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INSTRUMENTAL METHODS OF ANALYSIS: AN INTRODUCTION


Analytical methods are usually classified as being either classical or instrumental. In classical methods, also
known as wet-chemical methods, the measurement depends on the chemical properties of the sample. A reagent is
made to react completely with the analyte and the relationship between the measured signal and the analyte
concentration is determined by chemical stoichiometry. Separation of components of interest in a sample is by
precipitation, extraction or distillation. Qualitative analyses of the separated components are performed based on
colors, boiling or melting points, solubility in different solvents, odors, optical activities or refractive indices of products
formed upon treatment with reagents. Quantitative analyses is done using gravimetric or volumetric measurements.
Instrumental methods of analysis are based on the measurement of physical or chemical properties of the
analyte. Separation of components of complex mixtures are performed using chromatography and electrophoretic
techniques. Quantitative analyses is based on measurements of physical properties like conductivity, electrode
potential, light absorption or emission, mass-to-charge ratio and fluorescence.
Classical
More suitable for analysis of major constituents
Used to certify analytical standards
Generally cheaper
More accurate and precise
More robust and less susceptible to environmental
fluctuations

Instrumental
Ability to perform trace analysis
Most are multi-channel techniques
Shorter analysis time
Amenable to automation
Large numbers of samples may be analyzed quickly
Less skill and training required

Table 1. Types of Instrumental Methods of Analysis


Classification
Characteristic Properties
A. Spectrometric Methods
Emission of radiation

B. Chromatographic Methods
C. Electrochemical Methods

D. Miscellaneous Methods

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Instrumental Methods
Emission spectroscopy (X-ray, UV, visible, electron,
Auger), fluorescence, phosphorescence and
luminescence (X-ray, UV and visible)
Absorption of radiation
Spectrophotometry and photometry (X-ray, UV, IR);
photoacoustic spectroscopy; nuclear magnetic
resonance and electron spin resonance
spectroscopy
Scattering of radiation
Turbidimetry; nephelometry; Raman spectroscopy
Refraction of radiation
Refractometry; interferometry
Diffraction of radiation
X-ray and electron diffraction methods
Rotation of radiation
Polarimetry; optical rotary dispersion; circular
dichroism
High Performance Liquid Chromatography
Gas Chromatography
Electrical potential
Potentiometry
Electrical charge
Coulometry
Electrical current
Amperometry; polarography
Electrical resistance
Conductometry
Mass-to-charge ratio
Mass spectrometry
Thermal characteristics
Thermal gravimetry and titrimetry; differential
scanning calorimetry; differential thermal analyses;
thermal conductometric methods
Radioactivity
Activation and isotope dilution methods

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Analytical Instruments
An instrument for chemical analysis converts information about the physical or chemical characteristics of the
analyte to information that can be manipulated and interpreted by a human. Thus, an analytical instrument can be
viewed as a communication device between the system under study and the investigator. To retrieve the desired
information from the analyte, it is necessary to provide a stimulus, which is usually in the form of electromagnetic,
electrical, mechanical, or nuclear energy. The stimulus elicits a response from the system under study whose nature
and magnitude are governed by the fundamental laws of chemistry and physics. The resulting information is contained
in the phenomena that result from the interaction of the stimulus with the analyte. (Figure 1.1)

TRANSDUCER
OR
DETECTOR

Stimulus

Chemical
system

Energy source

SIGNAL
PROCESSOR
COMPONEN
T

READ-OUT
DEVICE

Analytical signal
Electrical signal

SIGNAL GENERATOR

Figure 1. Diagram showing the general components of an instrumental measurement


The signal generator consists of the chemical system interacting with the stimulus from the energy source
which results in the production of an analytical signal reflecting the presence and usually the concentration of the
analyte. The transducer or detector transforms the analytical signal produced by the signal generator into an electrical
signal. The signal processor modifies and cleans up the electrical signal to make it more convenient to interpret.
Finally, the read-out device converts the electrical signal to a form usable to the analyst.
Table 2. Examples of Instrument Components
Instrument
Energy Source
Analytical
(stimulus)
Information

Photometer
Atomic
emission
spectrometer
Coulometer

Tungsten
lamp
Inductively
coupled
plasma
Direct-current
source

pH meter

Sample/glass
electrode

Mass
spectrometer

Ion source

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Information
Sorter

Input
Transducer

Attenuated
light beam
UV or visible
radiation

Filter

Photodiode

Monochromator

Photomultiplier
tube

Data
Domain of
Transduced
Information
Electrical
current
Electrical
current

Charge
required to
reduce or
oxidize
analyte
Hydrogen ion
activity

Cell potential

Electrodes

Time

Glass electrode

Glass-calomel
electrodes

Electrical
voltage

Mass-tocharge ratio

Mass analyzer

Electron
multiplier

Electrical
current

Signal
Processor /
Readout
Amplifier/
LED display
Amplifier/
Digital
display
Amplifier/
Digital
timer

