A comprehensive bibliography of recent separations of inorganic ions by electromigration in paper

A COMPREHENSIVE BIBLIOGRAPHY OF RECENT SEPARATIONS OF INORGANIC IONS BY ELECTROMIGRATION IN PAPER* R. A. BAILEY** AND L. YAFFE Radiochemistry Laboratory, Department o] Chemistry, McGill University, Montreal (Canada)

A large number of separations of inorganic ions b y the technique of electromigration in paper have been reported over the past ten years. These are widely scattered throughout the literature, and no complete collection of them has appeared, although ]3LASIUS has given a good compilation of m a n y of them 1. I t was felt that a thorough coverage of the inorganic separations studied b y this method would be useful, particularly to those considering a practical application of the techniques for the first time. The following compilation is believed to be complete up to March 196o. The various separations have been arranged according to an arbitrary classification. No system of grouping of the ions studied can be completely satisfactory. The ions considered in various separations have been chosen so widely that a good deal of overlap from one group to another is unavoidable. Often, the prime factor governing selection of the ions investigated seems to have been ease of detection. Most separations have been accomplished b y a discontinuous process utilizing migration along a strip of paper. A few have used electromigration in two dimensions in a rectangular sheet, and others have combined electromigration with paper chromatography in a two-dimensional procedure (electrochromatography). The latter appears in both continuous and discontinuous forms. Where the technique used differs from the common linear, discontinuous strip technique, this h a s been noted. No differentiation is made between the various forms of the latter procedure, i.e. hanging or horizontal strips, and open and closed strip operation. A separation b y one such technique can be accomplished also b y any other, although effects of evaporation and flow of the background electrolyte solution m a y modify the behaviour in some cases. Many partial separations which have been reported might readily be made complete if longer migration paths were used. A large amount of the published work gives migration distances of only a few centimetres. While a few voltage gradient and separation times are given in order to illustrate the results obtained, the same separation m a y be carried out in different times using any voltage gradient up to a * This work was carried out with financial assistance from the National Research Council of Canada. ** Holder of National Research Council of Canada Studentships 1957-58, 1958-59, and 1959-6o. Present address : Dept. of Chemistry, University College, University of London, London, England. Re/erences p. z74/z76.

159

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

m a x i m u m determined b y the amount of heat which can be dissipated. These factors therefore are not important. The work which can be considered historical, i.e. the small amount done prior to 195o, will not be covered here. I t is dealt with b y McDONALD 2, for instance. Some of the modern work in packed columns and gels is mentioned, but coverage of this technique m a y not be complete. The work of I~¢[ANECKEon the electromigration of cations and anions in columns of cation and anion ion-exchange resins m a y be noted here 3. The specialized "focussing" technique of SCHUMACHER, in which a complexing gradient is used, will not be dealt with in the following tables, although it has indeed given some striking results when applied to a number of metallic cations 4-s. A few lists of relative zone mobilities of some ions have been published. These m a y be useful in indicating whether a proposed separation is feasible. Such values are given for anions in o.I N N a O H b y GRASSlNI AND LEDERER ~, in (NH~),C03 b y GROSSl° and b y LEDERER11 (O.I M, and 2% solutions respectively) and in 2% Na2CO 3 b y BELLING AND UNDERDOWNTM. CETINI has given relative zone mobility values for cations in solutions of Na2CO3-1actic acid, HCl-potassium biphthalate, and HCl-sodium citrate TM,while MAKI has reported a few in electrolyte solutions made up with organic solvents 14. Although actual separations are not included, the work of DE ANGELIS et al. on the variations of the mobilities of Co, Mn, Fe, Zn, Cu, Pb, A1, and Mg as a function of p H in 0.05 M citric acid, 0.0I M SCN-, and KNOt solutions 15, and the studies b y YASUNAGA AND SHIMOMURAon the effect of p H on very m a n y anions and cations in NaNO3, KCNS, and tartaric acid electrolytes TMare of interest. Most of the separations are presented below in tabular form. The ions studied and the background electrolyte solutions used are given, along with a few comments which m a y be useful. In some reports, such a large number of background solutions were employed that it is not practical to list them here; in some cases those yielding the best results are indicated. I . THE ALKALI AND ALKALINE EARTH IONS TABLE 1 THE ALKALI AND ALKALINE EARTH IONS Background electrolyte

Migrants

Remarks

Ref .

Mg, Li, Na, K

(NH4)~CO 3

S e p a r a t e d all in 35 m i n a t 3 o V / c m . K, lib, Cs could n o t be s e p a r a t e d , l i e l a t i v e mobilities are Mg(o.34 ), Li(o.53 ), Na(o.72), K(lib,Cs) (i .oo)

17

Mg, Li, Na, K, lib, Cs

o.I M (NH4),CO 3

S e p a r a t i o n s a t IOO V / c m . C o m p l e t e in 37 m i n . R b a n d Cs still v e r y close t o g e t h e r . M i g r a t i o n s e q u e n c e (in order of i n c r e a s i n g m o b i l i t y ) : Mg, Li, Na, K, Cs, R b

18

(continued on p. i6o) R e # f e n c e s p. z 7 4 / z 7 6 .

R. A. BAILEY~ L. YAFFE

16o

T A B L E 1 (continued) Migrants

Background electrolyte

Renmrks

Ref.

