Oxidation of H,S to S by air with Fe(II1)-NTA as a catalyst: catalyst degradation

DIAN CHEN, RAMUNAS J. MOTEKAITIS, AND ARTHUR E.

AND

MARTELL'

Depnrtn~etzt of Chetnistry, Texas A&M Univet-sit},, TX 77843-3255, U.S.A.

DEREK MCMANUS
ARI Techtzologies, Geneva, IL 60134, U.S.A.

Received January 15, 1993

DIAN CHEN, RAMUNAS J. MOTEKAITIS, ARTHUR E. MARTELL, and DEREK MCMANUS. Can. J. Chem. 71, 1524 (1993). The oxidation of H2S to S by air is represented by the overall reaction: 2H2S + OZ+ 1 /4S8 + 2 H 2 0 The process is used with a catalyst for the removal of H,S from natural gas. A typical catalyst would be an iron(II1) che~ the trinegative anion). late system such as iron(II1)-nitrilotriacetate (NTA is a tribasic acid, H3L, and N T A represents The catalyst reactions are 2FeNTA H,S + 2FeNTA- + 1/8S8 + 2 ~ '

The main difficulty with the process is the degradation of the metal chelate catalyst. Thus the Fe(I1,III)-NTA system degrades through the formation of a number of weaker chelating agents and eventually to carbon dioxide, water, and ammonia. The degradation products identified are iminodiacetic acid (IDA), glycine, and oxalate. All of these degradation products were measured quantitatively by HPLC, and a degradation scheme is presented for the catalytic process. The fact that thiosulfate greatly decreases the degradation rate, and the fact that the degradation products were observed only in the stoichiometric reactions in which the ferrous NTA was oxidized by air, led to the interpretation that the hydroxyl radical or the superoxide radical ion is the reactive species that attacks the NTA and the intermediate degradation products and is responsible for the degradation of the organic ligands present.

DIAN CHEN, RAMUNAS J. MOTEKAITIS, ARTHUR E. MARTELL et DEREK MCMANUS. Can. J. Chem. 71, 1524 (1993).
On peut representer I'oxydation du HIS en S sous I'influence de l'air par la reaction globale suivante : 2H2S 0 2 + 1/4S, + 2H10 On utilise cette reaction catalyste pour enlever du H2S du gaz naturel. Un catalyseur typique est un systkme de chelate du fer(II), cornme le fer(I1)-nitrilotriacetate (NTA est un acide tribasique, H,L et NTA3- representent l'anion trinegatif). Les reactions du catalyseur sont 2FeNTA H2S + 2FeNTA- + 1 /8S8 + 2 ~ '

2FeNTA1/202 H 2 0 + 2FeNTA + 2 0 H La principale difficult6 associee a ce processus est la dkgradation du chelate metallique agissant comme catalyseur. Ainsi, le systeme Fe(I1,III)-NTA se degrade par formation d'un certain nombre d'agents chelatants plus faibles et Cventuellement en bioxyde de carbone, en eau et en ammoniac. Les produits de degradation qui ont pu &tre identifiks sont I'acide iminodiacktique (AID), la glycine et l'oxalate. Faisant appel a la CLHP, on a mesure quantitativement tous ces produits de degradation et on prksente un schema de degradation pour le processus catalytique. Le fait que le thiosulfate diminue beaucoup la vitesse de degradation et que I'on a observe les produits de degradation uniquement lorsqu'on a effectue des reactions stoechiomCtriques dans lesquelles de NTA aqueux etait oxydk par l'air conduit 2 suggerer que le radical hydroxyle (ou l'ion radicalaire superoxyde) est l'espkce reactive qui attaque le NTA et les produits intermediaires de degradation et qu'il est responsable de la degradation des ligands organiques presents. [Traduit par la redaction]