Amplifier/
Digital
display
Amplifier/
Computer
system

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Calibration of Instrumental Methods


Calibration determines the relationship between the analytical response and the analyte concentration.
Usually this is determined by the use of chemical standards. There are several types of calibration procedures:
(1) Comparison with standards, (2) External standard calibration, (3) Standard addition method, and (4) internal
standard method.
Comparison with standards may be done by direct comparison or titrations. In direct comparison, the property
of the analyte is compared with standards such that the property being tested matches the standard. For example, in
early colorimeters, the color produced as the result of a chemical reaction of the analyte was compared with the color
produced by reaction of standards. If the concentration of the standard was varied by dilution, for example, it was
possible to obtain a fairly exact color match. The concentration of the analyte was then equal to the concentration of
the standard after dilution. Titrations are among the most accurate of all analytical procedures. In a titration, the
analyte reacts with a standardized reagent (titrant) in a reaction of known stoichiometry. Usually the amount of titrant
is varied until chemical equivalence is reached, as indicated by the color change of a chemical indicator or by the
change in an instrument response. The amount of the standardized reagent needed to achieve chemical equivalence
can then be related to the amount of analyte present.
An external standard is prepared separately from the sample. External standards are used to calibrate
instruments and procedures when there are no interference effects from matrix components in the analyte solution. A
series of such external standards containing the analyte in known concentrations is prepared. Ideally, three or more
such solutions are used in the calibration process. Calibration is accomplished by obtained the response signal
(absorbance, peak height, peak area) as a function of known analyte concentration. A calibration curve is prepared by
plotting the data or by fitting them to a suitable mathematical equation, such as the slope-intercept form used in the
method of linear least squares. The response signal is then obtained for the sample and used to predict the unknown
analyte concentration from the calibration curve or best-fit equation.
Standard-addition methods are particularly useful for analyzing complex samples in which the likelihood of
matrix effects is substantial. One of the most common form of standard-addition involves adding one or more
increments of a standard solution to sample aliquots containing identical volumes. This process is often called spiking
the sample. Each solution is then diluted to a fixed volume before measurement.
An internal standard is a substance that is added in a constant amount to all samples, blanks, and calibration
standards in an analysis. Calibration involves plotting the ratio of the analyte signal to the internal-standard signal as a
function of the analyte concentration of the standards. This ratio for the sample is then used to obtain their analyte
concentration from a calibration curve.
Signals and Noise
Every analytical measurement is made up of two components. One component, the signal, carries information
about the analyte that is of interest to the scientist. The second, called noise, is made up of extraneous information
that is unwanted because it degrades the accuracy and precision of an analysis and also places a lower limit on the
amount of analyte that can be detected.
Chemical analyses are affected by two types of noise: chemical noise and instrumental noise. Chemical noise
arise from a host of uncontrollable variables that affect the chemistry of the system being analyzed. Examples include
undetected variations in temperature or pressure that affect the position of chemical equilibria, fluctuations in relative
humidity that cause changes in the moisture content of samples, vibrations that lead to stratification of powdered
solids, changes in light intensity that affect photosensitive materials, and laboratory fumes that interact with samples
or reagents. Instrumental noise is associated with each component of an instrument, i.e. the source, input transducer,
signal-processing elements, and the output transducer. Noise that is observed is usually a complex composite of
several sources of noise that cannot be fully characterized. An example is environmental noise which is a composite of
different forms of noise that arise from surroundings.

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Selecting an Analytical Method


There is an enormous array of tools for carrying out chemical analyses. Selection of a suitable method may be
guided by answering the following questions:
(1) What accuracy is required?
(2) How much sample is available?
(3) What is the concentration of the analyte?
(4) What components of the sample might cause interference?
(5) What are the physical and chemical properties of the sample matrix?
(6) How many samples are to be analyzed?
Other considerations in method choice are speed, ease and convenience, skill required of operator, cost and
availability of equipment and per-sample cost.

References:
Harris, DC (2005). Exploring Chemical Analysis 3rd Ed. W.H. Freeman and Company: New York
Skoog, DA, Holler, FJ and Crouch, SR (2007). Principles of Instrumental Analysis 6th Ed. Thomson Brooks/Cole: USA.
pp.1-24
Tissue, BM (2013). Basics of Analytical Chemistry and Chemical Equilibria. John Wiley & Sons, Inc.: New Jersey.
https://facultystaff.richmond.edu/~rdominey/301/local/Intro_Instrum_Analysis.pdf (accessed July 01, 2014)

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