Distribution Coefficients and Anion Exchange Behavior of Elements in Oxalic Acid-Hydrochloric Acid Mixtures

F. W. E. Strelow, C. H. S. W. Weinert, and Cynthia Eloff

National Chemical Research Laboratory, Pretoria, Republic of South Africa

Anion exchange distribution coefficients with AG b X 8 , a strongly basic quarternary ammonium anion exchanger with a polystyrene matrix, are presented for 36 elements in oxalic acid-hydrochloric acid mixtures. The coefficients are presented in two tables ordered according to their numerical value in 1M HCI plus 0.05M (or 0.25M) oxalic acid. When this value is lower than 1, the values in 0.1 or 0.01M HCI are taken. A number of the possibilities of this system for separations are pointed out, and some aspects of the elution behavior of various elements are discussed. The versatility of the system is demonstrated by sequential elution of the mixtures Mn(l1)-Ni(l1)-V(V)-Nb(V)U(VI); Mg-AI-Ga-In; Co(1l)-Cu(l1)-Ti(1V)-Mo(V), and Cu(ll)-AI.

acid mixtures. Two oxalic acid concentrations 0 . 0 5 M and 0.25M were selected and the hydrochloric acid concentrations were varied from 0.01M to 4.OM.
EXPERIMENTAL

WHILE OXALIC ACID or oxalic acid-mineral acid mixtures have been used successfully for the ion exchange separation of elements such as Sc, Ti(IV), and V(V) ( I ) , Ti(IV), Zr, Nb, Ta, W(VI), and Mo(V1) (2); and Ta and Nb(V) ( 3 4 ) ; and oxalic acid or oxalates have been used for the elution of Te(IV), Sb(V), and Sn(1V) (5); Ga(II1) (6); U(V1) (7); and Cu(II), Ni(II), and A1 (8), the only systematic anion exchange study in oxalate media seems to be that undertaken by De Corte et a[. (9), who have determined distribution coefficients for 12 elements in oxalic acid solutions with Dowex 1-X8 resin. While only separations of radio tracer amounts were reported, separations of milligram amounts should be possible in some cases, though most of the elements investigated have limited solubilities in oxalate solutions. Some common multivalent elements such as Al, Fe(III), and Ti(1V) do form oxalate complexes with stability constants several orders of magnitude larger than those of Cu(II), Ni(II), Mn(II), etc. Oxalic acid in appropriate mixture with a strong mineral acid, which could be used to control the dissociation of the oxalic acid and therefore effect selective complex formation, therefore should offer excellent prospects for the separation of multivalent from divalent elements. Furthermore, the anion of the mineral acid will compete for exchange sites in the resin and the strength of this competition is governed not only by the concentration, but also by the kind of the anion. This provides more variables the analyst can use when looking for selective separations. This paper presents a systematic study of anion exchange distribution coefficients of 36 elements in oxalic-hydrochloric
(1) R. I. Walter, J , Znorg. Nucl. Chem., 6 , 58 (1958). (2) W. R. Bandi, E. G. Buyok, L. L. Lewis, and L. M. Melnik, ANAL. CHEM., 1275 (1961). 33, (3) J. Gillis, J. Hoste, P. Cornand, and A. Speeke, Meded. Kon. Vlaam. Acad. Wetensch. Belg., 15,63 (1953). (4) M. Herman, Ind. Chim. Belge, 23, 123 (1958). ( 5 ) R. K. Preobrazhensky and L. M. Moskvin, Radiokhimiya, 3, 309 (1961). (6) E. P. Tsintsevich, I. P. Alimarin, and L. F. Marchenkova, Chem. Abstr., 53,10898 (1959). (7) Z. Dizdar, Recl. Tral;. Inst. Recherches Structure Matiere, 2 , 85 (1953). (8) M. R. Zaki and K. Shakir, 2.Anal. Chem., 185,422 (1962). (9) F. De Corte, P. Van Den Winkel, A. Speeke, and J. Hoste, Anal. Chim. Acta, 42,67 (1968). 2352

