SPECTROCHIMICA

ACTA
PARTB
ELSEVIER Spectrochimica Acta Part B 50 (1995) 1679-1685

High current power supply for electrothermal atomic

absorption spectrometry1
Giancarlo Torsi*, Sergio Valcher, Pierluigi Reschiglian, Lino Cludi,
Luca Patauner 2
Department of Chemistry, "G. Ciamician", Via F. Selmi 2, 40126 Bologna, Italy

Received 14 November 1994; accepted 3 February 1995

Abstract

A new power supply for electrothermal atomization - atomic absorption spectrometry (ETA-AAS)
with associated equipment for temperature control is presented. The system is composed of two high
current commercial batteries and a MOSFET switch which controls the temperature of the atomizer by
switching the current in an on-off way through a feedback loop connected to a personal computer and
suitably programmed peripherals. The delivered power can be changed from 0 to 100% in 1% steps
which gives the possibility of roughly controlling both the temperature at low power when the temperature
sensor is not working and the heating rate. With this system, curves for which the simultaneous presence
of all atoms injected in the atomizer is claimed, have been extended to Pb, Ag, T1 and Zn. With a more
conventional power supply previously used, such a claim could be made only for Cd and Hg.
Keywords: Power supply; Standardless analysis

1. I n t r o d u c t i o n

The preferred approach to higher sensitivity in electrothermal atomization - atomic absorp-

tion spectrometry ( E T A - A A S ) has been the increase of the heating rate and therefore an
increase of the concentration of atoms in the optical beam depending on the atomizer and
beam geometry. The process, however, cannot go on indefinitely because a saturation stage is
eventually reached. If the atomizer cross section is constant, the source beam is also constant
and homogeneous and the atoms in the atomizer are distributed homogeneously in planes
perpendicular to the optical beam; then the saturation stage is reached when all the atoms are
simultaneously present in the atomizer [3,4]. Theoretical curves that can be obtained when all
the atoms are instantly atomized and can diffuse out of the atomizer extremities only by dif-
fusion, have already been studied [ 1-4] on the assumption that the atoms are stable only inside
the atomizer.

* Corresponding author.
~This paper has been published in the special issue of the East European Furnace Symposium, Warsaw, 4--7
September 1994.
2 Current address: TORGGLER Chimica spa, V. Verande, 1A, 1-39012 Merano (Italy).

0022-2313/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0584-8547(95)01320-2
1680 G. Torsi et al./Spectrochimica Acta Part B 50 (1995) 1679-1685
Curves that closely resemble those predicted by the theory cited above have recently been
obtained with a laboratory-made atomizer and power supply [5].
A very fast rise in absorbance (A), followed by a constant signal, was obtained only for Cd
and Hg, because these are easily atomized. For other elements, curves more like those given
by a commercial atomizer were obtained. These data were interpreted in the light of what has
been said above, i.e. as the attainment of the saturation stage for the two elements mentioned
above. If there is no loss of atoms in the steps preceding the atomization and if the atomization
efficiency is 100%, then the constant value of A (from now on called Ao) is related to the
number of atoms injected into the atomizer No by the equation
Ao = KNo/Sc (1)
where K (cm 2 atom -~) is a spectroscopic constant and Sc (cm z) is the atomizer cross section.
The interval of time At (s) during which Ao is constant is given by [1,3,4]
At = [1/,tr2 ln(4/Tr)- 1/24(Al/l)]F/D (2)
where Al (cm) is the central section of the atomizer in which the atoms are assumed to be
homogeneously distributed at the beginning of the atomization, l (cm) is the length of the
atomizer and D (cm 2 s-~) is the diffusion coefficient of the element under study.
From Eq. (2) it can be seen that, once the instantaneous atomization is reached, the interval
of time during which Ao is constant can be increased by increasing the length of the atomizer
or decreasing D, for instance by increasing the inert gas pressure. The length of Al probably
depends on the increase in volume of the inert gas as a consequence of the fast increase of
temperature at the beginning of the atomization step and the distribution of the analyte when
introduced in the atomizer. Its reduction is, therefore, rather troublesome. Of course, the time
interval during which A is constant is very important from the analytical point of view because
a long constant signal permits a more precise measurement of Ao.
In this paper, we present experimental results obtained with a new and more powerful power
supply with which curves similar to those previously obtained with Cd and Hg have been
obtained with the less volatile elements Pb, T1, Zn and Ag.
The improvement obtained by fast atomization is not apparent from Eq. (2) because it is
assumed that the atomization is instantaneous which, of course, can never hold true. The
improvement can be clearly seen from Fig. 1 where a curve obtained with the old power supply
is compared with the curve obtained with the new one. High heating rates have already been
used (up to 40000 K s-~). However, the sought constancy of the peak was not reached and the
plateau has never been observed, probably as a consequence of the presence of the injection
hole [6,7].

