4

1.
2.
3.
4.

2547

1. (The Language of Analytical Chemistry)

2. (Essential techniques)
2.1 (Classifying analytical techniques)
2.2 (Selecting an analytical method)
2.3
(Developing the Procedure)
2.4
(Calibration, Standardization and blank correction)

3.
(Classification of environmental analysis)
3.1 (Separation and Extraction)
3.2 (Gravimetric methods)
3.3 (Titrimetric methods)
3.4 (Spectroscopic methods)
3.5 (Electrochemical methods)
3.6 (Chromatographic methods)

7
8
13
15

18
18
23
25
27
31
35

18

1 , ,

2 Soxhlet extractor
3 purge and trap
4
5

22
22
27
28

6 3
7
8 Clark
9
10 High Performance Liquid Chromatograph

32
33
35
38
39

1. (The Language of Analytical Chemistry)

1.1 Analysis, Determination, and Measurement

(Analysis)


(Analytes)
(Matrix)
(Determination)

(Measurement)

(Analysis)
(Analyte)
(Analysis)
(Determination)

(Measurement)

1.2
(Techniques, Methods, Procedures Protocols)

(Technique)

(Graphite furnace atomic absorption spectroscopy)

(Atomization) (Absorption)

(Method)
(Matrix)


(
)

(Anodic stripping voltammetry)
(Procedure)


(Method)


(Protocol)

5

Graghite furnace
Atomic absorption spectroscopy

Techniques

Methods
Procedures
Protocols

Pb in Water

APHA

Pb in Soil

Pb in Blood

ASTM

EPA

1 , ,

(Protocol) (Procedures)
(Method)
(Technique)
1

2. (Essential techniques)
2.1 (Classifying analytical techniques)
(signal)
(analyte)


(absolute amount) (relative amount)

2.1.1 (Total analysis techniques)

(signal)

SA = knA
SA A
nA A
k ()

classical techniques
gravimetry, titrimetry, coulometry

2.1.2 (Concentration techniques)

SA = kCA
CA A
k
optical
electrical instrumental techniques

k

2.2 (Selecting an analytical method)

(method) (technique)


(gravimetric)
(complexation titration)

(spectrophotometric)
(Atomic absorption spectroscopic)

(requirement)

(design criteria) (accuracy),
(precision), (sensitivity), (robustness),
(ruggedness), (analysis time), (available of
equipment), (scale of operation) (cost)
8

2.2.1 (Accuracy)

(expected value)

(relative percent error)
3
1,
1 5 5
, ,

(total analysis method)
(concentration method)
2.1.1 2.1.2
2.2.2 (Precision)

2.2.3 (Sensitivity)

2
9

 (Method detection limit)

()


( k)
nA

= SA
k

( total analysis method)

CA

= SA
k

( concentration method)

SA

+ 0.0001 0.200

nA

+ 0.0001
0.200

+ 0.0005

+ 0.0005

2.2.4 (Selectivity)



10

Ssamp = SA + SI = kA nA + kInI ( total analysis method)

Ssamp = SA + SI = kA CA + kICI ( concentration analysis method)
Ssamp
SI (interferences)

(selectivity coefficient); KA,I
KA,I = kI
kA
KI ()
KA ( A)
KA,I +1
-1

2.2.5
(Robustness and Ruggedness)


(robust)


(rugged)

11

2.2.6 (Equipment, time and cost)

2.2.7 (Making the final choice)

(design criteria)

(selectivity) (precision)
(accuracy)

(matrix) (selectivity)

12

2.3
(Developing the Procedure)

(procedure)

(Standardization)
(validation)

2.3.1 (Compensation for Interferences)

(reagent) method blank

method blank
2.3.2
(Calibration and Standardization)
(Calibration)


(Standard weight)
13

 (Standardization)

(total analysis method) stoichiometry
(concentration method)


(calibration curve)

2.3.3 (Validation)
(procedure)
(validation)




(standard sample)


(Intralaboratory and Interlaboratory differences)

14

2.4
(Calibration, Standardization and blank correction)
2.2.4
(k)

Smeas

k nA + Sreag

Smeas

k CA + Sreag

nA
A
CA
A
k

Smeas
Sreag
reagent
nA CA
Smeas , k Sreag

2.4.1 (Calibration and Standardization)

2.3.2

(standard)
(signal)

(Reference standard weight)

15

(buoyancy)



(laboratory
equipment) (known response)

