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Sergio Petrozzi

Practical Instrumental Analysis

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Practical Instrumental Analysis

Methods, Quality Assurance and Laboratory Management

Sergio Petrozzi

The Author

Sergio PetrozziZurich University of Applied SciencesInstitute of Chemistry and Biological ChemistryEinsiedlerstrasse 318820 WaedenswilSwitzerland

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V

PrefacetotheGermanEdition XV PrefacetotheEnglishEdition XIX Dedication XXI Foreword XXIII

1 Introduction 11.1 AnalyticalChemistry–TheHistory 11.2 AnalyticalChemistryandItsRoleinToday’sSociety 2

2 IntroductiontoQualityManagement 52.1 HistoricalBackground 52.2 Variability 62.3 TheFourPillarsofWisdom(fromShewharttoDeming) 102.4 Zero-DefectTolerance 102.5 WhyStandards? 112.6 TheControlledProcess 112.7 ISOGuidelines9004 122.8 QualityManagementSystem(QMS)Requirements 15

3 FundamentalsofStatistics 173.1 BasicConcepts 173.1.1 PopulationandSample 193.1.2 DistributionofValues 203.2 ImportantTerms 223.2.1 Mean,ArithmeticMean,Average(x) 223.2.2 StandardDeviation(σ,s) 223.2.3 Variance(Var,V) 233.2.4 StandardDeviationofMeanValues(S) 243.2.5 RelativeStandardDeviation(RSD)andCoefficientofVariation(CV) 243.2.6 ConfidenceInterval(CI),ConfidenceLimits 253.3 QualityofResults(AccuracyandPrecision) 253.3.1 MeasurementDeviations 28

Contents

VI Contents

3.3.2 RandomDeviations–InfluenceonPrecision 303.3.2.1 Precision 303.3.2.2 DeterminationofRandomDeviations 303.3.2.3 CausesofRandomDeviations 313.3.3 SystematicDeviations–InfluenceonAccuracy 313.3.3.1 Accuracy/Trueness 313.3.3.2 Bias 313.3.3.3 CausesofSystematicDeviations 323.3.3.4 EffectsontheMeasurement 323.3.3.5 DeterminationofSystematicDeviations 323.3.3.6 RecoveryExperiments 333.3.4 GrossErrors 333.3.4.1 CausesofGrossErrors 343.3.5 UncertaintyofMeasurementResults 343.3.5.1 StandardUncertaintyofSingleMeasurements 343.3.5.2 CombinedUncertainty 353.3.5.3 ProcedureforDeterminingtheCombinedUncertainty 353.3.5.4 RulesforUncertaintyPropagation 373.3.5.5 ExtendedUncertainty 383.3.6 Non-statisticalMethodsofEstimation 383.3.6.1 Tolerance 383.3.7 ExpressingAnalyticalResults 393.3.7.1 ExpressingtheMeasurementUncertaintyintheValueofa

Quantity 393.3.7.2 AccordancewiththeNationalInstituteofStandardsandTechnology,

U.S.DepartmentofCommerce(NIST) 393.3.8 SignificantFigures–“Box-and-Dot”Method 403.3.9 OutlierTests 423.3.9.1 The2.5sBarrier 423.3.9.2 TestaccordingtoGrubbs 423.4 Regression 433.4.1 RegressionAnalysis 433.4.2 CalibrationFunction 433.4.3 The“Optimal”TrendLine 443.4.4 LinearRegression 453.4.4.1 Linearity 453.4.4.2 StatisticalInformationfromLinearRegression 463.4.4.3 AnalyticalSensitivity 463.4.4.4 CorrelationCoefficient(R) 463.4.4.5 CoefficientofDetermination(R2) 473.4.4.6 RegressionEquation 47