Apparatus. Borosilicate glass tubes of 20-mm i.d. with fused-in glass sinters of No. 2 porosity and a buret tap at the bottom and a B 19 ground glass joint at the top were used as columns. A Zeiss PMQ I1 and a Perkin-Elmer 303 instrument were used for spectrophotometric and atomic absorption measurements, respectively. Reagents. Analytical reagent grade chemicals were used whenever possible. Hafnium oxide, the chlorides of Ti(V), Ta(V), Nb(V), Ga, and In(II1) and chloroplatinic acid were obtained from Fluka A.G. ; Buchs, Switzerland. Standard solutions containing 1 millimole of the element in 25 ml of 0.10M HCl were prepared. Solutions of W(VI), Mo(VI), Fe(III), and V(V) also contained 1 of hydrogen peroxide, and those of Ti(IV), Nb(V), Ta(V), and Sn(1V) 0 . 5 0 M oxalic in addition to HC1 and hydrogen peroxide. Less concentrated solutions were prepared by dilution when required. The resin used was AG 1-X8 strongly basic anion exchanger supplied by Bio-Rad Laboratories, Richmond, Calif. Resin of 100- to 200-mesh particle size was used for determination of distribution coefficients and of 200- to 400-mesh for column work. Procedure. Distribution coefficients were determined by equilibrating in a mechanical shaker 250 ml of a solution containing 1 millimole of the element and the given concentrations of oxalic and mineral acid with 2.500 grams of AG 1-X8 resin in the chloride form, which had been dried at 60 "C in a vacuum pistol with phosphorus pentoxide as drying agent. Solutions of W(VI), Mo(VI), Fe(III), V(V), Ti(IV), Nb, Ta, and Sn(1V) contained 0.1% of hydrogen peroxide. Only 0.05 millimole of the element was used in the case of the elements Bi(III), Cu(II), Ni(II), Co(II), Zn, Pb(II), and Cd because of the limited solubility of their oxalates. Equilibration time was 24 hours and equilibration temperature 25 "C, except in the case of Fe(II1) where an equilibration time of 2 hours was used to minimize the amount of reduction to the divalent state. After separation of the resin from the aqueous phase, the amounts of the elements in both, aqueous phase and resin, were determined by appropriate analytical methods and weight equilibrium distribution coefficients were calculated from the results.

D =

amount of element in resin amount of element in solution

ml solution gram dry resin (1)

The coefficients are presented in Tables I and 11.

RESULTS
The coefficients in Tables I and I1 indicate numerous possibilities for separations. A few of these were selected for further investigation and a few typical multielement elution curves using synthetic mixtures were prepared to demonstrate the versatility of the system. Separation of Mn(I1)-Ni(I1)-V(V)-Nb(V)-U(V1). A solution containing 0.5 millimole each of Mn(II), V(V), Nb(V),

ANALYTICAL CHEMISTRY, VOL. 44, NO. 14, DECEMBER 1972

Table I.

Element Sn(1V) W(V1) Pd(I1) MO(VI)~ Bi(III)b,c WI) Mo(V1) Ta(V)a Cd(II)b In(II1) Nb(V)a U(V1) Zn(II)b Ti(IV) Fe(I11p Zr(1V) Ta(V) Hf(IV) Ga(II1) Ti(IVp Pb(II)bfc
sc

0.01M

> 104
3450
>io4 >io4

... 1500
>io4

3 78

> 104 > 104 > 104

28.7
>io4

51

> 104
103 4030
>io4

>io4

> 104

Al(II1) >io4 Cu(1I)b 620 Be(I1) 68 Ni(II)b 84 9.2 Co(I1)b Mn(II), Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs 1 ml of 30% HZOZ present. 0.05 millimole of element. 2-hour equilibration time.

WV) V(V)