60.60 K2Cr2O7 0.0050 M H2SO4
350.0 nm 0.640 + 0.010

2.4.2 (Standardization Methods)

2.3.2

k 2.4 k

16

 (Reagents used as standards)

-
(titrant)

( )

- (Primary and Secondary reagents)

(Primary reagents)
primary reagent

(secondary reagent)

- (Other reagents)

17

3.
(Classification of environmental analysis)
3.1 (Separation and Extraction)




(separation) (analyte)
(interferente)


(selectivity)

1
Basis of Separation

Separation Technique

Size

Filtration
Dialysis
Size-exclusion chromatography
Centrifugation
Distillation
Sublimation
Recrystallization
Precipitation
Ion exchange
Electrodeposition
Volatilization
Extraction
Chromatography

Mass and density

Complex formation
Change in chemical state

Partitioning between phases

18

1) (size)

(porous medium)
(filtration)
dialysis
semipermeable membrane
1-5 size-exclusive
chromatography

2) (mass or density)

(centrifugation)



3) (complexation reactions)
masking

pseudo-separation technique
4) (change of state)


,
(distillation)
19


(vaporization) (condensation)
sublimation

NH4+
(NH3)
(precipitation)
(ion exchange)

5) (Partitioning between phases)

KD

[Sphase2]
[Sphase1]

KD (partition coefficient)
[Sphase2 ] (solute) 2
[Sphase1 ] (solute) 1
(extraction)

5.1) Liquid-liquid extraction

(partition)
(organic solvent) diethyl ether,
20

 (immiscible)
(equilibrium constant)
-,

5.2) Solid-phase extraction

(solid particulates)

octadecyl (C-18) (hydrophobic)
(elute)
liquid-liquid extraction

solid-phase micro extraction
fused silica fiber (syringe needle) fiber
poly (dimethyl siloxane)

5.3) Continuous extraction

(partition coefficient)

soxhlet extrator ( 2)
microwave assisted extraction soxhlet extraction

56
soxhlet 150

21

Extraction
thimble
Upper
reservoir
Sample
Return tube

Lower
reservoir

2 Soxhlet extractor

purge and trap

(Volatile organic compounds; VOCs)
liquid-gas extration VOCs
adsorbent trap 2
VOCs ( 3)

Primary
adsorbent trap

Sample
Secondary
adsorbent trap

Purge gas

3 purge and trap

22

 supercritical fluid extraction

()

preconcentration
(organophosphorus) 1000
15 solid-phase extraction
67 ()

(metal chelator) methyl isobutyl ketone (MIBK) ammonium pyrrolidine
dithiocarbamate (APDC) 10

3.2 (Gravimetric method)

Gravimetry





(Pb2+)
PbO2
Pb2+

PbO2
23




()
()




(loss)

(Types of Gravimetric Methods)

4
1) Precipitation gravimetry
(PO33-)
HgCl2 Hg2Cl2 Cl2) Electrogravimetry

(Pb2+) PbO2
3) Volatilization gravimetry
species

4) Particulate gravimetry


24

 (gravimetry)

(Conservation of Mass)

-
=

SI units
( 12C)

(standard reference material)

3.3 (Titrimetric Methods)

Titrimetry (reagent)
18
(gravimetry)
20 titrimetry gravimetry
stoichiometry

gravimetry 20
4
- (acid-base titration) (complexometric
titration) (redox titration)
25

 (precipitation
titration)

1) (Equivalence Points and End points)
(titrant)
(analyte) (equivalence
point volume, Veq)

(end point)

2) (volume as a signal)
3




back titration


3) (Titration curve)

26

3.4 (Spectroscopic methods)

20
20
(trace level)
(colorimetry) Nesslers method
.. 1856

1 9 (absorption)
(emission) (visible)
20
(photon spectroscopy) (particle
spectroscopy)

27

 (electromagnetic
radiation)

(amplitude) (frequency) (phase angle) (polarization)

(-ray, X-ray, ultraviolet, visible infrared, microwave, radiowave

Wavelength (m) 10-14

Frequency (s-1)
Type of
transition
Spectral
region

10-12

1022

1020

10-10

10-8

1018

10-6

1016

10-4

1014

10-2

1012

1010

100

102
108

Nuclear

Core-level
electrons

Valence
electrons

Molecular
vibrations

Molecular
rotations;
electron spin

Nuclear
spin

y-ray

X-ray

UV

IR

Microwave

Radio wave

Visible

Wavelength (nm)

380

Violet

480

580

680

780

Blue Green Yellow Orange Red

(transition) 2 (absorption)
(emission)


