SPECTROCHIMICA ACTA PART ELSEVIER setrochimica Acta Part B 54 (1999) 1045-1062, wwwelsevierniovate’sab Effect of magnesium nitrate vaporization on gas temperature in the graphite furnace D.A. Katskov*, G. Daminelli*, P. Tittarelli® inment of Chemistry and Physies, Technikon Pretoria, Private Bag XO80, Pretoria, 0001, South Africa Stazione Sperimentale per i Combustibl,V.le De Gasperi 3, 20097 San Donato Milanese, Ml, Hay Received 15 October 1998; aocepted 5 February 1999 Abstract The vaporization of magnesium nitrate was observed in longitudinally-heated graphite atomizers, using pyrocoated and Ta-lined tubes and filter furnace, Ar or He as purge gas and 10-200-pg samples. A charge coupled device (CCD) spectrometer and atomic absorption spectrometer were employed to follow the evolution of absorption spectra (200-400 nm), light scattering and emission. Molecular bands of NO and NO} were observed below 1000°C Magnesium atomic absorption at 285.2 nm appeared at approximately 1500°C in all types of furnaces. The intensity and shape of Mg atomization peak indicated a faster vapor release in pyrocoated than in Ta-lined tubes. Light scattering occurred only in the pyrocoated tube with Ar purge gas. At 15001800°C it was observed together with Mg absorption using cither gas-flow or gas-stop mode. At 2200-2400°C the scattering was persistent with gas-stop mode. Light scattering at low temperature showed maximum intensity near the center of the tube axis. Magnesium emission at 382.9, 383.2 and 383.8 nm was observed simultaneously with Mg absorption only in the pyrocoated tube, using Ar or He purge gas. The emission lines were identified as Mg *P°="D triplet having 3.24 eV excitation energy. The emitting species were distributed close to the furnace wall. The emitting layer was thinner in He than in Ar, The experimental data show that a radial thermal gradient occurs in the cross section of the pytocoated tube contemporaneously to the vaporization of MgO. This behavior is attributed to the reaction of the sample vapor with the graphite on the tube wall. The estimated variation of temperature within the cross section of the tube reaches more than 300-400°C for 10 wg of magnesium nitrate sampled. The increase of gas temperature above the sample originates a corresponding increase of the vaporization rate. Fast vaporization and thermal gradient together cause the spatial condensation of sample vapor that induces the light scattering. © 1999 Elsevier Science B.V. All rights reserved, Keywords: Graphite furnace atomic absorption spectrometry (GFAAS): Magnesium modifier; Absorption spectra: Light scatter Gas temperature * Corresponding author, E-mail address: katskow(@techpta.c.2a (D.A. Katskov) 884.8547 /99 /8- s PH: S0584-8547(99)000 ¢ front mater © 1999 BI vier Science B.V. All rights reserved.1046 DAA. Katskow et al. / Spectrochimica Acta Part B: Atomie Spectroscopy $4 (1999) 1045~ 1062 1. Introduction ‘The guiding principle in analytical applications of graphite furnace atomic absorption spectrome- tty (GFAAS) is the stabilized temperature plat- form furnace (STPF) concept introduced by Slavin et al, [1]. The main aspects of the concept are the modification of the sample by addition of chemi- cal reagents, and the fast vaporization of the sample into the analytical zone having constant temperature. The gas temperature of the analyti cal zone is considered independent either on the mount of sample and modifier, or on the vapor composition, The STPF concept enables the use of the isothermal heterogeneous equilibrium for the cal- culation of vapor composition, according to the nature of the sample, modifier or substrate mate~ rial, and presence of active gases in tube atmo- sphere [2.3]. The energy evolved in chemical rea tions occurring in the atomizer is distributed among all participants at constant temperature. ‘The inert gas is not included into calculations and is considered only as a diluting medium. Either STPF concept or isothermal equilibrium approach are correct as far as the energy evolved into the gas phase, or consumed by the gascous species during the atomization, is negligible. Re: sonable doubts in the consistency of these con- cepts arise when large amounts of sample or modifier are vaporized. In this context the effects related to light scattering attract special attention [4-7] Lyov et al. [4] observed non-homogeneous dis tribution of particles, that induced light scatter ing, across the furnace in the vaporization of micrograms of AKNO,),. The light scattering was attributed to the presence of soot particles formed during the thermal decomposition of gascous aluminum carbide. This explanation was rejected after the observation of light scattering produced by particles of gold and silver [5]. The data re- ported by Frech et al, [5] were inconsistent with the explanation of the light scattering given by Gilmutdinov et al. [6], who suggested the forma- tion of solid particles of oxide in the center of the graphite furnace due to high concentration of oxygen near the dosing hole. Frech et al. [5] and Hughes et al. [7] observed that non-specific ab- sorption occurred due to the spatial condensation of vapors at the center and ends of the tube when micrograms of sample were vaporized in end- cooled graphite tube. These two effects of gas- phase condensation were partially time-resolved. and the condensation at the tube ends could be suppressed by the presence of internal gas flow. Although the attribution of these effects to ther- mal non-homogeneity was solid, the reasons for the proposed temperature distribution across the tube remained unclear. Suggestions were ad- inced by Frech et al. [5] and Hughes et al. [7] about the dependence of temperature gradient on the design and operation of the atomizer, ie. on the presence and orientation of the dosing hole, internal gas flow, atomization temperature and heating rate, but not on the presence of sample. According to