Spectrochimica Acta Part B 56 Ž2001.

1397᎐1405

Effect of palladium modifier on the analyte vapor

transport in a graphite furnace atomizer

Yuri M. Sadagov 1, Dmitri A. Katskov U

Department of Chemistry and Physics, Technikon Pretoria, 0001 Pretoria, South Africa

Received 8 February 2001; accepted 24 May 2001

Abstract

The effect of Pd modifier on vapor transport of In, Ga, Mn, Pb and Sn in a graphite furnace atomizer was
investigated using a Quant-ZETA atomic absorption spectrometer. The fast heating of the furnace Žramp time
0.15᎐0.25 s. followed by temperature stabilization at 2500᎐2800 K enabled us to measure the vapor dissipation rate
using the ‘tails’ of the atomic absorption signals. The analyte, 0.02᎐0.5 ng, was vaporized alone or together with Pd.
Pd was introduced and thermally treated before the sampling of the analyte. Small amounts of Pd Ž0.1 ␮g.
significantly changed the vaporization pattern and residence time of the atomic vapors, but affected the peak area
only slightly. In this case, the vapor removal is 1.5᎐1.8 times slower than that predicted by theory for the diffusion
mechanism of vapor release. The involvement of vapor adsorption by the wall and molecular diffusion in the vapor
transport is suggested. The increase of Pd amount Žup to 2.5 ␮g. causes the gradual reduction of residence time and
peak area, due to the increase of diffusion rate of atomic vapor. Using the two-line method of temperature
measurement, it is shown that this effect is accompanied by a temperature increase of 75᎐200 K, when 0.5᎐4 ␮g Pd
are vaporized. The hypothesis is advanced about an exothermal interaction of Pd vapor with graphite. The variations
of atom residence time in the furnace are discussed as practical limitations of the theory of absolute analysis. 䊚 2001
Elsevier Science B.V. All rights reserved.

Keywords: Graphite furnace atomizer; Diffusion of atomic vapor; Pd modifier

U
Corresponding author. Tel.: q27-12-318-6369; fax: q27-12-318-6286.
E-mail address: katskov@techpta.ac.za ŽD.A. Katskov..
1
On leave from Cortech Ltd, Ozernaya St., 46, Moscow, 119361, Russia.

