AN EPRSTUDY OF SO2-
ON
323
MgO
An Electron Paramagnetic Resonance Study of SO,- on Magnesium Oxide
by R. A. Schoonhepdt and J. H. Lunsford* Department of Chemistry, Texas A&M University, College Station, Texas 77843 (Received July 26, 1971) Publication costs assisted by the Environmental Protection Agency
When SO2 is adsorbed on thermally activated and uv-irradiated MgO, two Sot- species are formed. The principal values of the g-tensor are gtt = 2.0028, g,, = 2.0097, and gzz = 2.0052 for 802- (A) and g,, = tensor are 2.0014, g,, = 2.0078, and 8. = 2.0033 for SO2- (B). The principal values (in gauss) for the a,, = 59 and a,, = 9.4 for aaSOz-(A); uZt = 55 and a,, = 9.4 for aaSOt- (B). The values for "0 are a,, = 36 and ut* = 29 for 502- (A) and SOz- (B), respectively. The odd electron, transferred from the surface of MgO to S02, occupies a 2bl" antibonding molecular orbital and is mainly concentrated on the S atom. 802(A) is thermally more stable than SO2- (B), and their concentration ratio depends on the pretreatment of MgQ. Both SOZ- (A) and 502- (B) are believed to be located on oxygen ion vacancies. The S02- ion is probably oriented with its oxygen atoms towards the surface. The binding forces are purely electrostatic.
Introduction The epr spectrum of the radical ion 502- has been described both in solution and in solids. I n solutio? it was first identified as a result of the equilibrium S2022S02- by Rinker and coworkers.' This decomposition of the dithionite anion was easily achieved because of the unusually long S S bond. Atkins, et u Z . , ~ found an isotropic hyperfine coupling constant of 14.5 G which is due to 33s in SOz-. The spectrum of y- or X-ray irradiated solid dithionite was also attributed to SO2-. From a comparison of the isotropic hyperfine splitting in S02- and C102, and a consideration of Walsh's energy level diagram4 it was c o n ~ l u d e dthat ~ . ~ (a) there is a slight increase of spin density in the 3s orbital of S02as compared to C102, (b) the odd electron is in a 2bl" orbital and largely concentrated on the central S atom, and (c) a weak spin-orbital coupling exists. The possible d-character of the 2bltf orbital of the odd electron in S02- has only been postulated by Clark and coworkers. a More recently, Dinse and Mobius6described the 2bl" molecular orbital of electrolytically generated 802- as consisting of pure 3p and 2p character for S and 0, respectively. These authors used the experimental results obtained by Schneider, Dischler, and Riiubere to calculate the spin density on the sulfur 3p, and oxygen 2p, orbitals. They found the odd electron largely concentrated on s. By assuming a bond angle of 115' 5" they could account also for the shift of the g value from the free-electron value. This work was confirmed and extended by Reuveni and coworkers' on aqueous solutions of NazS204 and yirradiated, solid KZS205. By using samples enriched with and ' 7 0 these authors obtained experimentally both the 33Sand lVOhyperfine tensors of the SO2- radical ion. They could account for their experimental results by assuming a pure p type 2blf' molecular orbital p
*
for the odd electron. Moreover, the g tensor was asymmetric, but the hyperfine tensors were axially symmetric within the limits of experimental error as one would expect for this type of orbital. The slightly isotropic part of the hyperfine tensors could be accounted for by spin polarization. The d orbitals were neglected from the 2b1" orbital. The bond angle was also assumed to be 115'. $ 0 ~has - also been ascribed to epr signals observed in several y- and X-ray irradiated crystals such as thiosulfatess~eand sulfates.loJ1 Usually, S02- is not the only paramagnetic species present in these irradiated crystals. There is no complete agreement among different authors concerning the assignment of the various epr signals to chemical ~ p e c i e s . ~ ~ -I~n6general, however, it appears that SO2- is well described in the literature and its characteristics established. Such a radical ion may be an active intermediate in (1) R. G. Rinker, T. P. Gordon, D. H. Mason and W. H. Carcoran, J . Phys. Chem., 63,302 (1969). (2) P. W.Atkins, A. Horsfield, and