the data reported by Welz et al. [8], the distribution of temperature in the central part of the furnace was uniformly independent of the gas flow. To explain the disagreement, it was underlined [5,7] that the precision in temperature measurements reported [8] (50 K) was not suffi- ient to detect thermal non-uniformities responsi- ble for light scattering. This argument did not take into account a supersaturation ratio required for the particles formation and growth. According to Hinds [9], the condensation occur at supersatu- ration ratios from 2 to 10, The calculations for gold yielded a ratio equal to 16.4 [7]. The differ- ence in saturated vapor pressure by 2~16-fold at 2000-2200 K is related to temperature change of approximately 70-300 K [10]. Hence, the differ- ence in gas temperature between the areas with and without condensation should exceed the pre- cision estimated by Welz et al. [8]. A donut-shaped distribution was observed at the vaporization of Al [6], Au, Pd+ Mg(NO,)., La(NO,);, MgCl, [7], and Cu [11]. A different distribution of scattering with maximum in the upper part of the furnace was observed for am- monium phosphate [7]. The localization of some reactions on the furnace wall, reported by Gilmutdinoy et al. [12], and the specific distribu- tion of particles for different substances, cannot be explained within the frame of isothermal equi- librium model. In fact, the only meaningful dif-DLA. Katskow et al. / Spectrochimica Acta Part B: Atomic Spectroscopy 54 (1999) 1045-1062 1047 ference between the experiments reported by Welz et al. [8] and by Frech et al. [5] and Hughes et al. [7], which could possibly affect the tempera- ture, was the presence of sample vapor in the atomizer [5,7] A different approach can be suggested instead of the isothermal equilibrium model. The energy evolved in chemical reactions is transferred to the gas in the proximity of the reaction area. The consequent temperature gradient will depend on the amount of energy, location of the reaction, and parameters of heat transfer. Apparently, the intensity of the effect should depend on the chemical form of the main matrix components. Carbon or graphite of the tube can be active participants of the reaction. The heat evolved in the exothermic reactions of the sample vapor with graphite will cause a radial symmetry of tempera- ture distribution The reaction between gaseous products of dis sociation of AKNO,),, Ma(NO,)s, La(NO,),, and graphite can be taken into account to evaluate the validity of this approach, as the behavior of these compounds was already studied [5~7]. The oxides of these elements are stable up to temper- atures between 1300 and 2000°C. In this tempera- lure range, a substantial part of vapors above the solid phase consists of gaseous element and oxide, both capable to react with graphite to form CO, CO, and carbides [13-16], Among the nitrates listed above, Mg(NO,)> displays the best properties as modifier [17,18]. It can be used as a test compound to examine the advanced hypothesis. also in connection with its broad analytical applications. In this paper, the effect of heat transfer deriving from the vaporiza- tion of Mg(NO,), is discussed using experimental results and dats already reported [19,20] 2. Physical model and preliminary estimations According to Langmuir’s theory of metals va~ porization, an equilibrium is established at atmo- spheric pressure above the vaporization surface in the gas layer corresponding to mean free path of the particles that vaporize, due to the multiple collisions. between vaporizing particles and molecules of the ambient atmosphere [21]. The particles are moved away from the boundary layer via concentration diffusion. Particle transporta- tion beyond the layer can be attributed to diffu- sion, convection or capture by the carrier gas, depending on the vaporizer design. ‘The idea of boundary layer was applied in the theory of atomization of oxides in the electrother- mal atomizers [22-24]. It was advanced that ther- modynamic equilibrium at a given temperature is established for all dissociation products present in the boundary layer above solid oxide. The vapor- ization rate is affected by the total vapor pressure of all gaseous components above the sample. Heat transfer to the boundary layer is performed mainly through collisions of atoms of the purge gas with the sample surface. To apply the model, the size of vaporization area should be large enough in comparison to the mean free path of particles. For the molecular species as Oy, Ny, at temperature T (K) and atmospheric pressure, the mean free path is ap- proximately 7.2 x 10° x (7/300) cm [25]. Then, the thickness of the boundary gas layer is approxi- mately 6X 10-* cm at 2500 K. Accordingly, the sample surface should have a diameter at least larger by an order of magnitude, ie. approxi- mately 0.001 cm. A single particle with 0.001-cm diameter would have approximately 2-ng_mass, for oxides having 3-4 gcm_* density [13]. Hence, Partial pressure of the vapor components above solid magnesium oxide, N/m? [13] Femperature (K MgO Mg 1500 20x ° 2.00 10-5 2000 22% 10 38x! 250 150 9 3000) 129x108 6.01 10° ° 0; Total ax we" Bax? 35x10 S 2x10? Las x! Rib j0"! 