Practical Instrumental Analysis E-Book

Sergio Petrozzi

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 729

Veröffentlichungsjahr: 2012

Beschreibung

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 organization 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 program of analytics at universities and universities of applied sciences.

Leseprobe

Table of Contents

Cover

Related Titles

Title page

Copyright page

Preface to the German Edition

Preface to the English Edition

Dedication

Foreword

1 Introduction

1.1 Analytical Chemistry – The History

1.2 Analytical Chemistry and Its Role in Today’s Society

2 Introduction to Quality Management

2.1 Historical Background

2.2 Variability

2.3 The Four Pillars of Wisdom (from Shewhart to Deming)

2.4 Zero-Defect Tolerance

2.5 Why Standards?

2.6 The Controlled Process

2.7 ISO Guidelines 9004

2.8 Quality Management System (QMS) Requirements

3 Fundamentals of Statistics

3.1 Basic Concepts

3.2 Important Terms

3.3 Quality of Results (Accuracy and Precision)

3.4 Regression

4 The Analytical Process

4.1 The Analytical Process in the Overall Context

4.2 Planning Phase

4.3 Analysis

4.4 Assessment

4.5 Validation

4.6 Final Documentation

5 Example of a Validation Strategy

5.1 Determination of Phenol in Industrial Waste Water

6 Organizational and Practical Procedures in the Teaching Laboratory Program

6.1 Goals

6.2 Safety in the Laboratory Class

6.3 Experimental Project Workflow

6.4 Reports

7 Literature

7.1 Cited Literature

7.2 Recommended Norms (Selection)

7.3 Suggested Books (Selection)

8 Projects

8.1 Chromatography

8.1.1 Gas Chromatography – GC, Project: Tanker Accident

8.1.2 Gas Chromatography Coupled with Mass Selective Detection – GC/MS, Project: “Circumvention of the Formerly Mandatory Declaration of Fragrances in Perfumes?”

8.1.3 High-Performance Liquid Chromatography – HPLC, Project: “Stricter Control of Drugs”

8.1.4 High-Performance Liquid Chromatography Coupled with Mass-Selective Detection – LC/MS, Project “Cocaine Scandal: Hair Sample with Consequences”

8.1.5 Ion Chromatography (IC), Project: “Water Is Life”

8.1.6 High-Performance Thin-Layer Chromatography (HPTLC), Project: “Ensuring Regulatory Compliance by Quantification of Lead Compounds (Markers) in Herbal Combination Products”

8.2 Spectroscopy

8.2.1 UV–VIS Spectroscopy, Project: “Evaluation of Potential Saving through Use of Optimized Alloys”

8.2.2 Fourier-Transform Infrared Spectroscopy (FTIR), Project: “Benchmarking with a New Competitive Japanese Product”

8.2.3 Near-Infrared (NIR) Spectrometry, Project: “Accelerated Raw Material Intake Control”

8.2.4 Atomic Absorption Spectroscopy (AAS), Project: “Recycling of Sewage Sludge in Agriculture”

8.3 Electrophoretic Separation Methods

8.3.1 Capillary Electrophoresis, Project: “Preservatives in Cosmetics: Friend or Foe”

8.4 Automation

8.4.1 Flow Injection Analysis (FIA), Project: “Phenol-like Flavor in Beer: a Quality Parameter to be Mastered”

8.5 Mass Analytical Determination Methods

8.5.1 Karl Fischer Water Determination, Project: “Water Content as a Quality Parameter”

8.6 General Analytical Methods

8.6.1 Nitrogen and Protein Determination according to Kjeldahl, Project: “Official Control at the Swiss Alps Dairy Ltd”

8.6.2 Determination of Dissolved Oxygen (DO), Project: “Monitoring the Efficiency of the Biological Stage in a Sewage Treatment Plant”

8.7 Universal Separation Methods

8.7.1 Field Flow Fractionation (FFF), Project: “Characterization of Nanoparticles”

Appendix A Selection of Recommended Sources by Subject Area

A.1 General Sources

A.2 Analytical Chemistry

A.3 Inorganic and Organometallic Chemistry

A.4 Chemical Engineering/Technical Chemistry/Process Engineering

A.5 Chemicals: Directory of Suppliers

A.6 Organic Chemistry

A.7 Physico-chemical Data

A.8 Polymers and Materials

A.9 Spectra

A.10 Toxicology and Safety

Appendix B Statistical Tables

Appendix C Obligatory Declaration for Students

Appendix D The International System of Units (SI) – and the “New SI”

