COMPARISON OF ATOMIZERS

FOR ATOMIC ABSORPTION SPECTROSCOPY

Introduction
Atomic spectroscopic methods are all based on the interaction of light and analyte atoms in the gas
phase. Thus, a common component of instruments used in atomic spectroscopy is the atomizer, which
converts the analyte in the sample to vapor-phase free atoms that can interact with a light beam. The
properties and efficiency of the atomizer is crucial in determining the characteristics of a atomic
spectroscopic method.
In this experiment, you will compare two methods based on atomic absorption in the gas phase: flame
atomic absorption spectroscopy (FAAS) and graphite furnace atomic absorption spectroscopy (GFAAS).
Specifically, you will compare the detection power (i.e., the ability to detect trace concentrations of
analyte), the linear dynamic range and the measurement precision of these two techniques. You will
also analyze the copper concentration in the laboratory tap water using both methods.

Background
Atomizers
Most atomizers require that the sample be in the form of a solution; introduction of the solution into
the atomizer is usually accomplished by a nebulizer, which converts the solution into a fine mist of
small droplets. Vaporization of the sample requires thermal energy, so that the atomizer is essentially a
reservoir where rapid and high-energy collisions occur between gaseous species. The following are the
atomizers that have been used most commonly in atomic spectroscopy.
• combustion flame atomizers, in which a fuel is burned in the presence of an oxidant. The exothermic
nature of the combustion reaction supplies the thermal energy needed to vaporize the solution
droplets that are introduced by the nebulizer into the flame. Flame atomizers are used for both atomic
absorption and emission spectroscopies, although the former application is more common.
• electrothermal atomizers. In this type of atomizer, the atomizer is a resistive element that is heated
by the passage of a large current. The most common electrothermal atomizer by far is the graphite
furnace atomizer, in which the heating element is a graphite tube. The sample is introduced directly
(usually as a solution) into the graphite tube. Electrothermal atomizers are used almost exclusively for
atomic absorption spectroscopy.
• plasma atomizers. A plasma can be defined simply as a hot gas that contains a significant number of
ions. The mechanism of plasma generation varies, and will be discussed in class. The most common
plasma atomizer is the inductively coupled plasma, but the direct current plasma and the microwave
plasma have also seen some application in atomic spectroscopy. Sample introduction into the plasma
is by nebulization of a solution. Plasma atomizers are the most widely used atomizer in atomic
emission spectroscopy.

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• arc and spark atomizers vaporize the sample through the creation of an electrical discharge between
two electrodes. Arcs and sparks have historically been used as atomizers in atomic emission
spectroscopy, but have been largely replaced by plasma atomizers. Arcs and sparks can be easily used
for the analysis of solid samples, unlike plasmas, and so they still find some limited use for samples
that are not conveniently dissolved.
The two most common atomizers in atomic absorption spectroscopy are combustion flames and
graphite furnaces. We will now discuss in a little more detail the mechanism by which these atomizers
work.

Combustion Flame Atomizers

The following figure gives some idea of the most common type of flame atomizer, complete with the
nebulizer and spray chamber.

combustion
flame

fuel small
spray chamber droplets

oxidant

spoilers

auxiliary
sample oxidant
solution drain

The fuel and oxidant mix in the spray chamber; small droplets of the sample solution are carried along
by this mixture into the combustion region of the flame. The most common fuel is acetylene, C2H2, and
the two most common oxidants are air and nitrous oxide, N2O. The hottest part of the acetylene-air
flame may be about 2200 °C, while the temperature of the N2O-C2H2 flame can get as hot as 3100 °C.
It is possible to adjust the temperature of a flame by changing the fuel:oxidant ratio. A stoichiometric
flame mixture is one in which, theoretically, neither the fuel nor oxidant are present in excess;
stoichiometric flames are generally pretty close to their maximum temperature. A rich (or fuel-rich)
flame is one in which the fuel is present in excess, while a lean flame contains an excess of oxidant.

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The mechanism of combustion is not fully understood, but there are many species in a flame: reactive
radicals, ions, small molecules, and free electrons. The following figure delineates the main regions of
the flame:

secondary
combustion
zone

combustion interzonal
flame region

primary
combustion
zone

fuel/oxidant
mix

The mixed gases flow rapidly through the burner and are ignited at the top of the burner. The reaction
between fuel and oxidant takes place largely in the primary combustion zone; vaporization of solvent
and dissociation of analyte species also occurs in this region. By the time the gases reach the interzonal
region, the combustion reaction is more or less completed; this is the hottest region of the flame, and
the one used for many spectroscopic measurements. The rapidly rising gases entrain the surrounding
air, and create a secondary combustion zone on the outside of the flame, a region that is chemically
oxidizing in nature.
The chemical environment of the flame is complex and, by its very nature, reactive - after all, the
thermal energy of the atomizer is sustained by the chemical reaction between the fuel and oxidant. The
analyte atoms, after volatilization, can undergo a number of reactions, such as ionization and oxidation.
Indeed, some analytes (such as alkali metals) exhibit a significant degree of ionization, while some
others (such as Al, Ba and Sn) form very stable oxides, called refractory oxides. Analytes that form
species that are difficult to dissociate in the flame are sometimes called refractory elements; these
generally benefit from using the hotter N2O flames, and/or from fuel-rich flames, which create a more
reducing chemical environment.

