Spectrochimica Acta Part B 56 Ž2001.

1625᎐1644

Energy transfer caused by reactions in a graphite

tube atomizer 夽

Dmitri Katskov a,U , Rita Mofolo a , Paolo Tittarelli b

a
Department of Chemistry and Physics, Technikon Pretoria, Pri¨ ate Bag X680, Pretoria 0001, South Africa
b
Stazione Sperimentale per I Combustibili, V.le De Gasperi 3, 20097 San Donato Milanese, MI, Italy

Received 15 February 2001; accepted 18 May 2001

Abstract

A spectrometer with a charge coupled device detector is employed to measure the temperature inside a graphite
furnace using the wavelength distribution of the radiation continuum. For steady-state heating and blank firings, the
results are good approximations to those expected from the black body theory. The calculated temperatures from
1900 to 2700 K, can be affected by the emissivity of the tube wall and radiating area by "60 K. The vaporization of
microgram quantities of Mg, Be, Pd and Cu as nitrates is accompanied by transient light scattering and an emission
continuum. The effect occurs for Cu in both Ta-lined and pyrocoated tubes, and for Mg, Be and Pd only in the
pyrocoated tube. Wavelength distribution of the transient radiation is also characteristic of a black body radiator, but
with temperature increase of 400᎐600 K in comparison with that of the tube wall. The emission originates from the
clouds of condensed particles formed almost simultaneously with the vaporization of the sample. The effect is
accompanied by increased vaporization rate and appearance of some particularities in the vapor spectra. The concept
of isothermal atomization fails to explain both phenomena. Hence, the hypothesis is advanced concerning the
evolution of chemical energy during sample interaction with the tube material. Energy transfer and dissipation in the
vicinity of the sample control both mass output and kinetic energy of the released atoms. The exothermic process of
nucleation and aerosol formation causes release of energy through radiation. It is suggested that such phenomena
can occur in the tube furnace during trace element determination in the presence of microgram quantities of matrix
and chemical modifiers. 䊚 2001 Elsevier Science B.V. All rights reserved.

Keywords: Electrothermal vaporization; Vapor spectra; Emission continuum; Furnace temperature; Energy transfer

夽
This article is published in a special honor issue dedicated to Walter Slavin, in recognition of his outstanding contributions to
analytical atomic spectroscopy, in appreciation of all the time and energy spent in editing Spectrochimica Acta Part B.
U
Corresponding author. Fax: q27-123186286.
E-mail address: katskov@techpta.ac.za ŽD. Katskov..

