Journal of Applied Spectroscopy, Vol. 72, No.

2, 2005

KINETIC MODEL OF ENTRY OF FREE ATOMS INTO AN ELECTROTHERMAL ATOMIZER

A. N. Bugai, Yu. V. Rogulskii, A. N. Kulik, and L. F. Sukhodub UDC 543.422

A kinetic phenomenological model of the processes of atomization for atomic-absorptional spectrometry with electrothermal atomization that is based on solution of a one-dimensional equation of diffusion with two independent sources is suggested. The model takes into account the processes occurring both on the surface of a graphite furnace and inside its wall. The proposed model is used for describing the electrothermal atomization of copper and zinc. Keywords: atomization mechanism, diffusion equation, diffusion in graphite. Introduction. It is known that in the method of atomic-absorption spectrometry with electrothermal atomization (ETAAS), a metered amount of the sample analyzed is delivered onto the graphite surface of a furnace (or platform) on which its thermal treatment and atomization occur. A liquid sample not only spreads over the surface but also penetrates into the pores of the furnace material under the action of capillary forces, as a result of which the conditions of sample atomization are altered [1, 2]. It is evident that here the state and properties of the graphite surface play a significant role. It has been shown earlier [26] that the form of the analytical signal depends substantially on the state of the furnace surface and the degree of its wear, and the necessity of creating a model that would take into account penetration of a sample into the surface pores has been substantiated [2]. Such a model may also be of use in studying the influence of permanent modifiers on the mechanism of atomization [7]. To construct a correct phenomenological model of sample atomization in a graphite furnace it is necessary to consider two sources of free atoms: one on the furnace surface and the other inside its walls. The present work is devoted to the solution of this problem. For experimental checking of the model, we selected copper and zinc, the mechanisms of atomization of which are different. Theory. In constructing the model, we use some facts and assumptions. 1) The atomic absorption A(t) is proportional to the mass M(t) of the free atoms that are present in the analytical volume of the furnace in a gas phase. 2) In delivering metered amounts of a sample into the furnace (or onto the platform), a portion of the liquid sample penetrates into graphite under the action of capillary forces [1, 2]. As the total initial mass of the atoms M0 placed inside an atomizer we take the mass of the atoms participating in formation of an analytical signal. It can be represented as the sum of the masses of atoms on the surface of the furnace and inside its pores: M0 = M0
surf

+ M0 .

The initial mass of the atoms on the surface of the furnace wall is Msurf = 1M0; the initial mass of the atoms in a 0 p bound state in the pores is M0 = 2M0 (1 and 2 are the weighting factors, 1 + 2 = 1). 3) The mass of the atoms on the surface of graphite (on both the furnace surface and the walls of the pores) is decreased with time following the same law: * To whom correspondence should be addressed. Institute of Applied Physics, National Academy of Sciences of Ukraine, 58 Petropavlovskaya Str., Sumy, 40030, Ukraine; e-mail: alex_bug@hotbox.ru. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 241246, MarchApril, 2005. Original article submitted April 28, 2004. 0021-9037/05/7202-0255 2005 Springer Science+Business Media, Inc. 255

d [M (t)] n = k1 [M (t)] , dt

(1)

where k1 is a constant of the rate of the process of formation of free atoms and n is the order of kinetics. Atomization under isothermal conditions. Under isothermal conditions the process of entry of free atoms into a gas phase and their decrease can be described with the aid of a one-dimensional equation of diffusion with a source [8]. In our case, the function of the source density is described by superposition of two functions: q (x, t) = q
surf

(x, t) + q

wall

(x, t) ,

where qsurf(x, t) is the density of the source on the surface of the graphite furnace; qwall(x, t) is the density of the source inside the furnace wall. Suppose these functions are independent of each other. Then we obtain a one-dimensional equation of diffusion with two independent sources: (x, t) t =D (x, t)
2

+ (q

surf

(x, t) + q

wall

(x, t)) ,

(2)

where (x, t) is the density of the distribution of the atomic vapor and D is the coefficient of diffusion of free atoms in an inert gas. Under the initial and boundary conditions (x, 0) = 0, (0, t) = (l, t) = 0, the general solution of Eq. (2) with arbitrary sources can be written in the form k (x, t) = exp D l k=1 k + exp D l k=1
l 2 2

surf k k t Qk (t exp D t dt sin x+ l l 0

2

k wall k t Qk (t exp D t dt sin x, l l 0

(3)

where

Qsurf(t) k

k k 2 2 = qsurf(x, t) sin xdx, Qwall(t) = qwall(x, t) sin xdx. k l l l l

0 0

To describe the distribution of the density of sources along the furnace, we use the expression [9] q
surf