Electrothermal Atomizers

An electrothermal atomizer is constructed using a heating element through which a large current is
passed. The sample is placed on, or in, the atomizer. The temperature of the element can be set by
controlling the current, which is generally increased in a programmed series of steps called a
temperature program. There are usually at least four steps:

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1. a solvent vaporization step;

2. a pretreatment step (sometimes called a charring or ashing step), where organic components of the
matrix are oxidized and the more volatile matrix components are lost;
3. an atomization step, where the analyte (and presumably the rest of the sample) is vaporized; and
4. a cleaning step, where the last remains of the sample are (hopefully) removed.
The ability to control the temperature of an electrothermal atomizer by regulating the current is a big
asset, since we don’t have to evaporate the solvent, vaporize the sample matrix and atomize the analyte
all at once.
By far the most common heating element in electrothermal atomizers is a tube of graphite, into which
the sample solution is deposited. The maximum temperature of these graphite furnace atomizers is
about 3000 °C or so. The following figure gives some indication of how the furnace atomizer is used.

inject
sample water in
argon gas here
graphite
tube

from light source

insulator
water out sample
solution

A small volume (20–40 µL, usually) is deposited into the graphite tube, which is constantly bathed
with an inert gas such as argon. The purpose of the inert gas is twofold: (a) to protect the graphite from
oxidation during atomization, and (b) to provide a chemically inert environment for analyte
atomization, greatly reducing the formation of refractory oxides of the analyte.

Comparison of Atomizer Characteristics

The atomization efficiency is an important property of the atomizer used in atomic spectroscopy. It is
defined as the fraction of analyte species in the sample that will be converted to free atoms in the
atomizer. An atomization efficiency of 1 (or 100%) means that every analyte species in the sample can
be converted into free atoms.
The atomization efficiencies of graphite furnaces almost always exceed that of flames for the following
reasons:

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Atomizer Comparison Background

• sample introduction is far more efficient for furnaces than for flames. The nebulizers used with flame
atomizers are quite wasteful: about 95% of the aspirated sample solution goes down the drain, while
the fine mist that actually gets carried into the flame only constitutes about 5% of the aspirated
solution. Furnace atomizers have no need of a nebulizer.
• the solution droplets only spend a short amount of time (on the order of milliseconds) in the flame,
during which time the flame must evaporate the solvent and dissociate the analyte salt. Less is
demanded of the furnace, since the temperature program usually takes about 2 minutes, and occurs in
steps, leading to greater efficiency.
• after formation of free analyte atoms, the residence time of the analyte in the flame is much shorter
(milliseconds) than for the furnace (1-2 seconds). This means that the analyte atoms in the furnace
can absorb more photons, increasing the absorption signal, than analyte atoms in flames.
• the relatively inert chemical environment of the furnace is less likely to lead to the formation of
stable analyte species than is the case in flame atomizers.
The atomization efficiency in any atomizer cannot be any better than the efficiency of introducing the
sample into the atomizer, so the maximum atomization efficiencies achievable in flames is about
5-10%, and it is frequently less than this value. Of course, the actual efficiency will depend on the
nature of the analyte and on the choice of fuel and oxidant (and, to a lesser extent, on their mixing
ratios). Atomization efficiencies from “clean” aqueous samples can often approach 100% in graphite
furnaces; efficiencies for more complicated sample matrices are often considerably less than 100%.
In summary, furnaces have a number of advantages over flames for sample atomization in atomic
absorption spectroscopy. There are, however, also some disadvantages. Can you think of them?

Figures of Merit
Analytical figures of merit (FOM’s) are commonly used to compare the characteristics different
techniques. Imagine that you are out shopping for a new car: you will probably spend a lot of time
comparing different makes and models before the actual purchase. In making a final decision, you
might be influenced by factors such as price, maintenance, fuel economy, handling, buyer satisfaction,
appearance, etc.
There may be a number of distinct instrumental methods that can be used in the analysis of any
particular chemical species, and many minor variations can exists for each of these methods. Figures of
merit characterize an analytical method so that you can make an informed decision in choosing a
method for a particular application. They can also be used to evaluate the effects of technique
modifications.
Three very important characteristics of any analytical method are
• detection power: the ability of the technique to detect small concentrations of analyte in a sample.
• dynamic range: the range of concentrations over which the technique is useful.
• measurement precision, which characterizes the between-measurement variability of the method.

