FOUNDATIONS OF ANALYTICAL CHEMISTRY

BLOCK I
INTRODUCTION TO ANALYTICAL CHEMISTRY

Chapter 1. Principles of Analytical Chemistry

Chapter 2. Analytical properties

Chapter 3. Traceability. Reference materials

BLOCK II. THE ANALYTICAL PROCESS

BLOCK III. SOCIOECONOMIC PROJECTION OF ANALYTICAL CHEMISTRY

ANNEX 1. GLOSSARY OF TERMS

ANNEX 2. ANSWERS TO THE QUESTIONS 1-1
 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
 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

3
ANALYTICAL TRACEABILITY.
PROPERTIES REFERENCE
MATERIALS
1-3
 Chapter 1. Principles of Analytical Chemistry

1.1.2. Definition (I): Straightforward approaches

The discipline of Analysis, The discipline

the third basic component A C of (bio)chemical
of Chemistry measurements

The discipline The (bio)chemical

producing metrological
B D
(bio)chemical discipline
information

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 Chapter 1. Principles of Analytical Chemistry

1.1.2. Definition (II): Straightforward approaches

Placement of Analytical Chemistry in the Chemistry domain
Synthesis

Applications
Theory

Analysis
Analytical Chemistry 1-5
 Chapter 1. Principles of Analytical Chemistry

1.1.2. Definition (III): Straightforward approaches

Analytical Chemistry in the context
of interdisciplinarity
SYNTHESIS

Q
APPLICATIONS
THEORY

OTHER SCIENTIFIC
AND
ANALYSIS 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

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 Chapter 1. Principles of Analytical Chemistry

1.1.3. Aims and objectives of Analytical Chemistry (I)

FULFILLING THE CLIENTS
INFORMATION REQUIREMENTS
CONTRADICTION
METROLOGICAL SOLVING
QUALITY INFORMATION-RELATED PROBLEMS

THEORETICAL
AIMS PRACTICAL

OBJECTIVES
AUGMENTATION DIMINUTION
MATERIALS
CONTRADICTION TIME
MORE BETTER LESS EFFORT
COSTS
HAZARDS
(BIO)CHEMICAL
INFORMATION

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 Problem Augmentation Diminution

quality solving objectives objectives

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 Chapter 1. Principles of Analytical Chemistry

1.1.3. Aims and objectives of Analytical Chemistry (III)

ANALYTICAL CHEMISTRY
METROLOGY APPLIED
FACETS
AIMS HIGH ACCURACY SOLVING
LOWEST UNCERTAINTY INFORMATION-RELATED
PROBLEMS

OBJECTIVES AUGMENTATION DIMINUTION

(more, better information) (less materials, effort,
time, etc.)

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 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
Qualitative analysis
EXAMPLES Quantitative analysis
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 Chapter 1. Principles of Analytical Chemistry

1.1.4. Analytical chemical references (II)

Basic Analytical Chemical references

CLASSICAL

CHARACTERISTICS
MEASUREMENT WRITTEN OF USERS
STANDARDS STANDARDS REQUIRED
(norms, methods)
INFORMATION

PRACTICAL
METROLOGICAL QUALITY
QUALITY (problem
ANALYTICAL
solving)
QUALITY

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 Chapter 1. Principles of Analytical Chemistry

1.1.4. Analytical chemical references (III)

WRITTEN STANDARDS IN ANALYTICAL CHEMISTRY

1 4

NORMS
STANDARD
2 AND
ANALYTICAL
GUIDES
METHODS

LEGISLATION
(directives, regulations)
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 Chapter 1. Principles of Analytical Chemistry
1.1.4. Analytical chemical references (IV)

CEN-CWA 14924 (2004) ISO 26000:2010 WRITTEN

European guide to good Guidance on STANDARDS
practice in knowledge SOCIAL RESPONSIBILITY
management

OSHAS 180001:2007 ISO 9001:2008

Requirements for ANALYTICAL Requirements for
establishing an CHEMISTRY establishing a quality
occupational risk assurance system
prevention system

ISO 14001:2004
Requirements for
establishing environmental
management systems
ISO 17025:2005
General requirements
for the competence of
testing calibration
laboratories
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 Chapter 1. Principles of Analytical Chemistry

1.1.5. (Bio)chemical information (I)

Main product (output) of Analytical Chemistry
LEGISLATIVE
Significance POWER

EXECUTIVE
SOCIETY POWER

JUDICIAL
POWER

SCIENCE AND
TECHNOLOGY

CAPITAL

RAW
ECONOMY MATERIALS

LABOUR
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 Chapter 1. Principles of Analytical Chemistry

1.1.5. (Bio)chemical information (II)

NUTRITION
HEALTH HYGIENE

TRANSPORTATION

ANALYTICAL
BUILDING
CHEMISTRY SPORTS

DRESSING
HOUSEHOLD

CULTURE
Need to use
reliable
(bio)chemical information
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 Chapter 1. Principles of Analytical Chemistry