Mg, Li, Na, K , R b

NH4OH

All b u t K and R b separated

19

Na, K

NH4C1-HC1

Linear and radial techniques. A more fundamental study of the conditions for separations

20

Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, R a

HC1, lactic, tartaric and citric acids and their a m m o n i u m salts, EDTA a t several p H values, and others

K, Rb, Cs could not be separated. Ba, Cs separated in di- and tri-ammonium citrate, b u t Sr overlapped both. In N H a - E D T A solutions of pH 6, alkaline earths are anionic and easily separated from alkalis

2i

Mg, Ca, Sr, B a

0.05 M citric acid, p H 5-5

All separated in 45 min a t ioo V/cm. Also some separations from group 3 and 4 ions

i8

Mg, Ca, Sr, Ba

0.007 M citric acid in 5 N NHaOH, and others

Electromigration, and discontinuous electrochromatography. Ions of groups 3, 4 and 5 were also studied

22

Mg, Na, K, and anions

Ethanol-acetic acid-ammonium acetate

Discontinuous electrochromatography. Most of separation due to chromatographic effects. Electromigration separated only cations and anions

23

Mg, Ca, Sr, Ba

o.I N NH4C1, o.I N NH4NO v and others

Sr and Ba could not be separated. Ternary mixtures separated in given electrolytes. Binary mixtures separated in other electrolytes

24

Mg, Ca, Sr, Ba

Na4P2OT-HC1 of p H 3.2

St, Ba have similar mobilities, b u t ternary mixtures not involving this pair were separated

25

Ca-Ba; B a - L a ; Sr-Y ; S r - B a

0.05 M lactic acid

S r - B a only partially separated

26

Sr, Ba

Methanol-acetoneHC1

14

Ca-Sr; C a - B a

HPOs; p H 1. 5

27

Ca-Sr

(HPOa) ; p H 1.75

Sr-Ba

Also separated Ba from Zn, Pb, Fe, and Co, A1, Fe

27

Discontinuous electrochromatography

28

R a from Pb, Bi, and Po

o.i M lactic acid

Separation of Ra from its decay products

29

Sr-Y, Rb, Cs, Ca and others

o. I M lactic acid

A few separations

29

S e p a r a t i o n of t h e a l k a l i m e t a l s b y p a p e r e l e c t r o m i g r a t i o n h a s b e e n c a r r i e d o u t b y a f e w w o r k e r s , b u t t h e d i f f i c u l t y i n d e t e c t i n g t h e s e i o n s on p a p e r h a s o f f e r e d a c o n siderable obstacle. Flame photometry

h a s b e e n u s e d , b u t t h i s is t e d i o u s . T h e a l t e r -

native has been to use a background electrolyte such as ammonium carbonate which is e a s i l y v o l a t i l i z e d , h a v i n g a n a l k a l i m e t a l c o m p o u n d w h i c h c a n b e d e t e c t e d b y a n R e # r e m e s p. z74/z76.

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

161

acid-base indicator. Radioactive tracers, which offer the best means of detection, have so far seen little use. The most difficult ions to separate of the alkali metals are K +, Rb+, and Cs +. These have very similar mobilities. The separation of Li+ and Na + from the rest and from each other is not difficult. The alkaline earth ions are in m a n y ways similar to the alkalis; the mobilities of Ca, St, Ba, and Ra are very similar. Each alkaline earth ion migrates more slowly t h a n the corresponding alkali metal ion. Moreover, the former can form anionic complexes, thus giving a much wider scope for separatory procedures. MACH has used this technique in determining the radiochemical purity of Na, K, Rb, and Sr of this group 3°. ARNIKAR81has studied the electromigration of alkali metals in asbestos paper at 350 ° with fused NaNO 3 as background electrolyte. Mobilities (IO-* cmZ.sec-l.V -1) are: Li (3.75), Na (4.I6), K (3.74), Rb (3.58), Sc (3-38). Cs and K were not separated in 45 cm due to extensive low concentration regions behind and ahead of the main zones. 2. Sc, Y , THE RARE EARTHS, AND THE ACTINIDE ELEMENTS TABLE2 SC, Y , THE RARE EARTHS, A N D THE ACTINIDE E L E M E N T S

Migrates

Background electrolyte

Remarks

Ref.

Eu-Pm-Ce

0.035 M tartaric acid-o.o 15 M diammonium tartrate

Eu, P m anionic; Ce cationic. Separation accomplished

32

(Pr, Pm, Ce)(Y, Nd)-Sc

o.I M lactic acid

Separations accomplished. Ions in brackets had same mobilities

32

Sc, Sin, Nd, Y, Pr, Ce, La, Ac

Citric acid

Too short a migration distance for good separations to be achieved

33

Sc, Sm, Nd, Y, Pr, La, Ac

1% citric acid

As above

34

Ce, Y, U, Sr, Cs, Nb, Zr

o.I M lactic acid

Continuous electrochromatography. Some ordinary electromigration separations also reported

29

Y, La, Ce, Pr, Nd

o.05 M NaC1, o.125 At lower pH, all cationic; at higher pH, all to o.o 5 M citric acid anionic. Some ions separated in both instances pH 2.6 or 3.05

35

Sc, Y, La, Ce, Sin, Nd, Eu, Pr, Tb, E r

Acetic acid-oxine mixtures

36

Y, Ce, Pr, Nd, Th

Acetone-lactic acid All separated in 9o rain at 46 V/cm

37

Y, La, Ce, P m ,Eu

Citric acid

38

A few separations accomplished, but electrolyte not as good as citric acid

Continuous electrochromatography in cell packed with quartz powder. A study of conditions of separation, with very promising results

(continued on p. ~62) References p. z74/~76.

R. A. BAILEY, L. YAFFE

162

TABLE 2 (continued) Background electrolyte

Migrants

Remarks

Ref.

