Qualitative analysis: Identifying the components of a sample

Quantitative analysis: Measuring the amounts or concentrations of analytes in a sample

The three measurement terms of “analysis”, “determination”, and “characterization”
have different meanings.
Analysis = Qualitative and quantitative characteristics of chemical analytes
Determination = Quantitative measurements of specific analytes
Characterization = Experimental description of properties of materials

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Steps in an Analysis

Define the Problem Select a Method Obtain a Representative Sample

Perform Any Necessary

Perform the Chemical Separations Prepare the Sample for Analysis
Measurement

Data Processing
and Report
 1. Define the Problem
Factors:
• What is the problem--what needs to be found? Qualitative and/or
quantitative?
• What will the information be used for? Who will use it?
• When will it be needed?
• How accurate and precise does it have to be?
• What is the budget?
• The analyst (the problem solver) should consult with the client to plan
a useful and efficient analysis, including how to obtain a useful
sample.
 2. Select a Method
Factors:
• Sample type
• Size of sample
• Sample preparation needed
• Concentration and range (sensitivity needed)
• Selectivity needed (interferences)
• Accuracy/precision needed
• Tools/instruments available
• Expertise/experience
• Cost
• Speed
• Does it need to be automated?
• Are methods available in the chemical literature?
• Are standard methods available?
 3. Obtain a Representative Sample
Factors:
• Sample type/homogeneity/size
• Heterogeneity of sample composition increases from the fairly
homogeneous gas and liquid samples to solid samples that must be ground
up prior to dissolution.
• Analysis of grains from crops (rice, wheat, etc.) requires dehusking to yield
meaningful data.
• Milling and blending are usually parts of the sample preparation procedures.
• Sampling statistics/errors
• The quality of analytical data must support the measurement objectives and
hence the sampling procedures have to satisfy statistical requirements of
the analysis.
• The number of samples or sample size, the frequency and time of sampling,
and the location of sampling have to be consistent with the analytical
objectives.
 4. Prepare the Sample for Analysis
Factors:
• Solid, liquid, or gas?
• Dissolve?
• Ash or digest?
• Chemical separation or masking of interferences needed?
• Need to concentrate the analyte?
• Need to change (derivatize) the analyte for detection?
• Need to adjust solution conditions (pH, add reagents)?
5. Perform Any Necessary Chemical Separations
Factors:
• Distillation
• Precipitation
• Solvent extraction
• Solid phase extraction
• Chromatography (may be done as part of the measurement step as in
the hyphenated techniques of GC-MS or LC-MS)
• Electrophoresis (may be done as part of the measurement step as in
CE-MS and microfluidics)
 6. Perform the Measurement
Factors:
• Calibration
• Instruments must be properly calibrated according to analytical protocols; for
instance, the wavelength scale of a spectrometer has to be verified with a standard;
all sample preparation equipment from the balances to sample extraction devices
must also be checked or calibarated
• Validation/controls/blanks
• Suitable matrix blanks, trip blanks, lab control standards must be analyzed to
support the sample measurements.
• Replicates
• Appropriate number of replicates meeting the analytical statistical confidence is
necessary.
 7. Data Processing and Report
• Conversion of raw instrumental signals into meaningful results of
chemical identification and determination
• Interpretation of data by correlating chemical parameters of analytes (formula
mass, functional groups, etc.) with observed signals (energies of spectral peaks ,
retention times of chromatographic peaks, etc.)
• Calibration plot of standards at various concentrations is used to determine
quantitative results of sample constituents.
• Statistical analysis of quantitative results (reliability)
• Accuracy – Results for standard reference materials (SRMs) from National Institute
Standards and Technology
• Precision – Relative standard of deviation or coefficient of variation
• Blanks, correlation coefficients of calibration plots, spike recovery, detection
limits, and etc.
• Relating qualitative and quantitative results to the objectives of
analyses (i.e. how C-14 results are used to determine the age of an
archaeological artifact or whether an art piece is authentic).
 The sample size dictates what measurement techniques can be used.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Classification of Analytical Methods
Classical methods
• Gravimetry
• Titrimetry
Instrumental methods
• Electroanalytical
• Spectroscopy
• Chromatography
• Radioisotopic measurements
 Different methods provide a range of precision, sensitivity, selectivity,
and speed capabilities.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Types of Instrumental Methods
 Configuration of Instrumentation
Raw data
Instrument or Process
Machine-level commands