319 486 309 Lor 219% I 2.27% 10104s DAA. Katskov et al. / Spectrochimica Acta Part B: Atomic Spectroscopy 54 (1999) 1045-1062 the model can be applied for sample mass larger than 2 ng with arbitrary distribution of particles size The introduction of 3-15 wg Mg(NO,), into the furnace (the amount typically used for chemi- cal modification (16-18), originates a dry residue of 1-5 4g MgO after thermal pretreatment. The vaporization rate is defined by the total equilib- rium vapor pressure of all components (Table 1), by the sample surface, and by the mechanism of vapor removal ‘The evaporation rate in the tube furnace can reach a maximum if the vaporization surface exceeds the area through which the vapor is re- moved [26]. In this case, the equilibrium is es- tablished all over the space of the analytical zone, and the vaporization rate depends only on the equilibrium vapor pressure and on the removal mechanism: Mugo/t = Musgol Ps/RTV/t,), a@ where m (g) is the sample mass, M=40.3 (g mol!) is the molar mass of MgO, # (s) is the vaporization time, py (N m~*) is the total equi- librium vapor pressure, R= 8.31 (J K-! mol~') is the gas constant, V (m‘) is the furnace volume, and 7, (5) is the residence time of the sample particles in the analytical zone. Hence, the maxi mum of the vaporization rate of MgO in a graphite furnace can be evaluated and compared with the experimental data. The vaporization rate can reach from 0,002 to 0.016 wg s~! at 2000 K, and from 08 to 5.7 wg s-! at 2500 K by substituting into Eq. (1) the molar mass of MgO, the total vapor pressure ps from Table 1, the volume of the HGA-S00 atomizer (V= 0.8 x 10" m°), and a reasonable range of residence times for particles of different size (7, = 0.1-0.3 s) [27]. Non-specific absorption was recorded at 250 nm, when 2 yg Mg [from Mg(NO,),] was vapor- ized from the tube wall in HGA-500 atomizer at various temperatures [5]. According to Fig. 6 of Frech et al. [5], the half-width of the absorption signal at 1700°C (gas flow, 10 em’ min~') is approximately 0.75 s, while total duration is Jess than 3 s. Therefore, the vaporization rate of 3.3 hg MgO is approximately 1-2 wg s'. Thus, experimental data on the vaporization rate ob- tained from Frech et al. [5] are 60- to 1000-fold higher than the value calculated by the theoreti- cal model (0.002-0.16 wg s~'). It can be sug- gested that the real gas temperature near the sample is approximately 400-500°C higher than that indicated in the atomizer programmer. ‘The following reactions can be considered to be an additional source of energy: C+0;3C0,; C+0>C0 @ If the energy deriving from the interaction of the © and O, particles with graphite is completely transferred to the CO/CO, molecules, the tem- perature increase, AT,, can be found from the equation of adiabatic process AH,=C,AT,, (3) where AH, is the enthalpy of CO/CO, forma- tion and C, is the CO/CO, gas heat capacity at constant pressure. The result from the calcula- tions gives AT, equal to 2925 K for CO or 6380 K for CO, using the reference data for CO or CO, (13k AH, = 110 or 393 (kJ mol-') and C, = 37.6 or 61.6 (J K"! mol~'). The energy derived from the ‘hot’ CO or CO, molecules will be dissipated after several collisions with molecules of purge gas in the proximity to the wall. The rate of temperature increase of purge gas depends on the amount of gases involved either in CO or CO, formation or heat exchange. A minimum quantity of heat will evolve from the reaction of graphite with the oxygen fraction al- ready formed in the thermal dissociation of solid Mgo: Q=[AH,(n/M eg + 1X H,0n/M Neo (4) AS a consequence, the average temperature of the gas in the analytical zone will increase by 57 according to O/t=C, Tm, = C,,8TIV/(0.0224)(300/T 1/2, ()DAA, Katskov et al. / Spectrochimica Acta Part B: Atomic Spectroscopy $4 (1999) 1045-1062 toss where m, is the gas mass, C,,. the heat capacity of Ar or He gas (20.79 J K-! mol” *), 0.0224 (m? mol!) the molar volume of the ideal gas at 300 K, and 7, the residence time of purge gas parti- cles in the analytical zone. It can be concluded, using the data reported in Table 1, that the molar mass of O and O. formed in thermal dissociation of solid MgO, jelds approximately 30% of total vapor mass at 2000 K. Accordingly, it is possible to suggest that 8.3 x 10°° mol O and 15.0 x 10-” mol O, deriv- ing from 8.23 x 10°* mol MgO G.32 pg), used in the experiments [5], will react with carbon. As CO and CO, are formed by corresponding amounts of O and O,, the amount of heat evolved, caleu- lated from Eq. (4), is equal to 0.0068 J. According to the results reported by Frech et al. (5), during the vaporization of 2 4g Mg half Q energy is released during 0.75 s, ie. Q/t = 0.0045 Js” '. By substituting into Eq. (5) T = 2000 K and tp = Ty be. 0.10.3 8, BT close to 10-20 K is obtained. The calculated value represents an average temperature over the cross section of a graphite tube having 0.6-cm diameter. The upper limit of temperature, T+ AT, near the wall reflects the root-mean-square velocity of ‘hot’ CO/CO, molecules. Due to collisions, the temperature is reduced to T at a distance / from the wall. The thickness of ‘hot’ layer / should be approximately 0.001 cm to obtain the calculated average value @T, considering a linear thermal gradient close to the wall. The area near the wall, where the particles of purge gas have an excessive energy, includes the boundary layer above the sample. That should originate an increase of surfacial temperature and a consequent increase of vaporization rate. It can be predicted that an increase of sample mass would produce a decrease of thermal gradi- ent near the wall, due to the increase of average temperature across the furnace. The use of He instead of Ar should give rise to a more uniform distribution of temperature, because of higher thermal conductivity (thermal conductivity of He and Ar are, respectively, 1.41 and 0.16 mW cm K-' at normal conditions [28]. A quantitative evaluation of the effects of mass or type of purge gas on the temperature profile in the graphite furnace requires more complicated modeling, beyond the frame of this work The modeling and the estimations enable to advance a description of vaporization processes of MgO in the graphite furnace. MgO vapors appear in the furnace above 1360°C (Kantor et al. [29]). MgO vaporization is accompanied by thermal dissociation with release of Mg, MgO, O and O,. Collisions of dissociation products with graphite wall cause the formation of CO, CO, and the appearance of radial dis- tribution of temperature in the analytical zone. ‘The heat is partially transferred to the sample surface via purge gas with consequent