M. C. R. Symons, J. Chern. Soc.9 6220 (1964) (3) H. C. Clark, A. Horsfield, and M. C. R. Symons, ibid., 7 (1961). (4) J. Walsh, ibid., 2266 (1963). (6) K. P.Dinse and K. Mabius, 2.Naturforsch. A , 23,696 (1968). (6) J. Schneider, B. Dischler and A. Riluber, Phys. Status Solidi, 13,141 (1966). (7) A. Reuveni, 2. Luz, and B. L. Silver, J. Chem. Phys., 53, 4619 (1970). (8) R. L. Eager and D. S. Mahadevappa, Can. J . Chem., 41, 2106 (1963). (9) f. M. de Lisle and R. M. Golding, J . Chem. Phys., 43, 3298 (1966). (10) N. Hariharan and J. Sobhanadri, Mol. Phys., 17,607(1969). (11) T.Suzuki and R. Abe, J . Phys. SOC.Jap., 30,686 (1970). (12) J. R. Morton, Can. J. Chem., 43,1948 (1966). (13) V.V.Gromov and J. R . Morton, ibid., 44,627(1966). (14) J. R. Morton, D . M. Bishop, and M. Randiv, J . Chem. Phys., 45,1885 (1966). (15) K.Aiki and K. Hukuda, J . Phys. 80'00. Jap., 22,663 (1967). I
The Journal of Physical Chemistry, Vol. 76, No. 3,1972
R. A. SCHOONHEYDT AND J. H. LUNSFORD
324 the oxidation or reduction of SO2 on metal oxide catalysts. Mashchenlto, Pariiskii, and Kazanskii'B reported the formation of SO2- as well as diamagnetic species, on partially reduced Ti02 by adsorption of S02. These authors also presented evidepce that the reaction of SO2- with O2 on the TiOz surface leads to 02- and vice versa through intermediate surface sulfates, but they strongly emphasized that the reaction of SO2- with 02 leads mainly to diamagnetic species. It is our intention in this paper to extend these studies to activated MgO. It is possible to trap electrons on the surface of a suitably prepared MgO samp1e.l' Upon adsorption of SO2 the electron is transferred to the sorbed SO2molecule to form SO2-. The characteristic molecular parameters of the S02- on the surface of MgO have been determined by evaluating the g tensor 70 hyperfine tensors. These values and the 33Sand 1 are compared with those obtained from SO%-trapped in solid matrices. Also, the thermal stability of SOZ- has been investigated, as well as the effects of different pretreatments of the MgO catalyst. The results are interpreted in terms of the molecular orbital of the odd electron in SO2- and the nature of the adsorption sites on the MgO surface.
Experimental Section The MgO used in these experiments was obtained from reagent grade powder supplied by Mallinckrodt Chemical Works. The powder was boiled in distilled water for several hours, dried at 100" until a paste was obtained, extruded into pellets with a hypodermic syringe and dried at 100". The sample was then heated to 500 or 800" for 5 to 7 hr under high vacuum. The activated MgO was put in contact with very pure HZ and uv-irradiated owith a low-pressure mercury vapor lamp (A = 2537 A). The MgO became blue due to electrons trapped at surface centers18 (S-centers). Uv irradiation at liquid N2 temperatures produced more S-centers in a much shorter time than at room temperature. Alternately, the uv irradiation was performed after the SO2 adsorption. I n this case no hydrogen was used. Matheson anhydrous grade SO2gas was purified several times by the freeze-pumping technique prior to use. Sulfur enriched with 25 and 44% 33Sand oxygen enriched with 47y0 170were used to produce enriched 33S02and S16O170, respectively. Suitable amounts of oxygen and sulfur, respectively, were allowed to react at 450" for 4 hr with the enriched sulfur and oxygen. The evolution of the epr spectra of SO2- was followed by allowing very small amounts of SO2to adsorb in subsequent steps. The epr spectra were obtained with a Varian Model V-4500 spectrometer equipped with a 100-kc modulation unit. The cavity resonance frequency was 9500 MHz. Special care was taken to avoid saturation of the signal even at room temperature. The standard The Journal of Physical Chemistry, Vol. '76,No. I,19'7.8
10 0
Figure 1. The development of the SO*- spectrum from the S-center on MgO pretreated a t 500'. (a) Original S-center; (b), (e), (d), increase in intensity of SOZ- signal with concomitant dxrease in intensity of S-center signal; (e) final SO*- spectrum.
used to determine the g values of the radical was phosphorus-doped silicon with g = 1.9987.