Control Diagnostics Data

Processed data Processing
(Information)
High-level
commands Intelligent System

Integrated
Computers Output
User Interface
Device
User-level Explanation
commands (Knowledge)
Analyst
Components of a Typical Instrument

Electrical
Meter
or
or
mechanical Scale
Analytical input
Input signal
signal Output
Signal transducer Signal Recorder
signal
generator or processor
detector

12.301

Digital
unit
Some Examples of Instrument Components
 Selecting an Analytical Method
Defining the problem:
1. What accuracy and precision are required?
2. How much sample is available?
3. What is the concentration range of the analyte?
4. What components of the sample will cause
interference?
5. What are the physical and chemical properties of
the sample matrix?
6. How many samples are to be analyzed?
Validation involves
determining:
•selectivity
•linearity
•accuracy
•precision
•sensitivity
•range
•limit of detection
•limit of quantitation
•ruggedness/robustness

Standard reference
materials (SRMs) best for
determining accuracy.

General process for evaluation/validation of methodology

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
 Other Characteristics to Be
Considered in Choosing a Method
1. Speed of analysis
2. Ease of use and automation
3. Cost and availability of instrument
4. Per-sample cost (consumables and reagents)
5. Training and learning curve
6. Software features and compatibility with
databases and data processing programs
 COMPONENTS OF A QUALITY CONTROL
Suitable and
PROGRAM Maintained
Well well and well
trained maintained calibrated
personnel facilities equipment

Quality
GLP GMP
Control

Complete
SOP Evaluation Documentat
Samples ion
 IMPORTANT PROCEDURES IN QUALITY CONTROL
Measured parameter Procedure
Accuracy Analysis of reference materials or samples
of know concentration

Precision Analysis of replicate samples

Extraction efficiency Analysis of matrix spikes

Contamination Analysis of blanks

 POTENTIAL SOURCES OF SAMPLE CONTAMINATION
Steps in the analytical Contamination sources
process
Sample collection Equipment, Sample handling steps such as compositing, or
filtering, Sample preserving additives, Sample containers,
Ambient contamination

Sample transport and storage Sample containers, Cross contamination from ear reagents or
other samples

Sample preparation Sample handling, Dilutions, Glassware, Ambient

contamination

Sample analysis Instrument memory effects or carry-over, Reagents, Syringes,

Glassware, Apparatus
 TYPES OF ANALYTICAL BLANKS FOR QUALITY CONTROL
Blank type Purpose Process

System or Instrument blank Establishes the baseline of an analytical Determine the background signal with
instrument, in the absence of sample no sample present

Solvent or Calibration blank To measure the amount of the analytical signal Analytical instrument is run with
which arises from the dilution solvent. The zero dilution solvent only
solution in the calibration series.

Method blank To detect contamination from reagents, sample A simulated sample containing no
handling, and the entire analytical process analyte is taken through entire
analytical procedure

Matched-matrix blank To detect contamination from field handling, A synthetic sample which matches the
transportation, or storage basic matrix of the sample is carried to
the field and is treated in the same
fashion as the samples
Sampling media or trip To detect contamination in sampling media such Analyze samples of unused filters or
blank as filters and sample adsorbent traps traps to detect contaminated batches

Equipment blank To determine contamination of equipment and Samples of final equipment cleaning
assess the efficiency or equipment clean-up rinses are analyzed for contaminants
procedures
 REGULATORY LEVELS OF TCLP CONTAMINANTS
Metals Regulatory Pesticides Regulatory Other organics Regulatory
level (mg/l) level (mg/l) level (mg/l)

Arsenic 5 Chlordane 0.03 Benzene 0.07

Barium 100 2,4-D 1.4 Chloroform 0.07

Cadmium 1 Endrin 0.003 Cresol 10

Chromium 5 Lindane 0.06 1,4- 10.8

Dichlorobenzene

Mercury 0.2 2,4,5-TP 0.14 Pentachlorophen 3.6

(Silvex) ol

Lead 5 Heptachlor 0.001 Trichloroethylene 0.07

Silver 5 Methoxychlor 1.4 Toluene 14.4

Vinyl chloride 0.05
 REGULATORY LEVELS FOR AMBIENT AIR POLLUTANTS
Compound Regulatory concentration Averaging period