1.1.5. (Bio)chemical information (III)

General types according to quality
QUALITY

IDEAL
INTRINSIC TRUENESS
INFORMATION

REFERENTIAL INFORMATION U
A
HELD AS C N
TRUE C C
(e.g., CRMs) E
U
R
R
T
A A
C I
PRACTICAL ROUTINE Y N
ANALYTICAL T
INFORMATION Y
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 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 SOCIOECONOMIC
INFORMATION
Chapter 3
REQUIRED
TRACEABILITY

(BIO)CHEMICAL
INFORMATION
ANALYTICAL
Chapter 2
PROBLEM
ANALYTICAL Chapter 7
PROPERTIES

ANALYTICAL
QUALITY
PROCESS
Chapter 8
Chapters 46
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 Chapter 1. Principles of Analytical Chemistry

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

3 A
B
C

Mixed hierarchies
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 Chapter 1. Principles of Analytical Chemistry
1.1.6. Conceptual and technical hierarchies (II)
Information (I)
GENERAL
MEANING (BIO)CHEMICAL
CONTEXT
DIRECT
INFORMATION-RELATED PRIMARY SIGNALS FROM
COMPONENTS OF DATA
MEASURING
REALITY
INSTRUMENTS
collection
computation

DESCRIBING
REALITY RESULTS OF
INFORMATION
(BIO)CHEMICAL
interpretation
PROCESSED EXPRESSED
processing AS REQUIRED
UNDERSTANDING
AND INTERPRETING REPORTS CONTEXTUAL-
REAILITY.
KNOWLEDGE
IZING INFORMATION,
DECISION-MAKING
SUPPORTING DECISIONS,
creating STATING HYPOTHESES
CRISIS
new AND ESTABLISHING
breaking
paradigms MECHANISMS
boundaries

IMAGINATION
(Einstein)
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 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
To detect
data

To sense

Non-analytical Secondary
information data
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 Chapter 1. Principles of Analytical Chemistry

1.1.6. Conceptual and technical hierarchies (IV)

Technique Process Method Procedure (A)

Technique
Sample Results

concreteness
Increasing
Measurement Data handling
Preliminary and transducing of and processing
operations analytical signal

Analytical process
Method

Procedure

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 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
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 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.
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 Chapter 1. Principles of Analytical Chemistry

1.1.6. Conceptual and technical hierarchies (VIII)

Analyser Instrument Apparatus Device (C)

Examples

Type of Ranked
information elements Examples

Analyser for gases (O2, CO2) in blood

Analyser
Autoanalyser for C and H in steel

Analytical Balance
Instrument Polarograph
Mass spectrometer
Chromatograph (GC, LC, SFC)

Microwave digester
Apparatus Extractor (LL, SL)
Performance- Centrifuge
related
Device Pressure and temperature sensors
Electronic interfaces 1-26
 Chapter 1. Principles of Analytical Chemistry

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

(A.2) Sample 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 physicochemical 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
Aliquots of the object
Example 1 Contamination of a geopgraphic and Organic and inorganic
collected at different
river temporal contaminants
places and times
characteristics

Drug abuse at the Amphetamins, hormones,

Example 2 Olympic Games
Athletes Urine
-blockers, etc.

Adulteration of olive
Factory output Aliquots representative of Vegetable and animal fat
Example 3 oil with extrananeous
the output
fat

Surface scrapings from

Toxicity of yellow-
Toys from an several toys selected
Example 4 painted toys (cadmium
imported batch according to a sampling
Cadmium
paint)
plan

Economic feasibility of Samples of the object

gold recovery from The waste dump as collected at differents
Example 5 mining waste a whole depths at different places
Gold

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 Chapter 1. Principles of Analytical Chemistry

1.1.7. Classifications (I)

AN OVERVIEW OF COMPLEMENTARY CLASSIFICATIONS

Quantitative Structural Analytical

analysis analysis separation
systems
Qualitative Classical Instrumental
analysis Others analysis analysis

According According to
to purpose technique

1 2
General
classifications of
6 Analytical Chemistry 3
According to
According to nature
object availability 5 4 of sample/analyte
According to According to relative
initial sample size 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 3
- Quantification analysis
- Result: 2.30 0.03 g/L
Quantitative 2
STRUCTURAL ANALYSIS analysis
Elucidation of the spatial structureof
the sample (e.g., spatial arrangement
of a protein)
Qualitative 1
an analyte (e.g., a thalidomide analysis
enantiomer)

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 Chapter 1. Principles of Analytical Chemistry

1.1.7. Classifications (III): According to technique (*)

Classical Instruments 1. HUMAN SENSES
used 2. CLASSICAL BALANCE
analysis for centuries 3. CLASSICAL BURETTE

- FLUORIMETER
- MASS SPECTROMETER
Instrumental Other
- SPECTROPHOTOMETER
- VOLTAMMETER
analysis instruments - NMR SPECTROMETER
- POTENTIOMETER
- IR SPECTROMETER
- Others.
(*) Unscientific, but historically pertinent, classification