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 4 9 - X
1626 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
1. Introduction
The concept of isothermal atomization is fre-
quently used in the theory of graphite furnace
atomic absorption spectrometry ŽGFAAS. w1᎐16x.
According to the basic hypothesis, the tempera-
ture in the furnace is determined only by the
applied electric power and cooling system, irre-
spective of the chemical processes accompanying
sample vaporization and vapor transport. The as-
sumption provides a support to several theories.
The assumption of an isothermal heteroge-
neous equilibrium between the sample compo-
nents and tube material enabled Frech et al. to
evaluate gas composition in the analytical zone
w3x. The use of the Arrhenius equation enabled
Fuller, Sturgeon, Holcombe and Katskov w4᎐7x to
obtain a quantitative description of the vaporiza-
tion processes using the measured activation en-
ergy and substrate temperature. Langmuir’s hy-
potheses about the formation of an equilibrium
boundary sample᎐gas layer at normal pressure
w8x, provided Guerrieri et al. and later Katskov et
al. the grounds to find a connection between the
activation energies and thermodynamic character-
istics of the sample w9᎐11x. The theory developed
by L’vov about a crucial role of gaseous carbides
in the reduction and atomization mechanism gave
birth to a long-term discussion w12,13x. The admis-
sion of isothermal vapor transfer provided the
means for calculating diffusion coefficients and
spectral parameters necessary to evaluate abso-
lute characteristic masses w1,14,15x. Recently, an
attempt was made to explain the mechanism of
Pd modification using the isothermal concept w16x.
All the approaches and results noted above
assume an ideal situation when the energy evolved
or consumed in the chemical process during va-
porization is instantly re-distributed between all
other reaction participants. At constant tempera-
ture it should cause an immediate variation of
both vapor and solid phase composition.
The real situation is much more complicated.
The energy released in heterogeneous reactions is
dissipated in both the substrate and atmosphere
above the sample. The dissipation rate depends
on the thermal conductivity of both condensed
and gaseous media. Heat exchange between the
solid sample, its vapor, substrate and tube wall
occurs in the presence of a purge gas at normal
pressure. Accordingly, the heat transfer in the gas
phase occurs due to collisions between the sam-
ple atomsrmolecules and atoms of purge gas.
Heat propagation in the gas phase is determined
by a diffusion process similar to that of mass
transportation w17x. Therefore, any exothermic re-
actions during sample vaporization should in-
crease the kinetic energy of the participating par-
ticles above the level related to thermal equilib-
rium at the vaporization temperature. Some spe-
cific phenomena accompanying the deviations
from thermal equilibrium in the tube furnace can
be expected.
The application of a CCD spectrometer for
monitoring the vapor composition has already
enabled one to observe phenomena that cannot
be explained within the context of the isothermal
theory w18᎐22x. A significant difference in the
vaporization behavior of alkaline earth oxides and
halides was observed for the pyrocoated and Ta-
lined or Ir-sputtered tubes. Vaporization temper-
ature, the intensity of molecular and atomic spec-
tral bands in absorption and emission, and wave-
length distribution of the radiation and absorp-
tion continuum appeared to be specific for each
type of tube.
According to the hypothesis w18x, the interac-
tion of sample vapor with the tube material causes
an increase of purge gas temperature close to the
wall. This enhances sample vaporization and
causes the formation of an increased radial ther-
mal gradient in the tube cross-section. Both fac-
tors induce spatially-dependent vapor condensa-
tion along the tube axis. The reduction of oxides,
carbide formation, reaction of fluorine and some
metals with Ta-lining are considered to be re-
sponsible for the energy evolution.
It was observed that the emission occurring in a
pyrocoated tube during the vaporization of micro-
gram quantites of BeO showed a wavelength dis-
tribution characteristic of black body radiation
w19x. The black body temperature during the sam-
ple vaporization was estimated using the Planck
equation and found to be 200᎐300 K higher than
that of blank firings. It was suggested that the
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
radiation source was located on the tube wall
where beryllium carbide formation occurred.
Several problems were discussed recently
concerning both validity of temperature calcula-
tions w19x, and the concept of energy evolution
w23᎐25x. In particular, arguments were made
concerning the validity of the ‘black body’ ap-
proach for substances of unknown emissivity; lo-
cation of the radiation source and possible reac-
tions causing thermal effect. These problems are
investigated and discussed in this paper in light of
new experimental data. The results should give
better understanding of the processes occurring
in the graphite furnace when trace elements are
examined in the presence of an excess of matrix.
2. Theory and preliminary estimations
The radiation flux from a heated body with
surface area S is characterized w17x by
U␭ ,T s S = ␧ ␭ ,T = u ␭ ,T
where ␭ is wavelength Žnm., T the temperature
ŽK., ␧ ␭ ,T the spectral emissivity Žratio of radiation
intensity of the tested material to that of the
black body., and
u ␭ ,T s 2 ␲ hc 2 ␭y5r w exp Ž yhcrk␭T . y 1 x
is the Planck function that characterizes the black
body radiation. It includes: the Planck constant
h s 6.63= 10y3 4 J ⭈ s; Boltzman constant k s 1.38
= 10y2 3 J ⭈ Ky1 ; and the speed of light c s 2.998
= 10 8 m⭈ sy1 .
For wavelengths in the range 200᎐500 nm and
temperatures in the range 2000᎐2800 K, as those
discussed in this work,
u ␭ ,T ( 2 ␲ hc 2 ␭y5 exp Ž yhcrk␭T .
Considering the internal surface of the tube as
the radiation source, the length of isothermal
zone and the radiating area should be regarded as
temperature-dependent, SŽT . w26,27x. Firstly, it
can be assumed that there is only one source of
radiation, which is the isothermal zone. The tube
1627
can be pyrocoated or lined with refractory metals,
whilst the radiating area can be covered with the
solid sample having unknown emissivity.
If the radiation is registered using a CCD array
spectrometer, each pixel of the CCD array de-
tects light within ⌬␭ interval around ␭ wave-
length. Signal Q␭ from each pixel depends on the
radiation flux and sensitivity of the pixel, ␣ ␭:
Q␭ ,T ; ␣ ␭ = U␭ ,T Ž4.
Finally, the signal from each pixel can be de-
rived from Eqs. Ž1., Ž3. and Ž4.:
lnQ␭ ,T s yhcrk␭T q ln w S Ž T . = ␧ ␭ ,T x
q ln␣ ␭ q Const. Ž5.
If the reference temperature T 0 is known, Eq.
Ž5. can be rewritten as
ln Ž Q␭ ,T rQ␭ ,T 0 . s yhcrk␭ Ž 1rT y 1rT 0 .
Ž1. q ln S Ž T . ␧ ␭ ,T rS Ž T 0 . ␧ ␭ ,T 0
Ž6.
or
ln Ž Q␭ ,T rQ␭ ,T 0 . s AŽ 1r␭ . q B Ž7.
Ž2. where
A s yhcrk Ž 1rT y 1rT 0 . , and Ž8.
B s ln S Ž T . ␧ ␭ ,T rS Ž T 0 . ␧ ␭ ,T 0 Ž9.
Eq. Ž7. displays a linear function of inverse
wavelength, if the spectral emissivity of the radiat-
ing surface is not changed with temperature, that
is
Ž3. ␧ ␭ ,T ( ␧ ␭ ,T 0 Ž 10.
In this case parameter A remains constant,
independent of the absolute ␧ ␭ ,T value and radi-
ating area. Accordingly, Eqs. Ž7. and Ž8. provide
the means to determine the temperature T of the
radiating source in the tube using Q␭ ,T and Q␭ ,T 0 .
Eq. Ž9. provides a basis to compare the radiating
1628 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644