2

28

3.4.1 (energy transfer)

3.4.1.1 Absorption spectroscopy

(excited state)

visible electron

(vibration energy)
(attenuate)
(absorbance)
(signal)
(well-defined value)
(E)
3.4.1.2 Emission spectroscopy
(emission)

(thermal energy)
photoluminescence, chemiluminescence
3.4.2
(diffraction)
(scattering & dispersion) X-ray diffraction, nephelometry
()

29

1. (source of energy)
absorption
scattering spectroscopy emission luminescence
spectroscopy
2. (wavelength selection)



(filters)
(throughput)
(band width)

(absorption filter)
momochromator polychromator
interferometer
3. (detector)
transducer
(S)
(P)
photon transducer phototube, photomultiplier photodiode thermal
transducer
pneumatic transducer
4. (Signal processor)
transducer
analog digital meter recorder

30

3.5 (Electrochemical methods)

(potential) (current)
(charge)
2 (bulk methods)

(interfacial methods)
pH
interfacial method
interfacial 2 static
dynamic static
(Potentimetry)
dynamic
dynamic
(potential) (current) (coulometry)
(voltammetry)


indicator
electrode ( working electrode)
counter electrode
counter electrode dynamic

reference electrode
auxillary electrode

31

Power
supply

SW

V
i
A

R W

6 3

3
1.
2.
3.

3.5.1 (Potentiometry)


.. 1889
glass pH electrode .. 1906 potentiometer

potentimetric 2 (two
half-cells)

salt bridge (inert electrode) KCl
32

Potentiometer

CI-

2e-

KCI
Salt bridge

K+

CIZn2+

eAg+

Porous frit
CI-

Zn
0.0167 M ZnCI2
Anode

NO30.100 M AgNO3
Cathode

salt bridge 3
salt bridge
anode cathode
cathode (right half-cell) indicator electrode anode (left half-cell)
reference electrode


(standard hydrogen electrode,
SHE)
(calomel electrode)
Hg2Cl2 ( )
Cl-
Silver/Silver chloride AgCl Ag
potentiometric
pH
(CN- )
33

 (F- ) biosensor

3.5.2 (Coulometry)
dynamic
(exhausive)

(Q)
(Faradays Law)

3.5.3 (Voltammetry)

(time-dependent)

(polarography)

stripping voltammetry anodic cathodic
adsorption anodic voltammetry
scan




(trace element)
(speciation)
34

3.5.4 (Amperometry)

chemical sensor
oxygen sensor L.C. Clark .. 1956
sensor
KCl

To potentiostat

Pt Disk
electrode

Ag Ring
Membrane
electrode
Electrolyte
solution

8 Clark

3.6 (Chromatography)


(selectivity)

(separation) (analysis)
35

1) (Simple separation)


(distribution ratio)




2) (Separation mixtures)

extracting phase initial phase
extracting phase


(back and forth) counter-current extraction

mobile phase
stationary phase mobile phase
(partition)
stationary phase

36


19 Mikhail Tswett (pigment)
chromatography
Martin and Synge (1941) liquid-liquid extraction

(Classifying analytical separations)

3
1) (mobile phase)
2) (contact)
3) (mechanism)
()

gas-liquid chromatograph

gas chromatography
2 column
chromatography

planar chromatography ,
(chamber)
capillary action

adsorption chromatography
partition chromatography

37


1) Gas Chromatography

( carrier gas) packed
capillary

Flow meter
Flow controller
Pressure regulator

Injector block

Septum

Detector block

Oven
Mobile phase
gas supply

Column

9 (He),
(Ar)
(detector)


packed capillary column

38

2) High-Performance Liquid Chromatography (HPLC)

gas chromatography

HPLC

liquid-solid adsorption, liquid-liquid
partitioning, ion-exchange and size exclusion
10
Loop injector
Pulse damper

Solvent
proportioning
valve

Pump
Guard
column

Column

Mobile
phase reservoirs

Director

10 High Performance Liquid Chromatograph

2
guard column
HPLC (nonpolar) (polar)
particulate
HPLC GC
GC

ion-exchange chromatography, size-exclusion chromatography,
supercritical fluid chromatography
39

1. Harvey, D., 2000. Modern Analytical Chemistry, The McGraw-Hill Companies, Inc.,
International Edition ISBN 0-07-116-953-9

40

92 7 . 10400
. 0 2298 2000 0 2298 2002
http://www.pcd.go.th