increase of vaporization rate. The vapor from the hot area near the wall enters the cooler area along the furnace axis. If the amount of sample is sufficient to create over saturated vapor, then spatial con- densation occurs 3. Experimental 3.1, Instrumentation and experimental setup ‘The collection of absorption spectra during the vaporization of Mg(NO,), was performed using a Ocean Optics SD-1000 Charge Couple Device (CCD) spectrometer equipped with deuterium source. The spectrometer enabled the acquisition of spectra in the wavelength range 200-400 nm, with 0.3 nm/element spectral resolution and 20-50 ms collection time. The spectrometer was coupled with HGA-500 atomizer and AS-40 auto sampler. The operation of the spectrometer was already described [30]. A Perkin-Elmer Model 5000 atomic absorption spectrometer was used for the resolution and identification of magnesium emission lines, and for the observations of the spatial distribution of atomic emission and light scattering in the pyro- coated tubes. The spectrometer was equipped with a HGA-500 atomizer, and AS-40 auto sampler. In order to perform spatially resolved determina- tions, 1x I- or 2X 2-mm diephragms were em- ployed to narrow the light beam along the optical axis. A magnesium hollow cathode lamp (Perkin- Elmer) was used as a reference source for theoso D.A, Kaiskow etal. / Spectrochimica Acta Part B: Atomie Spectroscopy $4 (1999) 1045-1062 identifications of emission lines, and a deuterium lamp was used for light scattering measurements. A Keller Micropyrometer type PB 06 AF 3 was employed for temperature measurements. Pyrocoated and tantalum lined tubes of stan- dard geometry and filter furnaces were used in the HGA. In the lined tubes, a tantalum foil (Aldrich) having 0.025 mm thickness covered the entire internal surface of the tube except the dosing hole. The design of filter furnaces was already described [31] 3.2, Reagents and materials Pyrolytically coated graphite tubes were used for wall vaporization. The same type of tubes was used with tantalum lining. Union Carbide UF-4S graphite was used for both tube and filter of the filter furnace. The filter furnace tubes, manufactured by PYRO- CARBO SA, were pyrocoated. Graphite fabric G814-3K was placed into the ring cavity of the filter furnace. The samples were prepared by dilution of Mg(NO,), (Merck, Germany) in ultra pure water. 3.3. Procedure ‘The optical arrangement of CCD spectrometer is presented in Fig. la, the arrangements of the atomic absorption spectrometer are shown in Fig. Ib-e. 3.3.1. Evoluion of molecular absorption spectra (Fig. 1a) Ten or 20 yl of 1% solution of Mg(NO,), were sampled into the pyrocoated and Ta-lined tube or filter furnace and the atomizer was heated ac- cording to the thermal program listed in Table 2. At the vaporization step, 1-s ramp- and 7-s hold- time enabled gradual but sufficiently fast heating to obtain short absorption signals and temporal and thermal resolution. Forty spectra were recorded during the vaporization step. Ar and He were used as the purge gas at 30 ml min~! flow rate. ; es = 5 . ; i S| AA a | > v0 CS — Fig. 1. Experimental arrangements. (a) Collection of Mg(NO;), vapor spectra in the range 200-400 am; (b) sean ning of Mg radiation from hollow cathode lamp in the range 382-384 nm: (c) stepwise scanning of emission spectra from Mg(NO}); vapor in the pyrocoated tube; (@) stepwise scanning ‘of radial distribution of Mg emissien at 383.8 nm: (e) stepwise scanning of radial distribution of light seattering at 240 nm (1, deuterium lamp; 2, graphite furnace; 3, entrance slit; 4, fer optics CCD spectrometer: 5, Mg hollow cathode lamp: 6, atomic absorption spectrometer: 7, diaphragm [1 ¥ I- and 2x 2mm for the arrangement (d), and 2x 2mm for the arrangement (0)). 3.3.2. Identification of emission lines (Fig. 1b,c) The radiation of Mg lamp was scanned in the spectral area 382.5~384.0 nm, using the atomic absorption spectrometer and 0.07-nm slit (Fig. 1b). The preliminary identification of Mg emis- sion was performed using the wavelength values indicated by the spectrometer and confirmed by the data reported in (32). The emission spectrum obtained withD.A. Kaiskov' et al. / Specirochimica Acta Part B: Atomie Spectroscopy S4 (1999) 1045-1062 Table 2 ‘Temperature programs used in the experiments, 1051 Step Temperature Ramp Hold Purge Gas flow co time (9) time (8) mas (om min!) Drying 100 20 2 ‘At, He 300 Pyrolysis 400", 800° 1S 0 Ar, He 300 ‘Vaporization 2400 (pyrocoated, Ta-lined tube) t 1 ar 30, gas stop 2500 (pyrocaated tube) Ar, He 30, gas stop 2300 (filter furnace) ar 30, gas stop Cleaning 2500 (pyroeoated, Ta lined tube) 1 3 Ar. He 300 2400 (filter furnace) 1 5 Ar 300 Measurements using the CCD spectrometer. Measurements using the stomic absorption spectrometer. Mg(NO,), in the pyrocoated furnace was scanned stepwise at 0.1-nm intervals, to verify the attribu- tion of spectral lines already observed with the CCD spectrometer (Fig. 1c). Ten microlitres of 0.1% solution of Mg(NO,), were sampled at each step, and the furnace was heated according to the program reported in Table 2. 3.3.3. Spatial distribution of emission (Fig. 1d) The following procedure was adopted: @ The wavelength of one of the Mg emission lines observed in the furnace was set, and the light beam of the spectrometer was narrowed using a 2X2- or 1x L-mm diaphragm in- stalled on the entrance window of the spec- trometer (10 cm from the center of the atomizer). A 0.07-nm slit was employed. © The position of the atomizer was adjusted along the optical axis, using a filter furnace having narrow analytical zone cross-s (2.5-mm diameter). A pyrocoated tube was installed and 10 pl of 0.1% Mg(NO,), solution were vaporized a cording to the program reported in Table 2. After each firing, the furnace was shifted along the tube diameter at 0.25- or 0.5-mm steps. The emission was recorded during the atomization and cleaning steps. The measure- ments were performed in a range +3.0 mm using both diaphragms. 