areas within the range of possible emissivity vari-
ations.
In other cases, neglecting the thermal depen-
dence of spectral emissivity will cause a deviation
of calculated temperature, ⌬T, from the true
temperature, T. The deviation ⌬T can be esti-
mated using the equation derived from Eq. Ž6.,
ln w ␧ ␭ ,T r␧ ␭ ,T 0 x s hcrk␭ w 1rT y 1r Ž T q ⌬T .x
Ž 11.
Using the reference data on ␧ ␭ ,T of various
radiating substances w28x shown in Table 1, the
range of possible errors in temperature determi-
nation can be evaluated.
The highest ⌬T can be expected for carbon
and magnesium oxide, which are strongly affected
by the thermal dependence. The emissivities ␧ ␭ ,T
and ␧ ␭ ,T 0 extrapolated from the reference data
reported in Table 1 at 2000 and 2500 K, and 660
nm correspond to 0.88 and 0.84 for carbon, and
0.47 and 0.64 for magnesium oxide, respectively.
Considering 2500 K as the reference temperature,
the calculations after substituting the constants
and other parameters into Eq. Ž11. give a ⌬T
value at 2000K of y9 and q58 K for carbon and
magnesium oxide, respectively. These values indi-
cate the possible error associated with the un-
known spectral emissivity of the radiating surface.
According to Eq. Ž9., the radiating area can be
estimated within an accuracy of ␧ ␭ ,T r␧ ␭ ,T 0 factor.
Obviously, the maximum error can occur if the
sources of measured and reference radiation
within the tube are different. According to Table
1, the largest difference in ␧ ␭ ,T at equal tempera-
tures is a factor of 6 and the highest error in
evaluating the radiating area is related to the
carbon᎐copper pair. For other materials the error
is 2 to 3 times lower.
Non-isothermal heating of the tube due to the
cooled ends, is another predictable source of er-
ror in the temperature evaluation. Its effect can
be estimated from the following considerations.
It can be assumed that in the non-isothermal
tube, i radiating surfaces with areas si , and tem-
peratures Ti produce a total radiation flux:
U␭ ,T s ␧ ␭ ,T 2 ␲ hc 2 ␭y5 Ý w si ,exp Ž yhcrk␭Ti .x Ž 12.
The data presented by Welz et al. enable esti-
mation of the thermal gradient for the HGA tube
Ž28 mm in length. under steady-state heating con-
ditions w29x.
Measurements indicate that the gas tempera-
ture was 2723᎐2623 K within the central area Ž12
mm in length.. An almost linear drop of tempera-
ture was observed beyond the isothermal area
down to 1000᎐1100 K Ž0.5 mm from the tube
end.. Therefore, the average temperature between
the isothermal zone and tube ends is approxi-
mately 1800 K. Under the consideration that gas
temperature corresponds to that of the tube wall,
the radiating areas s1 and s2 are proportional to
12 and 16 mm, and the temperatures T1 and T2
are equal to 2675 and 1800 K, respectively. Using

Table 1
Spectral emissivity of different substances w28x

Substance Wavelength Temperature ␧␭ ,T ⌬␧␭ ,T r⌬T

Žnm. ŽK. Ž=10y5 .

Iron 660 1300᎐1800 0.39᎐0.35 y8.0

Copper 660 1375᎐1500 0.15᎐0.13 y1.9
Molybdenum 665 1300᎐2750 0.378᎐0.332 y3.2
Nickel 460 1200᎐1600 0.450 0
535 1200᎐1600 0.425 0
665 1200᎐1650 0.375 0
Platinum 660 1000᎐2000 0.29᎐0.31 q2.0
Tantalum 467 1400᎐2100 0.505᎐0.460 y6.4
Carbon 540᎐660 1600᎐2500 0.92᎐0.84 y8.8
Magnesium oxide 660 1300᎐2000 0.23᎐0.47 q34
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
Eq. Ž12., the calculated contribution of the tube
ends to the total radiation is less than 1%. There-
fore, the tube ends can be ignored in temperature
calculations.
The temperature distribution during pulse
heating was analyzed by Falk et al. w26x and
Chakrabarti et al. w27x. They proved that the
temperature near the tube ends during the initial
stage of the heating could be higher in compar-
ison to that in the tube center. Obviously, the
radiation area reaches a maximum when the tube
becomes isothermal. The length of the isothermal
area during pulse heating can reach 28 mm in
length, i.e. 2᎐3 times higher than the central area
under steady state heating w29x.
Several radiation sources besides the wall, can
appear in the tube due to the vaporization of
large samples. It might be solid particles, both
ejected by the sample or formed during condensa-
tion. In these cases, the calculated temperature
will deviate between the highest and lowest value
depending on the respective radiating area. In
order to find the temperature of the other radiat-
ing sources, the radiation recorded during the
blank firing can be subtracted from total radia-
tion recorded during sample vaporization. The
net radiation caused by sample vaporization can
be attributed to a single radiation source. The
temperature of such a source can be determined
using Eq. Ž7. and the reference temperature re-
lated to the radiation of the tube. The unknown
emissivity of the radiation source and its tempera-
ture dependence are unlikely to cause an error
exceeding the estimations reported above.
3. Experimental
The method of temperature evaluation using
the wavelength distribution of the emission from
the internal surface of the tube was examined in
the case of steady-state and pulse heating. The
results were compared with those obtained by
optical pyrometry.
Microgram quantities of Mg, Be, Pd and Cu as
nitrates were vaporized in pyrographite and
Ta-lined tubes. Light absorption of the contin-
uum source and emission from the tube were
1629
monitored in the range 200᎐475 nm during sam-
ple vaporization. The emission spectra were com-
pared with those obtained during blank firings
and used to evaluate the internal temperature of
the tube. Experimental technique and data acqui-
sition did not differ significantly from those al-
ready described w18᎐22x.
The vaporization of Mg and Be was already
investigated in detail w18,19x. The data presented
in this work were obtained using an extension of
the spectrometer spectral range up to 475 nm,
and using recent developments in emission mea-
surements and temperature calculations.
3.1. Instruments, reagents and materials
The experiments were performed using an
SD1000 ŽOcean Optics. fiber optic spectrometer
Žspectral resolution s 0.3 nmrpixel. coupled to a
deuterium light source and Perkin-Elmer HGA-
500 atomizer w18᎐22x. Commercial pyrocoated
graphite tubes without a platform, and the same
tubes lined with Ta foil Ž0.05 mm, Aldrich Chemi-
cal Co., USA., were employed. Radiation from
the deuterium light source was focused on the
center of the tube furnace and collected with the
collimating lenses of the fiber optic connectors.
The radiation from the tube wall at higher tem-
peratures superposed that of the deuterium light
source.
Independent measurements of temperature of
the tube internal wall were performed using an
optical micro-pyrometer PB06 ŽKeller, Germany.
having a certified precision of "5 K for the range
1973᎐2273 K.
Aqueous solutions of Mg, Be and Cu Ž0.1᎐1%
mass. were prepared from the corresponding ni-
trates ŽRiedel- de Haen,¨ Germany.. Pd nitrate
solution Ž1% mrm; Merck, Germany. was used
without dilution. Graphite fiber levertex was used
in the experiments for evaluating the stabilized
temperature.
3.2. Procedure
The wavelength distribution of emission from
pyrocoated or Ta-lined tubes was detected using a
1630 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644