4 TheAnalyticalProcess 534.1 TheAnalyticalProcessintheOverallContext 534.2 PlanningPhase 55

Contents VII

4.2.1 AnalyticalProblem 554.2.2 ObjectofInvestigation 564.2.3 Sample 564.2.4 Sampling 574.2.4.1 TypesofSampling 584.2.4.2 SamplingErrors 594.2.4.3 SampleHandling 604.2.4.4 DifficultiesofSampleProcessing 604.2.5 ExaminationProcedures 614.2.6 Analyte 624.2.7 LiteratureandDatabaseResearch 624.2.7.1 TypesofChemicalLiterature 634.2.7.2 FromtheQuestiontotheDocument 634.2.7.3 FromtheQuotationtotheDocument 634.2.7.4 TheQuestionofTopic 654.2.7.5 ScienceCitationIndexExpanded 664.2.7.6 Scopus 664.2.7.7 Medline 664.2.7.8 CurrentInformation 674.2.7.9 SpecificTypesofDocumentsSuchAsNormsandPatents 674.3 Analysis 674.3.1 Measurement 674.3.2 MethodOptimization 684.3.3 Calibration 694.3.3.1 ExternalCalibration 704.3.3.2 InternalStandard(IStd) 714.3.3.3 StandardAdditionMethod(SpikingMethod) 714.3.3.4 One-TimeAddition 714.3.3.5 MultipleAdditions 724.3.3.6 RecoveryStandard(RStd) 734.4 Assessment 744.4.1 Quantification 744.4.1.1 Traceability 744.4.2 (“True”)Content 744.4.2.1 Terminology 754.5 Validation 754.5.1 ValidationElements 774.5.1.1 Selectivity/Specificity 774.5.1.2 WorkingRange 784.5.1.3 Detection,DeterminationandQuantitationLimit 784.5.1.4 GermanStandardDIN32645 784.5.1.5 Calculations 814.5.1.6 LimitofDetectionaccordingtoKaiser 844.5.1.7 Robustness 864.5.2 UsingtheComputer 86

VIII Contents

4.6 FinalDocumentation 874.6.1 Review 88

5 ExampleofaValidationStrategy 895.1 DeterminationofPhenolinIndustrialWasteWater 905.1.1 ConfirmationofIdentity 925.1.1.1 Selectivity 925.1.1.2 Precision 925.1.2 SampleContentDetermination 935.1.2.1 Accuracy 935.1.2.2 CalibrationFunction–Calibration,Linearity,WorkingRange 945.1.2.3 DeterminationoftheDetection,Determinationand

QuantitationLimitsaccordingtoDIN32645–DirectandIndirectMethod 96

5.1.2.4 MeasurementUncertainty 995.1.2.5 Robustness 1015.1.3 Selection 1025.1.3.1 FinalDocumentation 102

6 OrganizationalandPracticalProceduresintheTeachingLaboratoryProgram 103

6.1 Goals 1036.2 SafetyintheLaboratoryClass 1046.3 ExperimentalProjectWorkflow 1046.3.1 Preparation 1046.3.2 LaboratoryNotebook 1056.4 Reports 110

References 114

7 Literature 1157.1 CitedLiterature 1157.2 RecommendedNorms(Selection) 1167.2.1 Calibration 1167.2.2 Inter-laboratoryTests 1167.2.3 QualityManagement 1177.3 SuggestedBooks(Selection) 117

8 Projects 1198.1 Chromatography 1218.1.1 GasChromatography–GC,Project:TankerAccident 1218.1.1.1 AnalyticalProblem 1218.1.1.2 Introduction 1238.1.1.3 MaterialandMethods 1358.1.1.4 Questions 139

References 139

Contents IX

8.1.2 GasChromatographyCoupledwithMassSelectiveDetection–GC/MS,Project:“CircumventionoftheFormerlyMandatoryDeclarationofFragrancesinPerfumes?” 139

8.1.2.1 AnalyticalProblem 1398.1.2.2 Introduction 1418.1.2.3 MaterialandMethods 1558.1.2.4 Questions 158

References 1598.1.3 High-PerformanceLiquidChromatography–HPLC,Project:“Stricter

ControlofDrugs” 1598.1.3.1 AnalyticalProblem 1598.1.3.2 Introduction 1618.1.3.3 MaterialandMethods 1708.1.3.4 Questions 173

References 1738.1.4 High-PerformanceLiquidChromatographyCoupledwithMass-

SelectiveDetection–LC/MS,Project“CocaineScandal:HairSamplewithConsequences” 173


References 1948.1.5 IonChromatography(IC),Project:“WaterIsLife” 1948.1.5.1 AnalyticalProblem 1948.1.5.2 Introduction 1968.1.5.3 MaterialandMethods 2158.1.5.4 Questions 220

References 2208.1.6 High-PerformanceThin-LayerChromatography(HPTLC),

Project:“EnsuringRegulatoryCompliancebyQuantificationofLeadCompounds(Markers)inHerbalCombinationProducts” 221


References 2368.2 Spectroscopy 2368.2.1 UV–VISSpectroscopy,Project:“EvaluationofPotentialSavingthrough

UseofOptimizedAlloys” 2368.2.1.1 AnalyticalProblem 2368.2.1.2 Introduction 2388.2.1.3 Bandwidth 2428.2.1.4 MaterialandMethods 243