Appendix E Evaluation Guide for Formal Reports

Appendix F Safety in the Analytical Laboratory

F.1 General Precautionary Measures

F.2 First Aid

F.3 Working with Chemicals

F.4 Chemical Reactions under Increased Pressure

F.5 Disposal of Chemicals

F.6 Gases

F.7 Liquids

F.8 Working with Electricity

F.9 Working with High Voltage

F.10 Handling of Compressed Gas Bottles and Gas

F.11 Risk and Safety Phrases (R/S Phrases)

F.12 GHS (Globally Harmonized System of Classification and Labeling of Chemicals)

F.13 GHS Pictograms

Index

Related Titles

Prichard, E., Barwick, V.

Quality Assurance in Analytical Chemistry

2007

Hardcover

ISBN: 978-0-470-01203-1

Funk, W., Dammann, V., Donnevert, G.

Quality Assurance in Analytical Chemistry

Applications in Environmental, Food and Materials Analysis, Biotechnology and Medical Engineering

2007

Hardcover

ISBN: 978-3-527-31114-9

Ratliff, T. A.

The Laboratory Quality Assurance System

A Manual of Quality Procedures and Forms

2005

E-Book

ISBN: 978-0-471-72166-6

Kellner, R., Mermet, J.-M., Otto, M., Valcarcel, M., Widmer, H. M. (eds.)

Analytical Chemistry

A Modern Approach to Analytical Science

2004

Hardcover

ISBN: 978-3-527-30590-2

Miller, J. M., Crowther, J. B. (eds.)

Analytical Chemistry in a GMP Environment

A Practical Guide

2000

Hardcover

ISBN 978-0-471-31431-8

Strobel, H. A., Heineman, W. R.

Chemical Instrumentation

A Systematic Approach

1989

Hardcover

ISBN: 978-0-471-61223-0

The Author

Sergio Petrozzi

Zurich University of Applied Sciences

Institute of Chemistry and Biological Chemistry

Einsiedlerstrasse 31

8820 Waedenswil

Switzerland

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Preface to the German Edition

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 information 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 validated 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 analytical 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, validation 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 educational institutions on a more or less voluntary basis and seldom is there the necessity 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 competitiveness, obliges the companies to comply with extensive legal requirements. The work to be carried out within the framework of quality assurance is not only necessary to guarantee correct and accurate analytical values, but can be absolutely necessary for Good Laboratory Practice (GLP)-compliant laboratories or laboratories 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 sensitize 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 measures. 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 workflows 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 outlined 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 diversity of problems and customer specifications. In the modern-day laboratory practice 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 requirements, 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 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 documentation, 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 understandable 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

Sergio PetrozziWädenswil, Switzerland, October 2009  

Preface to the English Edition

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.

Sergio PetrozziZürich, Switzerland, May 2012  

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 Information Center, ETHZ) for the section “Literature and Database Research” and Appendix 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 Chemistry, 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 laboratory 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)

The following projects were worked out thanks to valuable support and the willingness 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 Laboratory, 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.

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 analytics and pharmaceutical research depend on instrumental analytics. In the field of material sciences and in technical subjects, knowledge of the content of trace elements is, for example, an important prerequisite for ascertaining physical properties. 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 sciences 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 preparation 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.

Prof. Dr. Georg SchwedtBonn, Germany, June 2009  

1

Introduction

1.1 Analytical Chemistry – The History

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 Phlogiston 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 substance 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 attributable. 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 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 dissociation 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 investigations were limited to the composition of substances and/or of mixed substances 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 chemical 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 structure of molecules and investigation of the structure of solids also became important fields for the analyst.

1.2 Analytical Chemistry and Its Role in Today’s Society

Analytics is an interdisciplinary, scientific discipline also termed “analytical chemistry”. 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 discipline. Rather, analytics often has a predominant role in the industrial value chain. Increasingly, more quality characteristics are being allotted to products and processes, 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 security or water contamination, greenhouse gases or doping tests, gene analysis or certification of genuineness are visibly tied to the performance of analytical chemistry, 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 ecological 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 collecting analytical information, international guidelines, such as Good Laboratory Practices (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 Chemists (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 sciences 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 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 promotion 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 analytical 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

2

Introduction to Quality Management

Quality. There is hardly another term mentioned more often in connection with products and services. Entire branches thrive from “selling” quality or from supporting corporations in their quality efforts. However, what is actually the essence of quality? Where does quality come from and how has the term changed over the centuries?