0584-8547r01r$ - see front matter 䊚 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 5 8 4 - 8 5 4 7 Ž 0 1 . 0 0 2 5 0 - 6
1398 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405
1. Introduction
The use of stabilized temperature platform fur-
nace ŽSTPF. atomization is considered to be one
of the conditions necessary for the practical appli-
cation of the theory of absolute analysis by elec-
trothermal atomic absorption spectrometry
ŽETAAS. w1᎐3x. It is supposed that the theory can
provide the calibration of analytical signals on the
basis of the fundamental atomic and spectros-
copic constants, if the integrated absorbance Žpeak
area. is measured. According to the theory w4x,
the integrated absorbance is determined by the
number of absorbing atoms in the sample Ž N0 .
and residence time of atomic vapor in the analyti-
cal zone Ž ␶ ..
H AŽ t .dt ; N ␶ 0
When the STPF experimental conditions are used,
the residence time is determined by the diffusion
rate of the analyte atomic vapor in the furnace:
y1
␶ ; Ž DT .
where D T is the diffusion coefficient of atomic
vapors in the purge gas. The ratio between ␶ and
Ž D T .y1 is determined by the design of the tube
furnace. The diffusion coefficients are strongly
temperature dependent:
n
D T s D 0 Ž Tr273.
where T is thetemperature ŽK. of the gas in the
furnace, D 0 is a constant, and n is a parameter
between 1.67 and 1.98 for various elements w3x.
Obviously, the STPF atomizer may be con-
sidered as the instrumental basis for absolute
analysis if it can provide vapor transport at a
constant temperature, independent of the sample
nature and amount. The use of microgram sam-
ples and chemical modifiers makes this approach
vulnerable.
A substantial increase of effective gas tempera-
ture was reported by Frech et al. w5x when 45 ␮g
of Pd was vaporized in the Perkin-Elmer HGA-
600 atomizer. The higher temperature obtained
in the presence of a Pd modifier was explained by
secondary absorption effects at the cooler ends of
the longitudinally heated tube, which effectively
confined the atomic vapor to its central, hotter
part. Terui et al. w6x and Hirano et al. w7x observed
similar effects in the graphite furnaces of the
Hitachi Z8100 and Z9000 atomic absorption spec-
trometers. It was proposed that atoms and
molecules of the modifier transferred energy to
the analyte atoms, thus exciting them w6x. Katskov
et al. recently observed the appearance of Mg
atomic emission from highly excited atomic levels
during the vaporization of micrograms of Mg
oxide w8x. The radiation continuum, related to a
temperature higher than that of the tube surface,
was observed during the vaporization of Mg, Be,
Pd and Cu nitrates w9,10x. The results were inter-
preted as evidence of energy evolution during
Ž1.
chemical reactions occurring in the graphite fur-
nace.
If this interpretation w8᎐10x is correct, the va-
porization of micrograms of specific matrices or
modifiers in the furnace can cause deviations of
gas temperature and, consequently, variations in
Ž2. atom residence time in the furnace. The effect
should cause errors in the practical application of
absolute calculations. The comparison of the resi-
dence times of analyte atoms in the furnace, with
and without a chemical modifier, should allow the
evaluation of the effect.
The diffusion of metal vapor in argon was
studied recently by Sadagov using a Quant ZETA
Ž3. atomic absorption spectrometer equipped with
graphite furnace atomizer w11x. The graphite tube
in the Quant ZETA is relatively small, so that it
enables fast heating and temperature stabilization
at 2500᎐2800 K after 0.15᎐0.25 s w12,13x. The
decreased openings at the tube ends slow down
the vapor release. The tube design and heating
mode both provide the conditions for the measur-
ing ␶ with the use of the ‘tail’ of the absorption
signal:
AŽ t . ; exp Ž ytr␶ . . Ž4.
The validity of the experimental method was
proven by measurements of gas temperature dur-
ing the tube heating w12,13x. The atom residence
 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405 1399

