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CA:A@7E5?@FJ

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10
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11
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12
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15
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16
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18
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19
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20
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21
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22
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23
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24
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25
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47
 READ OUT MODULES

DC Signals produced in spectrophotometers are

amplified and the voltage is read on analog meters,
recorders, voltmeters or on computer displays.

High gain amplifiers are subject to significant drifts

and offset errors. The presence of low frequency
noise restricts the signal to noise ratio.

Therefore the signal is modified by AC amplifier and

converted back to DC output by a demodulator or
rectifier.
Sometimes the modulation is performed by
interrupting the beam of radiation by a rotating fan
or a chopper. The rotating chopper blocks the light
beam physically. Therefore the radiation alternates
between full intensity and total blackout resulting in
a square wave at the chopping frequency.

Alternatively the light sources can be pulsed

electronically to produce the same effect.
An AC Amplifier tuned to alternate in phase with the
chopper passes the sinusoidal signal during the
positive half cycle and blocks it during the negative
half cycle. This is a form of rectification. Usually a
reference signal is provided by the chopper to drive
a switch. The reference signal is of the same
frequency and has a fixed phase relationship with
the analytical signal.
Synchronous demodulation results in a DC signal
that can be sent through a low pass filter to provide
the final dc output.

The tuned amplifier, synchronous demodulator,

reference input and the low pass filter are integrated
into a single electronic module called as

lock in amplifier . Such amplifiers allow recovery

of signals which are otherwise obscured by noise.
Some lock-in amplifiers directly pass the sinusoidal
wave during the first half cycle and invert it during
the other half cycle to provide a fluctuating DC
signal. Such a signal is relatively easy to filter with a
low pass filter. Such devices are called analog
multipliers and used extensively in synchronous
demodulators.

A lock-in amplifier is generally relatively free of noise

because extraneous signals of different frequencies
and phase are rejected by the system.
MODULATOR DESIGNS
EFFECT OF MODULATION OF DC SIGNAL
 SOFTWARE METHODS

A variety computer programs are available to

enhance the signal to noise ratio. These include
various types of averaging , digital filtering, Fourier
transformation and correlation techniques which are
applicable to non-periodic or irregular wave forms
such as absorption spectrum, signals with no
reference wave and periodic signals.

These include:
i) Ensemble averaging
ii) Box car averaging
iii) Digital filtering
iv) Correlation Methods
a) Raw Spectrum (b) Quadratic 5 point smooth curve
(c) Fourth degree 13 point smooth curve (d) Tenth degree 77 point
smooth curve
For more information

i) G.Holic and G.M.Hieftje, Contemporary

topics in Analytical and clinical chemistry ,
D.M.Herculic et al., eds., Vol 3, pp 153 216
New York Plenum Press, 1978

ii) G.M.Hieftje and G.Horlick American

laboratory 1981, 13 (3), 76.
 COMMERCIAL INSTRUMENTS
A number of colorimeters and spectrophotometers are
available commercially. Their prices range from a few
thousand rupees to several lakhs depending on the type
of analysis and sophistication. At the low end are filter
photometers and colour comparators, and at the higher
end are uv-visible-near infrared spectrophotometers
fitted with computer controlled instrument operations
and microprocessors for data handling.
 COLOUR COMPARATORS

These are relatively inexpensive non-scanning filter

photometers useful for dedicated analysis of only a
few analytical parameters. The colour development
is obtained by adding the specified quantity of the
reagent to the sample which can be compared with a
predetermined colour chart. The concentration is
also marked on the colour chart. Colour comparators
are adequate for rough estimates of the analyte for
process monitoring or field studies or for specific
analysis such as chlorine in swimming pools, gold
estimation in jewelry etc.
 FILTER PHOTOMETERS

Colorimeters or filter photometers are single beam,

rugged direct reading instruments useful for visible
range. They use a tungsten lamp or LED as a source,
a lens to collimate, a filter for wavelength selection
and a barrier layer cell or a photodiode as the
transducer. The read out is in absorbance or
transmittance mode or in terms of concentration.
The 100% transmittance (or zero absorbance) is
adjusted with the solvent or the reference solution or
simply by changing the voltage applied to the lamp.
In modern instruments reference signal is stored in
memory. Then the reference is removed and sample
is inserted in the light path. The ratio of the sample
signal to that of reference is computed and the
absorbance is calculated and displayed.
FILTER PHOTOMETER
LED BASED COLORIMETER
 SINGLE BEAM SPECTROPHOTOMETERS

In general the term spectrophotometer is used for

visible (350 800 nm), uv-visible (190 900 nm) or
uv visible near IR (190 3000 nm). Single beam
grating instruments are relatively inexpensive, rugged
and readily portable. These are used for quantitative
analysis and scanning.