General definition:

Quality is understood to be synonymous with high value. It is not measurable, but rather it can merely be grasped (subjective term) by experience. Unsuited to corporate practice.

Product-related definition:

Quality is interpreted as being measurable. It becomes an objective characteristic, whereby subjective criteria are eliminated. (Example: The larger the cucumbers the more valuable, the better the quality)

User-oriented definition:

Quality only exists from the point of view of the user, that is, the customer.

Process-related definition:

Quality is equated with compliance with specifications. There exists a zero-defect policy (do it right the first time). (Example: Punctuality of a means of transport, a zero-defect product)

Value-related definition:

Taking into consideration the cost and/or price of a service, quality means a favorable price/performance ratio.

The consequence for corporate practice is that the various functional areas in a corporation develop varying opinions of just what quality is.

2.1 Historical Background

The pre-industrial technical production (as opposed to agrarian production) was handicraft production, whereby the so-called system of guilds played a decisive role from an organizational standpoint. The guilds determined the manufacturing procedures, tool types, tool use and even production quantities. On the one hand, they gave the craftsman social stability and ensured his company. On the other hand, their rigidity impeded innovation, technical progress and the expansion of production.

The link between the production of the craftsman according to the guild system and modern industrial production according to the factory system was the already more strongly centralized manufacturing system. They then continued to process the raw material on their own, or under their own control in centralized production sites.

With the industrial revolution in Great Britain, that reached its zenith between 1780 and 1820, technology changed drastically, as new machines were provided (for example, Watt’s steam engine).

The transition of the production method from individual producers to the factory first took place in the English wool-producing textile industry from about 1800 to 1820. Technically the era was characterized by the rapid transition from hydroelectricity to the steam engine, as the driving force for the new textile machines which led the mechanization process. What was also characteristic was the system by which work was divided, that is, the division of production into individual work steps and the distribution to hundreds and thousands of workers. Industrial work was now finally concentrated in one place, the factory and synchronized with the running machines. The economic consequences of the factory system were mass production, the fall in the price of industrial products and a distribution and marketing system that catered to mass-produced products.

The corresponding development and spread of precision tool machines, as existed in the USA, were indispensable prerequisites. In the 1890s the automation of work processes already existed with the use of these machines.

What was also of great significance was the rationalization of the workflow under the influence of the concept of scientific management developed in 1895 by the American production engineer Frederick Winslow Taylor (http://www.skymark.com/resources/leaders/taylor.asp, accessed May 2012).

This involved, for example, breaking down the production process into calculable elements and recording and eliminating redundant movements and hidden breaks.

Mass production of goods also induced a different understanding of quality. It was largely unclear why products did not have the required quality, although their production required only a few twists. The production processes were not predictable and people worked feverishly to control them. Walter Shewhart played a key role here (http://www.skymark.com/resources/leaders/shewart.asp, accessed May 2012).

2.2 Variability

All systems and processes demonstrate a certain variability. This variability is typical of each process. No two things are exactly identical. Even if they appear to be identical at a first glance, they turn out to have differences upon closer inspection that had been hidden from the observer. When we become interested in quality, we must understand where this variability comes from and how it influences the process or the work results, respectively. Shewhart, one of the early pioneers of quality management, divides variability into two categories according to its origin:

systematic influences (

common causes

), and

random influences (

special causes

)

For example: Whenever you write your signature ten times, you realize that no two signatures are exactly the same. Not even when you make the greatest effort. The deviations are predictable and move within certain limits (common cause). Should someone bump into you while you are signing a document, the signature seems totally different. You experience an extraordinary dispersion (special cause). This leads us to deduce that when extraordinary dispersions occur, the causes of the deviations must be immediately investigated, in order to re-establish the controllability of the process.

Accidental influences are numerous and mostly minimal in their impact. They are always present and have random (unpredictable) effects on the process and the work results.

Shewhart noticed that these random influences obeyed simply statistical laws.

As a result, he developed a concept that found its way into the literature as statistical process control (SPC) and that has been developed further by several people in quality management. According to Shewhart: “A phenomenon is regarded as controlled, when future behaviour can be forecast by experience at least in a limited area. A prediction within certain limits means that the likelihood that the phenomenon will move within certain limits in future can be estimated” [1].

A quality control chart (Figure 2.1a) is a form on which the test results of sample tests are graphically illustrated in a time sequence. Test values determined from the continuous production process indicate the current quality level.