times for different metals were evaluated w11x. Table 1

The calculated diffusion coefficients were close to Thermal program employed in the measurements of atom
residence times
those predicted by theory w3x.
In this work, the residence time of atomic Step Temperature, Ramp time, Hold time,
vapor in the analytical zone of the Quant ZETA ŽK. Žs. Žs.
atomizer are measured and compared for Ga, In,
Drying 483 1 20
Mn, Pb and Sn in the presence and absence of a Pyrolysis 773a , 1073 1 15᎐18
Pd modifier. The method and experimental tech- Atomization 2473᎐2723 0b 0.3᎐0.4
nique described by Sadagoff w11,12x and Sadagov Cleaning 2873 1 1
and Laptev w13x are used. a
In the experiments with Pb.
b
The setting provides the tube heating ramp up to
2500᎐2800 K during 0.15᎐0.25 s.
2. Experimental
␮l of Pd nitrate solution Ž20, 50, 200 or 500
The atomic absorption spectrometer Quant ␮grml. was injected in the furnace, dried and
ZETA ŽCortech, Russia. is designed according to held at 1200᎐1400 K for 15᎐18 s before the
a single-beam dual lens optical scheme. The lon- analyte sampling.
gitudinally heated graphite furnace in the longitu- The analytical lines employed in this work are
dinal magnetic field is mounted in the air gap Ž20 reported in Table 2. The peak height and inte-
mm. of alternating electromagnet. The field is grated absorbance were measured during the
alternated with the frequency of the power supply atomization step. The ‘tails’ of the absorption
Ž50 Hz. and the amplitude Ž7.5 T.. The system signals at stabilized temperature were used to
enables us to attain the Zeeman background cor- calculate the experimental value of residence time
rection by subsequent measurements of the total in the furnace, according to the equation:
Žzero-intensity field. and background Žthe field of
maximum intensity . absorbancies, made in 5-ms y1
␶U s  d w ln AŽ t . dt x4 Ž5.
intervals w12,13x.
The pyrocoated graphite furnaces are manufac- The parameters ␶U obtained experimentally as
tured by SGL carbon Group Ringsdorff-Werke the average of three measurements were com-
GmbH. The length of the tube is 16.5 mm and pared to ␶ calculated using the theory of vapor
external diameter 6 mm. The inside diameter at transfer for the end-cupped furnace w14x, dimen-
the central cross-section is 4 mm. Both the di- sions of Quant ZETA atomizer and parameters
ameter and the length of the end zones of the D 0 and n from w3x.
tube are equal to 3 mm. The diameter of the The effective gas temperature was measured
injection inlet is 1.5 mm. To increase the heating with and without Pd sampling using the two-line
rate and stabilize the temperature of the furnace, method based on 368.3 and 280.2-nm Pb lines,
the feedback by the irradiation of the internal and 286.3 and 284.0-nm Sn lines. The tempera-
walls of the furnace is applied. The maximum tures were calculated by the equations reported
input power of 2.2 kW provides a heating rate of by Sadagoff w11x:
approximately 10 K msy1 .
Aqueous solutions of In, Ga, Mn, Pb and Sn T Pb s 1770rlogw 3.68 A1Ž t . R 2rA 2 Ž t . R1 x Ž 6a .
nitrates were vaporized in the graphite furnace
with or without Pd nitrate. An element concen-
tration ranging from 4 to 100 ngrml was selected TSn s 2143rlogw 4.90 A1Ž t . R 2rA 2 Ž t . R1 x Ž 6b .
to provide a peak height of approximately 0.2᎐0.3
absorbance. A 5-␮l solution was introduced in the where A1Ž t . and A 2 Ž t . are the atomic absorption
furnace, and the thermal program ŽTable 1. was signals obtained with the first and second line of
applied. In the experiments with the modifier, 5 the pair, and R1 and R 2 are the Zeeman ratios
1400 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405

Table 2
Effect of Pd on residence time of atoms. Experimental conditions and results

Fig. Element Analyte Temperature Pd, Peak Experimental Theoretical

No. wavelength mass setting mass areaa Residence parameters from Ž2.
Žnm. Žng. ŽK. Ž␮g. Žms. time in the and Ž3. w11x
furnaceU D0 n ␶
␶U Žcm2 rs. Žms.
Žms.
1 In325.6 0.5 2573 0 33 " 7 89 " 5 0.091 1.84 50
0.1 40 " 1 63 " 4
2.5 21 " 2 41 " 3, 69 " 4
2 Ga294.4 0.2 2773 0 33 " 5 65 " 3 0.102 1.87 36
0.25 30 " 1 85 " 6
2.5 15 " 2 29 " 2
3 Mn279.5 0.02 2573 0 32 " 4 67 " 4 0.130 1.7 42
0.1 31 " 1 73 " 5
2.5 23 " 1 44 " 3
4 Pb283.3 0.15 2473 0 46 " 5 103 " 6 0.079 1.84 63
0.1 48 " 1 111 " 6
1.0 33 " 2 78 " 5
5 Sn286.3 0.5 2673 0 26 " 3 71 " 4 0.076 1.9 49
0.25 30 " 1 79 " 4
2.5 26 " 1 53 " 3
a
The error is determined from three independent measurements.

Žsensitivity ratios with and without magnetic field..
In this experiment, the Zeeman ratio values were:
R1Ž368.3. s 0.94, R 2 Ž280.2. s 0.70 for the Pb line
pair, and R1Ž286.3. s 0.89, R 2 Ž284.0. s 0.91 for
the Sn line pair. The absorbance peaks were
registered sequentially on both lines, and the
temperature was calculated using the absorption
measured at contemporaneous moments, with a
resolution of 0.01 s. The settings of the power
supply for the pyrolysis and atomization steps
were, respectively, 773 and 2473 K in the case of
Pb and 1073 and 2773 in the case of Sn.

3. Results

3.1. Residence time of atomic ¨ apor in the furnace

The experimental results are presented in Figs.