60 5180 5370

Anion Exchange Distribution Coefficients in Oxalic Acid-HC1 Mixtures 0.05M Oxalic Acid Various Concentrations of HCl Molarity HCI 0.1M 0.2M 0.5M 1.OM 2.OM 3.OM > 104 > 104 >io4 > 104 > 104 9700 7610 6720 699 163 > 104 9170 2850 440 >104 >io4 >io4 867 2310 920 660 > 104 >lo4 > 104 1900 1330 90 0 590 567 700 1230 1370 1500 1470 1480 837 1270 >io4 650 4100 487 >io4 303 367 364 201 17.7 118 269 171 195 48.9 289 472 2900 44.4 28.8 828 80 173 11.5 3410 7100 675 4.7 78 24.2 1630 66 250 6800 38.1 30.6 3.3 2.9 5.3 35.3 61 26.5 > 104 >io4 639 <OS 0.8 6.0 14.5 105 2790 1580 9.5 4040 1.4 >io4 0.5 11.4 138 39.5 102 10.9 104 5.5 6.1 3560 85 0.9 1700 8.1 1.7 43.5 6.6 485 1.2 >io4 7.9 1420 38.6 6.4 0.5 320 <0.5 3.4 17.7 2.4 3.1 4.3 1.9 523 152 19.1 2.7 1.1 1.5 2.3 570 160 0.6 17.1 <0.5 0.6 4.4 1840 <0.5 <O. 5 211 39.7 0.6 0.4 8.4 1.4 1.1 1.5 <0.5 <O. 5 8.1 <O. 5 <0.5 <0.5 <O. 5 <0.5 <0.5 0.8 <0.5 <0.5 <O. 5 <0.5 <O. 5 <0.5 <0.5

4.OM 3800 prec. 249 935 344 525 930 10.2 427 24.1 3.7 71 88 <0.5 39.0
<0.5

5.4 0.5 30.7 <0.5 1.1 0.9 <0.5 <0.5 2.2

<0.5

<0.5
<0.5
<O. 5

<0.5

<0.5

<0.5

<0.5

<O. 5

(0.5

Table 11. Anion Exchange Distribution Coefficients in Oxalic Acid-HC1 Mixtures 0.2JM Oxalic Acid Various Concentrations of HCl Molarity HCl Element 0.01M 0.1M 0.2M 0.5M 1.OM 2.OM 3.OM Sn(IV) > 104 > 104 > 104 >io4 > 104 9100 7200 Bi(III)b,c ... 700 669 104 641 3230 2760 Pd(I1) > 104 >io4 > 104 2190 9670 697 365 MO(VI)~ > 104 > 104 > 104 1910 5740 647 475 Mo(V1) > 104 7140 3050 696 1800 290 456 3260 1920 5790 239 582 84 46.3 W(W Ta(V)= 433 425 415 355 133 237 18.2 Ti(1V) >io4 7800 5200 213 1450 6.2 1.3 In(111) 5230 2340 1230 321 145 76 50 > 104 6650 2590 492 144 U(VI) 51 51 Nb(V)= 8220 5980 2830 445 123 21.6 9.4 Cd(I1)a 30.3 12.2 72 120 170 242 235 207 206 205 55 169 TaW) 10.2 6.9 Zn(I1)b 2.5 7.0 3.3 8.3 46.0 59 58 Fe(III)b > 104 3920 1450 236 35.2 6.6 8.1 Hf(1V) >io4 7320 >io4 261 22.0 2.8 0.9 Zr(IV) >io4 >io4 6800 258 21.4 3.1 1.7 Ga(II1) > 104 9300 120 1040 2.2 18.0 5.9 Ti(IV)a 2340 1280 457 15.0 80 2.8 1.7 1510 462 39.5 137 V(IV) 9.7 1.8 1.3 3110 445 38.1 185 V(VY 7.7 1.5 <0.5 Pb(II)b,c 54 4.1 2.0 2.9 1.o 2.4 1.7 Cr(III)d 76 66 34 10.6 2.4 0.5 <O. 5 Al(II1) 4250 1840 36.6 571 1.8 0.5 <0.5 Cu(I1)b 62 110 17.3 1.3 2.7 0.8 1.4 Be(I1) 16.3 6.4 <0.5 1.2 <O. 5 <0.5 <O. 5 Ni(II)b 13.1 1.7 1.1 <0.5 0.5 <0.5 <0.5 Co(1I)b 2.5 0.5 <O. 5 <O. 5 <O. 5 <0.5 <0.5 a 1 ml of 3 0 x H202 present. 0.05 millimole of element. 2-hour equilibration time. 5-day equilibration time.