CCD spectrometer through the tube end for tem- Table 2

perature calculations. Thermal program used in the experiments
The emission measurements at a stabilized Step Temp. Ramp Hold Ar flow Spectra
temperature in the range 1973-2673 K were per- ŽK. time time flow collected
formed using the pyrocoated tubes. Ar purge gas Žs. Žs. Žmlrmin.
flow through the furnace at 30 mlrmin was em-
1 383 20 20 300
ployed. Some experiments were performed with 2 673 15 20 300
the tube in which loose strands of graphite fiber 3 2673 1 14 30 67
were introduced through the sampling hole. The 4 2773 1 3 300
amount of fiber placed in the tube caused 20᎐30%
attenuation of light from the deuterium source,
but significantly increased the emission from the amined comparing the pyrocoated and Ta-lined
tube. The experiments with fiber were aimed to tubes’ behavior.
highlight the possible effects of increased radia- Absorption and emission spectra with and with-
tion area on temperature calculations. The out sample vaporization were collected in consec-
stabilized temperature of the internal wall of py- utive measurements to minimize possible effects
rocoated tubes was also measured through the of tube aging.
sampling hole using the optical pyrometer.
The absorption measurements during blank
firing and sample vaporization were performed in 4. Results and discussion
both pyrocoated and Ta-lined tubes according to
the procedure already reported w18᎐21x. The
emission spectra were registered using the same 4.1. Tube temperature and radiating surface area
procedure, but with the deuterium lamp off. The
tubes were heated according to the thermal pro- 4.1.1. Steady-state heating
gram reported in Table 2. The spectra were col- Stabilized temperatures in the pyrocoated tube
lected in the third step of the heating program. measured using the optical pyrometer are pre-
Several pyrocoated tubes of different ages were sented in Table 3. A good agreement with the
tested. The effect of spectral emissivity of the settings of the HGA power supplier was observed.
tube wall on temperature calculation was ex- The temperatures of four tubes of different ages

Table 3
Temperature and radiating surface area in the pyrocoated graphite tube ŽI. and in the same tube supplied with the graphite fiber
ŽII.

T ylogŽ Qn ,T r Qn ,T0 . s AŽ1r␭ . q B T, calculated SŽT .rSŽ2673 K.

ŽK. from Eq. Ž8. ŽK. calculated from Eq. Ž9.
yA yB
Settings Pyrometer I II I II I II I II
a b
2673 2659 0 0 0 0.82 2673 2623 1.0 6.7
2573 2569a 73.2 117.6 0.012 0.81 2592 2545 0.98 6.5
2473 2480a 174.0 216.2 0.044 0.82 2488 2447 0.90 6.7
2373 2390a 233.8 290.0 0.090 0.81 2431 2378 0.81 6.5
2273 2303 330.2 373.6 0.112 0.81 2343 2306 0.77 6.5
2173 2213 465.4 0.183 2231 0.66
2073 2113
1973 2038
a
Linear approximation of the experimental data for 1973᎐2273 K.
b
Reference temperature T 0 .
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
were very similar, when measured with the a
power supply set to 2673 K.
The intensity of CCD signals due to tube emis-
sion depended significantly on the adjustment of
the light-collecting lenses. The lowest emission
intensity was associated with the best lens adjust-
ment for the absorption measurements. The rele-
vant set of CCD signals from the pyrocoated tube
at different temperatures is shown in Fig. 1. The
uneven character of the profiles in the range
350᎐450 nm is attributed to variations of pixel
sensitivities of the CCD array employed w30x.
Emission intensity distributions in the 390᎐475-
nm range, normalized to the spectrum at 2673 K,
are presented in Fig. 2 using the co-ordinates
derived from Eq. Ž7.. The linear regressions cor-
responding to each processed spectrum, and the
calculated temperatures and estimated variations
of the radiating area are presented in Table 3.
Two measurements are reported corresponding to
an empty tube and a tube equipped with a graphite
fiber.
Fig. 1. Wavelength distribution of CCD signals at different temperatures in the pyrocoated graphite tube. Curves 1᎐6 are related to
2673, 2573, 2473, 2373, 2273 and 2173 K, respectively.
1631
The results in Table 3 show good correlation of
temperatures measured in the empty tube using
both the optical pyrometer and CCD spectrome-
ter. The 30% increase of radiating area occurs
with a temperature increase from 2173 to 2673 K.
The introduction of a graphite fiber in the tube
resulted in a 6.5᎐6.7-fold increase in radiation
intensity, which is attributed to the increased
radiating area. The calculated temperatures for
the tube with graphite fiber are slightly lower
than the corresponding temperatures of the empty
tube ŽTable 3.. The lower temperature of the
fiber might be attributed to the cooling effect of
the purge gas flowing through the furnace.
4.1.2. Pulse heating
Three pyrocoated tubes of different ages and
Ta-lined tube were heated according to the ther-
mal program reported in Table 2. The wavelength
distribution of emission during the vaporization
step is presented in Fig. 3 as a function of heating
time. The emission continuum appears after 4 s
1632 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644