The most celebrated filter photometer is spectronic 20

which was introduced in the mid 1950s. Modified
versions of this instrument employing concave
gratings and microprocessors are still being offered.
As in filter photometers, here also wavelength scan
is performed with the reference solution and stored
in the computer memory. Then the samples are
scanned and ratioed. The output options include log
absorbance, transmittance, derivative spectra,
overlaid spectra, repetitive scans, peak location,
peak height and peak area, kinetic measurements,
flow through cells etc.

Single beam instruments have the inherent

advantages of high energy throughput, low signal to
noise ratios and simple sample compartments. Their
disadvantage is the baseline stability.
 DOUBLE BEAM SPECTROPHOTOMETERS
In double beam spectrophotometers the
monochromatic radiation is split into two equal radiant
power beams. One beam passes through the sample
and other through a reference solution or blank.

The output of the reference beam is kept constant by:

a) Employing a feed back loop to regulate photodetector

sensitivity via dynode voltage or

b) Controlling slit width by means of servomotors or

c) By measuring the ratio of P/Po continuously

In these instruments uv or visible radiation enters
the Czerney - Turner configuration. The radiation is
collected in the photodiode. As long as the
intensities are identical the amplifier has a dc output.
Any difference in the intensities results in an AC
signal at the chopping frequency. The unbalanced
signal gives an ac output which is amplified and
used to drive an optical attenuator into or out of the
reference. The servomotor can also be connected to
a recorder pen which provides the scan.
Alternatively the servomotor can be digitized and
computer output of the scans may be obtained.
QUANTITATIVE ANALYSIS BY SPECTROPHOTOMETRY
1. METHOD DEVELOPMENT
In principle any coloured solution can be subjected to
chemical analysis by spectrophotometry. Numerous reagents
react selectively with non absorbing species to give products
that absorb strongly in the ultraviolet and visible regions. A
vast literature exists which detail reactions of this type.
Typical inorganic regents include: thiocyanate ion for Fe, Co
and Mo.

Hydrogen peroxide for Ti, V, Cr

Iodide ion for Bi, Pd, Td
Organic chelating agents: DOTC for Cn, Dithiozone for Pb,
1,10-Phenanthroline for Fe,
DMG for Ni etc.
Typical method development procedure involves:

i) Determination of the wavelength for maximum

absorption .

ii) Optimization of the experimental variables for

completion of the reaction. These include: pH,
reagent concentrations, temperature, stability of
the coloured product, effect of high electrolyte
concentrations, stoichiometry of the complex etc.
iii) Preparation of the calibration curve and

v) Evaluation of the interfering substances, matrix

effect, and other ionic species.

vii) Determination of molar absorptivity, Sandell

sensitivity, statistical evaluation of the bias.

vi) Applications in diverse matrices.

SIMULTANEOUS SPECTROPHOTOMETRIC ANALYSIS

Two dissimilar chromophores having different !max

and " if present in a given mixture can be analysed if
their absorbances are additive.

The procedure involves measurement of the total

absorbance of the mixture at both !max . Then two
simultaneous equations can be written ,

C1("1)!1 + C2("2)!1 = A!1

C1("2)!2 + C2("2)!2 = A!2

The equations are solved for C1 and C2.

Theoretically any number of components can be
determined by setting up simultaneous equations. But
at best 3 component systems are the limit. The !max of
the components must differ by at least 30 nm.
 DIFFERENTIAL OR EXPANDED SCALE

In spectrophotometry the analog scale varies from

zero absorbance to 100% absorbance. The latter is an
artificial requirement. Therefore when reference
solution transmits more radiant energy than another
standard, scale expansion techniques can be used to
increase the precision. Three cases result:

i. High absorbance method.

ii. Trace analysis method.

iii. Maximum precision method.

 DERIVATIVE SPECTROSCOPY

In derivative spectrophotometry spectra are obtained

by plotting the first or higher order derivative of the
absorbance with respect to wavelength as a function of
wavelength.

In a derivative spectrum the ability to detect and to

measure minor spectral features is considerably
enhanced. The enhanced spectral features can
distinguish between very similar spectra and follow
subtle changes in a spectrum.