3.3.4. Spatial distribution of light scattering (Fig. Le) The light absorption at 240.0 nm was measured using deuterium lamp and the procedure already described for emission measurements. Ten mi- croliters of 1% Mg(NO,), solution were sampled in these experiments. The slit of the spectrometer was set to 0.2 nm and the 2x 2-mm diaphragm was used. 3.3.5. Temperature measurements The temperature of graphite tubes of both HGA-S00 atomizers used with CCD and atomic absorption spectrometer was measured using the micropyrometer. The temperature of the external surface of pyrocoated Ta-lined tubes and filter furnace were also compared using the experimen- tal procedure already described [33]. 4. Results and discussion 4.1. Thermal characteristics of the vaporizers Pyrocoated tubes were purged with Ar and He gas (both external and internal), with gas-stop and 30 ml min“! gas-flow. During the vaporization step, the temperature reached the equilibrium within 6-7 s with both gases, independently of the gas flow rate. The temperature of the internal tube surface was approximately 100°C higher than that of the external surface, regardless of gas type and flow rate. The temperature was approxi- mately 300°C lower than the set temperatureWws2 DAA, Katskow et al. / Spectrochimica Aeta Part B: Atomic Spectroscopy $4 (1999) 1045-1062 (2400°C), when He was employed. In this case, the temperature set on the HGA programmer was increased up to 2500°C to provide complete vaporization in He (Table 2). The difference between the set and measured temperature de- crewsed to 150°C by setting the vaporization tem- perature at 150°C. No appreciable temperature difference was measured between pyrocoated tubes with and without Ta-lining. In the filter furnace, the external temperature of the tube was approximately 2500°C when the vaporization temperature was set to 2400°C. It was not possible to measure the temperature of the filter, as screened by the graphite fiber. How- ever, theoretical calculations indicate that the final temperature of the filter is 200-300°C higher than the external tube temperature [34]. The tem- perature of the filter furnace was set to 2300°C, to avoid fast destruction of the filter. The tempera- ture barely reached the equilibrium within 8 s during the vaporization step, due to the large mass of the filter furnace. 4.2. Evolution of Mg(NO,), vapor spectra 4.2.1, Absorption spectra below 1000°C ‘The absorption spectra observed below 100°C show the initial stages of the thermal decomposi- tion of Mg(NO,),. The salt is stable appro: mately up to 600 K [35]. Above this temperature, the following reaction occu Mg(NO,), > MgO + 2NO, + 1/20), a where NO, exists in equilibrium with NO, The evolution of vapors from Mg(NO,), de composition is presented in Figs. 2 and 3 (with respectively, Ar gas-stop and 30 ml min~! flow) and in Fig. 4 (pyrocoated tube with He gas flow), In all experiments, except those performed using the filter furnace, the absorption spectra showed at 500°C broad bands, respectively, above and below 250 nm, which could be attributed to NO, or to NO, and N,O, mixture [36,37]. The appear- ance of NO bands (205.3, 215.5 and 2269 nm) could be detected at approximately 600°C [36] Further increase of temperature resulted in the disappearance of broad bands and NO system in the case of Ar gas-flow mode (Fig. 3a,b). The appearance temperature of NO/NO, bands did not depend on the sample mass. The NO bands were persistent during the whole vaporization step, when the gas-stop mode with Ar, or both modes with He, was employed (Fig. 2a,b and Fig. 4). Apparently, the effect was caused by condensation of NO and NO, in the cooler parts of the atomizer. The condensation was pre- vented using Ar gas flow G0 ml min~!), Such effect was much less pronounced with He gas flow because of the high rate of vapor diffusion. The intensity of NO, (and N,O,) bands was less reproducible in the Ta-lined furnace than in the pyrocoated tube, possibly because of less re- producible distribution of sample onto the metal surface, In the filter furnace, only NO bands appeared for a short time when Ar gas stop mode was employed (Fig. 2c). There was no trace of NO and NO, bands for the gas flow mode (Fig. 3c). Ap- parently, in the filter furnace the reactions NO+C{s)>CO or NO,+C(s)>CO, (8) control the vapor composition at 500-600°C. These evidences can help in understanding the appearance of gaseous MgC, and Mg,C, in the graphite furnace at low temperature [38,39]. These species were detected by Prell et al. [38], who studied the vaporization of magnesium nitrate in N, using a furnace coupled with mass spectrome- ter. The formation of gaseous Mg acetylides at low temperature was explained by the reaction MgO(solid) + 3C(solid) >» MeC,(gas) + CO(gas) (9) where MgO particles were considered as adsor- bed on the defects of graphite surface, and ex- othermie C-O reaction could supply the energy required for the desorption of reaction products. The mechanism of solid particles interaction occurring in Reaction (9) cannot be established. ‘An excess of carbon in the atmosphere is re- quired to substantiate the presence of MgC, in the gas phase. It is more reasonable to advanceDA. Katskov etal. / Spectrochimica Acta Part B: Atomie Spectroscopy 54 (1999) 1045-1062 1083 ae Ta- lined tube al 7Ar i ns Fig. 2, Spectra collected during the vaporization of Mg(NO,); using the thermal program reported in Table 2, Ar gas-stop mode, and 100 j.g MNO), sample. (a) Pyrocoated tube, (b) Taclined tube, (c) filter furnace10s DA. Katskow et a. / Spectrochimica Acta Part B: Atomie Spectroscopy 54 (1999) 1045-1062 a | Tarlined tube b em Filter furnace b > nF an i vevelemgth, am Fig. 3. Spectra collected during the vaporization of Mg(NO,) using the thermal program reported in Table 2, 30 ml/min Ar flow, and 100 j.g Mg(NO,); sample. (a) Pyrocoated tube, (b) Ta-lined tube, (e) filter