Ozone 0.12 ppm 1h

Carbon monoxide 35 ppm 1h

9 ppm 8h
Nitrogen dioxide 0.05 1 year

Sulfur dioxide 0.14 ppm 24h

0.03 ppm 1 year
Particulate matter 150 µg/m3 24h
50 µg/m3 1 year
25 µg/m3 24h
Sulfates 25 µg/m3 24h

Vinyl chloride 0.01 ppm 24h

Lead 1.5 µg/m3 3 months

 You can’t have accuracy without good precision.
But a precise result can have a determinate or systematic error.

Accuracy and precision

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Figures of Merit for Precision of Analytical Methods
The precision becomes poorer at low concentrations.
(Also sometimes at high concentrations, as in spectrophotometric measurements
–see spectrometric error, Fig. 16.27.)

Dependence of relative standard deviation on concentration

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Random errors follow a Gaussian or normal distribution.
We are 95% certain that the true value falls within 2σ (infinite population),
IF there is no systematic error.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley) Normal error curve (Gaussian Curve)
 Bias
Bias = m - xi
where m => population mean

xi => measured concentration

 Sensitivity
2 factors limiting sensitivity:
• slope of calibration curve
– steeper slope, greater sensitivity
• reproducibility of measurements
– equal slope, better reproducibility, greater
sensitivity
 Sensitivity
IUPAC defined calibration sensitivity
S = mc + Sbl
where S => measured signal
c => concentration of the analyte
Sbl => instrumental signal for blank
m => slope of calibration line
ignores precision
 Sensitivity
analytical sensitivity => g
g = m/ss
where ss =>standard deviation of the signals
advantages:
- relatively insensitive to amplification factors
- independent of units
disadvantage:
- standard deviation of signal can vary with
concentration
Detection Limit & Quantitation Limit
Instrumental detection limit refers to the minimum
concentration or weight of analyte that can be
detected at a known confidence level and is
usually defined as being equivalent to 3 times the
signal background noise or the 3s-level.
Method or practical quantitation limit refers to the
level at which reliable quantitative analysis can
be performed and is commonly defined at 9s to
15s levels.
 Detection Limit
minimum distinguishable analytical signal => Sm
Sm = Sbl + ksbl
where Sbl => mean blank signal
k => some multiple (normally 3)
sbl => absolute standard deviation of the blank
measure 20-30 blanks over extended period of
time to determine Sbl and sbl
detection limit => cm = (Sm - Sbl)/m
 Raman spectra of Calcium ascorbate

SNR=17
100 ms, 50 um slit

SNR= 5
10 ms, 50 um

10 ms, 20 um SNR=2.8

SNR < 2
10 ms, 10 um

400 600 800 1000 1200 1400 1600 1800 2000

Raman shift, cm-1

 Signal averaging improves S/N

0.1 sec*

1.0 sec

30 sec

400 600 800 1000 1200 1400 1600 1800 2000

Raman shift, cm-1

* spectra were accumulated for period indicated
 Linear Dynamic Range

LOL
Instrument response

LOQ => limit of quantitative

measurement

LOQ LOL => limit of linear

response
Useful range

Concentration
 Selectivity
degree to which a method is free from
interference by other species contained in
the matrix
S = mAcA + mBcB + mCcC + Sbl

where S => analytical signal

cA, cB, cC=> concentrations of A, B, and C,
mA, mB, cC => calibration sensitivities of A, B, and C,
respectively, slope of calibration curve
Sbl => instrumental signal of blank
 Selectivity
kB,A = mB/mA and kC,A = mC/mA
where kB,A => selectivity coefficient for
B with respect to A
kC,A => selectivity coefficient for
C with respect to A
yielding
S = mA(cA + kB,AcB + kC,AcC) + Sbl
 The units ppm or ppb are used to express trace concentrations.
These are weigh or volume based, rather than mole based.

m
m m
m m

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

This is a time plot for analysis of the same sample, assumed to have only
random distribution, to check for errors in a method.
At 2s, there is a 1 in 20 chance a value will exceed this only by chance.
At 2.5s, it is 1 in 100.