(x, t) = f

surf

(t) sin (x l) , q

wall

(x, t) = f

wall

(t) sin (x l) ,

(4)

wher e f surf(t) and f wall(t) are the functions describing the dependence of the density of sources on time. In order to obtain an expression for the atomic absorption signal it is necessary to find the analytical form of the functions f surf(t) and f wall(t). This can be done on the basis of the following considerations. The mass of the atoms that entered into the gas phase from the surface of the graphite furnace wall is M
gas

(t) = M0

surf

surf

(t) ,

(5)

where Msurf(t) is the mass of the atoms present on the surface of the graphite furnace wall at the time t. At the same time, the mass of the atoms in the gas phase Mgas(t) can be expressed in terms of the source density qsurf(x, t):
gas

(t) = S

t l

surf

(x, t) dtdx .

(6)

0 0

Thus, from Eqs. (4)(6) we obtain 256

surf

(t) =

d [M (t)] . 2Sl dt

surf

(7)

The function f wall(t) describes the mass flux through the inner surface of the graphite furnace. An analytical expression of f wall(t) can be obtained by solving the source-involving diffusion equation in cylindrical coordinates:
wall 2 p 2 2 2 , (t) = exp Dgr1t A1 f (t ) exp Dgr1t dt 1Dgr 2 R11 0 t

where Dgr is the effective coefficient of the diffusion of metal atoms in graphite; 1 is the root of the characteristic equation (for our furnace, 1 + 3138.3166); R1 is the inner radius of the graphite furnace; f p(t) is the function that describes the dependence of the density of the source inside graphite on time, and A1 is a coefficient that depends on the initial distribution of atoms in the wall. Reasoning similarly as in the case of finding the function f surf(t), we obtain f (t) = A2
p

d [M (t)] , dt

wher e Mp(t) is the mass of the atoms present in the pores in a bound state at time t and A2 is a coefficient that depends on the initial distribution of the atoms inside the graphite wall. The final expression for the unknown function has the form
wall t p D 2t d [M (t )] exp D 2t dt , (t) = A31Dgr exp gr 1 gr 1 dt 0 2

(8)

. R12 1 Using Eqs. (1), (3), (4), (7), and (8) and carrying out simple mathematical transformations, we obtain an expression for the dependence of the atomic absorption on time at the kinetics of formation of free atoms equal to (n = 1): A (t) = C1

where A3 =

2A1A2

k1kgr exp ( ksurft) exp ( k t) + C 1 2 2 surf p k2 k1 kgr k1

k1 (9)

surf

p 1 1 exp ( k1t) exp ( k2t) exp ( kgrt) exp ( k2t) , p k k 2 gr k2 k1

where k2 = D2 l2; kgr = 2Dgr; C1 and C2 are proportionality factors. 1 Nonisothermal conditions. During formation of an analytical signal under nonisothermal conditions, it is necessary to introduce a correction into Eq. (9) to take into account the change in the temperature with time (T const). 5 As shown in [8], the time needed for establishing temperature equilibrium in the furnace is ,10 sec, 3 whereas the characteristic time of a change in the furnace surface temperature is 10 sec. This relationship allows one to use the principle of adiabatic approximation, when at each time instant t the change in temperature is small, and it is possible to assume that the gas in the furnace is in thermodynamic equilibrium at the temperature T(t). Then, allowance for the nonisothermicity of the process is reduced only to replacement of the constants ksurf, kp, k2, and kgr by 1 1 the functions of time, since they depend on the temperature: k1
surf

(t) = k0

surf

Ea Ediff Ea p p 2 gr exp , k1 (t) = k0 exp , kgr (t) = 1D0 exp , RT (t) RT (t) RT (t) 257