Derivative spectrophotometry is also quite useful for

the simultaneous determination of two or more
components in mixtures. Absorption spectra of the
analyte can be extracted from turbid solutions.
Examples:

i) Determination of trace amounts of Mn and

Zn in mixtures by complexion with
5,8-dihydroxy - 1,4 - napthoquinone.

ii) Tryptophan, tyrosine and phenyl alanine contain

aromatic side chains with !max in 240 300 nm region.
These sharp peaks are not apparent in spectra of
typical protein preparations but observed in first and
second derivative spectra.

iii) Derivative methods are widely applied to

pharmaceutical preparations and to vitamin mixtures.
 PHOTOMETRIC TITRATIONS

Photometric titrations are useful for locating the

equivalence point of a titration provided the titrant or
titrand or one of the reaction products absorbs the
radiation. The titration curve is a plot of the
absorbance corrected for volumetric changes as a
function of the titrant. The end point is obtained by
extrapolating the linear portions of the curve.
Photometric titrations can be automated to record a
fixed absorbance or by taking the second derivative.
a) Arsenic (III) with bromate bromide; Bromine absorbs

b) Copper (II) with EDTA; Cu (II) EDTA complex absorbs

c) P tolnidine in butanol with perchloric acid;

P tolidine colour disappears

d) Coloured titrant reacting with the titrand to produce

coloured product absorbing at the same wavelength

e) Bromination of a red dye stuff

f) Formation of two successive complexes

 KINETIC METHODS
In kinetic methods absorbance of the solutions are
measured as a function of time. Therefore the
measurements represent dynamic before attaining
equilibrium regime. A variety of chemical reactions can
be characterized in this way. For example,

1. Determination of trace quantities of iodide in the

reaction
[I ]!
2Ce(IV) + As(III) Ce (III) + As (V)

2. Determination of enzymes as catalysts

3.Determination of ascorbic acid in phosphomolybdenum

blue reaction
KINETICS OF REACTIONS
Kinetic methods can be classified into two types.
Differential methods compute the rate of reaction from
the slope of the absorbance Vs time curve and relate it
to the analyte concentration.

Integral methods use an integrated form of the rate

equation and determine the concentration of the
analyte from the absorbance changes that occur over
various time intervals. Curve fitting methods are used
to fit a mathematical mode to absorbance versus time
curve and compute the parameters of the model
including the analyte concentration.
Kinetic methods based on the reactions with half lives
greater than about 10 seconds are amenable for
spectrophotometric follow up. Temperature control of
to 0.10C required. In many commercial instruments
accessories are available as modules that can be
attached to spectrophotometers for kinetic
measurements.

For reactions with half lives of less than 10 seconds,

stopped flow mixing technique can be adopted. In this
technique streams of reagent and sample are mixed
rapidly and the flow of mixed solution is stopped
downstream suddenly. The reaction is then monitored.
 COMPOSITION OF COMPLEX IONS

The most common techniques used for complex ion

studies are :

1. Method of continuous variation

2. The mole ratio method and

3. The slope ratio method

COMPOSITION OF A COMPLEX
YOE S MOLE RATIO METHOD
 FLOW INJECTION ANALYSIS

FIA ( ) involves injection of a measured amount of

liquid sample into a moving non segmented stream of
reagent. As the injected sample plus reagent carrier
proceeds down a narrow tube propelled by a constant
flow pump the sample reacts to form a coloured
complex under dynamic flow conditions which passes
through a flow cell attached to the spectrophotometer
continuously. A sharp signal develops followed by a
trailing edge.
The peak height is proportional to the
concentration of the analyte. The sample peak can be
detected in about 15 sec after injection. Since the
system operates under dynamic conditions the
sample clears out of the reactor in 15 seconds and
be ready for another analysis. The whole system can
be made very compact.

Samples as small as 30 #l and reagent volumes of less

than 1 ml are possible.
 TURBIDIMETRY AND NEPHLOMETRY

The scope of spectrophotometry can be greatly

expanded if the optical inhomogeneity in a sample can
be reproducibly measured.

The presence of suspended matter in stable systems,

thermal density fluctuations, colloidal particles, etc.,
introduce optical inhomogeneity in an otherwise
homogeneous medium that results in elastic scattering
(measured at the same wavelength). The scattered
radiation is preferentially absorbed rather than
transmitted through the sample.
The intensity of the parallel and perpendicularly
polarized components of the electromagnetic radiation
is a function of the relative refractive index, the size of
the particle, the angle of observation relative to the
incident radiation and the concentration of the
scatterer.