2. Experimental

2.1. Experimental set-up

This was not very different from the system previously described [5] and is schematically
shown in Fig. 2. It is principally composed of (i) an AT-compatible personal computer (PC),
(ii) a spectrometer, (iii) an atomizer, (iv) two batteries in series with an electronic switch, and
(v) a series of interfaces and peripherals for linking all the different instruments that are neces-
sary for measuring and storing the absorbance signal. The temperature signal was measured,
if necessary, with an independent instrument (12-bit I/O programmable data acquisition board
Lab PC+ from National Instruments, Austin, TX) by acquiring the output of the temperature
sensor.
The PC is connected directly, through a serial port RS232, to the communication port of a
Perkin-Elmer Model 1100 B atomic spectrometer. Through this communication link the start
and the duration of the data acquisition are controlled, together with the type of data that have
to be stored (absorbance, absorbance minus background or only background) and the transfer
of the raw absorbance data from the spectrometer to the PC memory. It would seem (see
Fig. 1) that the data obtained in this way have a higher noise than the noise present in the
 G. Torsi et al./Spectrochimica Acta Part B 50 (1995) 1679-1685 1681

a
Ass.
/ \
J
O

i ':! Time (s)

Ass. [
li,i,,'L,!, ,
........................................

~~.',%.

i:i ;L,t,,L!
I

0 Z.e time (S)

Fig. 1, Comparison of A vs. time curves obtained with the old (a) and the new (b) power supply for Pb.

Personal Computer

I0 port 8255+ Interface

Timer 8253

Serial Port
RS232
Valve Controls
Temp: Sensor
Gas

A,A.Spectrophotometer Ba~e~
Fig, 2. Components and connections of the atomization system.
1682 G. Torsi et al./Spectrochimica Acta Part B 50 (1995) 1679-1685

curves directly observed on the Perkin-Elmer screen. However, this is not true because the
data displayed on the spectrometer screen are automatically smoothed. The spectrometer gives
a point every 9 ms when absorbance only is acquired.
The atomizer with the associated housing and electrovalves has already been described [5].
Here we want to recall that the atomizer is essentially a graphite tube without the central hole
for injecting the sample that is laterally introduced.
The control of the power supply and the electrovalves is obtained through the PC by means
of a commercial board based on an I/O port 8255 and a timer 8253 (Fig. 3). The timer is
connected and programmed in order to generate pulse trains with constant period (1/1000 clock
periods) and variable duty cycle, from 1 to 1000/1000, with steps of 1/1000. The above trains,
which are converted into high current pulses, through a MOSFET and associated driver (Model
SKM 450A 020 and SKHI 20 from Semikron, Nurnberg, Germany) allow for a fine control of
the power applied to the atomizer by two 12 V 400A/h batteries.
An IR photo transistor (TSI, Texas Instruments) is employed as temperature sensor. Its
output, suitably converted into voltage, is evaluated by comparison with a stated level, through
a digital to analogue converter. The comparator output may be simply read by the I/O port
and also be used to switch off the pulse train (SW is used to select the s/w-h/w function). The
8255 port is also used to activate, through suitable boosters, the electrovalves which control
the inert gas flow in the atomizer housing.
A measurement is composed of a maximum of 10 steps in all of which the step length, the
percentage of power supplied, the DAC level, the electrovalve status and the start of data
acquisition can be independently introduced. In the first two or three steps the temperature
comparator does not operate and the temperature is roughly controlled only through the percent-
age of the supplied power.
The photo-transistor was calibrated as previously described [8] by measuring the output of
a Pt/Pt-13%Pd thermocouple inserted in the graphite tube of the atomizer and of the photo-
transistor up to 1400 K. The higher temperatures given in this paper have been calculated by
extrapolation through the application of the Wien equation to the data at low temperature [8].
As already explained [5], an accurate determination of the temperature is not of primary
importance and only a measure of the heating rate is sought here.

> Bolnd ctk

Tlm.1 clk
i > I"Im.I ~ -~ Vcc 12V 12V
> "rlm.1 out

" nm.2~
>
v. v, v,

> Tim.3cld ~I rD Ref.~ 120m_35VL

> Tim.3 out
>

. ,<,,-,I]
<' s.1 m,i=r.. I1"1"
'" ~-~' VCc " .. . . . . . . . -7- 136

> " - -q V"-" .v

i ) ' l i b IJnv / -- ~ ."i" Vs i

/ t, {, #,v,
u. >" I ,1 ~ / I~ (~/~2N1711

Fig. 3. Detailed wiring of the power system control with the feed-back loop and electrovalves' control.
 G. Torsi et al./Spectrochimica Acta Part B 50 (1995) 1679-1685 1683
2.2. Chemicals

All solutions were prepared from reagent grade chemicals at high concentration (generally
100 ppm), which were diluted before use.