X Contents

8.2.1.5 Questions 246References 247

8.2.2 Fourier-TransformInfraredSpectroscopy(FTIR),Project:“BenchmarkingwithaNewCompetitiveJapaneseProduct” 247


References 2648.2.3 Near-Infrared(NIR)Spectrometry,Project:“AcceleratedRawMaterial

IntakeControl” 2648.2.3.1 AnalyticalProblem 2648.2.3.2 Introduction 2668.2.3.3 MaterialandMethods 2828.2.3.4 Questions 286

Reference 2868.2.4 AtomicAbsorptionSpectroscopy(AAS),Project:“RecyclingofSewage

SludgeinAgriculture” 2868.2.4.1 AnalyticalProblem 2868.2.4.2 Introduction 2888.2.4.3 MaterialandMethods 2968.2.4.4 Questions 299

References 2998.3 ElectrophoreticSeparationMethods 2998.3.1 CapillaryElectrophoresis,Project:“PreservativesinCosmetics:Friend

orFoe” 2998.3.1.1 AnalyticalProblem 2998.3.1.2 Introduction 3018.3.1.3 MaterialandMethods 3138.3.1.4 Questions 316

References 3168.4 Automation 3168.4.1 FlowInjectionAnalysis(FIA),Project:“Phenol-likeFlavorinBeer:a

QualityParametertobeMastered” 3168.4.1.1 AnalyticalProblem 3168.4.1.2 Introduction 3198.4.1.3 MaterialandMethods 3248.4.1.4 Questions 327

References 3288.5 MassAnalyticalDeterminationMethods 3288.5.1 KarlFischerWaterDetermination,Project:“WaterContentasaQuality

Parameter” 3288.5.1.1 AnalyticalProblem 3288.5.1.2 Introduction 3308.5.1.3 MaterialandMethods 344

Contents XI

8.5.1.4 Questions 347References 347

8.6 GeneralAnalyticalMethods 3488.6.1 NitrogenandProteinDeterminationaccordingtoKjeldahl,Project:

“OfficialControlattheSwissAlpsDairyLtd” 3488.6.1.1 AnalyticalProblem 3488.6.1.2 Introduction 3508.6.1.3 MaterialandMethods 3558.6.1.4 Questions 359

References 3598.6.2 DeterminationofDissolvedOxygen(DO),Project:“Monitoringthe

EfficiencyoftheBiologicalStageinaSewageTreatmentPlant” 3598.6.2.1 AnalyticalProblem 3598.6.2.2 Introduction 3618.6.2.3 MaterialandMethods 3668.6.2.4 Questions 369

References 3698.7 UniversalSeparationMethods 3708.7.1 FieldFlowFractionation(FFF),Project:“Characterizationof

Nanoparticles” 3708.7.1.1 AnalyticalProblem 3708.7.1.2 Introduction 3728.7.1.3 MaterialandMethods 3848.7.1.4 Questions 387

References 387

AppendixA SelectionofRecommendedSourcesbySubjectArea 389A.1 GeneralSources 389A.1.1 Römpp 389A.1.2 Wikipedia 389A.1.3 CRCHandbookofChemistryandPhysics,DavidR.Lide

(Ed.) 389A.1.4 MerckIndex:EncyclopediaofChemicals,Drugsand

Biologicals 390A.1.5 ChemSpider 390A.2 AnalyticalChemistry 390A.2.1 EncyclopediaofAnalyticalChemistry,RAMeyers(Ed.),John

Wiley&SonsLtd,Chichester(2000) 390A.2.2 OfficialMethodsofAnalysis,AssociationoftheOfficial

AnalyticalChemists(1990) 390A.3 InorganicandOrganometallicChemistry 390A.3.1 GmelinHandbookofInorganicChemistry 390A.3.2 DictionaryofInorganic(MetalsandOrganic)

Compounds 391

XII Contents

A.4 ChemicalEngineering/TechnicalChemistry/ProcessEngineering 391

A.4.1 Ullmann’sEncyclopediaofIndustrialChemistry 391A.4.2 Kirk-OthmerEncyclopediaofChemicalTechnology 391A.5 Chemicals:DirectoryofSuppliers 391A.5.1 DatabasesSubjecttoCharge 391A.5.2 FreeAccess(Selection) 391A.6 OrganicChemistry 392A.6.1 ScienceofSynthesis(“Houben-WeylMethodsof