Fig. 2. Wavelength distribution of emission of the pyrocoated tube normalized to the emission at 2673 K. Curves 1᎐5 correspond to
2573, 2473, 2373, 2273 and 2173 K, respectively.

Žspectra 17᎐18. and its intensity is stabilized after the Ca line at 422.7 nm is superimposed to the
approximately 10 s Žspectra 44᎐45.. Emission of continuum, and is due to Ca contamination. A

Fig. 3. Emission spectra collected during the vaporization step of blank firing.
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644 1633

complete cleaning of the tube from Ca would
have required a treatment at higher temperature,
but was not considered necessary for this work.
Each spectrum was plotted in the range
390᎐475 nm as in Fig. 2, taking as a reference the
last spectrum Žno. 67. recorded at an already
stabilized temperature ŽT 0 s 2673 K.. Parameters
A and B were determined from linear regressions
of each spectrum, while temperature and the
SŽT .␧ ␭ ,T rSŽT 0 .␧ ␭ ,T 0 ratio were calculated using
Eqs. Ž8. and Ž9..
Temperature calculations are presented in Fig.
4 Žcurves 1᎐4.. The temperature ramp of the new
tube was similar to that of the one exposed to 50
firings. Other tubes showed slightly different be-
havior at the beginning of vaporization step. The
maximum difference Žapprox. 100 K. was observed
between the new tube and the one exposed to
more than 100 firings Žcurves 2 and 3.. The calcu-
lated temperature in the Ta-lined tube Žcurve 4.
at 2300 K was approximately 50 K lower than that
obtained in the new pyrocoated tube.
According to Eq. Ž9., the radiating area SŽT . in
the pyrocoated tube decreased rapidly, but was
stabilized after 5 s ŽFig. 4, curve 5.. The tempera-
ture increase from 2350 to 2673 K occurred while
the radiating area was almost stabilized. A similar
behavior for the radiating area was observed for
all tested tubes. The stabilization of SŽT .␧ ␭ ,T
parameter of the Ta-lined tube occurred at a
level 1.5 times lower than that for the pyrocoated
tube. The difference can be attributed to the
spectral emissivity of the materials. Considering
␧ ␭ ,T of pyrographite close to that of carbon, an
emissivity ratio of 1.8 can be expected from the
data presented in Table 1.
It can be concluded that the emission of a
pyrocoated tube shows a wavelength distribution
typical of blackbody radiation. Therefore, it can
be used for temperature measurements during

Fig. 4. Temperature Žcurves 1᎐4. and radiating area Žcurve 5. of different pyrocoated tubes during the vaporization step. 1 s new
tube, 2 s aged tube after 50 firings, 3 s aged tube after 100 firings, and 4 s Ta lined tube. The radiating area of the tube 2 is
normalized to that at 2673 K.
1634 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644

Fig. 5. Net emission spectra due to the vaporization of 60-␮g Mg.

stabilized or pulse heating. Calculated tempera- 4.2. Sample ¨ aporization

ture differences caused by different surface emis-
sivity, thermal distribution or radiating area, do
not exceed 50᎐60 K at 2300᎐2700 K. Efficiency of
light collection and, hence, radiation intensity
does not affect temperature calculations.
4.2.1. Magnesium
The behavior of absorption spectra during the
vaporization of microgram quantities of Mg ni-
trate was already reported w18x. In the pyrocoated

Fig. 6. Temperature Žcurves 1 and 2. and radiating area Žcurves 1⬘ and 2⬘. during the vaporization of 60-␮g Mg Žcurves 1 and 1⬘.
and 40-␮g Mg Žcurves 2 and 2⬘.; temperature of a blank firing Žcurve 3..
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644 1635

tube, intense absorption at 285.2 nm and emission
at 383.5 nm overlapped the absorption continuum
caused by light scattering. Mg emission and ab-
sorption peaks appeared at the same time, but
absorption lasted longer. In the Ta-lined tube,
light scattering and emission at 383.5 nm were
not detected.
The measurements performed in this work show
that the light scattering, which accompanies Mg
vaporization, occurs simultaneously with the