2.3. Instrumental set-up

All measurement conditions were those predetermined in the Perkin-Elmer spectrometer

used with the P-E hollow cathode lamps operated at the lowest current proposed by the manu-
facturer. The slit width was always 0.2 nm. None of the solutions presented matrix problems
and, therefore, no background correction was necessary.
The electrovalves were closed 1 s before the atomization step in order to ensure that no gas
movement was present during this step. The small increase of pressure brought about by the
increase of temperature in the system does not change the A versus time curves [5].

3. Results and discussion

3.1. TI, Zn, Cd, Pb, Hg and Ag curves

The results obtained with the new power supply for TI, Zn, Hg, Cd, Pb and Ag are shown
in Fig. 4. Upon the A versus time curves are superimposed the T versus time curves. The T
plots were obtained with the simultaneous measurement of the voltage of the sensor amplifier
output with a second instrument and were subsequently superimposed upon the A versus time
curve. The translation was obtained through Wien's equation with the constants determined
in the temperature calibration. It can be seen that the approximate heating rate is around 6 0 0 0 -

05 3000 0.8 t

045 2SO0 0.7] ~>.,~

2000
0.4
~0
TI 18 ppb ~~v,~ 2~ o, Hg 0.7ppm

<
0.35

0.3

0.2S
~ .,"" DAC>IO00 100~
lSOo
0.4

o.~ , ,i , L ~
~ooo oaH '' •
.
:°
¢
~ DAC7OO or%
1500

E
Iooo ~_.

o.s[ 2500 I
2O0O
0.45

0.4
Pb 25 ppb i/
ZOO0
Cd 2 ppb TSOO

0.35 1500 Ec~

. i.J i.,! , / . . . . . . . ~ooo
0.,1
1000
025

0,4
. . . . . . . . . . . . . . .071
2soo

0.6
.... . . . . . . . .
2ooo _~

A~ 1.8ppb ~° Zn l ppb
, 0.35

" DAC>1000 100% 0.4 ~ ,,.:. ' DAC>10~ 100%

100'
o.3
70O0

1000 0.3
O.25

0"2,4 0.6 0.8 1 f.2 1.4 1.6500 O. 0.6 0.8 1 1.2 1.4 1.6500
time (s) time (s)

Fig. 4. A and T vs. time curves for the elements studied: (a) thallium; (h) mercury; (c) lead; (d) cadmium; (e) silver;
(f) zinc.
1684 G. Torsi et al./Spectrochimica Acta Part B 50 (1995) 1679-1685
8000 K s-~. The difference is probably due to the different resistances of the atomizers used
and to the slightly different voltages depending on the batteries' charge.
With some elements good curves were obtained only if specific chemicals were present in
the solution. In the case of Hg the need to add Pd (30 ppm) is well understood because, without
it, the solvent could not be readily eliminated. Less clearly understandable is the need to add
EDTA (10 -3 M) for Cd and thiosulfate (10 -4 M) for Ag. In the case of Cd, the EDTA addition
contributes only to a steeper increase of A, while in the case of Ag the presence of thiosulfate
is necessary not only for a good curve shape but, more importantly, for the reproducibility of
the plateau height. For the remaining elements, no improvements were observed by the addition
of chemicals except for a small improvement in the case of Pb by the addition of a zinc salt.
Palladium was used only for Hg, because the presence of Pd with the other elements increases
the atomization temperature too much for our atomizer. From a cursory inspection of Fig. 4
it can be seen that the time length of the plateau is longer for Cd and Hg, in agreement with
their higher volatility. The length of the plateau can be theoretically derived from Eq. (2) by
assuming Al = 0 and an appropriate value for I and D. The value of I is not easily determined
in our furnaces because the two graphite blocks used for electrical contact give, with holes of
the same diameter of the graphite tube, a kind of extension of the atomizer length with large
temperature gradients. It is, therefore, difficult to choose a limit. By assuming /--4.0 cm (the
graphite tube is 3.6 cm long) and D = 3 cm 2 s-~ for Cd, one gets a value for At of about 0.05 s
that is smaller than the experimentally found value (about 0.15 s). The ratio 12/D can be
obtained from the final portion of an A versus time curve [5] and its value for Cd is around
5 s. By using this experimental value, a more acceptable (0.12 s) value is obtained. Better
calculations could be made if an atomizer with a better defined geometry and temperature
distribution, such as the transverse heated atomizer recently introduced by Perkin-Elmer, could
be used in connection with these types of measurement. From the analytical point of view, a
long-lasting plateau is convenient because there are a larger number of points to average for
the measurement of Ao. Generally, a short plateau is related to a not very steep increase of A
and a rounded final part of the A versus time curve. This is an indication of a slow atomization
process, especially of the final fraction of the analyte. This situation is corrected for some
elements by the addition of chemicals, as already mentioned above, and it is probably related
to some analyte-surface interactions. None of these problems have, as yet, been investigated.
The standard deviation obtained from twelve measurements with six furnaces by varying
the heating rate (5000-8000 K s-1) and the final temperature (1500-2200 K) was 5% when Cd
was used as analyte. When the analysis was extended to four series of measurements made in
four different weeks, the standard deviation rose to 10%. Similar figures were obtained with
other metals. As expected, the final temperature has no influence, in definite intervals, on Ao
as already verified experimentally [9].