MolecularTransformations,MethodsofOrganicChemistry”) 392

A.7 Physico-chemicalData 392A.7.1 CRCHandbookofChemistryandPhysics 392A.7.2 Landolt-BornsteinNumericalDataandFunctional

RelationshipsinScienceandTechnology 392A.7.3 TRCThermodynamicTables 393A.8 PolymersandMaterials 393A.8.1 DECHEMAMaterialsTable 393A.8.2 PolymerHandbook 393A.9 Spectra 393A.9.1 PrintedDataCollections 393A.9.2 OnlineProductsRequiringaLicense 394A.9.3 FreeAccessOnlineProducts 394A.10 ToxicologyandSafety 394

AppendixB StatisticalTables 395

AppendixC ObligatoryDeclarationforStudents 399

AppendixD TheInternationalSystemofUnits(SI)–andthe“NewSI” 401

AppendixE EvaluationGuideforFormalReports 413

AppendixF SafetyintheAnalyticalLaboratory 415F.1 GeneralPrecautionaryMeasures 415F.1.1 MeasuresforPersonalProtection 415F.1.2 EyeProtection 415F.1.3 SkinProtection 416F.1.4 ProtectiveClothing 416F.1.5 HearingProtection 416F.1.6 RespiratoryProtection 416F.2 FirstAid 417F.2.1 Rescue 417F.2.2 AlertingEmergencyPersonnel 418

Contents XIII

F.2.3 TreatmentofUnconsciousVictim 418F.2.4 BleedingWounds 418F.2.5 Shock 419F.2.6 EyeInjuries 419F.2.7 Burns 420F.2.8 CausticBurns 420F.2.9 Poisoning 420F.3 WorkingwithChemicals 421F.3.1 Chemicals 421F.3.2 Solvents 422F.3.3 HandlingofGlassandGlassEquipment 423F.3.4 ElectricalApparatus,HeatingSources 423F.3.5 FirePrevention 424F.3.6 Sources 424F.3.7 FumeHood 424F.4 ChemicalReactionsunderIncreasedPressure 424F.4.1 Chemicals 425F.4.2 Apparatus 425F.4.3 WorkinginCleanRooms 425F.4.3.1 GeneralConduct 426F.4.3.2 HandlingofChemicals 426F.4.3.3 Devices 426F.5 DisposalofChemicals 427F.5.1 OrganicChemicals 427F.5.2 InorganicChemicals 428F.6 Gases 430F.6.1 CompressedGasBottleswithSmallLeak 430F.6.2 CompressedGasBottlewithLargeLeak 430F.6.3 Explosive,FlammableorOxidizingMaterialsThat

DevelopFlammableGasWhenCombinedwithWater 430

F.7 Liquids 431F.7.1 Aqueous 431F.7.2 Organic 431F.7.3 Mercury 431F.8 WorkingwithElectricity 431F.8.1 GeneralConduct 432F.9 WorkingwithHighVoltage 433F.9.1 GeneralFacts 434F.9.2 ExperimentalSetup 434F.9.3 Operation 434F.10 HandlingofCompressedGasBottlesandGas 435F.10.1 GeneralFacts 435F.10.2 Transport 435F.10.3 Storage 435

XIV Contents

F.10.4 ValvesandFittings 435F.10.5 AtthePlaceofUse 436F.11 RiskandSafetyPhrases(R/SPhrases) 436F.12 GHS(GloballyHarmonizedSystemofClassificationand

LabelingofChemicals) 443F.12.1 PrinciplesoftheGHS 443F.13 GHSPictograms 444F.13.1 PrecautionaryStatements 451

Index 457

XV

PrefacetotheGermanEdition

An integral part of the technical–chemical training of a student is the teaching laboratory in analytical chemistry. Analytical chemistry is a partial discipline that develops and applies methods, technologies and strategies in order to gain infor-mation on chemical compounds and processes. Principles of organic, inorganic and biological chemistry are supported by analytics, and the ever-increasing demand of society to make important decisions based on watertight data and vali-dated methods requires the reinforcement of analytical education and research.

Following several years of being a teaching adviser in a university chemistry laboratory, I concerned myself with the validation of methods in environmental analytics in my capacity as an application chemist for a manufacturer of analytical equipment. In so doing I became aware of the different priorities placed on ana-lytical processes in these various organizations.