+ +

Introduction In 1960 a patent issued to Hartley et al. (1) reported that the Fe(II1)-chelate rapidly oxidizes H,S to sulfur and this reaction is used to remove H2S from natural gas. The main factor that prevented industrial application was the magnitude of ligand loss. Since then, considerable work (2-5) has been done to solve this difficulty. McManus (2) described a liquid chromatographic technique that enabled quantitative measurement of aminopolycarboxylate ligands and their degradation products. Hamta and Soeta (4) described the conversion of H,S to Na,S,03 with the addition of tartrate for recovery. The use of iron(II1) amiincreasing the Na2S203 nopolycarboxylates for the oxidation of H,S was described by Diaz (6, 7) and by McManus and Kin (8). Other effec' ~ u t h o to r whom correspondence may be addressed.

tive polyvalent metal chelate catalysts were identified by Bedell (9). The catalysts employed were stabilized by a number of additives, such as sulfhydryl compounds used by Diaz (6, 7) and a larger number of inorganic and organic compounds used by Bedell (9). The use of thiosulfate by McManus and Kin (8) was found to greatly lengthen the lifetime of the polyvalent metal aminopolycarboxylate catalysts, and they also described the addition of sorbitol and other polyhydroxy organic compounds to be beneficial because of their ability to form soluble complexes of iron(II1) at high pH. Although the previous work examined the chemistry of catalysts and identified major degradation products, a plausible mechanism of degradation was not established. The metal complexes of the ligands that have been identified as catalysts, and their degradation products, are stable organic

CHEN ET AL.

1525

compounds that would not ordinarily b e expected to undergo degradation under the conditions that prevail in the process. Further information is therefore needed to explain why degradation occurs. to describe the reactions ii detail, and to point the way to further improvements in the process. This paper reports kinetic studies of the degradation of the Fe(I1,III)-NTA (nitrilotriacetate) redox system under operating conditions whereby H,S is continuously oxidized by air, a s well a s stoichiometric degradation reactions of the Fe(I1,III)-NTA complexes with one of the reacting species (O,, HrS) missing. T h e rate of degradation of N T A and of t w o other ligands that act as redox catalysts for the oxidation of HIS, E D T A (ethylenediaminetetraacetic acid) and H E D T A (hydroxyethylethylenediaminetriacetic acid), a r e also compared. This information, plus the fact that lowering p H increases the rates of degradation of N T A and of intermediate degradation products and that thiosulfate greatly decreases the rates of degradation, led to the conclusion that a free radical reaction is responsible for the degradation reactions. T w o possible candidates, the superoxide radical ion '0,-, and hydroxyl radical HO', a r e suggested as possible initiators of the free radical reactions. T h e evidence pointing to o n e o r the other of these intermediates is discussed.