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Detection Power

The most common FOM used to describe the detection capability of a technique is the limit of
detection, LOD, (sometimes called the detection limit) which is defined by IUPAC as
3s b
LOD =
b1
where sb is the standard deviation of measurements on the blank, and b1 is the slope of the (linear)
calibration curve (the sensitivity, which is another FOM). The LOD is the concentration that
corresponds to a signal that is just detectable above the random noise of the blank measurements. A
sample that contains the analyte at exactly the detection limit will have (approximately) a 50%
probability of being “detected” above the blank noise.
The LOD is a nice figure of merit, even if it is a little abstract (at least, to those who have no
background in statistics - unlike the students of CHM301 at the University of Richmond). There are,
however, two problems with it:
1. The detection limit usually gives an overly optimistic idea of the concentrations that can be reliably
detected; this is usually because the estimate of the blank noise generally does not include a number
of important sources of error, such as sampling error, sample treatment error, and calibration error.
2. IUPAC recommends that 16 measurements of the blank be used to calculate sb; in fact, to be strictly
proper, 16 different blanks should be prepared and analyzed. This process can be quite
time-consuming; many people estimate the LOD using fewer blank measurements.
In absorption spectroscopy, an alternate measure of detection capability is frequently used: the
characteristic concentration 1 (or the characteristic mass, if appropriate). The characteristic
concentration is the concentration of analyte in the sample that will cause an absorption of 1% of the
incident light (i.e., a transmittance of 0.99). This corresponds to an absorbance value of A = 0.0044, so
that the characteristic concentration can be calculated by dividing this value by the sensitivity of the
absorption method:

characteristic concentration [] char = 0.0044 [1]

b1
where b1 is the sensitivity (i.e., the slope of the calibration curve).
The characteristic concentration is generally significantly larger than the detection limit, and is usually
a more realistic assessment of the lower concentrations of analyte that can be analyzed with some
degree of precision. It is also fairly easy to obtain, since one usually must construct a calibration curve
during the course of an analysis. The principal disadvantage it has as a figure of merit is that it can only
be used to describe absorption-based analytical methods.
The detection capability of graphite furnace AAS is better described in terms of analyte masses rather
than concentrations. The characteristic mass is the analyte mass that, when deposited in the furnace,
will give a signal of 0.0044 AU. Since a discrete volume of sample is analyzed in the furnace, and the
characteristic concentration will depend on the actual sample volume being used (a disadvantage). The
characteristic mass, however, will not depend on the concentration.
1
confusingly, the characteristic concentration is often called the sensitivity, whereas IUPAC defines the
sensitivity as the slope of the calibration curve.

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Dynamic Range

The dynamic range is the range of concentrations over which there is a measurable change in
instrument response. It is advantageous to have a linear calibration curve, and so the linear dynamic
range (LDR) is usually of interest. As you might guess, the LDR provides the range of concentrations
over which the instrument response is linearly dependent on the analyte concentration.
In this experiment, we will consider the characteristic concentration as the lower limit of the LDR, so
all that is left is to find the upper limit of the LDR. Commonly, this value is defined as the value at
which the instrument response loses 10% of the value that it would have if it were truly linear. The
following figure illustrates:
signal

concentration

In the figure, the larger double arrow gives the net response if the calibration curve remains linear. The
smaller arrows show the difference between the actual and the projected linear response. When the
ratio of the smaller to larger arrows is 10% (i.e., when there is a 10% drop-off from a theoretical linear
response), then we have reached the upper limit of the LDR.

Measurement Precision

The random error in a measurement is characterized by its standard deviation. The relative standard
deviation, RSD, is a convenient way to compare the variability in the measurements when using a
particular analytical method. Another common method used to compare measurement precision is the
signal-to-noise ratio, S/N. As the name might imply, the S/N is simply the inverse of the RSD:
S/N = RSD–1 = x/σx
Both S/N and RSD are widely used to indicate the magnitude of measurement precision. Better
precision is indicated by a larger S/N or a smaller RSD. The RSD is frequently given as a percentage
value. Generally, RSD and S/N will depend on concentration, so it is desirable to specify the
concentration (or concentration range) when reporting the measurement precision.