In an academic environment the analytical chemistry laboratory serves, by way of experiments, to deepen what has been learned, to consolidate knowledge and to help apply it in a practical manner. The teaching laboratory complements the theoretical knowledge and understanding of analytical procedures learned during lectures. It serves to convey the knowledge and facilitate working techniques and practical skills through exercises. The lab courses are meant to consolidate the careful and independent execution of one’s own experiments, to train the ability to observe, and to encourage professional scientific work. Nowadays, the reports written after each experiment are evaluated with regard to the formulation, valida-tion and agreement of hypotheses. Often the basis for this is measurement results achieved in an academic environment. Perhaps even aspects of quality assurance are taken into consideration in the evaluation process. This all happens at educa-tional institutions on a more or less voluntary basis and seldom is there the neces-sity to apply international guidelines or norms.

In analytical laboratories in chemical industry the quality management system consists of aspects of corporate policy, ergonomics, measurement technology, product assessment and electronic data processing, and is certified by quality audits. Such extensive quality assurance measures are conducted for ecological and economic reasons. The maintenance of product quality, and thus of competi-tiveness, obliges the companies to comply with extensive legal requirements. The work to be carried out within the framework of quality assurance is not only

XVI PrefacetotheGermanEdition

necessary to guarantee correct and accurate analytical values, but can be absolutely necessary for Good Laboratory Practice (GLP)-compliant laboratories or laborato-ries that want to be accredited, and are, at the same time, critical for the survival of corporations.

After destiny led me back to the university, I decided to write this book to sen-sitize students to the issue of quality assurance. Analytical validation is a topic that has become increasingly important for practice over the past years as a result of increased efforts in quality assurance, and which will also continue to play an important role in the future. Validations are an integral part of analytical processes and are a part of the repertoire of chemists who work in analytics, such as study of the literature, experimental work and reporting. Reports of experiments run during lab classes are intended to illustrate theoretical explanations and have to contain experimental–methodological information about quality assurance meas-ures. There is a growing need to take account of the statistical evaluation of the results. All validation steps, from the analytical question to the evaluation of the results, are involved in the analytical process of a lab experiment and described together with plausibility assessments. What is to be conveyed to the student is the fact that analysts, in their capacity as problem solvers, perform a service for certain groups of customers. Based on information supported by the strategy, structure and culture of the customer, analysts apply their techniques and broad knowledge. The results must be precise and exact to be used by the customers for their purposes. Students must be made aware of aspects such as personnel costs, equipment, methods and improvements of the analytical process achieved by rationalization, increased competition and customer satisfaction. The solution to the problem should in any case be processed in such a way as to be “fit for purpose”. Moreover, analysts must be able to communicate clearly complex work-flows and connections as well as results to customers in management, marketing or legal departments who are not versed in the subject.

There are several good books on analytical chemistry, but most of them go into such detail on the theory that the relationship to the practical implementation is diluted. The standard procedure for finding solutions to analytical problems out-lined here should be a model for contemporary and practical work in analytical laboratories. It has been consciously kept general to be applicable to a wide diver-sity of problems and customer specifications. In the modern-day laboratory prac-tice there is quite a series of variations and modifications of the procedural model presented in this book. However, everyone is familiar with the phased approach, from the order entry to the end of the project, which is also an essential part of the workflow presented in this book.

In view of the fact that approximately eighty percent of analysts will work in industry in future, I regard it as crucial to illustrate clearly to students the role of analytical chemists in the industrial environment. In this environment analysts are engaged as problem solvers and will be confronted with corporate require-ments, such as time, costs and precision. Students will learn that there are no general values for the acceptance of measurement insecurity, selectivity or quality in an analytical process, but rather that the values must be defined prior to starting

PrefacetotheGermanEdition XVII

the project. The results achieved must suffice with regard to the purpose and depend on the legal goals and limitations of the customer. The selection and degree of optimization of the methods, as well as the scope of validation and docu-mentation, are reflected in the order and its execution.

This book is intended to serve as a practical support for students and as an aid to internship supervisors. It is meant as a guideline and attempts to be an under-standable course book on the present-day status of practice. The trials run during laboratory classes and described here are formulated as projects and are meant to be carried out by the students in teamwork. In so doing, not only will specialist knowledge be deepened, but one will also learn to make decisions in a broader context. Analytical problems vary from trial to trial. However, the solution process is retained in the examples given during the internship and consists of the following:

• understanding of the chemistry and physics on which the analytical method is based

• knowledge of the analytical processes from the order entry to reporting• awareness that analytical work is service

Wädenswil, Switzerland, October 2009 Sergio Petrozzi

XIX

PrefacetotheEnglishEdition

The German edition of this book aroused lively interest, and this has incited me to write an extended version for translation into English.