Fig. 7. Emission recorded during the vaporization of 60-, 40- and 20-␮g Mg, and blank firing Žcurves 1᎐4, respectively.. A is the Mg
line at 383.5 nm Žbackground subtracted .; B is the emission continuum at 460 nm; and C is the Ca line at 422.7 nm.
1636 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
emission continuum at long wavelengths. The
subtraction of emission recorded during blank
firing ŽFig. 3. from the total radiation provides
spectra originating from the sample vaporization
only. The net spectra originated from the vapor-
ization of 60-␮g Mg are reported in Fig. 5.
The spectra reported in Fig. 5 and those ob-
tained with 40-␮g Mg were transformed in a way
similar to that employed with stationary heating
ŽFig. 2., using the last spectra obtained during
blank firing for the normalization ŽFig. 3.. The
graphs were in good correlation with the linear
function given in Eq. Ž7.. The results are pre-
sented in Fig. 6. The temperature of the radiation
source reached 3400᎐3500 K at the end of the
emission pulse independent of sample mass. The
calculated values were generally 500᎐600 K higher
than the corresponding temperatures of the tube
wall. An increase in sample mass resulted in a
longer existence of the radiation source. Con-
sidering the lowest emissivity of the radiation
source from Table 1, i.e. 0.3᎐0.5, the radiating
area with the elevated temperature should have
been at least 20᎐50 times smaller than that of the
tube wall.
The appearance of the light source at high
temperature should be discussed together with
other spectral phenomena.
Atomic emission at the Mg resonance line
Ž285.2 nm; excitation potential, 4.35 eV. is hardly
detected in Fig. 5. However, emission at 383.5 nm
related to the transitions between 5.95 and 2.71
eV for the term and metastable term, respec-
tively, Žnon-resolved triplet at 382.9, 383.2 and
383.8 nm w31x. is prominent. The net emission at
383.5 nm during the vaporization of 20-, 40- and
60-␮g Mg is reported in Fig. 7a. Peak heights
show only slight dependence on sample mass.
Apart from the behavior of the triplet, the light
scattering at 300 nm increases proportionally with
sample mass, while the emission continuum in-
creases even more rapidly. Emission intensities at
460 nm during blank firing and sample vaporiza-
tion are reported in Fig. 7b. Peaks of larger
masses are shifted towards higher temperatures
and coincide with the position of Mg triplet emis-
sion ŽFig. 7a..
The interaction of gaseous Mg oxide with
graphite causes evolution of reaction heat near
the tube wall w18x. Mg emission can be caused by
the reaction followed by the dissipation of the
released energy or directly by the dissipated en-
ergy. In any of these cases, simultaneous excita-
tion of low atomic levels of other metals present
in the tube should be expected due to this process.
The thermal behavior of calcium emission at
422.7 nm Žexcitation potential s 2.9 eV w31x.,
whose presence is due to contamination of Mg
nitrate and memory effect, confirms the presence
of heat transfer ŽFig. 7c.. Ca emission does not
exhibit a prominent peak during blank firing ŽFig.
7c, curve 4.. In this case, emission slowly in-
creases until the end of vaporization. In fact, the
temperature is not sufficient for complete re-
moval of Ca. The introduction of Mg nitrate in
the tube causes the appearance of Ca emission
peaks ŽFig. 7c, curves 2᎐4.. Peak positions coin-
cide with those of Mg emission ŽFig. 7a. and
those of the emission continuum ŽFig. 7b..
The simultaneous appearance of atomic emis-
sion at 383.5 nm and emission continuum, and
the different effects of sample mass on emission
intensity suggest that these specific types of radia-
tion are issued from different, but mutually-
dependent, phenomena. This statement is coher-
ent with data already reported w18,32x. According
to Katskov et al. w18x emission at 383.5 nm is
observed close to the tube wall, unlike the light
scattering that is related to the central axial area.
The emission that accompanies spatial vapor con-
densation Žand light scattering . emanates from
the central area of the tube w32x. It can be ex-
pected, hence, that the source producing the radi-
ation continuum is also located at some distance
from the wall.
According to the calculations reported by
Katskov et al. w18x, the vaporization rate of Mg
oxide in the pyrocoated tube exceeds the rate
normally controlled by the saturated vapor pres-
sure w28x. It was suggested, in order to explain the
phenomenon, that part of the energy evolved
during reduction of Mg oxide on the graphite
wall, was transferred to the Ar purge gas w18x. The
presence of radiation at 383.5 nm from the area
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
near the tube wall justifies this suggestion. The
appearance near the sample surface of ‘hot’ Ar
atoms with kinetic energy higher than average at
the tube temperature should cause the increase
of both production and kinetic energy of the
atoms and molecules released from the sample
surface. The excessive compared to the equilib-
rium at the tube temperature vapor flow from the
sample surface, should cause nucleation and
aerosol formation at some distance from the sam-
ple surface. The energy consumed during sample
vaporization should be then evolved back during
the process of vapor condensation. Thus, appear-
ance of emission can be expected during aerosol
formation. The temperature of the radiation
source should be consistent with the kinetic en-
ergy of atoms and molecules involved in the for-
mation of condensed particles.
The results obtained are congruous with this
theory. The increased mass release from the sam-
ple on the graphite surface is accompanied by the
formation of condensed particles and, conse-
quently, by light scattering. The radiation evolved
simultaneously with particle formation is charac-
terized by elevated temperature.
It can be suggested that part of the energy
evolved during formation of condensed particles
is also dissipated in collisions with Ar atoms.
Then, non-radiative dissipation of the evolved
energy should be more characteristic for the
smaller samples. This probably explains the non-
linear relationship of emission intensity with sam-
ple mass ŽFig. 7b..
Fig. 8. Net emission spectra due to the vaporization of 80-␮g Be.
1637
4.2.2. Beryllium
The evolution of emission during the vaporiza-
tion of beryllium nitrate was already studied w19x.
The process was accompanied, in the pyrocoated
tube, by appearance of light scattering and emis-
sion continuum. The estimation using the wave-
length distribution of radiation continuum calcu-
lated the temperature of the radiating source as
being 420 K higher than that of the tube. The
effect was attributed to a temperature increase of
the vaporization surface.
In this work, temperature measurements were
carried using different sample masses and im-
proved thermal resolution. Visual observations
inside the tube were performed during vaporiza-
tion of 100-␮g Be.
Unlike other elements, the vaporization of Be
is accompanied by random emission spikes each
having the spectral distribution of black body
radiation. The spectra recorded during the vapor-
ization of 80-␮g Be are presented in Fig. 8. One
of the emission spikes is seen in spectra 53᎐55.
Visual observations indicate the presence of bright
particles moving up in the tube towards the dos-
ing hole.
Furthermore, the particle number increased
with sample mass. These particles were responsi-
ble for the emission spikes. Thus, the attribution
of emission to effects occurring on the tube sur-
face must be reconsidered w19x.
The calculated temperatures of the radiation
sources are presented in Fig. 9. The highest tem-
1638 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644