3.2. Influence of the heating rate

From what has been said, it is clear that the existence of the plateau can be thought of as
the attainment of the simultaneous presence in the vapor phase of all the atoms injected.
A further proof that the plateau is a limiting value which can never be exceeded can be
obtained by decreasing the heating rate. In our system, the heating rate can be changed by
software by entering the percentage of power supplied. Fig. 5 shows the results obtained with
Cd by changing the supplied power from 100% to 40%. It can be seen that, as expected, the
plateau is well evident at 80%, it does not exist at 60% even though the peak value is almost
unchanged, while at 40% power a broad maximum appears. This broad maximum cannot be
mistaken for the sought plateau because the absorbance at the beginning of the atomization
step increases rather slowly with time. We are presently trying to see if it is possible and
convenient to increase the heating rate further. With the system presented here, it is quite a
simple operation since it amounts to adding a new battery. Operating the system at 36V instead
of 24V should, in theory, double the heating rate. However, we do not know whether all the
components could withstand the associated high current and if an increase in the heating rate
also increases other negative effects such as, for instance, a distortion of the initial distribution
of the atoms in the atomizer, due to the increase of the expansion rate of the inert gas.
 G. Torsi et al./Spectrochimica Acta Part B 50 (1995) 1679-1685 1685

~I ~7
a
~ ,
i i ~I
b)........+. ")P~@~'L r
i
............. ' ~

+ ...........................

+
"

Cd +...............+....................................+

f+ 1I\;i
~i .liliU+ Jil
+i["+,
i i
Ii '
100% 80% '~0~

+ iI i
+'+ + ~",~+,~.+~+:vf.. a.,
,

Fig. 5. A vs. time curves of Cd at different percentage power: (a) 100%; (b) 80%; (c) 60%; (d) 40%.

4. C o n c l u s i o n s

It can be concluded that, when the heating rate is sufficiently high and the atomizer properly
designed, a constant absorbance with the highest possible value is obtained, at least for moder-
ately volatile elements. If there is no analyte loss during the previous steps and the atomization
efficiency is 100%, the absorbance at the plateau is related to the total number of atoms injected
into the atomizer by a very simple equation. In these conditions, standardless analysis is very
easy to attain.
With the present system, we can easily increase the heating rate. However, we think that a
better way to increase the plateau length and, therefore, the analytical usefulness of the tech-
nique, is to increase the atomizer length together with the power supply voltage. This approach
should maintain a constant heating rate but, at the same time increase the residence time of
the atoms in the optical beam.

Acknowledgements

Financial support from CNR (Rome) is duly acknowledged.

References

[1] W. M. T. G. van den Broek and L. de Galan, Anal. Chem., 49 (1977) 2176.
[2] B. V. L'vov, V. G. Nikolaev, E. A. Norman, L. Z. Polzik and M. Mojica, Spectrochim. Acta Part B, 41 (1986)
1043.
[3] H. Falk, Spectrochim Acta Part B, 33 (1978) 695.
[4] H. Falk and C. Schnurrer, Spectrochim Acta Part B, 44 (1989) 759+
[5] G. Torsi, P. Reschiglian, F. Fagioli and C. Locatelli, Spectrochim Acta Part B, 48 (1993) 681.
[6] C. L. Chakrabarti, H. A. Hamed, C. C. Wan, W. C. Lee, P. C. Bertels and S. Lee, Anal. Chem, 52 (1980) 167.
[7] C. L. Chakrabarti, C. C. Wan and R. J. Teskey, S. B. Chang, H. A. Hamed and P. C. Bertels, Spectrochim. Acta
Part B, 36 (1981) 427.
[8] G. Torsi and G. Bergamini, Ann. Chim. (Rome), 79 (1989) 45.
[9] G. Torsi, F. Fagioli, C. Locatelli and P. Reschiglian, Ann. Chim. (Rome), 83 (1993) 397.