The range of analytical methods introduced has been substantially enlarged and the number of the laboratory experiments has also been extended. The description of the new experiments also follows the proven standard and each starts with a small introduction (real presentation of problems involving different analyses) to the background and a short introduction to the procedure chosen by the analyst.

Translated from the originally published edition in German under the title Instrumentelle Analytik by Mrs. Maria Schmitz.

In her capacity as a freelance lecturer for the English Department of the University of Applied Sciences in Mainz, Economic Faculty, Mrs. Schmitz lectures on Intercultural Competence – German and American Business Styles. In addition, she lectures in the Communication Skills Faculty of the private academy accadis Bildung.

Zürich, Switzerland, May 2012 Sergio Petrozzi

XXI

Dedication

My sincere thanks go to Prof. Dr. Georg Schwedt for the foreword to this book and for giving me the opportunity to share his rich experience.

I owe a special thanks to Dr. Huldrych Egli (Büchi Labortechnik AG, Flawil/CH) for working out the project “N-Protein Determination according to Kjeldahl”.

For his contribution to the project Field-Flow Fractionation (FFF) I thank Dr. Tino Otte (Postnova Analytics GmbH, Landsberg/DE).

I am indebted to Dr. Oliver Mandal (Büchi Labortechnik AG, Flawil/CH) for his NIR project contribution.

For his contribution to the project GC-MS I would like to thank Lucio D’Ambrosio.

A hearty thanks to Dr. Martin Brändle (Chemistry Biology Pharmacy Informa-tion Center, ETHZ) for the section “Literature and Database Research” and Appen-dix A.

I would like to convey my appreciation to Dr. Markus Juza (DSM Nutritional Products, CH), Dr. Sebastian Opitz and Dr. Marc Bornand (Zurich University of Applied Sciences, ZHAW), and Dr. Thomas Schmid (Laboratory of Organic Chem-istry, ETHZ) for their proofreading of selected chapters.

I wish to thank Dr. Markus Zingg (ZHAW) for his critical scrutiny of the manuscript, Nick Bell (Language Services, ZHAW) for linguistic proofreading and Roland Kaulbars (Shimadzu GmbH, CH) for his support with the MS projects.

Thanks to Dr. Nestor Pfammatter (Safety, Security, Health and Environment, ETHZ) for his permission to implement the “Safety Manual” worked out for the ETH Zürich.

For their permission to use passages from the scripts of their lecture or labora-tory course documentation my thanks go to

• Prof. Dr. Gustav Peter (TWI Ingenieurschule Winterthur, CH)• Prof. Dr. Eduard Gamp (ZHAW)• Prof. Dr. Renato Zenobi and Dr. Thomas Schmid (Laboratory of Organic

Chemistry-ETHZ, Analytical Chemistry Laboratory)• Prof. Thomas M. Lüthi (ZHAW)

XXII Dedication

The following projects were worked out thanks to valuable support and the willing-ness to provide company documents such as training material, manuals, operating instructions and monographs:

• High Performance Liquid Chromatography Coupled with Mass Selective Detection – LC/MS (Agilent Technologies Sales & Service GmbH & CoKG, Waldbronn/DE and Shimadzu Schweiz GmbH/CH)

• High-Performance Thin Layer Chromatography – HPTLC (CAMAG Labora- – HPTLC (CAMAG Labora-tory, Muttenz/CH)

• Near-Infrared – NIR-Spectrometry (Büchi Labortechnik AG, Flawil/CH)

• Atomic Absorption Spectrometry – AAS (PerkinElmer AG, Schwerzenbach/CH)

• Karl Fischer Water Determination and Ion Chromatography (Metrohm Schweiz AG, Herisau/CH)

• N-Protein Determination according to Kjeldahl (Büchi Labortechnik AG, Flawil/CH)

• Field-Flow Fractionation – FFF (Postnova Analytics GmbH, Landsberg/DE)

Finally, I would like to thank everyone whom I have forgotten. Rest assured that this was not intentional.

XXIII

Foreword

Results from the application of instrumental analytical methods today often form the basis for political, legal and medical decisions that pertain not only to the recycling and maintenance of the quality of air, water, the earth or food, but also to the overall “quality of life”. In the medical field, particularly biochemical analyt-ics and pharmaceutical research depend on instrumental analytics. In the field of material sciences and in technical subjects, knowledge of the content of trace ele-ments is, for example, an important prerequisite for ascertaining physical proper-ties. Even such diverse sciences as geology, archeology and the restoration of works of art and antique books make use of analytical methods to solve the problems of their respective fields. In fact, there is hardly an area of experimental natural sci-ences that does not make use of chemical analytics in some form or another.