RIGHT

Analytical separation
Analytical separation systems Analytical separation
techniques methods
PARTLY RIGHT WRONG
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 Chapter 1. Principles of Analytical Chemistry

1.1.7. Classifications (IV):

According to technique and purpose

Qualitative
analysis
Classical
analysis
Quantitative
analysis
Instrumental
analysis
Structural
analysis

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 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
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 Chapter 1. Principles of Analytical Chemistry

1.1.7. Classifications (V):

According to nature of sample and analyte (B)
Examples
Sample Analyte Example

I i - Determination of the gold content of a mineral

I o - Determination of pesticides in soil
I b - Determination of traces of biochemical molecules in a meteorite (in order
to search for life on other planets)

O i - Determination of metal traces in organic pharmaceutical preparations

O o - Determination of nitrogen-containing organic compounds in petroleum

crude
O b - Determination of enzyme activity in an organic solvent

B i - Determination of calcium in biological fluids

B o - Determination of drugs and their metabolites in human urine
B b - Determination of the protein content of milk

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 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 IMMOBILIZED
REAGENT ENZYMES

USE THE CONTRACTION (BIO)CHEMICAL FOR

SIMPLICITY

EQUIVALENCE OF (BIO)CHEMICAL INFORMATION

AND ANALYTICAL INFORMATION
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 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 Semi- Macroanalysis

microanalysis microanalysis
difficulty
complexity

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 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: Analytes: pesticides
Complexity metal traces

Metal traces Traces of organo-

Trace
in a painting by chlorines in babys
microanalysis
Velazquez blood

Determination of Organo-phosphorus
Trace
mercury in compounds in
macroanalysis
seawater drinking water

Determination of Pesticides in
Macrocomponent
chromium in steel commercial
microanalysis
formulations

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 Chapter 1. Principles of Analytical Chemistry

1.1.7. Classifications (VIII)

Object availability

Pendulum

NANO ANALYSIS SPATIAL ANALYSIS

MACROANALYSIS
MICROANALYSIS
human level

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 Chapter 1. Principles of Analytical Chemistry

1.1.8. New paradigms of Analytical Chemistry (I)

Analytical Chemistry:
- has little weight in Chemistry Analytical Chemistry
- lacks identity starts at the
- is simply an application of laboratory door
Chemistry and ends at the printer
The relationships among
2 analytical properties
1 are unimportant

The teaching of 3
Analytical Chemistry Obsolete
should start with Only tangible and
calculations, ionic 8 paradigms in written standards
4
equilibria, tritrimetries Analytical Chemistry are relevant to
and gravimetries Analytical Chemistry

7 6 5
Quality assurance
systems suffice Contradictions
to ensure fulfillment Analytical results among aims and
of the aims of can only be objectives in
Analytical Chemistry qualitative Analytical Chemistry
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 Chemistrys present and future

ANALYTICAL CHEMISTRY

KNOWLEDGE
AND
AS TECHNOLOGY
THE DISCIPLINE TRANSFER
OF (BIO)CHEMICAL
INFORMATION
AT THE
BOUNDARIES WITH
OTHER SCIENTIFIC INDEPENDENT,
AND TECHNICAL EFFICIENT
AREAS R&D

1-41
 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, 31963209

ONE OF THE MOST CRUCIAL ANALYTICAL CHEMISTRY IS

STEPS IN STARTING NEW A MUCH MORE IMPORTANT
SCIENTIFIC AND TECHNICAL AREAS CHEMICAL DISCIPLINE
IS THE DEVELOPMENT OF THAN MANY BELIEVE
INNOVATIVE ANALYTICAL TECHNIQUES
TO FACILITATE ANALYSES
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 Chapter 1. Principles of Analytical Chemistry

1.1.9. Research and transfer in Analytical Chemistry (I)

RESEARCH
BASIC RESEARCH
TYPES APPLIED RESEARCH
First stage Second stage
STAGES 1 2

TOOLS
- Instruments
- Devices
PRODUCING
- Reagents
R&D IN QUALITY (BIO)CHEMICAL
PROCESSES INFORMATION AND KNOWLEDGE
ANALYTICAL
BASIC
CHEMISTRY APPROACHES

STRATEGIES

FULFULLING
INFORMATION DEMANDS
EXPANDING
OBJECTIVES THE ABILITIES
OF ANALYTICAL SOLVING
CHEMISTRY ANALYTICAL PROBLEMS 1-43
 Chapter 1. Principles of Analytical Chemistry

1.1.9. Research and transfer in Analytical Chemistry (II)

TRANSFER

ANALYTICAL
CHEMISTRY 4
R&D CENTRES
3

ROUTINE LABORATORIES CLIENTS

PRODUCING (BIO)CHEMICAL REQUIRING
1 INFORMATION ANALYTICAL
INFORMATION

Instruments ANALYTICAL TOOL

Reagents MANUFACTURERS
Extraction
devices
Others
1-44