Fig. 9. Temperatures of the radiating sources during the vaporization of 100-, 80- and 60-␮g Be, and blank firing Žcurves 1᎐4,
respectively..

Fig. 10. Most intense spectra recorded in absorption ŽA. and emission ŽB. during the vaporization of 100-␮g Pd in the pyrocoated
tube.
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644 1639

perature and significant scattering of results are ation temperatures. This can be illustrated by the
characteristic for the lower sample mass. The calculations performed using the spectra shown in
increase of sample mass can induce the random Fig. 8. The spectra 35᎐36 reported in Fig. 9, curve
appearance of the emission spikes at various radi- 2, and corresponding to the first emission maxi-

Fig. 11. Temperature and radiation from the furnace during the vaporization of 50- and 100-␮g Pd, and blank firing Žcurves 1᎐3,
respectively.: As temperature; B s emission continuum at 460 nm Žemission during blank firing subtracted .; and C s emission at
Pd line 363.5 nm Žbackground subtracted ..
1640 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
mum show a temperature approximately 800 K
higher than that of the tube. On the contrary, the
intense spectra 53 and 54, related to the second
emission maximum, give a temperature lower than
that of the tube ŽFig. 9, curve 2.. Most probably,
those spectra are due to the atomsrmolecules
released near the tube ends. The spectra obtained
with the largest mass Ž100 ␮g. show that the
temperature is almost constant and approximately
700 K higher than that of the tube wall ŽFig. 9,
curves 1 and 4..
According to the hypothesis already advanced,
reduction of BeO by carbon and carbide forma-
tion can be responsible for the thermal effect
w19x.
4.2.3. Palladium
The vaporization of Pd in the pyrocoated tube
is accompanied by the appearance of several
atomic lines that overlap the continuum due to
light scattering. The continuum intensity in-
creases proportionally with sample mass. At
longer wavelengths, light scattering and emission
continuum were superimposed. The spectrum re-
lated to maximum scattering with 100-␮g Pd is
presented in Fig. 10, curve a, while the spectrum
related to maximum emission is shown in Fig. 10,
curve b. The emission continuum is similar to that
observed in the case of Mg ŽFig. 5..
Light scattering and emission continuum are
undetectable in the Ta-lined tube. Atomic lines
are less intense and last longer than in the pyro-
coated tube. The calculated temperatures of the
radiation source are shown in Fig. 11a. The tem-
perature increases and reaches a maximum 460 K
higher than the tube temperature at the end of
the vaporization. The increase of sample mass
causes the stabilization of temperature and radi-
ating area. Apparently, the equilibrium between
energy supply and removal can be attained for
large samples as in the case of Be.
The evolution of emission at 460 nm in the
pyrocoated tube, caused by the vaporization of 50
and 100-␮g Pd, is shown in Fig. 11b. The wave-
length is chosen for the indication because of
maximum pixel sensitivity and absence of struc-
tural spectra. The peaks are observed at a tube
temperature of 2450 and 2500 K, respectively.
The peak for 100-␮g Pd is five times higher than
that of 50-␮g Pd. The peak half-width is approxi-
mately 1.0 s for both amounts.
The tube temperature and peak half-width en-
able the estimation of vaporization rate and con-
centration of atoms in the gas phase. The release
of 100-␮g Pd occurs during 1.0 s at an average
temperature of 2500 K and 0.5-mlrs Ar flow
Žmeasured at 300 K.. The average concentration
Ž c . of Pd atoms in the purge gas during the
vaporization pulse corresponds to 24.0 grm3. The
partial pressure ŽPa. derived from
ps Ž crM . RT Ž 13.
where the Pd atomic mass M is 103 grmol, and
R s 8.31 Jrmol, is 4840 Pa.
According to the reference data, the saturated
vapor pressure of Pd at 2500 K is 930 Pa w28x.
Hence, an isothermal vaporization cannot support
this rate of free atom formation w33x. Such a
vaporization rate is possible only if additional
energy is transferred to the sample and condensa-
tion occurs in gas phase. According to the specu-
lations for Mg and Be, the exothermic gas phase
condensation should cause appearance inside the
tube of the radiating source with elevated tem-
perature.
Therefore, the data presented support the oc-
currence of an exothermal reaction of Pd with the
pyrographite surface. For large samples, the
evolved energy is transferred to the sample sur-
face and increases the mass output during the
first part of the vaporization process. The release
of Pd from the reaction products will require
higher temperature and longer time. According to
this theory, the presence of Pd atoms in the tube
should be displayed longer than that of the emis-
sion continuum. The idea is confirmed by the
behavior of atomic emission of Pd at 363.5 nm
ŽFig. 11c..
4.2.4. Copper
The vaporization of increasing Cu mass Ž20, 40
and 60 ␮g. showed similar behavior in the pyro-
coated and Ta-lined tubes, unlike other tested
elements. The most intense absorption spectra
observed in both tubes are presented in Fig. 12.
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644 1641