Fig. 1. Atomic absorption signals of 0.5 ng In Ž1᎐3. and their
logarithmic approximations related to constant temperature
Ž1⬘᎐3⬘.. Curves 1 and 1⬘ without Pd, curves 2 and 2⬘ with 0.1
␮g Pd, and curves 3 and 3⬘ with 2.5 ␮g Pd. The dotted line
shows the tube wall temperature.
1᎐5 and Table 2. The atomization peaks are
shown in the figures with solid lines. The corre-
sponding functions lnw AŽ t .x are shown with dots
and straight lines for each individual regression.
The dotted lines show the approximation of the
tube wall temperature according to the settings of
power supply and measured ramp time.
 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405
Fig. 2. Atomic absorption signals of 0.2 ng Ga Ž1᎐3. and their
logarithmic approximations related to constant temperature
Ž1⬘᎐3⬘.. Curves 1 and 1⬘ without Pd, curves 2 and 2⬘ with 0.25
␮g Pd, and curves 3 and 3⬘ with 2.5 ␮g Pd.
3.1.1. Indium
When 0.5 ng In was sampled, the absorption
peaks consisted of two components ŽFig. 1, curve
1.. The first was observed during the heating
ramp. The RSD of total peak area reached 20%
ŽTable 2.. Regardless of the peak area variations,
the residence time ␶U remained stable; approxi-
mately 89 ms. The function lnw AŽ t .x and its ap-
Fig. 3. Atomic absorption signals of 0.02 ng Mn Ž1᎐3. and
their logarithmic approximations related to constant tempera-
ture Ž1⬘᎐3⬘.. Curves 1 and 1⬘ without Pd, curves 2 and 2⬘ with
0.1 ␮g Pd, and curves 3 and 3⬘ with 2.5 ␮g Pd.
1401
Fig. 4. Atomic absorption signals of 0.15 ng Pb Ž1᎐3. and their
logarithmic approximations related to constant temperature
Ž1⬘᎐3⬘.. Curves 1 and 1⬘ without Pd, curves 2 and 2⬘ with 0.1
␮g Pd, and curves 3 and 3⬘ with 1.0 ␮g Pd.
proximation for one of the runs are reported in
Fig. 1, line 1⬘.
The presence of a small amount of Pd Ž0.1 ␮g.
in the furnace drastically changed the pattern of
the absorption pulses ŽFig. 1, curve 2.. The vapor-
ization occurred as a single peak shifted into the
area of stabilized temperature. The integrated
absorbance increased slightly compared to that
Fig. 5. Atomic absorption signals of 0.5 ng Sn Ž1᎐3. and their
logarithmic approximations related to constant temperature
Ž1⬘᎐3⬘.. Curves 1 and 1⬘ without Pd, curves 2 and 2⬘ with 0.25
␮g Pd, and curves 3 and 3⬘ with 2.5 ␮g Pd.
1402 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405

obtained in the absence of Pd. The R.S.D. for the

peak area decreased to 3%. The residence time
of atomic particles, calculated from Fig. 1, line 2⬘,
decreased to 63 s.
A further increase in the amount of Pd up to
2.5 ␮g caused the decrease of the peak area ŽFig.
1 and Table 2. and the distortion of exponential
‘tails’. In fact, two ␶U could be obtained at 41 and
69 ms respectively, for the beginning and the end
of the ‘tail’ ŽFig. 1, line 3⬘..