4.OM
5 300

1080 224 282 599 33 .o 11.4 <0.5 31.9 104 5.4 226 6.5 56 27.6 0.5 0.9 36.7 0.8 1.1
<0.5

1.1 <0.5 <0.5 1.7

<0.5 <O. 5 <0.5

~~

~ _ _ _ _ _

ANALYTICAL CHEMISTRY, VOL. 44,

NO. 14, DECEMBER 1972

2353

m eluate l
Figure 1. Elution curve

Mn(I1)-Ni(I1)-V(V)-Nb(V)-U(VI)

46 ml (20 g) AG 1-X8, 200-400 mesh, resin (14 X 2.0 cm). Flow rate, 2.5 i 0.5 ml/min

T 8

4
I

8
1

In

Figure 2. Elution curve Mg-Al-Ga-In 46 ml (20 g) AG 1-XS, 200-400 mesh, resin (14 X 2.0 cm). Flow rate, 2.5 i 0.5 ml/min

q
E
--TOO
400

500

600

700

800
O M

L 1000 1 0 10
HNO,

F 0 5 M o x o ~ M - H C l t 0 0 5 Mo x a l T O M H T + 0 2 5 M oxalic

rnl eluate

and U(V1) and 0.1 millimole of Ni(I1) in 100 ml of 0.05M oxalic acid with 0.015% hydrogen peroxide was prepared and passed through a column of 46 ml (14 x 2.1 cm) AG 1-X8 resin of 200- to 400-mesh particle size. The column had been equilibrated with 100 ml of 0.05M oxalic acid containing 0.01M HC1 and 0.015% hydrogen peroxide. The elements were washed onto the resin with a solution of the same composition and then eluted with the following sequence of reagents: 250 ml of 0.05M oxalic acid, 0.01M HCI, and 0.015% H 2 0 2for Mn(I1) [wash solution included]; 300 ml of 0.OSM oxalic acid, 0.2M HC1, and 0.015% H202 for Ni(I1); 300 ml of 0.05M oxalic acid, 1.OM HC1, and 0.015 H202 for V(V); 250 ml of 0.10M oxalic acid, 4.OM HC1, and 0.015% H202for Nb(V); and 250 ml of 1 . 0 M H N 0 3for U(V1). The flow rate was kept at 2.5 i 0.5 ml per minute. Fractions of 25-ml volume were taken from the beginning of the adsorption step using an automatic fractionator and the concentrations of the elements in the fractions were determined by appropriate analytical methods. The experimental elution curve is presented in Figure 1. The synthetic mixture Separation of Mg-Al-Ga-Ln(II1). containing 0.5 millimole each of Mg, Al, Ga, and In(II1) in 25 ml of 0.05M oxalic acid was passed through a column as described above. The column had been equilibrated with 0.05M oxalic acid. The elements were then eluted with the
2354

following sequence of reagents: 200 ml of 0.05M oxalic acid (wash solution included) for Mg; 400 ml of 0.5M HC1, and 0.05M oxalic acid for Al; 250 ml of 2.OM HCl, and 0.05M oxalic acid for Ga; and 250 ml of 1.OM H N 0 3 for In. The flow rate was 2.5 f 0.5 ml per minute. The experimental curve is shown in Figure 2. Separation of Co(I1)-Cu(I1)-Ti(1V)-Mo(V1). A synthetic mixture containing 0.1 millimole each of Co(II), and Cu(II), and 0.5 millimole of Ti(IV) and Mo(V1) in 50 ml of 0.05M oxalic acid, 0.10M HCl, and 0.015% H2O2 was passed through a column of 46 ml AG 1-X8 resin as described above. The elements were then eluted by the following sequence of reagents: 250 ml of 0.05M oxalic acid, 0.10M HCl, and 0.015 % H z 0 2for Co(I1); 250 ml of 0.05M oxalic acid, 0.50M HC1, and 0.015% H 2 0 2for Cu(I1); 250 ml of 0.05M oxalic acid, 2.OMHC1,0.015 % H 2 0 ? Ti(1V); and 250 ml of 1.OM for N H 4 N 0 3containing 0.5M ammonia for Mo(V1). The flow rate was 2.5 i 0.5 ml per minute throughout. The experimental curve is shown in Figure 3.
DISCUSSION

General. For a fixed oxalic acid concentration, most elements show a decrease in distribution coefficients with increasing concentration of HCl. This can be ascribed to a combination of two factors : first, the increasing suppression