FeS and S that deposited in the tubing was cleaned out occasionally. The operation of the other experiments were carried out in the same manner except that the sulfur was filtered off every 7 or 8 h and the pH was continuously adjusted to 8.5 by the addition of NaOH solution. HPLC arzalysis proced~~r-e The analyses of NTA, IDA, and oxalatc were rneasured by Sollowing the method of McManus (2). Prepclration of irorz$ree samples To 12.0 mL of solution taken froin the contin~rousreactor, 140 mg of NaOH in 5 rnL water was added dropwise with stirring. The stirring was continued for 10 min and the reaction mixture was allowed to stand at room temperature for 20 rnin. The Fe(OH), that precipitated was filtered off carefully and was washed several times with water. The filtrate combined with the washings was transferred to a 50-mL volumetric flask. The solution was adjusted with acid to pH 4.2 and then diluted with water to 5 0 mL. Annlysis of NTA, IDA, L I I I ~oxalczte ns their copper(l1) cninplex-es A 7-mL sample of solution was taken from the volumetric flask and placed in a 10-mL volumetric flask. To this was added 2.5 mL of 0.050 M CuCl, solution and the inixture was diluted to 10 mL with water. The mobile phase contained: 0.0010 M Cu(II), 60:40 H,O: MeOH, 2% CH,COOH, 0.7% CH,(CH,),5(CH3),NBr, adjusted to pH 4.2 with NaOH solution. This phase is presumed to contain the alkyl ammonium salts of the negative copper coinplexes of NTA, IDA, and oxalate. Operating conditions Analytical column: IB-SIL 5 C8, reverse phase, 4.5 x 150 mm; coIumn temperature: ambient; flow rate, 1.5 cm3 min-'; detection, UV absorption at 280 nm; sample, 20 pL; recorder 10 mV full scale; chart speed, 0.5 cm min-I. Analysis oj'glycine and glyoxylrzre as their Ni(II) c.o~nplexes For the analysis of glycine and glyoxylate as the complexes formed with Ni(II), the procedure is identical to that described above for the copper complexes of NTA, IDA, and oxalate, the only difference being the use of 2.5 mL of 0.050 M Ni(NO,)? solution instead of CuCI, solution, and the mobile phase contained 0.0010 M Ni(I1) rather than Cu(I1) and was presumed to contain the alkylammonium salts of the negative nickel complexes of glycine and glyoxylate. For the measurement of glycine, the UV absorption was measured at 270 nm; for glyoxylate, the UV absorption was measured at 250 nm. The other operating conditions were the same as above. The retention time for IDA is about 3.0 min, 7.0 min for the oxalate, and 21 min for the NTA. The separations of these quantitative calibrations for the HPLC analysis of NTA, IDA, and oxalate and for glycine and glyoxylate were obtained from varying amounts of known samples of these compounds, and the peak heights at the indicated amplification settings vs. concentration of the species were plotted. The linear nature of these plots indicated accurate HPLC determinations of these n~olecularspecies over a considerable range of concentration. Identificatiorl oj'the hydr-o,xylation products by paper- chromatography The paper chromatographic measurements of the hydroxylation products of benzoic acid were made by the procedure of Grinstead (10). Benzoic acid and its hydroxylation products were separated from the Fe(III), the remaining NTA, and its degradation products by acidification of the reaction mixture and extracting five times with ether. The extracts were combined and reduced to a small volume by evaporation of the solvent. The ether residue was chromatographed on Whatman No. 1 filter paper, with 4 : 1 (by volume) isopropyl alcohol, 7 M NH,OH as the eluant. Under ultraviolet light six spots appeared on the paper. The R, value and the color of the spots were compared with those of standard cornpounds, and the six spots were assigned as follows:

Experimental
Materials The following materials were ordered in the highest purity available and were used without further purification: nitrilotriacetic acid trisodium salt (99+% Aldrich); Fe(NO), . 9 H 2 0 (Cer5 H z 0 (Reagent A.C.S., Fisher tified A.C.S.) and Na2S303. Scientific Company); FeC1,. 4H,O and Ni(N03),. 6 H 2 0 (Baker Analyzed Reagents); CuC12. 2H,O (Baker Analyzed Reagent); M~OH (~allinckrodt Chrom AR HPLC); hexadecy~trimeth~j ammonium bromide (99%, Sigma); H 2 0 double distilled water; H,S (99.5%, Gas Analytical Service). Catalase (Biomedicals, Inc., Ex: Bovine liver, E.C. 1.1 1.1.6; sterile aqueous solution; activity, 40 000 units per milligram solid; unit definition, one unit decomposes one micromole of H?O, per minute; 25.0C; pH 7.0; approx. 30 000 units per millilitre). HPLC equipment An IBM L. C. pump No. 771008 equipped with a chromatography accessory, UV-visible spectro monitor 3100 (LDC Analytical), and a chart recorder 6885 (Kipp and Zone) were used. Redo-- reaction conditiorls Iron-NTA solution: One litre of solution contained 7.24 g of Fe(NO)3. 9 H z 0 and 9.96 g of N(CH,COONa), . H 2 0 . The redox reaction was carried out in a glass apparatus, Fig. 1, and the pH and redox potential in both the absorber and oxidizer were monitored. The H2S flow rate was 2.0 mL min-' and the air flow rate was 1.0 L min-I. The temperature was maintained at 25 ? 1C throughout. NMR spectra The proton NMR spectra were recorded with a Varian XL-200 NMR spectrometer, and chemical shifts are reported in ppm. Degradation of Fe(ll1)-NTA with utlcontr-olledpH One litre of the NTA solution described above was placed in the oxidizer compartment (Fig. I ) . The pump was then started and some of the solution was pumped into the absorber compartment, with a flow rate of 100 mL min-I. The pH and redox meters were then turned on. At this stage the air pump was turned on and the air flow was adjusted to 1.0 L min-I. The valve of the H,S cylinder was turned on and the H,S flow was adjusted to 2.0 mL minPr.The time of the start of the reaction was recorded, and the pH and redox meter readings were recorded from time to time. Every half hour the flow rates of H,S and air were checked and adjusted if necessary. Any