Results When SO2 was allowed to adsorb on previously uvirradiated MgO, which had been degassed at 500°,the spectra of Figure 1 were obtained. This figure shows a decrease in intensity of the S-center with a simultaneous increase in the SO2- spectrum. It is also apparent that two SO2- species are formed on the surface of MgO. The species with the highest g values, S02- (A), appeared first followed by the SO2- with slightly lower g values, SO2- (B). With increased SO2 adsorption the S02- (B) becomes the predominant species. When all the sites are saturated, the ratio SO$- (B) :S02- (A) approximately equals two. When MgO was pretreated at 800", qualitatively the same results were obtained. The difference being the final ratio of SO2- (B) :SO2- (A) : as shown in Figure 2 the ratio for this case is less than unity if one considers the doubly integrated signal. A sample, previously saturated with SOZ-, undergoes exactly the reverse behavior when heated under vac(16) A. I. Mashohenko, G. B. Pariiskii, and V. B. Kazanskii, Kinet. Katal., 9,151 (1968). (17) J. H.Lunsford and J. P. Jayne, J.Phys. Chem., 70,3464 (1966). (18) J. H.Lunsford and J. P. Jayne, ibid., 69,2182(1965).
AN EPRSTUDY OF 502-
ON
325
MgO
g,,(A)=2.0103 gyy(B)= 2.0091
Table I : Principal g Values for Sot- Adsorbed on MgO and in Other Matrices Qzz
BUY
SOz- (A)" Sot- (B)" SO2- on TiOz (16) KzSz05 (7) NazSOd (10) d
H
NazSzOs (9) KC1 (6) KBr (6)
2.0097 2.0078 2.005 2.012 2.0218 2 * 0102 2.0100 2.0100
2.0052 2.0033 2,001 2.0057 2,0076 2.0057 2.0071 2,0075
2.0028 2,0014 2.001 2.0019 2.0069 2.0024 2,0025 2.0050
Every g value is an average of seven independent measurements.
Figure 2. SO2- on MgO pretreated a t 800'
uum. Although both SO2- species were stable under a dynamic vacuum of Torr at room temperature, the S02- (B) species disappeared far more rapidly than the SO2- (A) species with increasing temperature. Essentially no SO2- (B) is apparent following the treatTorr. A temperment at 200" for 2 hr under 1 X ature of 400" was necessary to remove SOZ- (A). Not all of the adsorbed SO2 is converted into SOZ-. Analogous to the results on TiOZ16the majority of the SO2molecules adsorb in a nonparamagnetic form. Indeed, after the MgO was degassed for several hours a t 500" under vacuum in order to remove completely the SO2- species, and subsequently submitted to uv irradiation, also under vacuum, the S02- spectra reappeared. When the irradiation was performed under a HZatmosphere, only the SO2- (A) species appeared. The existence of nonparamagnetic SO2 was further shown by infrared spectro~copy.~~ The ratio SOz- (B):S02- (A) is also influenced by whether the uv irradiation is applied before or after the SO2 adsorption. If no S-centers were produced prior to the SO2 adsorption, but uv irradiation was applied after the SO2 was adsorbed on MgO, the formation of SOZ- (B) was strongly favored, even when MgO was previously pretreated at 800". SO2- (A) can only be seen as a shoulder on the low-field side of SO2- (B). Moreover, SO2 adsorbed on MgO without uv irradiation, either before or after the adsorption, gave rise to small amounts of SO2-. The amounts increase with increasing pretreatment temperature with both SO2species being present. It was thought that this electron transfer from the solid to the SO2 may create Vtype centers; however, attempts to detect them failed, SO2 can also be adsorbed on low-surface area MgO after uv irradiation. Both 8 0 2 - species are present with a SOZ- (B) :SO2- (A) ratio equal to one-half. Table I summarizes the g values for SO2- adsorbed on
MgO. They are compared with the values obtained for SO2- in other environments. Sulfur-33 and Oxygen-I7 Hyper$ne Splittings, The 3% (nuclear spin 3/2) hyperfine lines for either of the two SO2- species could be determined by a suitable choice of the experimental conditions according to the results reported above. By pretreatment of MgO at 500" spectra were obtained with SO2- (B) predominantly present. Heating MgO at 800" gave S02- (B) and SO2- (A) in approximately equal amounts. Upon subsequent degassing at 200" only S02- (A) remained.