furnace that Reaction (8) provides at 500-600°C the re- 4.2.2. Magnesium absorption at 285.2 nm quired excess of carbon gaseous species and the Only Mg atomic absorption at 285.2 nm was energy necessary for the sublimation of Mg from. observed between 1500 and 2400°C in the Ta-lined MgO or Mg(NO;), tube (Fig. 2b and Fig. 3b). The appearance tem-DA, Katskow et al. / Spectrochimica Acta Part B: Atomic Spectroscopy $4 (1999) 1045~ 1062 oss ABsORaATICE Fig. 4. Spectra collected during the vaporization of Mg(NO,)> in the pyrocoated tube, using the thermal program reported in Table 2, 30 ml/min He flow, and 200 ug Mg(NO,): sample, perature of Mg was not affected by the sample mass (25-100 y.g), or by the pyrolysis tempera- tures (400-1100°C). The maximum absorption was observed at approximately 1750°C. Magnesium absorption slowly decreased during the increase of the tube temperature, but did not disappear at the end of the vaporization step. In the pyrocoated tube, either appearance tem- perature or duration of Mg absorption with He were similar to those observed using Ar, but the intensity was lower due to increased diffusion rate (Fig. 4). In the filter furnace, Mg absorption increased significantly in comparison to Ta-lined and pyro- coated tubes, remaining almost insensitive to the gas mode (Fig. 2c and Fig, 3c). However, it was not possible to establish if the increase occurred only because of the limited diameter of the ana- lytical zone or also because of the effective reduc- tion of oxides. Due to the high temperature of the filter at the end of the vaporization step, the slow release of Mg atomic species can be explained only by the following reaction: Mg(gas) + C(solid) «> MgC, (solid) a0) which occurs in the filter furnace due to the large excess of carbon. Magnesium absorption at 285.2 nm appeared in the pyrocoated tube at the same temperature as observed in the Ta-lined furnace. The appearance temperatures reported by Kantor et al. in the ‘carbon rod-flame’ atomizer are 100°C lower than those reported in this work, due to the capability to detect all Mg species [29]. However, the ther- mal behavior of Mg absorption shows that the total vapor pressure of Mg species changes simul- taneously with Mg vapor pressure [29]. Hence. it can be advanced that equilibrium exists between Mg and MgO above the sample. The different substrates of pyrocoated and Ta- lined tube do not effect the initial stage of the vaporization process, as the appearance tempera- tures are very similar. When the temperature increase the absorption behavior becomes sig- nificantly different between pyrocoated and Ta- lined tubes, as absorption is approximately two-threefold higher in the pyrocoated than in the Ta-lined tube, while the vaporization time is shorter. This behavior indicates an increase of vaporization rate in the pyrocoated tube and pos- sibly some increase of atomization degree in com- parison to the Ta-lined tube. Two hypotheses can be advanced about the change of the vaporization rate. The first hypothesis is based on a traditional1056, approach. The presence of graphite induces a reduction of MgO in the condensed phase, which facilitates the vaporization. Reaction (9) occurs at a specific temperature, when its standard free energy becomes zero (AG = 0). However, the cal- culations used by Kantor et al. [29] for Reaction (9) show that AG = 0 occurs at 1890°C, that is at a temperature much higher than the appearance temperature of Mg atomic absorption, In addi- tion, it is difficult to advance the direct interac- tion between solid MgO (melting temperature 2800°C [13]) and pyrographite. ‘The second hypothesis is described in the pre- vious sections: interaction of the sample vapor with graphite with consequent localized increase of the temperature of purge gas, which transfers its energy to the surface of the sample. 4.2.3, Magnesium emission at 382.9, 383.2 and 383.8 nm The appearance of Mg emission around 383.5 nm is shown in Figs. 2~4. The emission was observed only in the presence of graphite. In the case of pyrocoated tubes, it was detected contem- porancously with Mg absorption at 285.2 nm us- ing Ar and He (Fig. 2a, Fig. 3a and Fig. 4), In the DAA, Katskov et al. / Spectrochimica Acta Part B: Atomie Spectroscopy $4 (1999) 10 1062 guised by some other bands and was detected after the appearance of Mg absorption. The experiments performed using the atomic absorption spectrometer enabled to conclude that the emission at 383.5 nm, obtained with the CCD spectrometer, in fact consisted of three Mg lines: 382.94, 383.23 and 383.83 nm. The emission spec- tra, obtained stepwise with sequential firings and using the arrangement of Fig. Ic, were completely resolved from the background radiation and coin- cided, within 0.1 nm, with the emission lines recorded from a Mg hollow cathode lamp (Fig. 5). The emission lines can be attributed to the triplet system *P°—*D, represented in Fig. 6 [32] The components of the triplet are in fact six, but only three lines *P*\-*D,, *P%-*D,, and 'P*,-*D, 2, are detected due to the inadequate dispersion of the atomic absorption spectrometer. ‘These lines can be observed only in emission due to the low population of these energy levels. Fig. 7 shows the thermal behavior of emission at 383.8 nm using the optical arrangement indi- cated in Fig. 1d. Two emission signals were observed during the atomization and cleaning step. The emission observed during the cleaning filter furnace, the emission at 383.5 nm was dis step in the area close to the wall overlapped to Singlet sytem Triplet tom ‘1 4D, a aera a ‘So O a 1 i a3. ssh z _ z : Bass - 4 a 3032 . 