This makes it all the more important for students to become acquainted with the practice and problem orientation of instrumental analytics. That means they must learn to select a method suitable to a given task. Analytical procedure, in general, consists of several phases, ranging from sampling and sample prepara-tion to the evaluation and assessment of the results of the analysis. In so doing, planning and assessing analytical data with regard to their reliability and accuracy (in other words the validation of an analytical procedure) plays a very important role. For students it is therefore necessary to learn not only the theoretical aspect of chosen analytical methods and applications, but also to practise how to perform the necessary steps to solve analytical tasks efficiently. This laboratory course book can be an essential contribution to such a procedure.

Bonn, Germany, June 2009 Prof. Dr. Georg Schwedt

1

Introduction

1.1AnalyticalChemistry–TheHistory

Already in ancient Egypt, knowledge of chemistry existed and was used when embalming pharaohs and dignitaries. Greek philosophers such as Plato (428–347 BC), Aristotle (384–322 BC) or Empedocles began to look for rules to explain natural phenomena. Plato believed that diverse atoms could be differentiated by their constitution. According to this theory, the atoms of an element could be changed into those of another element by simply modifying the form. Aristotle postulated that all elements and the substances formed by them were composed of a kind of original substance. This original substance, however, could, in the course of time, take on many forms, such as shape and color. Empedocles, who lived sometime between 490 and 430 B.C., explained that all substances were composed of four elements, namely fire, earth, water and air.

Ever since the beginning of alchemy in the Middle Ages, men have sought for a material with which to best convert metal fastest and most simply and that could be exploited best. That was the stone of wisdom. The ability to illustrate this was generally regarded as an Act of God’s mercy, even if someone owned a functioning specification, it would have been useless without God’s intervention. The Phlogis-ton Theory was introduced by the German physician and chemist Georg Ernst Stahl (1659–1734) in 1697. According to this theory, all flammable substances contained Phlogiston (gr. phlox, the flame). When it was burned and/or oxidized the flame escaped as a gas-shaped something. Phlogiston was a hypothetical sub-stance that could be used without having necessarily to be proven. This assertion was applied to all appearances of fire in nature and ruled the thoughts of chemists for almost one hundred years. A substance would burn more readily, the more Phlogiston it had.

The spiritual aspect went hand in hand with the scientific aspect. Aristotle added a fifth, supernatural element to these four. The quintessence as the most inner core of all substances and to which a sustaining and healing power was attribut-able. Quintessences were gained by extraction, that is, by separating all ineffective or unpurified ingredient. These were material essences which were the sum of a body’s own effective powers and/or qualities. The idea of a microcosm and a

1

Practical Instrumental Analysis: Methods, Quality Assurance and Laboratory Management, First Edition. Sergio Petrozzi.© 2013 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2013 by Wiley-VCH Verlag GmbH & Co. KGaA.

2 1 Introduction

macrocosm stated that everything that occurred in the universe (macrocosm) had its correspondence and effect on earth (microcosm). As early as in Babylonian astronomy the planets were linked to certain materials (e.g., moon – silver, sun – gold). The constellation of the planets was important for chemical reactions to be successful.

The Renaissance witnessed the birth of attempts to renew chemistry. People wanted to get rid of everything, one by one, which was not rationally explicable. The making of gold and the associated magic, astrology and magic methods could not be reconciled with chemistry which was grounded in insights and based on reason. More and more chemists turned their backs on alchemy and finally began to fight against it. The chemists upheld research and the critical ability to think, reason, as the highest judge of the truth of a theory. In parallel to chemistry, analytical chemistry developed its own experimental skills. The first quantitative determination in chemistry was conducted by A.L. Lavoisier (1743–1794) and as early as the nineteenth century, analytical chemistry had become an established branch of chemistry. In a book published in 1894, W. Ostwald described “The Scientific Foundations of Analytical Chemistry”. In this book he introduced dis-sociation constants, solubility products, ion products, water ion products and indicator equilibrium into analytical chemistry.

Analytics today determines the success of science, technology and medicine and is an interdisciplinary field. At the beginning of this development, analytical inves-tigations were limited to the composition of substances and/or of mixed sub-stances with regard to their main components. At the same time the need for generalization of analytical methods, not only on the basis of the theory of chemi-cal reactions, but also on the basis of the physical theory of the structure of atoms and molecules arose. Later, procedures were developed to analyze trace amounts of an element or a chemical compound in a mixture. Determination of the struc-ture of molecules and investigation of the structure of solids also became impor-tant fields for the analyst.