CAN. J . CHEM. VOL. 71, 1993

FROM TANK

FIG. 1. Continuous apparatus. surements, and the yield of each was concluded to be less than 5%, which is the limit of sensitivity of the NMR technique. Identification of the hydroxylation products by mass spectral measurements 'The mass spectra were obtained with a VG analytical 7 0 s highresolution double-focusing mass spectrometer with an attached VG analytical 11/250J data system. The operator was Dr. David Jacobs of the Departmental Research Services Facility. Mass spectral data of the hydroxylation products gave the molecular weight 138 for the three monohydroxybenzoic acids, which had been partially separated on a silica gel column.

Compound 1. 2. 3. 4. 5. 6. o-Hydroxybenzoic acid Benzoic acid 2,5-Dihydroxybenzoic acid 2,3-Dihydroxybenzoic acid m-Hydroxybenzoic acid p-Hydroxybenzoic acid

Rf value
0.78 0.64 0.54 0.41 0.25 0.090

Iderztificatioti of the hydroxyiation products by NMR The ether r ~ s i d u e obtained as described above was loaded on a silica gel (60 A) column and eluted first with benzene and then with a benzene and ether mixed solvent beginning with 1% ether, which was slowly increased to 20%. At the end MeOH was used as the eluant. Each 30 mL of eluate was collected; after the solvent was removed its NMR spectrum was determined. 'The benzoic acid was eluted first. The second eluate was salicylic acid, which was then followed by m-hydroxybenzoic acid and p-hydroxybenzoic acid. The NMR measurements of the silica gel separation products confirm the formation of salicylic acid, tn-hydroxybenzoic acid, and p-hydroxybenzoic acid: salicylic acid: 'H NMR (D,O):6.51 (t, lH, phenyl), 6.56 (d, l H , phenyl), 7.00 (t, l H , phenyl), 7.16 (d, lH, phenyl); m-hydroxybenzoic acid: 'H NMR (DZO):6.56 (d, lH, phenyl), 6.86 (rn, 2H, phenyl), 6.96 (t, l H , phenyl); p-hydroxybenzoic acid: 'H NMR (D20): 6.39 (d, 2H, phenyl), 7.45 (d, 2H, phenyl). The dihydroxybenzoic acids were not found in the NMR mea-

Results The degradation of the Fe(II1)-NTA catalyst in a continuous reaction system with no control of pH is shown in Table I and illustrated in Fig. 2. The NTA decreases rapidly with time, and over 95% of it is lost in 100 h. During this time the pH, which starts at 8.6, drifts gradually downward, reaching 3.6 at the end of the run. IDA was the first and main reaction product (Fig. 2). Its concentration increased steadily throughout the run, although its rate of formation seemed to decrease slightly toward the end. The second and subsequent degradation product containing nitrogen was glycine, as indicated in Fig. 2. The amount of glycine produced was considerably less than IDA, showing that the rate of degradation of the latter is slower than that of NTA. The sum of the concentrations of NTA, IDA, and glycine in Fig. 2 shows

CHEN ET A L

TABLE 1 . Degradation of Fe(II1)-NTA with uncontrolled pH (8.6 + 3.6) at 25.O"C Tirne (h) NTA (M) IDA (M) Oxalate (M) Gylcine (M)