La-Ba; Y-Sr; Y-La

0.05 M lactic acid

Ba much faster than La. Sr much faster than Y. Y and La could be separated in a fairly long time

26

Th (IV), u (vI), Pb (IV), Zr (IV), Nb(V), Ti (IV)

HF, and HF-HC1 Separated Fe, Th, U, Zr, Bi, and Pa; Fe, Pa, and mixtures of various Zr; and Pa-Zr, as well as others. concentrations Chiefly for purification of Pa

39

U, Pa, Zr separated in former, Pa, Fe, and Zr in latter electrolyte. Chiefly for purification of Pa

4°

UO v Co, Fe(III)

Migrated as 'complexone' complexes in various background electrolytes

41

UO~ and ions of 0.05 M citric acid, groups 3, 4, 5, and 7 pH 3.1, and other values

Separated in 3° min at 14o V/cm

Z8

Th(IV), U02(II ) and others

Many

Deals with the members of the third analytical group. See Section 3 and 7

42

UOi, Th, Pu

o.I M lactic acid

Separated as radioactive tracers. Pu formed long, diffuse zone, overlapping both others

29

UO~ from Pt, Pd, Bi, and Fe

Many

UO 2 separated from the rest. Migration sequences given. Chiefly binary mixtures.

43

PAW), Fe(III), Bi (iii), Ta(V), Po(III),

U, Pa, Ta, Nb, Zr, Ti, Fe

5% H F - 5 % HC1, and 1% H F

The rare earth elements and their homologues have such similar mobilities and chemical p r o p e r t i e s t h a t s e p a r a t i o n s b y e l e c t r o m i g r a t i o n a r e q u i t e difficult. BACHELET et al. h a v e g i v e n t h e d i r e c t i o n of m i g r a t i o n of U O , ( I I ) in m a n y e l e c t r o l y t e s , b u t n o s e p a r a t i o n s o r q u a n t i t a t i v e i n f o r m a t i o n a r e g i v e n 44. MAKI h a s s e p a r a t e d t h e r a r e e a r t h s in m o n a z i t e 45 b y t h e m e t h o d o u t l i n e d in ref. ss

3- Cr, Mn, Fe, Co, Ni, Z n AND A1 TABLE 3 Cr, Mn, Fe, Co, Ni, Zn AND A1 Migrants

Background electrolyte

Remarks

Re.[.

Fe(III), Co(II), Ni(II)

Alcoholic KCNSN/2 HCl

Separation readily accomplished

46

Co(II), Ni(II)

i N H C I ; 7% KCNS in 66% ethanol

Ni anionic, Co remains cationic. Separation as above

47

(continued on p. z63) Re[erences p. I74/x76.

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

163

T A B L E 3 (continued) Background electrolyte

Migrants

Remarks

Ref.

H P O v p H 1.5; (HPO3) v pH 1.6 and 1.75

Separations from each other and from some copper and arsenic group ions. Quaternary mixtures considered

27

Fe(III), Zn(II), Co(II), Ni(II), Al(III), and the copper group

Many

Chiefly a separation of Fe(III) from the others. Only pairs of ions were separated

48

Zn(II), Mn(II), Co(II), Ni(II), a n d the copper group

Many

Zn and Mn separated from each other and the rest. Migration sequences given

49

Zn, Co, Ni, and the Many copper and arsenic groups

Chiefly deals with the separation of members of the arsenic group from the others

50

Co, Ni, Ag, and the Many copper group

Chiefly deals with the separation of Ag and Hg from m a n y other ions, including Co and Ni

5i

Fe(II), Fe(III), Co, Ni, Zn, A1

o.o 5 M citric acid a t various p H values

High voltage separations from each other and other ions of groups 2, 4, 5, and 7

18

Co, Ni, and the copper group

Many

Separations from quaternary copper group ions

mixtures with

52

Fe(III), Co(II),

Many

Separations of these ions from some of groups 2 and 7 (the 3rd analytical group). Only a few separations of quaternary mixtures obtained

42

Ni, Zn, Co, Mn

KCN a t p H 6.0. Many others tried

Co, Zn always formed overlapping zones in KCN. Complete separation of any 3 possible

53

NiIII), Co(II), Mn(II), Zn(II), AI(III), Cr(III), Sn(II), Sb(V)

o.I M a m m o n i u m t a r t r a t e in 4 N NH4OH. Other proportions used also

Co-Ni-Mn-Zn, and Sb(V)-Sn(II)-Cr(III)AI(III) were the groups separated

54

Fe, A1, and CrO42from As, Sb, Sn

Na4P,O ~- HCI, pH 2. 4

Studied quaternary mixtures only

25

Mn, Co, Ni, Zn

Ethanol-acetoneHC1

Separation of Ni, Co, and Mn from Zn

14

Fe(II)-Fe(III}Co(II)-Cd(II)Pb(II)-Cu(II)

2 N acetic acid-o.6 Sequence (in order of decreasing speed) : Fe(II), N formic acid Co, Cd, Pb, Cu, Fe(III). Fe(II) and Co zones very close together

Fe(III), Co(II),

Ni(II), Zn(II),

Al(III), Ba(II)

AI(III), and others

55

Fe, Ni, Co, A1, and some copper group ions

Discontinuous electrochromatography

28

Mn, Co, Ni, Zn, Fe, Many A1, CrO 4, Cu, Ag

One- and two-dimensional techniques. Not all separated in one experiment

56

(continued on p. z64J References p. z74/~76.

x64

R. A. BAILEY, L. YAFFE

T A B L E 3 Ico~tinued)

Migrants

Background electrolyte

Remarks

Ref.