Typical quality control chart

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Select a confidence level (95% is good) for the number of samples analyzed (N).
Confidence limit = x ± ts/√N.
It depends on the precision, s, and the confidence level you select.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 F = s12/s22
You compare the variances of two different methods to see if there is a
significant difference in the methods at a given confidence level.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

QCalc = outlier difference/range.
If QCalc > QTable, then reject the outlier as due to a systematic error.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

The median may be a better indicator of the true value than the mean for
small numbers of observations.

And the range times a factor (K) may be a better measure of spread than the
standard deviation (sr = RKR).

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

A least-squares plot gives the best straight line through experimental points.
Exel will do this for you.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Straight-line or Linear Regression Plot
 Main Purposes of Solid Phase Extraction
Purpose How Performed Usage Application Examples

Removal of interferences Interferences are allowed to pass 50% Removal of proteins from biological fluids,
unretained through the cartridge with fats and lipids from food, ionic compounds
analytes remained sorbed, or analytes from aqueous samples and drugs of abuse
pass through the cartridge, with from urine, and extractions of dioxans from
interferences remaining on the cartridge waste water.

Analyte Concentration Conditions are chose to achieve strong 35 Trace enrichment of ppb of polynuclear
retention values (retentive stationary aromatics from water, trace pesticides in
phase/ weak mobile phase); elution in a urine, caffeine from beverages, and
small volume of volatile organic solvent. therapeutic drugs from plasma.

Phase exchange Analyte present in emulsion, suspension, 5 Exchange of aqueous solvent for
or undesirable solvent is sorbed on SPE nonaqueous one with intermediate dry
cartridge, dried, and eluted with desired nitrogen flush.
solvent
Solid-phase derivatization Specifically coated SPE phases 5 2,4-dinitrophenyl hydrazine-coated
selectively derivatize analytes as they cartridges that selectively derivatize
pass through the cartridge. carbonyl-containing compounds; amines
and polyamines in air; organic acids in
water.
Sample storage and Vapor or liquid samples are collected at 5 Soil gas analysis; trace organics in water.
transport factory or in field on an SPE cartridge or
disk and transported to laboratory.
 Comparison of Extraction Methods for Sample Preparation of Solids

Parameter Sonication Soxhlet Soxhlet SFE ASE (ESE) Microwave- Microwave-

(traditional) (modern) Assisted Assisted (open
(closed container)
container)
Sample size, g 20-50 10-20 10-20 5-10 5-15 2-5 2-10

Solvent 100-300 200-500 50-100 10-20* 10-15 30 20-30

volume, ml
Temperature, Ambient-40 40-100 40-100 50-150 50-200 100-200 Ambient
°C
Pressure Atmospheric Atmospheric Atmospheric 2000-4000 psi 1500-2000 psi 1500-2000 psi Atmospheric

Time, hr 0.5-1.0 12-24 1-4 0.5-1.0 0.2-0.3 0.2-0.3 0.1-0.2

Degree of 0 0 ++ +++ +++ ++ ++

Automation**
Number of High 1 6 44 24 12 12
Samples***
Cost§ Low Very low Moderate High High Moderate Moderate

* When organic modifier is used to effect polarity

** For the most complete commercial instrument;0= no automation, += some automation, ++= mostly automated, ++= fully automated
*** Maximum number that can be handled in commercial instruments
§ Very low = < $1000, Low= $10,000, Moderate= $10,000-20,000, High= > $20,000
 Modern Extraction Methods for Solid Samples