a material balance of about loo%, indicating that very little of the ligand degraded all the way to ammonia, even after 100 h. The formation of oxalate, presumably from the acetate side chains of NTA, IDA, and glycine, starts off more slowly than expected at first, but rises above the rate of IDA formation. This behavior is not considered unusual since oxalate is expected to form both in the formation and degradation of IDA. It shows a somewhat slower rate of formation near the end of the run and it is suggested that this may be due to the further oxidation of oxalate to carbon dioxide (13). It is noteworthy that no glyoxylate was found among the degradation products. The degradation of the Fe(I1,III)-NTA chelate in an experiment in which the pH was kept constant at 8.5 and in which the sulfur was removed by filtration every 6-7 h (Table 2 and Fig. 3) gave a lower rate of degradation of NTA. In fact glycine, which was produced in a small amount at pH 7, was not formed at pH 8.5. Thus, it appears degradation is promoted under acidic conditions. To further determine the effect of pH, the redox reactions were run at pH 7.0 and 5.5. The pH was regulated by the addition of NaOH solution initially and at short time intervals (every 30 min or less). The NTA degradation at these

pH values is compared in Fig. 4 with the degradation observed at pH 8.5 (also shown in Fig. 3). The results confirm that the rate of degradation of NTA increases as the pH is decreased. Kinetic analysis of the degradation of NTA at 25.0C at pH 8.5, 7.0, and 5.5 (Fig. 4) suggests that the degradation of NTA is a first-order reaction. The observed degradation rate constants of NTA obtained from the data in Fig. 4 are
TABLE 2. Degradation of Fe(II1)-NTA at pH 8.5 at 25.OoC Tirne (h) NTA (M) IDA (M) Oxalate (M)

Time (h)
FIG. 2. Degradation of Fe(II1)-NTA with uncontrolled pH (8.6+ 3.6): @, NTA; W , IDA; A , oxalate; glycine; % is rnole per cent of species based on initial concentration of NTA, 0.036 M = 100%.

20

40

60

80

+,

Time (h)
FIG.3. Degradation of Fe(II1)-NTA at pH 8.5;% is mole per cent of species based on initial concentration of NTA, 0.036 M = 100%.

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CAN. J. CHEM. VOL. 71, 1993

Time (h) l i m e (h)

FIG.4. Degradation of Fe(II1)-NTA at pH 8.5, 7.0, and 5.5; 25.0C; H2S flow rate (2.0 mL/min); % is mole per cent of species based on initial concentration of NTA, 0.036 M = 100%. s-I; pH 7.0, 7.0 X pH 8.5, 4.4 x s-'; pH 5.5, 1.1 X s-I. This increase in rate constant with a decrease in pH agrees with the qualitative observation, stated above, that degradation is more rapid at low pH. A similar run at pH 8.5 with 32 g of Na,S20, in the solution as a stabilizer is shown in Table 3 and illustrated in Fig. 5. It is seen that the sodium thiosulfate greatly reduces the rate of degradation of the NTA. A small amount of IDA was found as the only degradation product in concentrations large enough to measure. To determine which part of the process involved degradation of NTA, a number of stoichiometric reactions were carried out. A ferric-NTA solution of the same concentration as used in the redox runs at pH 8.5 was treated with air for 2 days. HPLC analysis carried out as described above indicated the presence of only NTA after 1 and 2 days, and that no degradation reaction had occurred. Also, a ferricNTA solution was treated with H,S at the same rate as the experimental redox runs for 2 days, and analysis of the reaction products in the same manner showed the absence of degradation products. However, when a similar ferrous-NTA TABLE 3. Degradation of Fe(II1)-NTA at pH 8.5 with 32 g NaZS2O3 at 25.072 Time (h) NTA (M) IDA (M) FIG. 5. Degradation of Fe(II1)-NTA at pH 8.5 with 5% Na2S203. 5H,O: e,NTA; B, IDA; % is mole per cent of species based on initial concentration of NTA, 0.036 M = 100%. solution was treated with air for 2 days and the results were subjected to HPLC analysis, the results showed evidence of degradation with the formation of 1.7% of IDA and slightly less than 1.O% of oxalate. These experiments indicate that the degradation of NTA is a side reaction that occurs during the oxidation by air of the ferrous-NTA to the ferric-NTA chelate system. To obtain information on the question of whether H 2 0 2is an intermediate in the reaction, the Fe(LI1)-NTA solution was mixed with catalase (catalase solution added to a dilution of 1 : 100) and the redox reaction was carried out at pH 7.0 for 50 h. The results show that the NTA degradation slowed down on the addition of catalase. This result confirms the formation of H 2 0 2as an intermediate product, because the enzyme rapidly catalyzes the decomposition of H,O, and should slow down reactions requiring H,O, as an intermediate. To investigate the possible formation of the hydroxyl radical, an equimolar amount (0.0362 M) of benzoic acid was mixed with Fe(1II)-NTA, and the redox reaction was carried out at pH 8.5 for 100 h, as described above. The results indicate that the benzoic acid was hydroxylated to a mixture of o-, m-, and p-hydroxybenzoic acid. The products were characterized by NMR, paper chromatography, and mass spectra. This is strong evidence for the formation of the hydroxyl radical, because the benzene ring is not hydroxylated by molecular oxygen. There still remains the possibility that the less reactive -0,- radical is involved. This question is addressed below. These results are similar to those obtained by Grinstead (10). He reported that when a solution of Fe(II1)-NTA is mixed with ascorbic acid and benzoic acid under oxygen, the latter is hydroxylated to a mixture of o-, m-, and p-hydroxybenzoic acid. He also confirmed the formation of H,O, as an intermediate by the use of catalase. Because the iron chelates of EDTA and of HEDTA have been used as redox catalysts for the oxidation of H,S to S,