Fe(III)-Co; Fe (III)-Mn; Fe(III)-Mg; A1-T1-As(III)

0.0 5 M malonic acid-o.oI M acetic acid

Continuous separations using a tapered paper sheet

57

Fe(II), Ni, Co, Cu

1% N a K t a r t r a t e

Continuous electrochromatography of the a,~'dipyridyl complexes. They are all anionic, sequence of mobilities F e > N i > C o > C u . I,io-Phenanthroline complexes also studied

58

Fe(II), Fe(III)

1% N a K t a r t r a t e

Continuous electrochromatography. Fe(II) as a, a'-dipyridyl complex, Fe(III) as acetylacetone complex

58

Fe(II)-Fe(III)

o,I N H~SO 4 and o.i N H2SO 4glycerol (i :I)

Separation in 90 rain at io V/cm. Fe(II) faster

59

Fe(II)- Ni(II) ; Fe(II)-Cr(III) ; Fe(II)-Fe(III)

i % citric acid, and Continuous electrochromatography. Fe(II) pres0.5% N a K t a r t r a t e ent as dipyridyl complex, FePy~(II). Also separation of F e ( I I ) - F e ( I I I ) - F e P y ~

6o

"Complexone" complexes in several electrolytes

4I

Used for quantitative analysis after elution

6I

F e ( I I I ) - N i ; Ni-Ag; Several Ni-Cu ; Co-CuCd-Ag; A1-Co-Fe(III)

Two-dimensional discontinuous technique; chromatography used in one dimension

62

Ni-Cu; Ni-CrO4~-; Several Fe(III)-A1; Fe(III)-Ni-Cu-Ag

Continuous electrochromatography

62

Fe(III) from elements of groups 2 and 7

See groups 2 and 7

39 40

Fe(III), Co, UO 2 Ni-CrO4a-; Ni-Cu

I M acetic acid. o.i M lactic acid

HF, and HC1-HF

Fe(III), Cr, A1, Mn, 0.007 M citric acid Electromigration, and ions of groups in 5 N NH~OH, chromatography I, 4 and 5 and others

and

discontinuous electro-

22

Since these ions offer considerable scope for the use of complexing agents of various sorts, they have been investigated extensively. In addition, separations of some precious metals from some of these ions are given b y MUKERJE#a-e5 (see group 6). CETINI~ has separated some ions of this group and of groups 4 and 5 in a starch gel, using NaOH-potassium biphthalate and NaOH-lactic acid electrolytes. Best results were given by the former at pH 3.5. KAKIHANAet a/. s7 separated Co and Cu byelectromigration in a column packed with Amberlite IRC-5o ion exchange resin. Re]erences p. z74#76.

165

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

4. THE COPPERGROUP(Cu, Cd, Hg(II), Pb, Bil,

AND

Ag, Hg(I), T1, Po

TABLE 4 THE COPPER GROUP (Cu, Cd, Hg(II), Pb, Bi) AND Ag, Hg(I), T1, Po Background electrolyte

Migrants

Remarks

Ref.

Cu, Cd, Bi; Hg(II), As, Cu

I N HC1

Also separated Cu from Au, Pd, and P t

68, 69

Cu, Cd, Pd, Bi, Hg(II), Tl(I), and elements of groups 2, 3, 5 and 7

0.05 M citric acid at various pH values

Ions separated from each other and from ions of other groups. A high voltage separation

I8

Hg(II)-Pb-Ag

3 N NH4OH; 3 ° ~o Could not obtain complete separations under the formic acid; 0.05 M conditions used. Reported two zones formed by citric, lactic, acetic Ag in many of these electrolytes and tartaric acids

7°

Cu, Cd, Hg(II), Pb, Bi

o.I, 0.5, and I.O N HC1

Separation complete in 15 min at 12 V/cm. Cu cationic at all concentrations; Bi, Hg(II) anionic

46

Cu, Cd, Pb, Bi, Co, Ni

Many

Separations of quaternary mixtures

52

Cu, Cd, Hg(II), Pb, Bi

o.I N KC1; several others

KCI gave best separation, but other electrolytes also gave separations

71

Hg(II), Pb, Ag, TI(I)

I N NaC1, K C 1 , KCN, and several others

Separations complete in 3 h. Other electrolytes failed to give complete separations

72

Cu, Cd, Hg(II), Pb, Bi

NaC1-HCl-glycine, Bi motionless, Hg(II) anionic, remainder cationic p H i .8

73

Cu, Cd, Pb, Bi, Ni, Fe(III)

H P O v p H 1.5; (HPOs) 3 pH 1.5

Separations of some ions from group 3 as well as the copper group ions

27

Ag, Hg(II), Cu, Cd, Many Pb, Bi, Co, Ni

Chiefly a separation of Ag and Hg(II) from t h e others

51

Cu, Cd, Pb, Bi, Ag, Many Fe, Be, A1, Zn, Co

Separations of pairs only

48

Cu, Cd, Hg(II)

o.I N KC1, HC1 of various concentrations

Chiefly a study of migrational behaviour. Separations not given

74, 75

Cu, Cd, Hg(II), Pb, Bi

I, 2,

and 4 N HC1

Excellent separations, but the high conductivity means t h a t much heat is produced

76

Cu, Cd, Hg(II), Pb, :Bi

KC1, KBr and H B r at various concentrations

Best separation in 0. 5 N KBr, or 0.5 N HBr. As above, high conductance causes much heating, but separations in less than i h are possible. Much information given about the behaviour of halide complexes

77

One- and two-dimensional separations

56

Cu, Cd, Hg(II), Pb, Bi

(continued on p. I66) R e f e r e n c e s p. z 7 4 / i 7 6 .