Method of Sample Principles of Technique Comments

Accelerated Sample is placed in a sealed container Greatly increased speed of liquid-solid extraction process and is
(enhanced) solvent and heated to above its boiling point, automated. Vessel must withstand high pressure; extracted sample
extraction (ASE or causing pressure in vessel to rise; in diluted form requires further concentration; safety provisions are
ESE) extracted sample is automatically required.
removed and transferred to vial for
further treatment
Automated Soxhlet A combination of hot solvent leaching Manual and automated versions are available; uses less solvent than
extraction and Soxhlet extraction; sample in traditional Soxhlet and solvent is recovered for possible reuse.
thimble is first immersed in boiling Extraction time is decreased due to two-step process.
solvent then thimble is raised for
Soxhlet extraction with solvent
refluxing.
Supercritical fluid Sample is placed in flow-through Automated and manual versions are available; to affect "polarity"
extraction (SFE) container and supercritical fluid (such of supercritical fluid, density can be varied and solvent modifiers
as CO2) is passed through sample; after added. Collected sample is usually concentrated and pure because
depressurization, extracted analyte is CO2 is removed after extraction; matrix has an effect on extraction
collected in solvent or trapped on process.
adsorbent, followed by desorption by
rinsing with solvent.
Microwave-assisted Sample is placed in an open or closed Extraction solvent can range from microwave-absorbing (MA) or
extraction (MASE) container and heated by microwave non-microwave-absorbing (NMA); in MA case, sample is placed in
energy, causing extraction of analyte. high-pressure, non-microwave-absorbing container and heated well
above its boiling point. Also in MA case, the sample and solvent
can be refluxed at atmospheric pressure, analogous to solid-liquid
extraction, in NMA case, container can be open, with no pressure
rise, safety provisions are required.
 Modern Extraction Methods for Solid Samples
Method of Sample Principles of Technique Comments

Accelerated Sample is placed in a sealed container Greatly increased speed of liquid-solid extraction process and is
(enhanced) solvent and heated to above its boiling point, automated. Vessel must withstand high pressure; extracted sample
extraction (ASE or causing pressure in vessel to rise; in diluted form requires further concentration; safety provisions are
ESE) extracted sample is automatically required.
removed and transferred to vial for
further treatment
Automated Soxhlet A combination of hot solvent leaching Manual and automated versions are available; uses less solvent than
extraction and Soxhlet extraction; sample in traditional Soxhlet and solvent is recovered for possible reuse.
thimble is first immersed in boiling Extraction time is decreased due to two-step process.
solvent then thimble is raised for
Soxhlet extraction with solvent
refluxing.
Supercritical fluid Sample is placed in flow-through Automated and manual versions are available; to affect "polarity"
extraction (SFE) container and supercritical fluid (such of supercritical fluid, density can be varied and solvent modifiers
as CO2) is passed through sample; after added. Collected sample is usually concentrated and pure because
depressurization, extracted analyte is CO2 is removed after extraction; matrix has an effect on extraction
collected in solvent or trapped on process.
adsorbent, followed by desorption by
rinsing with solvent.
Microwave-assisted Sample is placed in an open or closed Extraction solvent can range from microwave-absorbing (MA) or
extraction (MASE) container and heated by microwave non-microwave-absorbing (NMA); in MA case, sample is placed in
energy, causing extraction of analyte. high-pressure, non-microwave-absorbing container and heated well
above its boiling point. Also in MA case, the sample and solvent
can be refluxed at atmospheric pressure, analogous to solid-liquid
extraction, in NMA case, container can be open, with no pressure
rise, safety provisions are required.
 Comparison of Extraction Methods
Parameter Sonication Soxhlet Soxhlet SFE ASE (ESE) Microwave- Microwave-
(traditional) (modern) Assisted (closed Assisted (open
container) container)

Sample size, g 20-50 10-20 10-20 5-10 5-15 2-5 2-10

Solvent 100-300 200-500 50-100 10-20* 10-15 30 20-30

volume, ml
Temperature, Ambient-40 40-100 40-100 50-150 50-200 100-200 Ambient
°C
Pressure Atmospheric Atmospheric Atmospheric 2000-4000 1500-2000 psi 1500-2000 psi Atmospheric
psi

Time, hr 0.5-1.0 12-24 1-4 0.5-1.0 0.2-0.3 0.2-0.3 0.1-0.2

Degree of 0 0 ++ +++ +++ ++ ++

Automation**
Number of High 1 6 44 24 12 12
Samples***
Cost§ Low Very low Moderate High High Moderate Moderate

* When organic modifier is used to effect polarity

** For the most complete commercial instrument;0= no automation, += some automation, ++= mostly automated, ++= fully automated
*** Maximum number that can be handled in commercial instruments
§ Very low = < $1000, Low= $10,000, Moderate= $10,000-20,000, High= > $20,000
 Extraction Methods for Various Types of Samples and Analytes