382.9 383.8 3 a an bong —< —- i _[-—™ ° Fig, 5. Identification of emission tines observed durig the vaporization of 10 j1g Mg(NO,), inthe pyrocoated tube. Full ine shows the emission spectrum of Mg hollow cathode lamp; the arrows indicate the pestion of Mg lines belonging to the *P°-"D triptetDAA. Kaiskov et al / Spectrochimica Acta Part B: Atomie Spectroscopy S4 (1999) 1045-1062 0s7 — Emission ofthe Mg hollow cathode WEEE 4g crission inthe pyrocoated tab, atomization sep Emission, arbitrary units Wavelength, nm Fig. 6. Energy-Jevel diagram for magnesium, from Eliashevich [32] (simplified) the emission from the wall, when the gas stop mode was used (Fig. 7b). The first signal was apparently related to the sample vaporization in the center of the furnace while the second to the re-evaporation from the ends, where the sample vapor was condensed in the gas-stop mode. Fig. 8 shows Mg emission at 383.8 nm from different areas of the pyrocoated tube section recorded using the arrangement indicated in Fig. le. The emission signals were detected sequen- tially with 2 2-mm and 1x I-mm diaphragms, using Ar and He. The curves (1) were obtained in two sets of measurements, with the 2X 2-mm diaphragm, when the atomizer was moved along the tube diameter. The curves show the symmet- rical distribution of emission and the repro- ducibility of the measurements, The use of the 1x I-mm diaphragm enhanced the spatial resolution (Fig. 8, curves 2 and 3). Hence, the emission distributions using Ar and He could be distinguished, although both are affected by poor spatial resolution. The distribu- tion of the emitting particles near the tube wall should be much steeper than the recorded de- crease of emission intensity (Fig. 8). Emission intensity J, is determined by the tem- perature of source of radiation 7, and by energy of the spectral transition A. 1, ~ expl- AE/AAT, J], ap where k= 1.38 10" J K7'=86x 1075 eV K7! is the Boltzmann constant. The data reported in Fig. 8 and Eq. (11) enable the estimation of the minimal temperature dif- ference between tube center [7,(0)] and at mm from the center [7,(2.5)] suggesting a uniform distribution of neutral atoms across the tube. The following relationship is obtained from Eq. (11). if the ratio of radiation intensities in these positions is considered close to 20-30: exp{(-AE/k)[T>'(2.5) ~ 7 '(O)]} = 20 + 30 a2)1058 DAA. Katskov etal. / Spectrochimica Acta Part B: Atomic Spectroscopy 54 (1999) 1645~ 1062 38 “Temperature, 8 8 ion , arbitrary units a 0 on BR 6 Time,s Fig. 7. Emission observed at 383.8 nm during the vaporization of 10 wg of Mg(NO,)5. (a) Furnace temperature (1, set: 2 micasurcd); (b) emission observed at distance 0.5 mm from the wall; (&) emission along the asis of the furnace, Solid and dashed lines are related to Ar gas-stop and 30 ml/min flow, respectively. 7,(2,5) can range from 2378 to 2440 K, by substi- tuting AE =3.24 eV and 7,0) = 2000 K. Hence, the calculations show that the temperature at 0.5 mm distance from the tube wall is 400 K higher than in its center. This observation is in qualita- tive agreement with the temperature difference between the wall and the center calculated from the theoretical model, although the temperature difference found in the experiments is much lower than that calculated. Such discrepancy is due to the limited spatial resolution employed in the measurements, and to the theoretical approach, sbitrary units Emission intensity, Distance from the furnace axis, mm Fig. 8. Radial distribution of emission at 383.8 nm observed during the vaporization of 10 wg Mg(NO,); in the pyrocoated tube, Curves 1 (+ and x) were obtained using 2x 2mm, diaphragm and Ar gas flow: curve 2 (4) was obtained using 1x 1-mm diaphragm and Ar gas flow: curve 3 (@) was ob- tained using 1% I-mm diaphragm and He gas flow that takes into account only the heat transfer to the gas phas According to the model described in Section 2 the emission observed in the pyrocoated tube derives from exothermic reactions. Emission is not detected in the Ta-lined tube due to the lack of carbon, In the filter furnace, having excess of carbon, emission cannot be observed at low tem- perature because of the separation between reac- tor and analytical zones by graphite partition. Between reduction and carbide formation, that could be responsible for the discussed pheno- mena, the first reaction looks preferable. In fact, the preliminary calculations of the reduction re- action showed results close to the experimental Furthermore, the reduction can be preferred due to the complexity of heat transfer in case of carbide formation, as the energy evolved in the formation of solid carbide could be transferred to the gas phase only after its dissipation in the graphite. Although less probable, carbide forma- tion cannot be excluded, especially in the case of pyrographite having low thermal conductivity across the pyrolytic layer.DA. Katskow etal. / Spectrochiica Acta Part B: Atomic Spectroscopy $4 (1999) 1045-062 4.2.4, Light scattering Light scattering was observed in the pyrocoated tube with Ar at two distinct temperature ranges, The low temperature range corresponded to the presence of Mg absorption and emission (Figs. 2 and 3). The scattering was observed either using gas stop or gas flow mode. The high temperature scattering was significant only when the gas stop mode was used. These results are in agreement with those already reported by Frech et al, [5] and Hughes et al. [7], where the low- and high-tem- perature scattering were attributed to the processes occurring, respectively, at the center and at the ends of the tube. No scattering was observed in the Ta-lined tube and in the filter furnace using Ar, or in the pytocoated tube using He. The spectral distribution of scattering at three different temperatures is reported in Fig. 9 together with the corresponding fitting curves. Magnesium absorption and emission lines were not considered in the calculation of the curves. Furthermore, the wavelength range between 200 and 220 nm was not taken into account, as the light intensity was too low for calculations. 