Figure 2.1 (a) Example of a quality control chart (A upper limit value, B upper intervention limit, C process mean, D lower intervention limit, E lower limit value), (b) intervention limits exceeded, (c) controlled process, (d) trend behavior.

To have a record of quality, control chart samples are taken at prescribed intervals. The indicators are calculated from the sample and recorded on the quality control chart.

Previously calculated warning (upper limits/lower limits) and intervention limits (upper intervention limits/lower intervention limits) represent limit values which signal an impermissible worsening of quality whenever the limits exceed/fall short of these values.

If the intervention limits are exceeded, the causes must be analyzed and suitable corrective action taken (Figure 2.1b).

A process is regarded as controlled when the changes caused by such a process are effected exclusively within the control limits (Figure 2.1c).

The consistent, relative changes in the variables of interest are defined as a trend. In order to recognize trends by virtue of their measurement values, trend rules are defined, for example.

7 consecutive values are above the mean

7 consecutive values are below the mean

7 consecutive values demonstrate a falling tendency

7 consecutive values demonstrate a rising tendency

One of the first steps towards improving the process is to find out whether dispersion is systematic or accidental because only when all systematically conditioned dispersions have been eliminated can attempts be made to reduce the accidental dispersion.

In the case of a systematic dispersion, the process is said to be out of control. In the case of accidental dispersion, the process is said to be stable. Only in this case can it be expected that the points will always lie once on one side and once on the other side of the process mean. As long as this is the case, the process remains predictable with regard to consistent quality, productivity and costs. As a consequence, statistical process monitoring becomes an integral part of corporate management.

A further merit of Shewhart was the development of the so-called Plan–Do–Check–Act (PDCA)-control circuit, a problem-solving technique that allows systematic proceedings in uncontrolled processes.

This circuit consists of four consecutive steps:

With consistent use, this control circuit leads to continuous improvement as a basic model. As a result, this circuit has been used and propagated by several authors. In the literature it is variously called the Deming circuit, Shewhart circuit or Ishikawa circuit (http://www.skymark.com/resources/leaders/deming.asp, http://www.skymark.com/resources/leaders/ishikawa.asp, accessed May 2012).

2.3 The Four Pillars of Wisdom (from Shewhart to Deming)

William Edwards Deming was a scholar of Shewhart. Through close contact with Shewart, Deming had already learnt about and understood the principle of variation in manufacturing products during the early years of his career. After the Second World War, Deming was invited to Japan, which had a ruined economy, to demonstrate his basic model of continuous improvement, based on Shewart’s PDCA circuit.

Deming was the first to understand the organization as a process and depict it accordingly. He understands the system as a quantity of elements, parts of an organization, function, duties, which together work towards achieving the goal of the entire system. There must be a goal. The aim of the organization must be known, because without an essential aim, there is no system. The goal of a system brings profit for everyone, for shareholders, employees, suppliers, customers, the society, the environment and the economy. The goal of knowledge management and quality management is the customer orientation, whereby the term “customer” refers to both external and internal customers. System optimization is the common goal.

Deming’s teachings are presented in the literature as “The System of Comprehensive Knowledge”. The system is composed of four main components:

Understanding the system

Understanding dispersion (in the meaning of the work published by Shewhart)

Understanding the theory of knowledge (How do we learn? How do we improve ourselves?)

Understanding psychology and human nature.

2.4 Zero-Defect Tolerance

The American Philip Crosby (http://www.skymark.com/resources/leaders/crosby.asp, accessed May 2012) developed the Zero Defects Concept, which was aimed at eliminating deviations in production without scrap and rework. His insight that in corporations several practices exist that run counter to this goal, such as, for example, determining deviation quotas, accepting rework as being unavoidable, and the attitude that manufacturing quality produces costs, led him to demand a corporation-wide transition based on four principles:

Quality does not mean excellence but rather meeting the specifications (conformity).

Quality does not arise by discovering deviations, but by avoiding them.

The aspired quality standards are not acceptable quality levels, but zero defects.

Quality is not measured by indices, but by the price of deviation.

2.5 Why Standards?

In order to guarantee that milestones and delivery parts, respectively, comply with the finished project and finished product, respectively, a common language had to be invented to ensure that misunderstandings, false interpretations of regulations and so on were not the cause of failures. Many things had to be standardized. Thus the first “norms” originated.

Norms ensure that one thing fits the other, be it as a market ordering instrument for the elimination of trade barriers, for alleviating routine tasks or guaranteeing safety and health by defining the status of technology for products and services.