Sample

Solid Liquid

Organic
Analytes

Metals

Organic Solid Phase Solid Phase Liquid/liquid

Analytes Microwave Acid Extraction Extraction
Digestion Digestion Micro-
extraction

Supercritical Accelerated
Soxhlet Ultrasonic
Fluid Solvent
Extraction Extraction Dissolved Metals
Extraction Extraction

Chelation/Organic Ion Exchange Solid

Extraction Phase Extraction
 METHODS FOR ANALYSIS OF AIR POLLUTANTS BY IMPINGER METHODS
Compound Absorbing solution Analytical method Range Interferences
Ammonia Dilute sulfuric acid React with phenol to form blue 20-700 Some metal ions
indenophenol, Colorimetric micrometers/m3 (EDTA prevents some
measurement interference)
LOD 0.2
micrometers/ml in
solution
Nitrogen Triethanol amine, o- React with sulfanilamide and 8- 20-700 HNO2, N2O3
dioxide methyl-phenol, sodium anilino-1-naphthalenesulfonic micrometers/m3
metabisulfite acid- colorimetric measurement

Sulfur Sodium React with formaldehyde and 500 ml/m3 to 10 None (note high
dioxide tetrachloromercurate pararosaniline, Colorimetric micrometers/m3 toxicity of abs. soln)
measurement
Phosgene 4-(4’-nitro-benzyl) Colorimetric measurement Down to 40 Acid chlorides, high
pyridine in microliters/m3 humidity
diethylphthalate
Chlorine Methyl orange at pH3 Bleaching of the methyl orange is Down to 1 ml/m3 in Free bromine, SO2,
measured colorimetrically air. 5-100 NO2, (used for Cl
micromoles/ 100 ml spills, in emergences)
of soln
Ozone and Buffered KI soln I3 formed is measured 0.01-10 ml/ m3 in NO2
oxidizers colorimetrically air

Acrolein 4-hexyl-resorcinol in ethyl Colorimetric measurement Down to 0.01 Dienes (slight)

alcohol and trichloroacetic ml/m3 in air
acid
 EXAMPLES OF COLORIMETRIC AIR SAMPLING TUBES
Compound Range Description Interference
Mercury vapor 0.1-2 Hg reacts with CuI reagent to give a Cl2 gives low
mg/m3 yellow-orange complex readings

Carbon 5-150 CO reacts with iodine pentoxide giving I2, Acetylene will
monoxide ml/m3 and a preconditioning layer removes interfere
halogenated hydrocarbons, benzene, etc.

Ozone 0.05-1.4 Blue indigo dye is cleaved and bleached to Cl2 and NO2 when
ml/m3 white present above 5
ml/m3 will turn
indigo gray
Sulfur dioxide 0.5-5 SO2 react with blue complex of I2 and H2S will make
ml/m3 starch, changing to white indicator gray

Tetrachloro- 5-50 ml/m3 First layer contains MnO4- which cleaves Free halogens,
ethylene the analyte forming Cl2, which reacts in hydrogen halides
second layer with N,N’-diphenylbenzidine and easily cleaved
to give a gray-blue product halocarbons
 SORBENT MATERIALS FOR AIR SAMPLING
Sorbent Useful for Desorption method

Tenax (polyphenylene oxide) Nonpolar VOC with BP from Thermal desorption

approx. 40-200 ̊C

Carbon molecular sieve C2-C5 hydrocarbons Thermal desorption

Activated charcoal Low to medium boiling polar Solvent extraction

and nonpolar organics

Polyurethane foam Polar and nonpolar Solvent extraction

semivolatile compounds

Activated silica Amines and polar organics Solvent extraction

Graphitized carbon C4 to C14 hydrocarbons, Thermals desorption, Solvent

heavy organics such as PCBs desorption

XAD-2 resin Semivolatiles, PAH Solvent desorption

 SOME COMMON COLORIMETRIC REAGENTS
Analyte Color system Measurement wavelength
(nm)
Metals