109 The spectral distribution of the scattering at lowest temperature is described by the function A,=7%10" x ~**, where A is the wavelength (nm) (Fig, 9, curve 1). If A, is considered propor- tional to the scattered radiation J,, it can be deduced that the distribution follows the Rayleigh scattering relationship [,~d~* [7]. When the gas-stop mode is employed, the following curves are calculated A,=6 x 10°A~*? at 2140°C (Fi 9, curve 2), and A, = 0.667 — 0.0014 — 1.x 10-* at 2260°C (Fig. 9, curve 3). According to theory of, light scattering, a decrease of the wavelength power factor indicates an increase of particles size [7]. The spatial distribution of absorbance at 240 nm, due to the light scattering, is presented in Fig. 10. The distribution of low temperature scat- tering across the tube diameter is almost symmet- ric with maximum close to the longitudinal axis when gas stop or gas flow mode are used (curves 1 and 2). These results confirm the suggestions advanced by Frech et al. (5] and Hughes et al. (7] In the pyrocoated tube, the spatial condensation occurs firstly in the center near the longitudinal axis due to the presence of axial thermal gradient. — _ | oe os TAs Txt att 2 10749? 3. A= 0.687 - 0.0012- 1x 102? es | 03 | : | } 1 " a ~ | O41 ee —_ oI eae nee een Fig. 9. Spectral distributions of absorbance, attributed to light scattering, and the corresponding fitting curves. (1) From Fig, 3a at at 2260°C, 17S0°C: (2) from Fig, 2a at 2144PC: and (3) from Fig1060 DA. Katshow et al. / Spectrochimica Acta Part B: Atomic Spectroscopy 54 (1999) 10451062 | 015 Distance from the furnace axis, mm Fig. 10, Radial distribution of light scattering at 240. nm observed during the vaporization of 100 ug Mg(NO,), in the pyrocoated tube using the thermal program employed for Fig. 2a and Fig. 3a. Curve 1 (4) and curve 2 (m) refer to the low temperature scattering (sce Fig. 2a and Fig. 3a) curve 3 (@) refers to the high-temperature scattering (see Fig. 2a) However, unlike the interpretation given by Frech et al. [5] and Hughes et al. [7], it is. pro- posed that the thermal gradient across the tube diameter occurs together with the vaporization of, MgO. The emission profiles reported in Fig. 8 provide experimental support to this approach. Both the appearance of an axial thermal gradi- ent and increase of vaporization rate in the pres- ence of graphite should occur near the cool ends after re-vaporization of condensed material. Ac- cordingly, similar behavior of the scattering at high temperature could be expected. On the con- experimental data from Fig. 10 show that tering, occurring at high temperature, in- creases towards the walls. Together with the in- crease of particle size, deduced from Fig. 10, it gives an indication that the predominant light scattering after re-evaporation from the tube ends occurs outside the tube. In the Ta-lined tube, the vaporization rate is not sufficient and the axial thermal gradient is absent. In the pyrocoated tube, with He purge gas, the increase of vaporization rate is not ade- quate to compensate the fast vapor removal. In the filter furnace, the condensation near the ends is hindered due to specific design (special slits at the tube ends) [31]. The vaporization of the sam- ple cannot originate a thermal gradient because of the separation between reactor and analytical zone. 4.2.5. Other bands or lines ‘A weak absorption band was recorded at 376.3 nm using gas-stop mode (Fig. 2b), probably at- tributable to MgO. Hutton et al. reported the emission spectra obtained in the graphite furnace at 2800°C during the vaporization of Mg(NO,), [40]. The spectra, assigned to MgO, consisted of several broad bands between 366 and 386 nm. ‘The discrepancy between this assignment and the spectra reported in Figs. 2 and 3 can depend on the significant temperature difference between Hutton et al. [40] and this work. Other bands were observed in the filter fur- nace: a band at 358.5 nm in absorption (Fig. 2c), and group of overlapping bands between 379 and 391 nm in emission and absorption, also including Mg triplet at 383.5 nm. Some of these bands could probably indicate the presence of gaseous Mg carbides formed due to the large excess of carbon. 5. Conclusion The results show that the heterogeneous ex- othermal reactions in the graphite furnace cause a significant impact on the processes of mass and heat transfer. Magnesium emission, correspond- ing to excited energy levels, indicates the forma- tion of ‘hot’ particles having energy much higher than that of the gas. The transfer of this energy to the purge gas gives rise to a non-uniform temper- ature distribution near the graphite wall, and causes an increase of sample vaporization rate with consequent condensation evidenced by light scattering Due to steep gradient, the increase of average gas temperature is barely adequate to the preci- sion of the two-lines method employed in temper- ature measurements to investigate the effect of modifiers on the temperature distribution in a graphite furnace [41]. However, the steep axial gradient is evidenced in spatially resolved obser- vations using Mg emission lines. The presence of such gradient provides also a solid explanation onDA, Katskow et al. / Spectrochimica Acta Part B: Atomic Spectroscopy 54 (1999) 1045-1062 1061 the reversal of MgCl bands from absorption to emission in the graphite furnace [33]. The observed phenomenon also gives support to ex: plain the appearance of MgC, gaseous species at low temperature [38,39]. This phenomenon is important either in GFAAS or in electrothermal vaporization com: bined with inductively coupled plasma-mass spec- trometry (ETV-ICP-MS). Light scattering and non-uniform or non-constant temperature are negative features in GFAAS, but acquire a posi- tive meaning for the ETV-ICP-MS, by providing efficient mass transport from the vaporizer to the IcP (7). The experimental results and the calculations support the involvement of the reduction reaction in the transfer of excess energy into the analytical zone. 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