Norms are not passed “top down”, but are made precisely by those who need them: the economy, consumers, administration and science. Their representatives invest time and know-how in creating norms – in their own interest, and also in the interest of the public at large.

Norms are – put simply – rules of technology. The demand rationalization, facilitates quality assurance, serves workplace safety, and standardizes test methods, for example, in environmental protection, and facilitates in general the communication between the economy, technology, science, administration and public life, to name just a few examples.

2.6 The Controlled Process

Basically, a process describes a workflow and pursues a superior goal. Characteristically, a process is distinguished by the fact that it supersedes functional, organizational or personal limits.

Someone is made responsible for each process – the “process owner”. One person can be responsible for several process steps.

The person responsible for the individual process step must be able to assume that the input received complies with the quality specifications. This also applies to the next step. That means, therefore, that the owner’s responsibility lies in letting the small process run as required and guaranteeing the next owner the required input.

Clear instructions must be given for each process step. Only in this manner is the responsible person in a position to fulfill their duties. The instructions must, as far as possible, be given in such a way as to enable the online monitoring of the process step.

Should the process get out of control, that is, should certain limits be exceeded, the person in charge must react and bring the process back into line using continuous improvement methods (for example, the PDCA control circuit, Figure 2.2).

Figure 2.2 PDCA-control circuit.

There are, therefore, two essential measures to point out:

Limits which, when exceeded, establish that the process or the process step is out of control and no longer guarantees product quality.

Specifications that tell the person in charge how to react in the case of exceeding the limits.

The measures to be taken can vary widely:

interrupt the process

call the superior

change machine fittings

and so on.

Disturbances in the process or process step are all those factors that can cause the process to get out of control. Knowledge of these disturbances is of vital significance for controlling the process. Awareness of these factors permits monitoring, the specification of limits and the definition of measures. Knowledge of the disturbances and their possible effects is processed in cause and effect, and danger and risk analyses.

Important instruments for recording and evaluating deviations can be any of the following:

The Ishikawa or fishbone diagram (

Figure 2.3

)

Hazard analysis and critical control point (HACCP)

Failure mode and effect analysis (FMEA)

Figure 2.3 Ishikawa diagram.

2.7 ISO Guidelines 9004

ISO 9004:2009 provides guidance to organizations to support the achievement of sustained success by a quality management approach. It is applicable to any organization, regardless of size, type and activity. The standard is based on quality management (QM) principles, which promote understanding of QM and its use to improve the management of an organization (company). The standard is not a guideline for implementing the ISO 9001 norm. Nor is it meant for certification. The primary element is to attain customer satisfaction based on an organization that not only seeks to be effective, but also to be efficient. The entire standard observes the quality of the whole organization from an entrepreneurial standpoint. Apart from the classical customers who buy the products, other interested parties are the investors, employees, suppliers and society.

ISO 9004:2000 contains a section dedicated to self-evaluation of a company that has implemented a quality management system. Even if this is still just a guide, some companies may find that guide useful, especially when limited experience exists. The questions set in the guide are mainly general, but may be detailed according to the specifics of the company. The performance process consists of activities performed to get a better understanding and control of application performance. A maturity level is a well-defined evolutionary plateau towards achieving a mature process. Five levels of maturity are identified:

Level 1No formal approach. Companies with quality management systems which have this level have unpredictable results, and are characterized also by lack of evidence regarding quality. They run a business in a very unpredictable way, rather than managing the business.

Level 2Reactive approach. Usually, companies that fall into this level have a system based on corrections for solving problems. From time to time, minimum data regarding the results of improvements are taken into consideration. For them, the rule “make and correct” is a usual style of life, neglecting the understanding of what they are doing or how capable they are. Production costs in such companies are high and also, in many situations, there is no or poor vertical communication. Employees are seen as simple machines, and the superiority of managers over them is similar to that of the human race over monkeys. Unless changes occur in such companies, in order to improve things, most will end up closing their business.

Level 3Stable approach of a formal system. This level characterizes companies which have a systematic process approach. Also, there are visible signs of systematic improvement (continual improvements, most of the time, but only simple or very simple). There is available data regarding the conformance with stated objectives. Managers of such companies take into consideration the trends of processes and have a suitable understanding of what their business means. However, elements of a level 2 maturity still exist, such as the reactive approach. Part of the middle management of these companies has had or attends management training regard. Often, their achievements are not used within the company as they should be. These companies have lows and highs in their activity, and are not capable all the time of fully understanding the real causes of this. They will be made happy by highs, and upset by lows. Recovering from lows is a painful process, not always successful. Most companies have systems which fall into this level.