7
io a
__f
n
Figure 3. (a) WOt- on MgO pretreated at 800'. Both asso%(A) and a8S02- (B) are present. (b) ssSO2- 011 MgO pretreated a t 800", followed by subsequent degassing a t 200'; only a3S02- (A) is clearly present. (19) R. A. Schoonheydt and J. H. Lunsford, to be published.
The Journal of Physical Chemistry, Val. 76, No. 8, 1079
326
R. A. SCHOONHEYDT AND J. H. LUNSBORD
Table 11: Principal Values of the 33Sand a.2.
SO2- (A)
Hyperfine Tensors (gauss) of SO2- Adsorbed on MgO and in Other Matrices
w---
7
59 f 1
SO2- (B) 55 f 1 KzSzOs (7) 58 f 0.5 KC1 ( 6 ) 52.5 f 1 KBr ( 6 ) 54.3 I1 a Estimated from other work.*J
.
(6.6 i 2)O (6.6 f 2)B 4 f 4 8.6 I 1 7.1 f 1
170
C
azs
aza
aUY
9.4 f 1 9.4 f 1 4 f 4 7.1 f 1 7.1 + 1
Comparison of the different spectra obtained in this way enabled us to distinguish between the 38Shyperfine splitting constants of S02- (€3) and SO2- (A) as indicated in Figure 3 and summarized in Table 11. The linesLCorrespondingto the J: direction are clearly resolved for 33S02- (A) and 33S02- (€3) ; however, the hyperfine lines corresponding to the y and x directions overlap with the 32S02-spectrum. Of the four lines separated by azz and centered around g,, only the two extreme lines may be observed as small peaks on the tails of the 32S02-spectrum. From the separation between these two lines we calculated a,, = 9.4 & l G. This value should be regarded as a maximum limit to uzz. The four lines centered around ayvcould not be resolved from the SO2- spectrum. We adopted, therefore, the arithmetic mean of the values of avureported by other author^:^,^ a,, = 6.6 f 2 G. A nearly axially symmetric 33Shyperfine tensor is obtained in agreement with previous The experimental procedure used to obtain the 170 (nuclear spin "2) hyperfine tensor is the same as for 33S02-. Due to the larger number of lines and the overlap with the Sl6O2- spectrum, ayvand azzcould not be calculated from the experimental spectra. Therefore we adopted Reuveni's value7 of 3 f 3 G. The spectra are given in Figure 4 and the I7O hyperfinesplitting constants in Table 11.
p
-
36 f 1 29 f 1 30 f 0 . 5
(3 f 3)" (3 f 3)" 3 + 3
(3 f 3)" (3 f 3)" 3 f 3
...
...
...
...
l e LA
...
...
,
I I
J2L
,
I I
7
aez
aYY
axx
as1
I
I
Figure 4. S1*O17O- on MgO pretreated a t 800'.
The qualitative agreement between the esr spectra obtained with SO2 adsorbed on MgO before or after uv irradiation of the solid, the similarity of our g values with those of other authors (Table I),and the hyperfinesplitting data unambiguously reveal that our esr signal is due to SO2-. Moreover, the two different signals indicate two slightly different adsorption sites on MgO. Characterization of the SO2- iTi4olecule. S02- has 19 valence electrons. The odd electron occupies a 2bl" molecular orbital according to Walsh's diagram.' Reuveni7 and Dinse6 have given an explicit wave function for this 2bl" MO neglecting the sulfur 3d-orbital contribution
The molecular orbital occupied by the odd electron is thus a linear combination of atomic pz orbitals, perpendicular to the plane of the molecule. According to Reuveni, et aZ.,7 one expects the following characteristics for the SO2- molecule and its g tensor and hyperfinesplitting tensors : (a) two magnetically equivalent oxygens, (b) axially symmetric 1 7 0 and 33Shyperfine tensors with their unique components parallel to each other and perpendicular to the molecular plane, and (c) along this unique hyperfine direction the g value should be close to the free-electron value. The maximum g value should be along the 0-0 direction, which is the y direction. Sulfur and Oxygen Hyperfine Interactions. The 33S and 170hyperfine tensor may be resolved into an isotropic part (Aiso) and a traceless anisotropic part ( A ) as described in Table 111. The choice of the sign is made so as to be in agreement with Aiso for SO2- in solution7 where Aiso for 1'0 = 8.96 f 0.05 G and A i s 0 for 33S= 14.67 f 0.05 G. For the pure 3s orbital of 3 3 5 the coupling is 970 G and for the pure 2s orbital of 1 7 0 a value of 590 G is reported.20+21 Comparing with our values, we conclude that the spin density in the 3s orbital of sulfur and 2s
where l / h is a normalization constant.