166

R. A. BAILEY, L. YAFFE TABLE 4 (continued) Migrants

Background electrolyte

Cu-Ag; Cd-Ag-Bi- o.oi M EDTA in A1; TI(I)-A1; TI(I)- I M NH4OH. o.o5 A1-As(III) M ammonium malonate. 0.o 5 M citric acid, and others

Remarks

Ref.

Continuous separations

57

2 N acetic acid0.6 N formic acid

See Section 3

55

Bi, Pb, and groups HF and HF-HC1 2 and 7 mixtures

See Section 2

39

Cu-Ni

o.i M lactic acid

Used for quantitative analysis after elution

61

Cu-Cd

Aqueous acetic acid-pyridine

Cd faster than Cu

78

Ag-Pb--Hg(II) ; CuCd-Pb-Bi-Hg(II)

Discontinuous electrochromatography

28

Ag-Ni; Cu-Ni; Many Hg(I)-Pb-Ag; Hg(II)-Ag; (HgBi)-(Cu-Pb-Cd) ; Ni-Ag-Cd-(Cu-CoFe)

Discontinuous electrochromatography. Ions in brackets formed overlapping zones

62

Cu-Ag-Ni-Fe

Continuous electrochromatography. The electrolyre given separated all

62

Cu, Cd, Bi, Ag, Pb, 0.007 M citric acid Electromigration, and discontinuous electroHg(II) in 5 N NH4OH , chromatography. Ions of groups i, 3, and 5 and others considered also

2:2

CufromPdandPt

i NHC1

Cu is cationic, others anionic

79

Pb-Bi-Po-Ra

o.i M lactic acid

Separation of Ra decay products including RaD, E, and F. Bi is adsorbed near the starting point, Po moves slowly as an anion. Po, Bi zones overlap somewhat

26, 29

Cu, Cd, Pb, Co, Fe(III), Fe(II)

A basic tartrate~ oxalate mixture. Others also used

T h e copper group ions h a v e been s t u d ie d quite e x t e n s i v e l y , since t h e y form co m p l ex es w i t h m a n y reagents, a n d are all r e a d i l y d e t e c t e d on paper. T h e o t h e r ions f r e q u e n t l y h a v e been considered w i t h t h e copper group. Separations of some precious m e t a l s from some of these ions h a v e been g i v en b y MUKERJEE ~3-s5 (see group 6). Separation of Zn and Mn from t h e s e ions is given in ref. ~9, an d As, Sb, and Sn f r o m t h e copper group in ref. 5°. Separation of Cu f r o m F e ( I I ) , Ni, a n d Co was given in ref. m. CETIN186 has s t u d i e d some ions of this group and o f groups 3 an d 5 in a starch gel, using N a O H - p o t a s s i u m b i p h t h a l a t e an d N a O H - l a c t i c acid electrolytes. LEDERER AND COOK80 s e p a r a t e d Cu, Bi, an d H g in a 2 % agar gel

Re#fences p. z74/z76.

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

167

w i t h 0,5 N NaCI as electrolyte. T h e s e p a r a t i o n of Cu an d Co in an ion e x c h a n g e resin was accomplished b y KAKIHANA et a l F .

5- THE ARSENIC GROUP (As, Sb,

Sn)

TABLE 5 THE ARSlgNIC OROUP (As, Sb, Sn)

Migrants

Background electrolyte

Remarks

Re.[.

Sb, Sn, As, Cd

0.05 M citric acid, pH 5.5

Also considered many other ions of groups 2, 3, 4 and 7

18

Sb-Sn

I N HC1

Also separated As f r o m Cu and Hg(II), and A u , Pd, Pt

68

As, Sb, Sn

Many

Separated in pairs. All three ions could not be separated in one run

7t

Sb(V), Sn(II), Al(III), Cr(III)

o.I M ammonium tartrate- 4 N NH~OH

Complete separation in 4 h at 4 V/cm

54

As(III), Sb(III), Sn(II)

o.I M triethanolamine-o.i M ammonium tartrate

As, Sb, Sn, Ag, Pb, Many Cu, Bi, Cd, Zn, Co, Ni As, Sb, Sn

25

Separation of binary and ternary mixtures of these ions

5o

0.o2 M lactic acid- Discontinuous and continuous electrochromato- 62 o.o2 M tartaric graphy acid-o.o 4 M alanine, and others

As, Sb, Sn

Discontinuous electrochromatography

28

As(V), Sb(III)

o.oo 7 M citric acid-5 N NH4OH, and others

Also considered ions of groups I, 3 and 4

22

As, Sb, Pt, Pd, Ru, Au

Many

Chiefly a separation of As and Sb from the rest. It is claimed here that Sn cannot be separated from the Pt metals by electromigration because of chemical interaction

43

As, Sb, Sn, A1, Fe(III), CrO42-

Na,P2OT-HC1, pH 2.4

25

T h i s g r o u p of ions has been fairly well studied. F o r some work i n v o l v i n g t h e separation of t h e o x y a n i o n s of t h e s e ions (AsO, 3-, for example) f r o m o t h e r c o m m o n anions, see Section 9. GARRISON et al. s e p a r a t e d r a d i o a c t i v e arsenic in carrier-free form f r o m a Cu(OH) 2 p r e c i p i t a t e b y e l e c t r o m i g r a t i o n in a s t a c k of filter-paper discs sl. ~¢[AKI has s e p a r a t e d Re#fences p. z74[r76.