Fig. 1. Atomic-absorption signals of copper (a) and zinc (b) at different temperatures; point, experiment; solid line, model approximation. where ksurf and kp are pre-exponential factors, Ea is the energy of formation of free atoms on the surface of the fur0 0 gr nace and in its pores; D0 is the pre-exponential factor for diffusion in graphite, Ediff is the energy of diffusion activation in graphite, and R is the universal gas constant. We note that the energy of formation of free atoms Ea on the surface and inside the graphite furnace wall is the same. The difference may be observed when the radius of the pores in graphite is commensurable with that of the metal atoms and when the fields of the adsorption forces of the pore walls influence the desorption. In our case, the radius of the pore is much larger than the dimensions of the metal atoms, and these forces do not play a noticeable role. The sweeping out of the atomic vapor from the furnace is described by the expression (see, e.g., [9, 10]) D0 T (t) k2 (t) = 2 , l 273 where D0 is the diffusion coefficient of the atomic vapor in an inert gas at a temperature of 273 K; m + 1.61.9. Experimental. Equipment. Experiments were carried out on a KAC 120.1 two-beam atomic absorption complex (Selmi, Ukraine) with a deuterium corrector of nonatomic absorption. A lamp with a hollow cathode served as a source of radiation. A tubular graphite furnace with pyrolytic coating of length 28 mm and inner diameter 6 mm (an analog of HGA-500) was used as an atomizer. The furnace temperature was assigned by a programmer and was controlled by a tungsten-rhenium (W-Re) thermocouple. The atomic-absorption signal was scanned and processed by an IBM PC/AT 5 86 computer. Reagents. We used calibration aqueous solutions 0.1 mg/liter copper and 5 mg/liter zinc (in the form of nitrates in a 0.1N solution of nitric acid). The solutions were prepared from standard samples of aqueous solutions of metal salts. Procedure. Measurements of the atomic-absorption signal of copper were carried out at a wavelength of 324.7 nm at a slit width of 0.4 nm, of zinc at a wavelength of 307.6 nm at the same slit width. A sample of volume 20 liter was batched directly into the inner surface of the furnace. Matrix and surface modifiers were not used. The temperature regime of the furnace was as follows: for copper drying of a solution at 360 K for 60 sec with blowing by argon at 0.007 m3/h; pyrolysis at 1273 K for 30 sec, the flow rate of argon was the same; atomization at temperatures 2373, 2573, 2773, and 2973 K in the "gasstop" regime for 510 sec; for zinc drying of a solution at 360 K for 60 sec, pyrolysis at 773 K for 30 sec; atomization at temperatures 1873, 2073, 2273, and 2473 K for 510 sec. Results and Discussion. The obtained experimental atomic-absorption signals of copper and zinc at different temperatures as well as approximating model curves for each signal plotted according to Eq. (9) are presented in Fig. 1. Using LevenbergMarquardts iteration method, we determined the kinetic and diffusion parameters: the energy of p formation of free atoms Ea; pre-exponential factors ksurf and k0; energy of diffusion activation in graphite Ediff, and the 0 gr pre-exponential factor for diffusion in graphite D0 . The results of calculations are given in Table 1. As is seen, the 258
2

TABLE 1. Kinetic (ksurf, kp, Ea) and Diffusion (Dgr, Ediff) Parameters of Formation of Copper and Zinc ETAAS Signals 0 0 0 Temperature of atomization, K 2373 2573 2773 2973 1873 2073 2273 2473 Dgr, m2/sec 0 (1.03 (0.79 (1.02 (1.60 (3.37 (4.33 (3.68 (3.33 Ediff, kJ/mole
6

ksurf, sec-1 0 Cu 8627.8  3652.4 5896.2  676.8 3243.7  317.1 2055.9  91.4 (9.4  2.3)106 (10.2  2.8)106 (8.5  1.6)106 (4.2  3.6)106

kp, sec-1 0 6271.3 5579.4 3395.8 2012.9

Ea, kJ/mole 159.4 157.7 149.7 146.2 172.0 186.0 187.9 197.2

       

0.2)10 0.3)106 0.3)106 0.4)106 0.6)10 0.1)105 0.7)105 0.1)105

5

80.2 79.3 81.6 81.1 79.9 81.0 76.6 81.3

       

6.2 8.3 5.9 7.0 Zn 24.0 25.3 28.9 24.0

 497.7  1033  680.9  418.5

       

