineral Determination of pesticides in soil Determination of traces of biochemical molecules in a meteorite (in order to search for life on other planets) Determination of metal traces in organic pharmaceutical preparations Determination of nitrogen-containing organic compounds in petroleum crude Determination of enzyme activity in an organic solvent Determination of calcium in biological fluids Determination of drugs and their metabolites in human urine Determination of the protein content of milk 1-35

According to nature of sample and analyte (C) Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (V): According to nature of sample and analyte (C) BINOMIAL: Chemical and biochemical information WEAK DISTINCTION BETWEEN “CHEMICAL ANALYSIS” AND “BIOCHEMICAL ANALYSIS”. THE TERM TO BE USED DEPENDS ON THE NATURE OF THE SAMPLES ANALYTES TOOLS SOIL /KIDNEY TISSUE CHLORIDES / PROTEINS ORGANIC REAGENT IMMOBILIZED ENZYMES USE THE CONTRACTION “(BIO)CHEMICAL” FOR SIMPLICITY EQUIVALENCE OF “(BIO)CHEMICAL INFORMATION” AND “ANALYTICAL INFORMATION” 1-36

Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (VI) Relative analyte content (%) (100 ppm) 0.01 % 1 % Traces Microcomponents Macrocomponents Determinations difficulty complexity Initial sample size 0.001 g 0.01 g 0.1 g Ultra- microanalysis Microanalysis Semi- microanalysis Macroanalysis difficulty complexity 1-37

Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (VII) Complexity of analytical processess depending on Sample size Analyte content Example 1 Example 2 Analytes: metal traces Analytes: pesticides Complexity Metal traces in a painting by Velazquez Traces of organo- chlorines in baby’s blood Trace microanalysis Determination of mercury in seawater Organo-phosphorus compounds in drinking water Trace macroanalysis Pesticides in commercial formulations Determination of chromium in steel Macrocomponent microanalysis 1-38

Chapter 1. Principles of Analytical Chemistry 1.1.7. Classifications (VIII) Object availability Pendulum NANO ANALYSIS SPATIAL ANALYSIS MACROANALYSIS MICROANALYSIS human level 1-39

1.1.8. New paradigms of Analytical Chemistry (I) Chapter 1. Principles of Analytical Chemistry 1.1.8. New paradigms of Analytical Chemistry (I) Analytical Chemistry: has little weight in Chemistry lacks identity is simply an application of Chemistry Analytical Chemistry starts at the laboratory door and ends at the printer The relationships among analytical properties are unimportant 2 1 The teaching of Analytical Chemistry should start with calculations, ionic equilibria, tritrimetries and gravimetries 3 Obsolete paradigms in Analytical Chemistry Only tangible and written standards are relevant to Analytical Chemistry 8 4 7 6 5 Quality assurance systems suffice to ensure fulfillment of the aims of Analytical Chemistry Contradictions among aims and objectives in Analytical Chemistry Analytical results can only be qualitative or quantitative 1-40

Chapter 1. Principles of Analytical Chemistry 1.1.8. New paradigms of Analytical Chemistry (II) General paradigms regarding the general approach to Analytical Chemistry’s present and future ANALYTICAL CHEMISTRY KNOWLEDGE AND TECHNOLOGY TRANSFER AS THE DISCIPLINE OF (BIO)CHEMICAL INFORMATION AT THE BOUNDARIES WITH OTHER SCIENTIFIC AND TECHNICAL AREAS INDEPENDENT, EFFICIENT R&D 1-41

«REINVENTING CHEMISTRY» Chapter 1. Principles of Analytical Chemistry 1.1.8. New paradigms of Analytical Chemistry (III) IMPORTANCE OF (BIO)CHEMICAL INFORMATION «REINVENTING CHEMISTRY» M. Whitesides (Harvard Univ., USA) Angewandte Chemie Int. 2015, 54, 3196–3209 ONE OF THE MOST CRUCIAL STEPS IN STARTING NEW SCIENTIFIC AND TECHNICAL AREAS IS THE DEVELOPMENT OF INNOVATIVE ANALYTICAL TECHNIQUES TO FACILITATE ANALYSES ANALYTICAL CHEMISTRY IS A MUCH MORE IMPORTANT CHEMICAL DISCIPLINE THAN MANY BELIEVE 1-42

Chapter 1. Principles of Analytical Chemistry 1.1.9. Research and transfer in Analytical Chemistry (I) RESEARCH APPLIED RESEARCH Second stage 2 3 PRODUCING QUALITY (BIO)CHEMICAL INFORMATION AND KNOWLEDGE FULFULLING INFORMATION DEMANDS SOLVING ANALYTICAL PROBLEMS EXPANDING THE ABILITIES OF ANALYTICAL CHEMISTRY BASIC RESEARCH First stage 1 TOOLS Instruments Devices Reagents BASIC APPROACHES STRATEGIES PROCESSES TYPES STAGES R&D IN ANALYTICAL CHEMISTRY OBJECTIVES 1-43

Chapter 1. Principles of Analytical Chemistry PRODUCING (BIO)CHEMICAL 1.1.9. Research and transfer in Analytical Chemistry (II) TRANSFER ANALYTICAL CHEMISTRY R&D CENTRES 4 3 CLIENTS REQUIRING ANALYTICAL INFORMATION ROUTINE LABORATORIES PRODUCING (BIO)CHEMICAL INFORMATION 1 2 ANALYTICAL TOOL MANUFACTURERS Instruments Reagents Extraction devices Others 1-44