3.1.2. Gallium
The vaporization of Ga showed a pattern simi-
lar to that of In. The absorption profile consisted
of two distinct components ŽFig. 2, curve 1.. The
␶U term related to the second component occur-
ring at stabilized temperature was 65 ms. In the
presence of Pd, only one peak was observed ŽFig.
2, curves 2 and 3.. When a small amount of Pd
Ž0.25 ␮g. was added, the peak area was slightly
reduced, but ␶U increased to 85 s. The addition of
2.5 ␮g Pd caused the reduction of the residence
time of Ga vapor to 29 ms and a significant
decrease of integrated absorbance ŽTable 2..
3.1.3. Manganese
In the absence of Pd, the absorption signal of
0.02 ng Mn was broad and the vaporization began
at low temperature ŽFig. 3, curve 1.. The ‘tail’ at
stabilized temperature could be described by the
exponential function with ␶U s 67 ms. In the pres-
ence of Pd, the signals were narrower and shifted
towards the region of stabilized temperature ŽFig.
3, curves 2 and 3.. The peak position was almost
not affected by the amount of Pd Ž0.1᎐2.5 ␮g..
The presence of 0.1 ␮g of Pd caused an increase
in ␶U to 73 ms and an insignificant decrease of
the peak area. The addition of 2.5 ␮g of Pd
caused a change of the vapor transportation rate.
The beginning of the ‘tail’ showed much faster
vapor release than the end ŽFig. 3, line 3.. The
decrease of ␶U to 44 ms was accompanied by a
reduction of integrated absorbance ŽTable 2..
3.1.4. Lead
The initial part of the atomic absorption signal
of 0.15 ␮g Pb was observed during the tempera-
ture ramp and the tail at stabilized temperature
Fig. 6. Measurements of gas temperature using Pb Žcurves 1,
2, 3. and Sn Žcurves 4, 5. line pairs. Curves 1 and 4 without Pd,
curve 2 with 0.5 ␮g Pd, curve 3 with 1 ␮g Pd, and curve 5 with
4 ␮g Pd. Dotted lines show the tube wall temperature.
ŽFig. 4.. The presence of Pd shifted the signal
towards higher temperatures. The addition of 0.1
␮g Pd caused a slight increase of both ␶U and
peak area. The increase of Pd mass to 1 ␮g
caused a significant decrease of both parameters
ŽTable 2..
3.1.5. Tin
The behavior of tin with and without Pd dif-
fered from other tested elements. In fact, the
atomic absorption signal of 0.5 ng Sn did not
change its position, with or without Pd ŽFig. 5..
Nevertheless, tin showed the same tendency as
already observed in the case of Ga, Mn and Pb.
The residence time slightly increased in the pres-
ence of small amount of Pd Ž0.25 ␮g., and de-
creased when 2.5 ␮g Pd was added ŽTable 2..
3.2. Temperature measurements
The calculations of gas temperature using Pb
and Sn line pairs are reported in Fig. 6. The
stabilization of the gas temperature occurs 0.05 s
later than that of the tube wall. Random devia-
tions of calculated temperature at times longer
than 0.35 s were caused by too low AŽ t . values.
The gas temperature in the tube without modi-
fier was approximately 50᎐75 K lower than the
 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405
atomization temperature setting Ž2473 K., as
shown in Fig. 6, curve 1. A similar tendency was
observed when the atomization temperature was
set to 2773 K ŽFig. 6, curve 4.. The vaporization of
0.5 and 1.0 ␮g Pd was accompanied by an in-
crease of gas temperature, approximately 75 and
150 K respectively ŽFig. 6, curves 2 and 3.. The
addition of a higher amount of Pd Ž4 ␮g. caused
an even more significant increase of temperature,
up to 200 K ŽFig. 6, curve 5..
4. Discussion
The presence of different amounts of Pd caused
significant deviations of residence time of the
analyte vapor in the furnace. Several reasons can
be suggested to explain the phenomenon.
According to Grinshtein et al., the increase of
residence time can be caused by an involvement
of the adsorption᎐desorption processes on the
tube wall in the vapor transport w15x. It is as-
sumed that there is equilibrium between numbers
of atoms in gas phase and on the tube surface. In
this case, the residence time in the tube measured
experimentally will be longer than that related to
the gas phase transport, that is ␶U ) ␶. Obviously,
the adsorption᎐desorption processes should not
affect peak area as far as ␶, residence time in the
vapor phase, remains constant.
Furthermore, the formation of free atoms can
occur as a result of thermal dissociation of molec-
ular vapor during the move through the tube, or
due to the interaction of molecular vapor with the
furnace wall, as suggested by Gilmutdinov et al.
w16x. In this case, the release of atomic vapor