(20) G.W. Chantry, A. Horsfield, J. R. Morton, J. R. Rowlands and D. H. Whiffen, Mol. Phys., 5,233 (1962). (21) 2.Luz, A. Reuveni, R. W. Kolmberg and B. L.Silver, J. Chem. Phys., 51,4017 (1969).
Discussion
The Journal of Physical Chemistry, Vol. 76, No. 3,1079
AN EPRSTUDY OF SOZ- ON MgO -
~~~~
327
~
Table 111: Isotropic and Anisotropic Parts of the 8% and 1 7 0 Hyperfine Tensors (gauss) Az5
Aim
“S0a- (A) “SOa- (B) S1e01’0- (A) S’eo’’0- (B)
14.3 f 2 13 =k 2 10 f 4 7.7 f4
orbital of 0 is between 1 and 2%. This number is negligibly small and can be accounted for entirely by spin polariaation. The wave function adopted in the previous section can therefore be considered as a good representation of the molecular orbital of the odd electron, a t least in the LCAO scheme. The coefficients bl and cl of the 2bl” molecular orbital may then be calculated by comparing the experimental values of A,, with the theoretical values for an odd electron in a p orbital on 33Sand 170,respectively. The theoretical value of A,, for 33Swas calculated with the aid of the numerical value, ( r - 9 8 = 3.41 X reported by Dinse and Mobius.S Using the value ~ m 22- the ~ theoretical value of ( r - 3 ) ~= 3.36 X of A,, for 170was also calculated. Table IV lists the 2p,Z) together spin densities on S(3p,) and 0(2pz1 with the total spin density calculated in this manner. It must be remarked that the spin density on the oxygen reported here is higher than for SOZ- trapped in a solid matrix,’ while the values for 33Sare nearly the same. This difference, however, may only be due to the approximations made during the calculation.
+
Table IV: 2bl” MO Coefficients and Spin Densities on S and 0 for SO*- on MgO c1 bi ela big cia
+
bi*
SOX- (A)
802- (B)
0.86 0.52 0.75 0.27 1.02
0.84 0.48 0.71 0.23 0.94
The g Tensor. The dominant contribution to the g shift comes from mixing the 2bl” orbital with the 3al’ and 2b2’ ~ r b i t a l s . ~ The J wave functions of these orbitals are 637
and
AZlP
44.7 f 2 42 =k 2 26 f 4 21.3 f 4
-20.9 -19.6 -13 -10.7
Aaa
f3 f3 f5 i5
-23.7 -22.4 -13 -10.7
f2 =k 2 f5 f5
Exact values for the different coefficients occurring in these wave functions are not available. We assume, as Reuveni’ did, c3 = b3 = 0. The ratio c2/c4 can be obtained from the bond angle of S02- with the aid of Coulson’s relation between the degree of hybridiaation and bond angle.23 The bond angle of S02- is not available. We adopted, therefore, the angle of SO2 in the state as calculated by Brand and coworkers.24 This value is 126.2’ and gives c2/c4 = 1.71. Assuming with Reuvenil that c22 = 2bZ2 and that b4 = b5, and applying the normalization condition of the wave functions +(3al) and \1.(2b2),including one obtains the following values for the coefficients: c4 = 0.36, cz = 0.63, bz = 0.40, and b4 = bg = l / d 2 . Then the deviations from the free-electron g value are A h =0 AQ,, = Agz, =
2(CIC2X,
+ blbzXo)(clcz + blb2)
E(2bl”) - E(2b2’) 2b12b52Xo E(2b1”) - E(2b2’)
where A, = 386 cm-’ is the spin-orbit coupling constant for S and XO = 157 cm-’ is the spin-orbit coupling constant for 0. The energy differences in the denominators have been estimated by Dinse and M o b i ~ s : ~ E(3al’) - E(2b1”) = 34,500 cm-I E(2bz’) - E(2bl”) = 38,500 cm-’ We obtain then for SOZ- (A) Ag,, = 0, Ag,, = 0.0011, and Ag,, = 0.0140; whereas, for SOz- (B) Ag,, = 0, Ag,, = 0.0009, and Ag,, = 0.0136. The agreement with experiment is only qualitative in the sense that we predict the right sequence of Ag shifts. No conclusion about the bond angle of SO2- can be obtained. We adopted the 126.2’ bond angle because we feel that the SOz- bond angle is closer to that of the 3B1 excited state of SO2 than to that of the ground state of S02. A widening of the bond angle of SO2- with respect to SO2 is not unreasonable when one considers (22) J. S. M . Harvey, Proe. Roy. Soc., Ser. A , 285,581 (1965). (23) P.W.Atkins and M. C. R. Symons, “The Structure of Inorganic