1.2AnalyticalChemistryandItsRoleinToday’sSociety

Analytics is an interdisciplinary, scientific discipline also termed “analytical chem-istry”. The terms quantity and quality owe their existence to the results of analytics. Analytical issues are all-pervasive, and by no means only a part of scientific disci-pline. Rather, analytics often has a predominant role in the industrial value chain. Increasingly, more quality characteristics are being allotted to products and pro-cesses, which increasingly correspond to the need for analytics in all areas of life. Our society is demanding analytically secured data and judgments instead of empirical or traditional foundations for general or industrial decision-making. In this manner medical diagnostics, for example, is being shaped more and more by methods of analytical and bioanalytical chemistry. Buzzwords such as food secu-rity or water contamination, greenhouse gases or doping tests, gene analysis or

1.2AnalyticalChemistryandItsRoleinToday’sSociety 3

certification of genuineness are visibly tied to the performance of analytical chem-istry, visible for every citizen. Good analytics create trust and thus are a pre-requisite for production and marketing.

Responsible political and economic decisions have long been based on ecologi-cal insights, that is, findings based on environmental analytics. The concept of sustainability will be even more important in future, and this draws on analytical competence even more than any concept of human action has ever done. In a nutshell: More and more ideological, medical, legal and economic decision-making rests on analytical data. This applies both to the governmental control of such areas as health, the environment, security and resources, and to the control of trade and economic processes. Similarly, the decisive spurt in the development of high technology (microchips, high-tensile materials, medical diagnostics) is always based on highly developed analytics. Increasing globalization and the progressive growing together of the countries of Europe have reduced trade barriers at their borders. The goal is to facilitate a free and unprohibited exchange of products and services. With this development, it is becoming more necessary than ever, however, to make the quality of goods transparent, because only supplementary information on the composition, purity or reliability of goods makes them salable commodities.

In order to guarantee uniform procedures across national borders when collect-ing analytical information, international guidelines, such as Good Laboratory Prac-tices (GLP), Good Manufacturing Practices (GMP) or standards for good analytical work (e.g., International Organization of Standardization – ISO 17025) have been introduced.

These aspects make it clear that analytics is of fundamental significance and that this trend will continue. Analytics is the common task of several partners including universities, industry, analytics laboratories, the equipment industry and the authorities. Thus Europe will in future increasingly need the respective analysts, laboratories, educational and research institutions, more than ever before.

Only 40% of German universities have specialist analytical departments in the faculty of chemistry. This is the result of a study by the Society of German Chem-ists (SGCh). In some 50% of these it is tied to the subject “inorganic chemistry” since, traditionally, beginners in chemistry were introduced to the subject by way of simple analytical laboratory tasks. A cross-discipline like analytical chemistry, with increasing research roles in the whole area of material sciences, food science and medicine suffers from such a wrong allotment or subordination.

The concept of sustainability, which also takes a central position in the code of conduct of the GDCh (https://www.gdch.de/home.html, accessed May 2012), requires an extended concept of education: Beyond the difficult issue of the sci-ences the education must take into consideration the consequences of insights and their material implementation. Herein lies one of the most demanding tasks of the universities that have to convey high chemical analytical understanding. The specialist areas/faculties of chemistry and the university management are called upon to reinforce analytical chemistry in the further and new development of the curricula and to ensure and make use of their interdisciplinary function. Research

http://https://www.gdch.de/home.html

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promotion should clearly set priorities. Chemical analytical research is dependent on taking a leading position in methodology development and in giving preference to the application of expressly demanding issues. Only a quality-oriented promo-tion of research in stable interdisciplinary research structures of analytics can create the prerequisites that pave the way for industry (equipment manufacturers and users) in increasingly more areas to successfully offer automated or reliable practicable methods, and to market and use these globally.

It is therefore in the long-term interest of universities, politicians and the economy to firmly establish strong structures of education and research in analyti-cal chemistry.

Excerpt from: Society of German Chemists (GDCh) – Memorandum Analytics 2003.

The Gesellschaft Deutscher Chemiker (GDCh) is the largest chemical society in continental Europe with members from academe, education, industry and other areas. The GDCh supports chemistry in teaching, research and application and promotes the understanding of chemistry in the public.

I’m not afraid of storms, for I’m learning to sail my ship.Aeschylus