The size parameter ($ = 2%r/!) determines the phase

distribution of the scattered radiation around the
scattering center.

The scattering envelope is symmetrical when the size

parameter is smaller than one tenth of the
wavelength and the refractive index of the particle
Is almost same as that of the surrounding medium
(Rayleigh scattering).
As the size parameter reaches one fourth the
wavelength of the incident radiation, scattering is
concentrated in the forward direction.

If the particles are larger than the wavelength of the

incident radiation, scattered intensity would be a very
complex function of the angle of scattering, but still a
large amount of it scattered in the forward direction.
This is known as Mie scattering.
For very large particles, scattering does not depend
upon the wavelength but depends upon the particle
geometry, molecular absorption, sample concentration
and size distribution and sometimes even in the
physical design of the instrument used for
measurement. Therefore the results are essentially
empirical and exhibit variance in the data even though
same calibration standard is used.
There are two methods for measuring the turbidity of a
sample, in the same axis and perpendicular to the
incident radiation. When measurements are performed
in the forward direction analogous to absorbance, it is
called turbidimetry. When the scattered radiation is
measured at right angles to the direction of the
incident beam, it is called Nephelometry .
Usually nephelometric measurements are preferred for
samples having transmittance greater than 90% as in
water and waste water analysis. At 900 the
concentration is least sensitive to variation in particle
size and simple optical systems can be used for the
determination that is relatively free of stray radiation.

When a very narrow beam of radiation strikes the

surface of the sample at a very small angle, part of the
reflected beam strikes the water surface and escapes
into a light trap. The remaining portion enters the
sample at 450 angle. If particle turbidity is present, then
radiation scattering occurs and some of the scattered
radiation reaches the detector. Such an instrument can
detect turbidities upto 0.01 NTU.
In turbidimetry small amounts of insoluble compounds are
prepared in a state of aggregation so that moderately
stable suspensions are obtained. When light is passed
through such a suspension, the fraction of the energy
dissipated by absorption, reflection and refraction,
scattering etc., is ratioed with respect to the incident
radiation and displayed as absorption or transmittance.

Beer s law is obeyed for such suspensions up to a

particular concentration and analysis can be performed
just like a spectrophotometry. Since the results for
turbidity are at best empirical. Construction of
calibration curves is recommended for every analysis
owing to the uncertainties in reproducibility. The
experimental conditions should also be exactly
reproducible as far as possible.
In turbidimetry the following conditions need to be
adhered to:

1. Concentrations of substances participating in the

reaction

2. Order of mixing and rate of mixing

3. Use of protective colloids such as gelatin, gum

arabic, dextrin, polyvinyl alcohol etc

4. Presence of other salts and

5. Temperature
In theory, any precipitation reaction can be converted
into a turbidimetric procedure provided they can be
prepared in a reproducible manner. Excellent results
in sub PPB levels have been obtained for:

The determination of BaSO4 using glycerol-alcohol

as stabilizer

The determination of phosphate as strychnine

phosphomolybdate

The determination of ammonia using Nessler s

reagent
Nephelometers and turbidimeters resemble filter
photometers in instrumentation. They are also
available as accessories to ultraviolet and visible
spectrophotometers. Such instruments provide a
practical way to continuously monitor turbidity in
water, determination of the clarity of beverages and
pharmaceutical preparations, product quality
control, boiler feed waters and condensates etc.,
 SPECTRA OF SOLIDS
Quite often in the real world, turbid liquids, powders
opaque and translucent substances, glossy and
semi-glossy painted surfaces are encountered. The
reflection of the incident radiation falling on such
compounds can be measured with a specular
reflector available as a standard accessory to
spectrophotometers. Since every contact of a light
beam with a solid particle results in specular
reflection at every few millionth of a centimeter any
surface appears uniformly bright in all directions.
This is referred as sheen or gloss. This is the diffuse
component of any component that is coloured
otherwise it appears white.
The whiteness and reflectance increase as the
diameter of the component decreases. The reflectance
of a substance follows a semi-empirical relationship,

S = log Po/P = k bcd3

D4+$!4

where d is the particle diameter, ! is the wavelength,

c is the concentration, b is the path length, and k is a
geometric factor, D is a method constant .
For using reflectance a mgo standard is employed as a
reference and all other measurements are made with
reference to this standard.

Reflectance measurements are routinely performed in

paints, textiles and paper industries.
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