168

R . A . BAILEY, L. YAFFE

Sb(III) from Ni, Cu, and Fe(III), using solutions of complex phosphates as background electrolytes*~. CETINIse separated Sn(II)from some ions of groups 3 and 4 in a starch gel, with NaOH-potassinm biphthalate and NaOH-lactic acid electrolyte. 6. THE PLATINUMMETALS (Ru, Rh, Pd, Os, Ir, Pt) AND Au TABLE 6 THE

PLATINUM METALS ( R u , ~ h , Pd, Os, Ir, Pt) AND i u Background electrolyte

Migrants

Remarks

Ref .

82, 83

Pt(iv), Pd(II), Rh(III), It(IV)

EDTA solutions of various p H values

In o.I M ' E D T A at p H 9, complete separation of all 4 in 45 min at 15 V/cm. Rh(III) precipitated at starting point; Pd, P t move in t h a t order toward anode

Pt(IV)-Pd(II) ; Pd(II)-Ir(IV) ; Rh(III)-Ir(IV) ; Rh(III)-Pt(IV) ; Rh(III)-Pd(II)Ir(IV)

Various EDTA solutions

Continuous electrochromatography. Separations 82, as shown 83

Pd(II), Pt(IV), Ir(IV), Rh(III), Ru(III), Os(IV), Au(III)

Several

Separations of quaternary mixtures studied

84, 85

Pt, Pd, and ions of groups 3 and 4

Many

HC1 and sodium citrate best electrolytes. Separations of binary mixtures

63

Ru(III), Pt, Pd,

Many

Ru(III) separated from P t and P d in KCN, NaNO 2 and HC1. Separation of Ru(III) from binary mixtures with other ions also given

64

Pt, Pd, Ru, Au, and some ions of groups 3 and 4

Many

Au separated from P t in KSCN and oxalic acid, from P d in KSCN, and from Ru in KC1 and KSCN. Separations of Au from some ions of groups 3 and 4 also given

65

Os(IV) and copper group ions

Many

Separation of Os(IV) from the others

43

Pt, Pd, UOz, Fe(III)

Separation of UO 2 from the others in binary mixtures

43

Pt, Pd, Ru, An, As, Sb

As, Sb separated from the others in binary mixtures

43

Separation in 2% agar gel. Present as PdClz and NaAuC14

8o

and ions of groups 3 and 4

Pd, Au

o.5 N N a C 1

This group has been quite thoroughly investigated b y a few workers. Complicated behaviour may occur in some systems--for example, SATO e2 al. report that Ru(III) forms as many as 8 zones in o.I M lactic acid s*. Relerences p. z74/~76.

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

169

Cu has been separated from Au, Pd, and Pt in I N HC1~, 69. It may be noted here that LEDERER claims that R h - P t and R h - P d cannot be separated reliably by paper electromigration~. 7. Ti, V, Zr, Nb, Mo, Tc, Ta, W AND Re TABLE 7 Ti, V, Zr, Nb, Mo, Tc, Ta, W AI~D Re Background electrolyte

Migrants

Ti(iv), Zr(IV), Th(IV), Fe(III),

Remarks

Re.[.

Separations of binary, ternary, and a few quatern a r y m i x t u r e s were made. Mobilities of these ions are generally low

42

HF, and HF-HC1 Z r - P a - F e ; Z r - N b ; Z r - P a - U - T h ; and a few m i x t u r e s of various other separations are given concentration

39

Several

AI(III), Cr(III),

UOdlI ), Be(II) Ti(IV), Zr(IV), Ta(V), Nb(V), PAW), Fe(III), Bi(III), Pb(IV), Th(IV), Po(III),

u(vi) Ti(IV), Zr(IV), Ta(V), Nb(V), PAW), Fe(III), U(VI)

5% H F - 5 % HC1 and 1% HF-1% HC1

Z r - P a - U , a n d Z r - P a - F e separated

4°

Mo(IV), ¥(V), Ti(III), and elements of groups I, 2, 3, 4 a n d 5

0.0 5 M citric acid, p H 2.9. Other p H values also used

Other elements also studied, and some separated from this group

18

Ti, V, Mo

0. 5 N HC1

Separated as t h e per-ions

87

Nb-Ta

Citric acidp o t a s s i u m citrate, p H 3.4 2. Oxalic acid-ammonium oxalate

I n first electrolyte, Nb faster. Two zones are formed b y Ta in the second electrolyte; one coincides with Nb zone. This is a detailed s t u d y

88

W-Mo

Oxalic acid of various concentrations a n d p H

MoO42- faster t h a n WO4~-

89

Nb-Ta

Sodium b o r a t e N a O H in various proportions

T a n t a l a t e m u c h slower t h a n niobate. Separation 89 accomplished in o.oi M N a O H - o . o i M Na4B20 ~ at p H lO.15, or in o.oi M N a O H

MOO42-, W O 4 ~ - , CrO~ 2-, CrY+

o.i M a m m o n i u m citrate, a n d o.I M lactic acid

Cr3+-CrO4~-; CrO42--WO42-; CrO4Z--MoO42separated in a m m o n i u m citrate. Lactic acid gave best separation of MoO4~- and WO42-

9o

T c - R e and Tc-Re-Mo

Hydrazine sulfatehydrazine hydrate, p H 9 ; 1% SnCI~ in I MHC1;o.I M HBr; I M HI

TcO 4- a n d ReO 4- h a v e similar mobilities. These electrolytes reduce Tc(VII) to Tc(IV) w i t h o u t affecting Re(VII). I n first electrolyte, Tc(IV) slow b u t cationic, ReO 4- anionic. MoOa2- also separated here (faster t h a n R e O ( ) . I n second electrolyte, Tc cationic, Re streaks as anion. Tc is cationic, Re anionic in the last two

91

Re#fences p. z74#76.