Fig. 12. Absorption spectra observed during the vaporization of 40-␮g Cu: As pyrocoated tube; and B s Ta lined tube.

Fig. 13. Temperatures Žcurves 1 and 2. and radiating areas Žcurves 1⬘ and 2⬘. during the vaporization of 60-␮g Cu Žcurves 1 and 1⬘.,
and 40-␮g Cu Žcurves 2 and 2⬘.. Temperature of a blank firing Žcurve 3..
1642 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
Each spectrum includes absorption continuum
due to light scattering. It changed to emission at
long wavelengths, and overlapped by Cu atomic
lines at 324.7 and 325.4 nm, and unidentified
bands having intensity maximum at 217, 224, 238,
253 and 276 nm, respectively. The bands appear
contemporaneously with the atomic lines, which
suggests their attribution to the molecular Cu
species.
The intensity of light scattering in the area free
of overlapping bands Žat 300 nm. increases pro-
portionally to the sampled mass. The emission
spectra show a behavior similar to those of other
elements. The emission peak height of 60-␮g Cu
is 2.2 times higher in the pyrocoated tube than
the Ta-lined tube. A non-linear increase of emis-
sion intensity with sample mass is observed in
both tubes.
Two sets of temperature calculations were per-
formed with 40- and 60-␮g Cu in pyrocoated and
Ta-lined tubes. Temperature evolution and the
radiation surface area of the pyrocoated tube are
shown in Fig. 13. The radiating surface decreases
simultaneously with temperature increase. Both
processes are delayed when larger samples are
vaporized. The highest temperature, approxi-
mately 3500 K, is reached at the end of vaporiza-
tion. The average temperature of the radiating
source is approximately 600 K higher than that of
the tube. The calculations of temperature and
radiation source area of the Ta-lined tube were
similar to those obtained with the pyrocoated
tube. It was impossible to determine the tempera-
ture difference between the emission source and
tube wall because of low radiation from the wall.
The half-width of the vaporization peak for 40
␮g of Cu vaporization at 2150 K is approximately
0.45 s. Calculations similar to those applied to Pd
give an average concentration of 24.8 grm3 of Cu
vapor in the purge gas. The partial pressure Ž7045
Pa. is more than six times higher than the satu-
rated vapor pressure of Cu at 2150 K, i.e. 1030 Pa
w28x.
The discrepancy between the experimental rate
of vapor release and theoretical rate Žunder the
assumption of thermal equilibrium. is consistent
with the suggestion advanced with Pd about sam-
ple interaction with the tube wall. Spectral bands
in Fig. 12 can be attributed to the evolution of
molecular species that precede the spatial vapor
condensation.
5. Conclusion
A comprehensive description of the pheno-
mena can be gathered under the consideration
that all effects observed for different metals have
a similar origin.
The vaporization of samples in microgram
quantities can be accompanied by transient emis-
sion continuum with wavelength distribution
characteristic of black body radiation. The effect
is selective towards the sample and material of
the tube surface. The continuum radiation source
is formed due to exothermic gas phase condensa-
tion of the sample atoms and molecules. The
radiation temperature is specific for each sample
and, in most cases, higher than the tube tempera-
ture. The effect appears together with a high rate
of mass release, and can be accompanied by tran-
sient emission due to excited atomic levels of the
sampled element or emission due to the presence
of impurities.
The results show that the number and kinetic
energy of atoms and molecules released from the
sample surface in the tube furnace are controlled,
irrespective of tube temperature, by interaction
between tube material and the sample. The en-
ergy evolved during the exothermal interaction is
partially transferred to the gas phase by the sam-
ple vapor and released via radiation during aero-
sol formation.
The data obtained in this work give additional
information on phenomena already studied, in-
cluding the nature of the radiation w32x, and the
location of the radiation source w18,19x. The re-
sults also explain the effect of ionization of In in
the presence of MgO, recently observed in
GFAAS w34x. The experimental results, apart from
their interpretation, show the presence of the
processes in the tube atomizers that are not ex-
plained by the isothermal approach.
A definitive explanation to several observed
phenomena cannot be advanced yet. The nature
of reactions of Pd or Cu with graphite at high
 D. Katsko¨ et al. r Spectrochimica Acta Part B: Atomic Spectroscopy 56 (2001) 1625᎐1644
temperature is not clear, although the existence
of interactions is known w35x. Also, the nature of
Cu᎐Ta interactions, formation of large BeO par-
ticles during spatial condensation, and assignment
of individual bands observed during Cu vaporiza-
tion are not clear. Further studies are required
to provide a satisfactory explanation for these
effects.
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