should be slowed down by the molecular diffu-
sion.
Finally, a temperature increase due to exother-
mal reactions of major sample components with
the furnace wall should cause a simultaneous
reduction of residence time and peak area due to
the change in diffusion rate. The direct measure-
ments reported in Fig. 6 show an increase of gas
temperature in the presence of Pd.
All these processes can be involved in vapor
transport, depending on the characteristics of each
element.
1403
Substantial variations of peak area and the
double mode character of atomization evidentiate
an incomplete atomization of In without Pd addi-
tion. The comparison of curves 1 and 2, Fig. 1,
shows that the first component of the absorption
signal, most probably attributable to the molecu-
lar fraction, disappeared due to the presence of
0.1 ␮g Pd, and the peak area reached maximum
when ␶U decreased ŽTable 2.. It appears that the
presence of Pd causes an increase in both the
atomization degree and diffusion rate, as a conse-
quence of molecular species decomposition.
In the case of Ga, Mn, Pb and Sn, the peak
area with and without small amounts of Pd is
changed less than in the case of In. Therefore,
the atomization degree is not affected signifi-
cantly. The increase of ␶U can be caused by vapor
adsorption on the tube wall, more intense in the
presence of Pd. The effect probably has a similar
nature to the delay of the analyte vaporization in
the presence of Pd.
The decrease of both peak area and ␶U is
observed for all tested elements in the presence
of 1.0᎐2.5 ␮g Pd. The temperature measurements
ŽFig. 6. make it possible to address the pheno-
menon of the increase of diffusion rate of atomic
vapor. Both results confirm the data obtained by
Frech et al. w5x. However, the temperature in-
crease is observed for much lower amounts of Pd
than those employed by Frech et al. w5x, due to
the smaller volume of the atomizer.
The discussed phenomena deserve special in-
vestigation beyond the frame of this paper. How-
ever, the suggestion about the interaction of Pd
vapor with graphite can be advanced as a possible
explanation. The chemical properties of both
reagents do not discard the idea. According to
Sosedov w17x, liquid Pd has a tendency to dissolve
carbon. Cooling of the solution is accompanied by
the release of carbon as pyrographite.
The enthalpy of the possible reaction that initi-
ates the effect, ⌬ H, can be roughly estimated
considering the balance of energy evolved and
transferred to argon gas in the tube Žif the tem-
perature distribution is considered to be uniform
and the dissipation of heat in the furnace wall is
neglected.:
1404 Y.M. Sadago¨ , D.A. Katsko¨ r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1397᎐1405
y1
⌬ Hm Pd s ␯C p Ž ⌬T . 300 Ž V0 T . Ž7.
where m Pd is the molar mass of Pd, ␯ s 0.18 cm3
is the furnace volume w13x, C p s 20.8 Jrkmol is
the Ar heat capacity w18x, T is the tube tempera-
ture, and V0 s 22 400 cm3rmol is the standard
volume of ideal gas. Taking into account that 1
␮g Pd Ž m Pd ( 1 = 10y8 mol. caused an increase
of gas temperature ⌬T s 150 K, and substituting
other parameters in Eq. Ž7., a ⌬ H s 290 kJrmol
is obtained. Although the value is quite high, it is
still in the range for possible chemical reactions.
The suggested explanation of the experimental
results will remain arguable until the nature of
the reaction causing the elevated gas temperature
is not specified.
5. Conclusion
The results presented in this work have con-
firmed the idea about the dependence of gas
temperature on the tube furnace and, respec-
tively, of the analyte vapor diffusion rate on the
sample composition.
Matrix modification and effective background
correction used in contemporary atomic absorp-
tion spectrometry enable to analyze the samples
containing tenths or even hundredths of micro-
grams of substances capable of reacting with the
graphite environment. The use of appropriate ref-
erence materials enables to discard possible er-
rors caused by the variation in residence time
when the peak area is measured. The error can
hardly be neglected in the case of the absolute
analysis. It is probably possible to avoid the errors
by using the atomizer, providing fast vaporization
and long residence time. It would enable the
measurement of the absorbance peak height from
all analyte atoms independent of the variations of
diffusion rate w19x.
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