UV-VIS AAS AES
- molecule, ions or - The electrons of the Uses the intensity of
Principle atoms absorbs atoms in the atomizer can
ultraviolet or visible be promoted to higher
radiation it undergoes orbitals (excited state) for
a change in its excited a short period of time
state. (nanoseconds) by
absorbing a defined
- determine the quantity of energy
absorbance, we can (radiation of a given
calculate wavelength). This amount
concentration of of energy, i.e.,
analyte. wavelength, is specific to
a particular electron
transition in a particular
element
Intrusment -filter photometer, - Single or double beam
single or double beam optics, Atomizer( flame,
spec, diode array spec, electrothermal atomizer)...
sample cell, detector
Accuracy -Under normal - When spectral and
condition a relative chemical interferences are
error of 1-5% is easy minimized, accuracies of
to obtained 0.5–5% are routinely
possible
- Determinate errors for
electrothermal atomization
are frequently greater than
that obtained with flame
atomization due to more
serious matrix
interferences.
PS ICP-MS
Deals with transitions from the
light emitted from a excited state to the ground
flame, plasma, arc, or state,
spark at a particular
wavelength to Light is directed onto a sample,
determine the quantity where it is absorbed and
of an element in a imparts excess energy into the
sample. The material in a process called
wavelength of the photo-excitation. One way this
atomic spectral line excess energy can be dissipated
gives the identity of by the sample is through the
the element while the emission of light, or
intensity of the emitted luminescence. In the case of
light is proportional to photo-excitation, this
the number of atoms luminescence is called
of the element. photoluminescence. The
intensity and spectral content of
this photoluminescence is a
direct measure of various
important material properties.
Atomization and It is the same as UV-VIS
exitation, Flame or method but the most important
Plasma sources, difference is the dectector
cannot be placed directly along
Multielemental sources axis. Instead we rotate
Analysis that allows it and place it at 90 to the
for the simultaneous resources.
monitoring of many
analytes Fluorometer: the excitation
and emission wavelengths are
selected with absorption or
interference filters. The
excitation source for a
fluorometer is usually a
lowpressure
mercury vapor lamp that
provides intense emission lines
distributed throughout the
ultraviolet and visible region.
Spectrofluorometer: a
monochromator is used to
select the excitation and
emission wavelengths
- When spectral and -The accuracy of a fluorescence
chemical interferences method is generally 1–5%
are insignificant, when spectral and chemical
atomic interferences are insignificant.
emission is capable of - limited by the same types
producing quantitative
results with accuracies of problems affecting other
of 1–5%. spectroscopic methods. In
addition, accuracy is affected
– flame
emission by interferences influencing the
frequently is fluorescent quantum yield
limited by
 chemical
interferences
– plasma
emission
often is
limited by
stray
radiation
from
overlapping

emission lines

Precision -Precision is generally - For absorbances greater -the relative standard -When the analyte’s
worse with very low than 0.1–0.2, the relative deviation for concentration is well above the
absorbances due to the standard deviation for detection limit, the relative
uncertainty of atomic absorption is 0.3– both flame and plasma standard deviation for
distinguishing a small 1% for flame atomization, emission is about 1– fluorescence is usually 0.5–2%.
difference between P0 and 1–5% for 5%
and Pt, and for very electrothermal - The precision
high absorbances atomization. -flame’s or plasma’s
when Pt approaches 0. temperature affect for phosphorescence is often
precision will vary precision limited by reproducibility in
with transmittance preparing samples

for analysis, with relative

standard deviations of 5–10%
being common.

Sensitivity -Sensitivity is – influen – stro – quantum

improved by ced strongly by ngly yield and the effect of
the flame’s influenced temperature and
selecting a composition, by the solution composition
wavelength when position in the temperature affect sensitivity
absorbance is at a flame from of the – the
maximum or by which excitation sensitivity of an
increasing the absorption is source and analysis can be
pathlength. monitored the improved by using an
– influen composition excitation source that
ced by the of the has a greater
sample’s matrix sample emission intensity
matrix (P0) at the desired
– Wit wavelength and by
h plasma selecting an
emission, excitation
sensitivity is wavelength that corresponds
less to an absorption maximum (e).
influenced –
by the
sample
matrix

Selectivity – R – each The selectivity of – Not every compound

arely a element has atomic emission is that absorbs radiation
problem in different set of similar to that of is fluorescent or
molecular energy levels atomic absorption. phosphorescent
absorption and lines very – selectivity between
spectrophot narrow Atomic emission has
an analyte and an
ometry the further advantage
– Atomic interferant is possible
of rapid sequential or
absorption can if there is a difference
 – In be used for the simultaneous in either their
many cases analysis of over excitation or
it is possible 60 elements at analysis. emission spectra
to find a concentrations – The analysis of a
wavelength at or below the sample containing n
at which level of parts per components,
only the millions – therefore, can be
analyte accomplished by
absorbs or measuring the total
to use emission intensity at
chemical n wavelengths
reactions in
a manner
such that the
analyte is
the only
species that
absorbs at
the chosen
wavelength

Detection – – Weak Better than 10-1000 times to

limit absorbers compare to other spec
(forbidden absorbance methods.
transitions)
– Detection
– Metallo
limit can reach ppb
ids and non-
– Wide linear
metals (absorb
range
in UV)
– Metals
with low IP
(alkali metals)

Application Quantitative – determi – Det –

determination of nes the presence ermination
solutions of transition of metals in of alkali and
metal ions, highly liquid samples. akaline earth
conjugated organic Metals include metal (flame
compounds, and Fe, Cu, Al, Pb, emission)
biological Ca, Zn, Cd and especialy in
macromolecules. many more. It biological
also measures fluids and
(Solutions of the tissue
transition metal ions concentrations –
can be colored (i.e., of metals in the
absorb visible light) samples. Typical
because d electrons concentrations
within the metal range in the low
atoms can be excited mg/L range.
from one electronic –
state to another,
Organic compounds,
especially those with a
high degree of
conjugation, also
absorb light in the UV
or visible regions of
the electromagnetic
spectrum,
 charge transfer
complexes also give
rise to colours)

Time, Cost - Relatively rapid, Rapid,250–350 Rapid, sampling rates – Fluorescent

and although additional determinations per hours of 3000 determinations and phosphorescent
Equipment time may be required using flame atomization, per hour have been methods provide a
when it is necessary to 20–30 determinations achieved using an ICP rapid means of
use a chemical with simultaneous analysis and are
reaction to transform a per hour using analysis, and 300 capable
nonabsorbing analyte Electrothermal determinations per
into an absorbing atomization hour with a sequential of automation.
form.
$10,000 to $50,000 for ICP. Flame emission is – relatively
- diversified, from flame atomization and often accomplished inexpensive, ranging
hunder dollars for $18,000 to $70,000 for using an atomic from several hundred
simple or several electrothermal atomization absorption to several thousand
thousand dollars for spectrometer, which dollars, and often are
higher models typically costs very satisfactory for
$10,000–50,000. quantitative
Sequential ICPs range
– work.
in price from $55,000
Spectrofluorometers
to $150,000, whereas
are more expensive,
an ICP capable of
with some models
simultaneous
costing as much as
multielemental
$50,000.
analysis

costs $80,000–
200,000. Combination
ICPs that are capable
of both sequential

and simultaneous
analysis range in price
from $150,000 to
$300,000