Radicals,” Elsevier, Amsterdam, 1967,p 257. (24) J. C.D. Brand, C. di Lauro, and V. T . Jones, J . Amer. Chem. Soc., 92,6095 (1970). (25) R. 5. Mullikan, C. A. Rieke, D. Orloff, and H. Orloff, J . Chem. Phys., 17,1248(1949). The Journal of Physical Chemistry, Vol. 76, No. 3,1076
328 Walsh's diagramb4 The 2bl" molecular orbital increases only slightly in energy in going from 90 to 180" bond angle. The 4a1' orbital which is the highest filled orbital of SO2has a much greater energy increase in going from the 90" bond angle to the linear form. A bond angle close to 90" is therefore more likely. The Nature of the Adsorption Sites. When MgO is degassed and subsequently uv irradiated in a Hz atmosphere, two different epr signals are developed, corresponding to a pretreatment temperature of 500 and SOO", respectively. The center obtained after the 500" pretreatment has an axially symmetric g tensor and is believed to be an electron trapped at an oxygen ion vacancy.17>26 The center obtained after the 800" pretreatment was first ascribed to an electron trapped at an anion-cation vacancy pair by Lunsford and Jayne." Nelson and coworkers,26however, showed that this epr signal involves a hydrogen hyperfine splitting and that two centers are present. The existence of two different paramagnetic centers is clearly confirmed in this work by the presence of two different types of SOz-. Moreover, each SO2- species retains its same asymmetric g tensor whatever the pretreatment of MgO. This suggests that only the relative number of the two adsorption sites changes with changing pretreatment temperatures. We think that it is reasonable to ascribe both the electron trapping centers and the SOZ- adsorption sites to oxygen ion vacancies at the surface. As a working model one may consider that the sites giving rise to
The Journal of Physical Chemistry, Vol. 76, No. 3,1979
R. A. SCHOONHEYDT AND J. H. LUNSFORD SOz- (B) are oxygen ion vacancies on the edges of the microcrystals: the centers forming SO2- (A) are then oxygen ion vacancies on the flat surface of the microcrystals, The change of their relative number with increasing pretreatment temperature is in agreement with this assignment; that is, one can imagine that the decrease in surface area at 800" is due to a smoothing out of the surfaces of MgO crystallites, thus resulting in a decrease in the number of edges present on the nonideal crystal surfaces. The number of sites (a maximum of 10ls/g) can easily be accounted for in this manner. No explicit proof can be offered to show the orientation of SO2- with respect to the surface. The odd electron is entirely located on the SO2- ion as suggested by our calculations. Since it plays no role in any kind of covalent bond, the bonding forces are purely electrostatic. The oxygen ion vacancies have a positive character and are likely to attract the more electronegative oxygen atoms instead of the sulfur atom. An analogous orientation has been proposed by Bennett and coworkers27928 for C02- and CS2- bonded to alkali metals.
Acknowledgment. This investigation was supported by research grant AP 01181, Air Pollution Control Office, Environmental Protection Agency. (26) R. L. Nelson, A. J. Tench, andB. J. Hamsworth, Trans. Furuday Soc., 63,1427 (1967). (27) J. E. Bennett, B. Mile, and A. Thomas, ibid., 61,2357 (1966). (28) J. E. Bennett, B. Mile, and A. Thomas, ibid., 6 3 , l (1967).