5.6 5.6 3.4 2.9 34.3 37.6 26.9 13.6

(4.6  0.7)106 (72.3  2.3)106 (65.9  1.6)106 (37.6  3.6)106

average value found by the proposed method for the energy of formation of free atoms of copper is 150 kJ/mole, which is close to those known from the literature. For example, Fuller [11] obtained Ea = 138 kJ/mole (T > 1720 K) and ascribed this energy to the process of reduction of copper oxide with carbon; Rojas [12] obtained Ea = 145 kJ/mole. In [13, 14], based on the assumption that desorption on the graphite furnace surface is the mechanism of formation of free atoms, an energy equal to about 130 kJ/mole was obtained. To interpret the data of Table 1 and get some insight into the physics of the process of atomization, of great interest is the value of the pre-exponential factors ksurf and kp. Proceeding from the dimensions of the pre-exponential 0 0 factors ksurf and kp, we may assume that these factors are inversely proportional to the average time of residence of 0 0 atoms in a bound state (i.e., to the average time of residence of atoms in a source). As shown in [2], a copper sample before atomization is on the surface of graphite in the form of a pure metal in an adsorbed state (on both the furnace surface and the walls of the pores). In an ideal case (where the atom that leaves the source cannot return into it and the sources are independent of each other), the average time of residence of atoms in a bound state is equal to the period of vibration of the atoms in the direction normal to the surface. In this case, the coefficients ksurf and kp have 0 0 values of the order of 10121014 sec 1. In an actual case, the atom that desorbed from the surface collides with the furnace walls (pores) while wandering and can be reabsorbed, i.e., can come back into the source. This leads to an increase in the average time of residence of atoms in a bound state (it would be more correct to call it the apparent average time of residence), since this time is proportional to the average number of collisions of the atom with the furnace walls (pores) as well as to the probability of reabsorption, which depends on the ability of atoms to interact with graphite. Probably, the pre-exponential factors ksurf and kp have different values, since the average number of col0 0 lisions of the atom with the furnace walls differs from the average number of collisions of the atom with the pore walls. From this, the conclusion follows that the ability of atoms to interact with graphite determines the values of the pre-exponential factors. For the metals that more strongly interact with graphite (in our case copper), ksurf and kp 0 0 have values that are lower than for metals having a lower degree of interaction. From the data of Table 1, the value of the pre-exponential factor for zinc is three orders of magnitude higher than for copper, which confirms the inertness of zinc with respect to graphite. The foregoing reasoning concerning the values of the pre-exponential factors ksurf and 0 kp allows the assumption that the desorption of free atoms from the surface of graphite is the process that determines 0 the form of the atomic-absorption signal of copper. Unfortunately, in practice there are almost no works in which pre-exponential factors were used in interpreting the mechanisms of atomization. In [15], the value 1012 sec 1 is given for a pre-exponential factor as the lower limit of the range in which weak interactions with a surface are observed. This, in principle, coincides with our arguments. In [16, 17], the values for the pre-exponential factors for copper and nickel are given, but with the opposite interpretation. A characteristic feature of the copper signal is the hang-over of the absorption profile the so-called "tail." In [2], it is shown that the presence or absence of the "tail" depends on the morphology of a graphite surface. Simu259

Fig. 2. Characteristic atomic-absorption signal of copper at 2573 K and its approximation by model curves; points, experiment; dashed line, model curve describing the process of atomization from the graphite furnace wall; dash-dotted line, model curve describing the process of atomization from the graphite furnace surface; solid line, net model curve. lation of the signal (Fig. 2) shows that its tailing is caused by diffusion of copper atoms in graphite. Because of the strong interaction with graphite, copper diffuses slowly, and precisely this leads to the tailing of the rear edge of the ETAAS signal. This is confirmed by the values of the diffusion parameters (Table 1), which agree well with the literature data obtained by other methods [18, 19]. In contrast to copper, considerably fewer publications were devoted to investigation of the mechanisms underlying the atomization of zinc. In [20], as the mechanism of zinc atomization the process of the dissociation of its oxide in a gas phase was suggested. However, theoretical and experimental investigations of the composition of the gas phase above zinc oxide show that the fraction of ZnO molecules in the gas phase is negligibly small (0.3% at a temperature of 2000 K) [21]. These investigations prove that the dissociation of zinc oxide in a gas phase cannot be the determining process in zinc atomization. We obtained an average value of the energy of formation of free atoms for zinc +185 kJ/mole, which is close to the activation energy for the reaction of carbothermal reduction of zinc oxide [22]. Electronic microscopic and mass-spectrometric investigations of the state of the sample before atomization have shown that, in contrast to copper, zinc was in the form of oxide before atomization (whereas copper was in the form of a reduced metal). Taking this into account, it is logical to assume that precisely the process of carbothermal reduction is determining in zinc atomization. We have managed to find literature data for comparing the diffusion coefficient of Zn atoms in graphite. However, it follows from [23] that the diffusion coefficient for zinc is much higher than for copper and is commensurable with the coefficient of diffusion of silver in graphite. This conclusion qualitatively confirms our results. Conclusions. The proposed model of the processes of atomization with two sources of free atoms allows one to successfully study the physicochemical processes proceeding in atomization of a sample and to correctly interpret the results obtained. Application of the model in investigation of the atomization of copper shows that the process that determined the form of the signal is desorption of copper atoms from the graphite surface and that the tailing of the ETAAS signal is caused by delayed diffusion of atoms in graphite. At the same time, the determining process in zinc atomization is the reaction of carbothermal reduction of zinc oxide.

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