ANALYTICAL CHEMISTRY, VOL. 44, NO. 14, DECEMBER 1972

E
L

Figure 3. Elution curve Co(11)-Cu(11)Ti(1V)-Mo( VI) 46 ml (20 g) AG l-XS, 200-400 mesh, resin (14 X 2.0 cm). Flow rate, 2.5 i 0.5 ml/min

p 5 0 $2: 1

7 - 5 0 0 0 5 M oxalicC M H

0 0 5 M HCI - M malic

0 5 M NH4 NO3 OH

0 015/o HCI
ml eluate

0 015% H2 02

Figure 4. Elution curve Cu(I1)-A1 with 0.05M oxalic 0.20M hydrochloric acid

46 ml (20 g) AG l-XS, 200-400 mesh, resin (14 X 2.0 cm). Flow rate, 3.0 f 0.5 ml/min. 0.1 millimole Cu 1.0 millimole AI

ml

eluate

of the dissociation of the oxalic acid and second, the increasing competition of the chloride anion for exchange sites. Mo(IV), U(VI), Fe(III), and Ga(II1) show a minimum in their distribution curve at about 2 or 3M HCI. At higher concentrations of HCl, these elements increasingly are adsorbed as chloride complexes. Zn and Cd show irregular distribution curve patterns at low HCl concentrations, but are more strongly adsorbed as chloride complexes at higher concentrations. N b shows about equal adsorption in the presence and the absence of hydrogen peroxide but the adsorption of Ta is very appreciably increased and that of Ti(1V) decreased when about 0.1 H 2 0 2 present. At the lowest concentrais tions of HCl, the distribution coefficients are larger in 0.05M than in 0.25M oxalic acid; at higher concentrations of HCl, it is vice versa. AI, Fe(III), Ti(IV), Zr, Hf, V(1V). The elements are strongly adsorbed at low concentrations of HC1 and can easily be separated from Ni(II), Co(II), Mn(II), Mg, Ca, Sr, Ba, Li, Na, K, Rb, Cs, and Be by eluting these elements with O.05M oxalic acid in 0.1M HC1 with or without hydrogen peroxide present, while A1 etc. are retained. Oxalate precipitate formation of Ni(II), Co(II), etc. can be suppressed to some extent by adding boric acid. This has been utilized for a group separation of the R2O3 elements from alkalies, alkaline earths, and divalent heavy metals in silicate analysis

(10). Cu(I1) requires fairly large volumes of 0.05M oxalic

acid in 0.2M HCl for its elution and separation from the Algroup. A typical elution curve is shown in Figure 4. A1 can be eluted selectively with 0.5M HC1 containing 0.05M oxalic acid after Cu(II), Ni(II), etc. have been eluted at lower concentration of HC1. Only V(1V) accompanies A1 partially under these circumstances, but can be separated in a subsequent cation exchange step. This has been applied to the direct determination of A1 in silicate rocks (11). In, Ga, U(V1). These elements are somewhat more strongly adsorbed than A1 and are probably partially adsorbed as chloride complexes at the highest concentrations of HC1. They can be separated from Cu(II), Ni(II), and the other elements named above by eluting these with 0.2M HCl containing 0.05M oxalic acid. Separation from A1 can be obtained by eluting A1 with 0.05M oxalic acid in 0.5M HCl while In, Ga, and U(V1) are retained (Figure 1). Ga can be separated from In by elution with 0.05M oxalic acid in 1.5M or 2.OM HCl, In being retained (Figure 1). At the lower HC1 concentration, U(V1) will accompany In quantitatively, provided a fairly large column is used. (10) F. W. E. Strelow, C. J. Liebenberg, and F. Von S . Toerien, At7al. Chim.Acta, 47, 251 (1969). (11) F. W. E. Strelow, C. J. Liebenberg, and F. Von S . Toerien, ANAL. CHEM., 2058 (1969). 41,