CHEN ET AL

by air, it was considered of interest to compare the rates of degradation of the iron chelates of these ligands with that described above for NTA. Figure 6 shows the measured rates of degradation of all three iron chelate systems starting with the same concentration of Fe(II1) in each case, with the molar ratio of ligand to metal being 2 : 1 for NTA, EDTA, and HEDTA. No stabilizer or additional ligand was added. It is obvious from Fig. 6 that NTA degrades more slowly than do the other two ligands and the most rapid rate of degradation was observed in the case of HEDTA. The superiority of NTA over the other ligands with respect to degradation was first pointed out by McManus and Kin (8).

Discussion Graphic formulas indicating the reaction of H,S with the catalyst, the Fe(II1)-NTA chelate, to produce sulfur and the Fe(I1)-NTA chelate, and regeneration of the ferric-NTA catalyst by oxidation with air, are illustrated in Scheme 1. The iron(II1)-NTA system is shown to consist of two complexes in equilibrium, a 1 : 1 monohydroxo iron - NTA complex and a 1 :2 iron(II1)-NTA complex, in accordance with the description given by Motekaitis and arte ell.' The six-coordinate representation of the 1:2 complex represents one of the possibilities for this complex. It may very well be seven-coordinate, in view of the seven-coordinate crystal structure of the 1 : 2 complex described by Clegg et al. (1 1). However, it is possible that the structures and coordinate bonding of the Fe(II1)-NTA complexes in the solid state and in solution may be different. The degradation reactions illustrated by Figs. 2, 3, and 5 show that IDA is the first compound produced, and that it is followed by the formation of glycine. The oxalate that is formed apparently comes from the side chains (acetate groups) that are cleaved from the NTA, IDA, and glycine. On the basis of the evidence now available, the following degradation scheme is tentatively suggested. Because the ligands undergoing degradation are usually very stable, and the degradation occurs during the re-oxidation of the ferrous-NTA system with air (molecular oxygen), it is suggested that only free radicals have enough energy to degrade these chelating ligands. The review by Walling (12) (see also the paper by McManus (2)) indicates that the hydroxyl radical may be formed under the reaction conditions that prevail, leading to the following sequence of reactions.
FeNTA-

Time (h)
FIG. 6. Degradation of Fe(II1)-NTA, Fe(II1)-EDTA, and Fe(II1)-HEDTA at p[H] 8.5 and 25.0C; HZSflow rate = 2.0 mL/ min. % is mole per cent of species based on initial concentration of NTA, EDTA, and HEDTA, 0.036 M = 100%.

formation of the free radical. The formation of carbon dioxide from oxalate has been described (13). The stabilizing effect of thiosulfate (Fig. 4), reported previously by McManus and Kin (8), as well as other stabilizers described by Diaz (6, 7) and Bedell (9), can be understood since they have one property in common. They are all free radical scavengers, and decrease the degradation represented by eqs. [I]-[4] by decreasing the concentration of free radical in the reaction mixture. While the above reaction sequence describes the degradation of the NTA on the basis of the intermediates actually detected in the reaction mixture, it does not give a rationale for the initial attack on the NTA, and the degradation products, iminodiacetic acid and glycine. The following reactions involve species and intermediates that have been inferred but not demonstrated to be present.