17o

R.A. BAILEY, L. YAFFE

These elements are not easy to work with, but some very good studies have been made of a few systems. GARRISONeta/. separated carrier-free Nb from a MnO, precipitate, and Nb and Zr from Y and rare earths, b y electromigration in a stack of filter-paper discs moistened with I M ammonium oxalate sl. 8. I N O R G A N I C IONS O F TABLE

N, P, S, Se

AND

Te

8

INORGANIC IONS OF N, P, S, So A N D Te Background electrolyte

Migranls

Remarks

Ref.

A mixture of all of these could be resolved in 3 runs

92

NH4+ , N2H8 +, NHaOH+, NOa-, NO2-, N~O8 s-, N~Os~-

o.ooi N H,SO 4, Na,SO4-NaOH, Na2SO4-NaOHFe(OH)q, NasSO 4Ag~SO~

S ~-, S2Oa~-, SO32-, SO42-

8 N NH4OH

$306~-, $406 a-, S~O62-

i % sodium potasslum t a r t r a t e

SeO3~--TeOa 2-

0. 5 N HC1

SeOa 2-, SEO42- , TeOa~- , TeO4~-

o.I N HzSO 4, and 0. 4 N Na2SO 4

Mobilities in Na2SO 4 : SeO4~->SeOa2->TeO32->TeO4 z-. Complete separation in 3 h a t 7-5 V/cm in this electrolyte

95

$203 ~-, and di-, tri-, tetra-, penta-, and hexa-thionate ions

0.05 M potassium biphthalate of pH 4.2 and 6.2

Mobility decreases with increasing n u m b e r of S atoms

96

Thiosulfate, tri-, tetra-, and pentathionates, seleneand tellurodithionates, tetrathionates

As above

Se lowers the mobility with respect to the corresponding S compounds; Te lowers it still more

97

93 Continuous electrochromatography

60 94

Sulfite, thiosulfate, Citric acidand other photophosphate mixture graphic reducing of pH 7 agents

98

SO42--po4 a-

o. 5 N HC1

Separation of " c a r r i e r - f r e e " radioactive materials 94

H~POa-, HPO42-,

Phosphoric acid

A comparison of mobilities

o.i M acetic acid, and o.I M lactic acid

Long (2 m) migration paths. Radioactive species ioo employed. Used also for identification

99

po43-

Oxyacid anions of phosphorus

(continued on p. ~7~J Re[erences p. I 7 4 / I 7 6 .

171

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION TABLE 8 (continued) Migrants

Background electrolyte

Remarks

Ref,

Trimeta-, tetrameta-, mono-, di-, tri-, and tetra- i o i phosphates, and others from commercial preparations

Various polyphosphate ions

Borax-HsBO s NaC1 buffer of p H 8.5

Various condensed phosphate ions

A number of buffer solutions at various pH values

Various condensed phosphate ions

NaOH-borate buffer, and others

A high voltage technique. Mono-, di-, tri-, lO3 trimeta-, tetrameta-phosphates, among others, were separated

Condensed phosphate ions

Sodium borateNaOH, pH io

Continuous electrochromatography

Phosphate-silicate Sodium borateNaOH, and others

102

lO4

Silicate slower than phosphate

89

Section 9 will deal with phosphates, sulfates, and others when considered in relation to other common anions. I t will also cover CN- and SCN-. 9. SOME COMMON ANIONS TABLE 9 SOME COMMON A N I O N S

Migrants

Background electrolyte

Remarks

Ref,

23

POse-, CNS-, CI-, Br-, and cations

Ethanol-acetic acid-ammonium acetate

Discontinuous electrochromatography. Most of the separation is due to chromatographic effects; electromigration separated only the anions and cations

CI-, Br-, I -

o.I to 2. 5 M lactic acid

Br-, I - have similar mobilities. All were separated lO 5

B r O a - - B r - ; I O s - - o.oi M NaOH I - ; AsOaa--AsOaa-

Separation of products of Szilard-Chalmers reactions

POaa- , AsOaa- , AsOaa- , SO42- , SiFsS- , Ss-, SOsS-, H F 2 - , S~Oa2-, CrO4~- , Cr2072-

I M f o r m i c , acetic, A number of separations accomplished and lactic acids, 8 M NH4OH, and o.i and 0.05 M ammonium acetate

Cr~O~2-, PO4a- , CNS-, Fe(CN)e 3-, Fe(CN)64-

0. 5 M lactic acid

Cr~O72- decomposed during migration. Separations in groups of 3 and 4

Fe(CN)e4-, Fe(CN)6a-

0. 5 N HC1

Separation in 5 ° min at 5 V/cm

lO6

93

10 7

94

(continued on p. z72) References p. z74/z76.