Cr (VI) 1,5-Diphenylcarbazide 540

Pb Dicyclohexyl-18-crown-6-dithizone 512
Fe(III) Thiocyanate 460
Fe(II) Pyrocatecol violet 570
Cd Iodide/Malachite green 685
Hg 2-Pyridylketone 2-quinolylhydrozone
Organics
Phenol 1-nitroso-2-napthol/Ce(IV)
Inorganic Ions
NO2- TiCl3/sulfanilamide 530
SO42- Fe(III)/HClO4 355
CN- Isonicotinic acid, 3-methyl-1-phenyl- 548
2-pyrazoline-5-one
Gases
O3 KI 352
NH3 Glutamate dehydrogenase 340
Candidates for electrochemical detection: Biomedical
Acetylcholine* Neutral phenols
Amino acids* Nitrosothiols
Benzoic acids Oxalate
Cinnamic acids Peptides*
Coenzymes Phenylpropionic acids
DNA adducts Phenylpyruvic acids
Enzymes Thiols and disulfides
Estrogenic hormones Tryptophan metabolites
Glucose* Tyrosine metabolites
Lactic acid* Vitamins
Mandelic acids
* Require chemical or enzymatic derivatization before detection.
 Candidates for electrochemical detection: Ions
Bromide Nitrite
Cyanide Sulfite

Candidates for electrochemical detection: Pharmaceutical

Alkaloids Disulfides
Analgesics L-DOPA and related
compounds
Antibiotics Nitrogen heterocycles
Anticancer Phenothiazines
Antimalarial Thiols
β-mimetics and β-blockers Tricyclic antidepressants
Candidates for electrochemical detection:

Environmental and Industrial

Analines Herbicides
Antioxidants Naphthols
Aromatic amines PCB metabolites
Biphenyls Peroxides
Chelating agents Pesticides
Ethylenethiourea Phenols
Explosives
 Typical Functional Groups

Oxidizable Reducible
Aromatic amines Aliphatic nitro
Ascorbic acids Aromatic nitro
Hydroquinones Azo compounds
Indoles Azomethine
Phenols Nitrosamines
Phenothiazenes N-oxides
Thiols Organometallics
Vanillyl Peroxides
Xanthines Quinones and Thioamides
Standard Calomel Reference Electrodes of the Type //
KCl/MCl(satd.)/M
MCl/M KCl E˚’ at 25˚C D(E˚’)
25 dt
(mV deg-1 at
25˚C)
AgCl/Ag 3.5 M (at 25˚C) 0.205 -0.73
Saturated 0.199 -1.01
Hg2Cl2/Hg 0.1 M (at 25˚C) 0.336 -0.08
1.0 M (at 25˚C) 0.283 -0.29

3.5 M (at 25˚C) 0.250 -0.39

Saturated 0.244 -0.67

 EXAMPLES OF ION-SELECTIVE ELECTRODES
Electrode Type Concentration Interferences
Range
Ammonia Gas sensing 1-5 X 10-7 M Volatile Amines

Chloride Solid state 1-5 X 10-5 M OH-, S-2, Br-, I-, CN-

Fluoride Solid state Saturated to 0.02 ppm OH-

Lead (Pb+2) Solid state 0.1-10-6 M Ag+, Hg+2, Cu+2, high

Cd+2 or Fe+
Oxygen Gas sensing 0-14 ppm

Silver or Sulfide Solid state 1-10-17 M (Ag+ or S-2) Hg+2

Water hardness (M+2) Liquid membrane 1-6 X 10-6 M Na+, Cu+2, Zn+2, Fe+2,
Ni+2, Sr+2, Ba+2, K+
Calcium (Ca+2) Liquid membrane 1.0-5 X 10-7 M Pb+2, Na+, Hg+2, H+,
Fe+2, NH4, Mg+2
 Relative Sensitivity of Some Electrochemical Techniques
Technique Limit of Detection for
Pb(II)
Ion selective electrode 10-5 M
DC polarography at DME 10-6 M
Differential pulse 10-7 M
polargraphy at SMDE
Differential pulse ASV at 10-10 M*
HMDE
DC ASV at mercury film 10-11 M*
Square-wave ASV at 10-12 M*
mercury film
* Deposition for 360 seconds; LOD varies with deposition time;S(H)MDE = (hanging)
mercury drop electrode