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References
• Skoog 8-9 (esp 8B & 9A)
• Harris 22 (esp 22.2)

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 ATOMIZER COMPARISON: PROCEDURE

Part I: Graphite Furnace Atomic Absorption

Check that the furnace atomizer unit is installed on the Perkin Elmer atomic absorption instrument (ask
your lab instructor or TA). You will need to prepare eight calibration standards of the following
concentrations: 5, 20, 35, 50, 100, 150, 200, and 250 ppb copper. Use deionized water for your blank
and in all dilutions. In addition, you should collect a small sample of tap water in a clean beaker.

Important: before actually performing the dilutions, have your instructor check your
calculations. The furnace can be damaged if the standards are too concentrated.

Once you have made your solutions, you will use the autosampler to measure the standards. You will
need to ask your instructor for help in operating the instrument. You should obtain three measurements
for each standard, and you are to inject 30 µL volumes into the furnace.

Part II: Flame Atomic Absorption

For this portion of the experiment, you will be using an air-acetylene flame atomizer. Prepare 100 mL
standards of the following concentrations: 5, 10, 15, 20, 30, 40, 50, 60 ppm copper. You will obtain
one measurement on each of these using flame atomic absorption spectroscopy; ask your instructor to
show you how this is done on the Perkin-Elmer instrument. You should also attempt to determine the
copper content of the tap water sample using the flame AA method.

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 ATOMIZER COMPARISON: DATA SHEET
In addition to filling out the following table, turn in copies of all printouts collected during the
experiment. Don’t forget to show your calculations on a separate sheet of paper.

Name:

Furnace Atomizer Flame Atomizer

sample conc (ppb) peak area (Av
vs) conc (ppm) absorbance
blank 0 0
std 1
std 2
std 3
std 4
std 5
std 6
std 7
std 8
tap water

Results
characteristic conc, ppb (95% CI) characteristic conc, ppm (95% CI)
characteristic mass, pg (95% CI) upper limit of LDR, ppm
upper limit of LDR, ppb 95% CI for [Cu] in tap water, ppb
measurement RSD, % measurement RSD, %
95% CI for [Cu] in tap water, ppb:
 ATOMIZER COMPARISON: DATA TREATMENT
You will need to fill in the “results” section in the DATA SHEET. Take special note of those values for
which confidence intervals (CI’s) are asked: the characteristic concentrations, the characteristic mass,
and the concentration of copper in tap water. You do not need to calculate a confidence interval for the
upper limit of the LDR or for the measurement RSD.
Looking at your results, you should ponder the questions such as the following:
• which method is more sensitive? (The answer to this question should be fairly obvious.)
• which method has the largest linear dynamic range? Can you think of any reasons why?
• which method has the best measurement precision? What are the main sources of random error for
each method? Is the difference between measurement RSD statistically significant?
• what are the advantages and disadvantages associated with each method? When would you prefer to
use the FAAS method, and when would you want to use GFAAS?

Estimate of Copper Concentration in Tap Water

In constructing your calibration curve, average the measurements for each standard, and for the tap
water (watch for outliers). Your calibration data should be curved (after all, one of the goals of the
experiment is to compare the linear dynamic ranges). A second-order polynomial linear regression
should give a reasonable fit for the data:
✙y = ✎2x2 + ✎1x + ✎0
You should use this equation to obtain a confidence interval for the copper concentration in tap water
using the GFAAS method. To obtain a point estimate, you will need to solve a quadratic equation. The
standard deviation of this estimate can be approximated by

s res (x u − x) 2
s(x u ) l 1 + 1n +
2b 2 x u + b 1 S xx
where b2 and b1 are the least-squares estimates of β2 and β1. To learn more about using polynomial
calibration curves for quantitative analysis, refer to the web-based Tutorial.

Characteristic Concentration
Calculate the point estimates of the characteristic concentrations using the equation given in the
BACKGROUND section. You can use propagation of error in order to determine the standard error in your
calculated value; if you assume a normal distribution for the estimate (a somewhat dubious
assumption), you may calculate a confidence interval for the characteristic concentration using t-tables.
To calculate the characteristic mass of the GFAAS method, you will need to know the volume of
solution sample that is analyzed (ask your instructor for more detail).
Linear Dynamic Range
The upper range of the LDR is when there is a 10% decrease from a hypothetical linear response.
Using a second-order polynomial fit, the upper range of the LDR, xupper, is thus
b1
x upper = −0.1
b2
The negative sign is necessary because b2 should be negative (if it isn’t, come see me with your data).

Measurement Precision
The RSD indicates the precision with which the method can determine the analyte concentration of a
sample. Calculate the RSD using the following equation:
s
RSD = res
y
where sres is the standard deviation of the residuals and y is the average of the y-values (i.e., the signals)
in your calibration data set. The RSD calculated in this manner includes the effects of both
measurement and calibration error.
If you wish, you may compare the RSD values for each method using an F-test, since the ratio of
squared RSD values should follow an F-distribution.