ANALYTICAL CHEMISTRY, VOL. 44,

NO. 14, DECEMBER 1972

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W(V1) and Mo(V1). These elements are adsorbed very strongly from 0.05M oxalic acid at the lower and still quite strongly at the highest HC1 concentrations. Large amounts of W(I1) tend to precipitate from 4 M HCl when hydrogen peroxide is absent. Both elements can easily be separated from Nb(V), Ti(IV), Fe(III), Al(III), Zr, Hf, Ga, V(IV), Be, Cu(II), Ni(II), Co(II), Mn(II), Mg, Ca, Sr, Ba, Li, Na, K, Rb, and Cs by eluting all these elements with 2.OM HC1 containing 0.05M oxalic acid, while W(V1) and Mo(V1) are retained. With 3.OM HC1 in 0.05M oxalic acid, Ta(V) is included in the separation, but elution of Ta(V) is somewhat erratic. Sn(IV), Pt(II), and Pd(I1). All three elements are adsorbed very strongly, possibly as mixed chloride-oxalate complexes over the whole range of HCl concentrations investigated and can be separated together with W(V1) and Mo(V1) from the elements named in the previous paragraph. Sn(1V) can be separated from halogens and many other elements by adsorption on a anion exchange resin from HCl containing oxalic acid. After the other elements have been eluted with an appropriate HC1-oxalic acid mixture, the chloride can be eluted with 0.2M nitric acid containing 0.25M oxalic acid. After this the resin can be ignited to SnOzwithout loss of tin. IVb(V) and Ta(V). Both elements are adsorbed fairly strongly. In the presence of peroxide, Ta(V) is adsorbed more strongly than Nb(V) and the separation factor is about 10 in 0.05Moxalic acid plus 2.OMHC1 and 6.5 in 0.25Moxalic acid plus 2.OM HCl. The separation requires the presence of hydrogen peroxide which increases the coefficients of Ta(V) and stabilizes the complexes of this element in solution probably through formation of ternary complexes containing H202. When large amounts of Ta(V) are present, separations are nevertheless not very satisfactory, apparently because of the strong tendency of Ta(V) to hydrolize. Fairly strong heading and tailing occur. Nb(V) can be separated smoothly from Ti(V), V(V), AI, Cu(II), and the elements of the Ni(II), Co(I1) group by eluting all these elements with 0.05M oxalic acid in 1.OM HC1 containing H 2 0 2 with 0.25M oxalic acid or in 1.25MHC1 containing H202. Fe(III), V(V), and V(1V). Fe(II1) and V(V) tend to undergo slow reduction to their lower oxidation states. The process is slowed down but not stopped by the presence of hydrogen peroxide. In the case of Fe(III), it becomes slow enough to

prevent iron from leaking through the column as Fe(I1). V(V) and V(1V) have fairly similar distribution coefficients. Fe(II1) can be separated from V(V) and V(1V) by eluting vanadium with 0.05M oxalic acid in 0.70M HCI containing H202, while Fe(II1) is retained. Al, Cu(II), Be, Ni(II), Co(II), Mn(II), the alkaline earth, and the alkali metals accompany vanadium, while U(VI), Nb(V), and many other multivalent elements are retained together with Fe(II1). Cu(II), Pb(II), Ni(II), Co(II), Mn(I1). These elements do form more or less sparingly soluble oxalates and only a limited amount therefore can be handled in a fixed amount of solution. To some extent, their precipitation can be delayed by addition of boric acid. Cu(II), Pb(II), and Ni(I1) are adsorbed fairly strongly at the lowest concentrations of hydrochloric acid. Co(I1) is adsorbed very weakly and Mn(I1) not at all. All elements are adsorbed more strongly from oxalic acid alone (9). Cu(II), Pb(II), and Ni(I1) can be separated from Mn(I1) by eluting Mn(1I) with 0.05M oxalic acid in 0.01M HC1; but manganese shows fairly strong tailing (Figure 1). Cu(I1) can be separated from Cl(1I) and Mn(I1) by eluting these elements with 0.05M HC1 in 0.10M HCI, while Cu(I1) is retained (Figure 3). It should be noted that solutions containing these elements should be passed through the column immediately after the oxalic acid has been added. Otherwise precipitation may occur in the column and lead to strong tailing. Be, Mg, Ca, Sr, Ba. Beryllium is adsorbed fairly strongly from 0.05M oxalic acid in 0.01M HC1 and can be separated from Mg, Ca, Sr, and Ba which are not adsorbed. Ca, Sr, and Ba tend to form insoluble oxalates, but up to 50 mg of Ca can be kept in 250 ml of 0.05M oxalic acid and 0.1M HC1 at room temperature for 2 hours without precipitation. When 10 grams of boric acid are present, up to 200 mg of Ca can be present without precipitation within 2 hours. Li, Na, K, Rb, Ca. These elements are not adsorbed at any oxalic and hydrochloric acid concentration and can be separated from most multivalent elements under a wide variety of conditions.

RECEIVED review May 26, 1972. Accepted August 14, for 1972.

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ANALYTICAL CHEMISTRY, VOL. 44, NO. 14, DECEMBER 1972