Level 4Sustained continual improvement. This level characterizes companies that have learned the useful lessons of their level 3 life. They understood that middle management has a key role in organization and employees are part of it. They are not simple machines, they have needs and expectations, which the company struggle to meet. A very good level of communication exists in these companies, no matter the direction. Plenty of data are recorded and analyzed and good decisions are made based on facts, not suppositions. Constant high quality of product is the focus in these companies and there exist signs that they are fighting also to exceed expectations, beyond fulfillment of requirements. Such companies have visions for the future and their mission is most of the time adequate. Improvements exist most of the time; they can be small or large and the company finds the necessary resources for them. Planning is an important part of the company’s life.

Level 5Best performance in class. At this level, companies are doing detailed benchmarking to prove their competitiveness against competitors. Their processes are strongly integrated. The future of such companies is sure, the security of jobs is provided. Customers have a high degree of confidence in the products or services of the company. Every person in the company is involved in processes, not because of constricts, but because of awareness. A high level of training is provided to personnel, according to their specific needs. Fulfillment of customer requirements is like “another day at the office” and anticipation of customer expectation is a constant focus. New products are made after extensive research of that initial expectation of the clients, to become new requirements for the company. Companies having this level of maturity are the best examples of how to manage a business rather than running the business.

2.8 Quality Management System (QMS) Requirements

The standards of the ISO 9000 series distinguish between QMS requirements and product requirements. The QMS requirements are laid down in ISO 9001. QMS requirements are of a general nature and apply to organizations in any industrial or economic sector, irrespective of the products offered. The ISO 9000 series does not determine any product requirements. Product requirements can be determined either by the customers (= specifications) or by the authorities (e.g., legal specifications).

Development of a QMS according to ISO 9000

A QMS according to ISO 9000 can be developed as follows:

by ascertaining the requirements and expectations of the customer and other interested partners and parties

by determining the organization’s quality policy and quality goals

by determining the necessary processes and responsibilities, in order to achieve the defined quality goals

by determining and providing the necessary resources, to achieve the quality goals

by introducing methods to measure the effectiveness and efficiency of each process

by applying this measurement to ascertain the current effectiveness and efficiency of each process

by determining the means of preventing deviations and eliminating the causes of such deviations.

by introducing and applying a process for the continuous improvement of the QMS.

Quality ensues when satisfaction is achieved. The needs of the user are defined by measurable criteria, which in turn become the guiding measure for product development.

W.A. Shewhart

The dependence on controls to improve quality must stop. In particular, comprehensive monitoring is superfluous when quality is built into the products by controlled processes.

E.W. Deming

The Japanese understanding of quality is based on the following pillars: “Quality first” – quality goals as a management priority, “conformance to consumer requirements” – the consumer defined quality, involvement of all corporate departments and all levels, continuous improvement and a social system that forms the basis of meaning and wellness for the employee.

K. Ishikawa

Quality means to keep the promise.

P.B. Crosby

3

Fundamentals of Statistics

3.1 Basic Concepts

An analysis result void of statistical evaluation is essentially worthless. Besides the actual numerical value, what is therefore important is a statement on its accuracy and on its uncertainty.

Books on mathematics and statistics are, with regard to their practical use and interpretation, essentially written in a complex and abstract manner. The students are penalized all the more with formulas, derivations and definitions which often prove to be somehow more confusing than they are helpful, at least in the case of a practice-related application (Figure 3.1). In addition, specialist literature describes procedures and explanatory approaches to determining some statistical parameters, for example, the limit of detection, in different ways. For the most part, statistics is taught separately from the accompanying concrete and practical issue, which makes the subject appear rather dry. In its practical application, a statistical method gains meaning for the overall result and delivers statements on the quality of the results.

Figure 3.1 Let’s keep it as simple as necessary.

(Source of picture: Richard R. Rediske, Ph.D., Grand Valley State University).

Statistics offers methods to summarize a collection of data. These methods may be graphical or numerical, both of which have their own advantages and disadvantages. Graphical methods are better suited for the recognition of patterns in the data, whereas numerical methods give well-defined measures of some properties. In general, it is recommended to use both approaches for the description of data. For the correct evaluation of analytical results only a basic knowledge of statistics is required in laboratory classes of analytical chemistry, which, in this section, is conveyed with a focus on the purely practical application. Only what is absolutely necessary is taught in an exemplary manner. Wherever it was acceptable, the author worked with estimated values, approximations and rules of thumb.