[2] [3]

+ HzOz+ FeNTA + OH- + HO'

R'R?NCH,COO-

'OH

[6]

R'R'NH

R'R'N~HCOO- + FeNTA

+ R'R'NCHCOO-

+ FeNTA-

R' R'

= =

H; R'

CH2COO- IDA Glycine

R'

Equations [ l ] and [2] are in accord with the fact that low pH increases the rate of degradation, in that low pH favors the

'TO

be published.

Reaction [5] is inferred by the presumed presence of 'OH generated by the Fenton reaction (Fe(I1) + H202),and the facile hydroxylation of benzoic acid in the reaction mixture. Reactions [6] and [7], favored by the considerable concentration of Fe(1II) chelate in the reaction mixture, may

CAN. J . CHEM. VOL. 71, 1993

SCHEME 1. Reactions for the oxidation of H,S to S with the Fe(I1,III)-NTA system as catalyst.

be considered as occurring in sequence or as concerted. The failure to detect glyoxylate in the reaction mixture may be due simply to its rapid oxidation to oxalate. Alternatively, its absence may be due to the superoxide radical as the oxidizing agent, rather than the hydroxyl radical, leading to the following sequence of reactions:

[9]

H202+ HO' + 0';

+ H,O + H+
~+ H+ , ~ ~ ~ -

'

+~ 0 ;

+ R'R'NCHCOO-

+ H202

CHEN ET AL.

NTA

IDA

Glycine

Oxalate
SCHEME 2. Proposed degradation scheme for NTA. 1. W. Hartley, R.S. Craig, and R.H. Sapiro. UK, Ltd. Ger. 1,091,696, Oct. 27, 1960 (Cl. 26d). 2. D. McManus. 41st Pittsburgh Conference and Exposition on Analytical Chemistry and Applied Spectroscopy, New York City. 1990. 3. W. Nanbu, T. Nanbu, andN. Nanbu. Japan Kokai 76,133,191 (Cl. BOlJ31/04), 18 Nov. 1976, Appl. 75/57,813, 15 May 1975,4 pp. 4. M. Haruta and M. Soeta. Kageno, Kenji Jpn. Kokai Tokyo Koho 79 57,467 (Cl. B01D53/34) 09 May 1979, Appl, 77/ 124,343, 12 Oct 1977; 4 pp. 5. D.A. Van Kleeck. U.S. US 4,876,075 (C1.423-226; C01B17/ 16), 24 Oct 1989, Appl. 258,425, 17 Oct 1988; 8 pp. 6. Z. Diaz. U.S. Patent No. 4,388,239, June 14, 1983. 7. Z. Diaz. U.S. Patent No. 4,518,576, May 21, 1985. 8. D. McManus and F.R. Kin. U.S. Patent 4,622, 212, Nov. 11, 1986. 9. S.A. Bedell. U.S. Patent No. 4,89 1,205, Jan. 20, 1990. 10. R.R. Grinstead. J. Am. Chem. Soc. 82, 3472 (1960). 11. W. Clegg, A.K. Powell, and M.J. Ware. Acta Crystallogr. Sect. C: Cryst. Struct. Commun. C40, 1822 (1984). 12. C. Walling. Acc. Chem. Res. 8, 125 (1985). 13. Y. Zuo and J. Holgne. Environ. Sci. Technol. 26, 1014 (1992).

+ R'R'NH

+ -00C-COO-

+ FeNTA

While the above reactions are somewhat speculative, all the have been inreactants are present, and both 'OH and 02'ferred as possible intermediates. The oxidation of the aminopolycarboxylate ligands is considered a free radical reaction because the ligands are not oxidized by oxygen, even in the presence of Fe(III), under the reaction conditions employed.

Acknowledgement This work was supported by a research contract with ARI Technologies, Inc. of Palatine, Illinois.