R. A. BAILEY, L. YAFFE

172

TABLE 9 (continued) Migrants

Fe(CN)64--

Background electrolyte

Remarks

o.I N KC1

Ref,

46

Fe(CN)e 3PO48--SO4 ~-

0. 5 N HC1

Separation of "carrier-free" radioactive material

94

Phosphate-silicate

SodiumborateNaOH, and others

Silicate slow

89

C103--BRO3--IO8-;

C10--C1Oz--C103-

Separation of first 3 in 5° min, second 3 in 3° rain, lO8 at 4° ¥/cm Mobilities: IOs->BrOa->C10,-; C1Oz->C1Oa->C10-

Since complex formation with the background electrolyte does not take place with anions as it does for many of the metal cations, the choice of the background electrolyte should not have as great an importance as with the latter. Besides the separations tabulated above, the work giving relative mobilities of many anions should be pointed out again 9-x*. This indicates a number of separations which are possible, and gives a good deal of information about the behaviour of these ions. Some metal anions such as Cr042- also appear in references given in their respective sections when no separations from non-metal anions are involved. Phosphates are treated here in relation to other common anions, but separation of various phosphate ions from one another is covered in Section 8. MACH3° used electromigration in paper to check the radiochemical purity of solutions containing radioactive P, S, C1, and I. CETINI6~ has studied Fe(CN)e 3-, Fe(CN)e 4-, CI-, Br-, I-, I0~-, As043-, As033-, S~-, and SCN- in a starch gel with ammonium acetate as background electrolyte. LEDERER AND COOK8° separated Fe(CN),3--Fe(CN)e 4-, I - -SCN-, I--Cr04 *-, and SCN--Cr04 *- in a 2% agar gel with I N NaC1 as background electrolyte. I0. SEPARATIONOF METALCOMPLEXIONS A number of workers have used electromigration in paper to separate various complex ions of some metals, and others have used it to investigate the behaviour of a metal ion in complex-forming systems. The latter consider for the most part the direction of migration and the mobility under various conditions, and are able to determine the sign of the charge on the complex, as well as something about the variation of its stability under different circumstances. However, since this does not include separations, it will not be dealt with here in any detail. KAWAMORA e/ al. 1°9-1n have studied the qualitative and quantitative separation of chromium complexes by electromigration in paper. Separations Re#fences p. z74/z76.

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

173

of [Cr(H~Oe)] 3+, [Cr(H20),(CzO,)] +, [Cr(H20)8(C20,)(OAc)], [Cr(HzO2)~(CzO,)2]-, [Cr(C204) ~]3-, and similar species with the ligands S04 ~-, SCN-, and NHa, were made. A good separation was achieved in 0.33 N HC104 in i h at 13 V / c m . Distances moved were proportional to the charge on the ion. MAKI has separated some complexes of Cr(III) in an HC1-KC1 electrolytem . At 4 V/cm, 2.5 h were required to separate ECr(H~O)~]3+, [Cr(H~O)sC1]~+, and [Cr(H20)4CI~]+. Under similar conditions, Cr~(S04)3 can be separated into the species [Cr(H~O)6] 3+ and [Cr(S04)]+. SHUTTLEWORTHhas investigated sulfate complexes of Cr(III) b y electromigration in 0.05 N HN03113, while KERTES AND LEDERER have studied these complexes using 35S as tracer x14. The kinetics of complex formation were followed in this way. BIGHIANDTRABANELLInSseparatedthecomplexions [Co(NH3)e] 3+, [Co(NH3)eC1]~+' ECo(NH3)4(NO~) 2] +, and [Co(NH3) 3(NO~)31, as well as similar Cr(III) species, by continuous electrochromatography in 0.25% NH4C1. MAKIlle,ll~ has separated the ions [Co(NHa)el 3+, [Co(NH3)sN02] ~+, cis and trans ECo(NH3)4N021 +, [Co(NH3)3(NO2)3] , [Co(NH 3)~(NO~)4]-, and [Co(NO2) s] 3- by a discontinuous strip technique in a chloride solution. RAUSCHER AND HARBOTTLElm separated the complex species [Co(CN)e] 3-, [Co(CN)sH20] 2-, [Co(CN)4(H,O),]-, and [Co(CN)4(NH,),I-, as well as Co*+, in an acetate buffer. These were products of the Szilard-Chalmers reaction in potassium cobalticyanide, and the method was used as an aid in identifying the species as well as estimating their relative amounts. SHUKLA124,1~7 and SHUKLA AND LEDERERI~, lm, by electromigration, have studied rhodium(III) as perchlorate, oxalate, and sulfate complexes. I I . SEPARATIONS OF PARTICULAR RADIOCHEMICAL INTEREST

A number of separations have been made which are of particular interest in one or another branch of radiochemistry. The earliest of these is the separation of "carrierfree" activities from precipitates of other elements in a stack of filter-paper discs moistened with a suitable electrolyte, made by GARRISON et al. 81. Elements separated include Nb from MnO 2, and Nb and Zr from Y and the rare earths in ammonium oxalate solution, and As from Cu(OH)2 in HC1. Other separations of interest include that of Ra D, E, and F b y SATO et al. ~e,~, the separation of "carrier-free"a2P043- and 35SO42- from one another by LEDERER~, and the separation of 45Ca and 3~P043- from each other and from other radioactive contaminants, b y continuous electrochromatography b y SATO et al.11% SCHUMACHERhas also used his focussing technique to separate "carrier-free" radioactive materials 5. Separations of the products of Szilard-Chalmers reactions in potassium cobalticyanide have been made by RAUSCHER AND HARBOTTLE118, and these separations, as well as those of the products of similar reactions in alkali bromates and iodates, and in arsenic pentoxide, have been described b y JACH, KAWAHARA, AND HARBOTTLEl°e. SATO et al. have done analogous work with phosphates 1~o. Re]erences p. I74/x76.

174

1~. A. BAILEY, L. YAFFE

MACH h a s u s e d e l e c t r o m i g r a t i o n in p a p e r t o e s t i m a t e t h e r a d i o c h e m i c a l p u r i t y of 32p, 35S, 22Na ' 4,.K, ~ R b , 1311, a n d 9°Sr, a n d r e c o m m e n d s it as a r o u t i n e m e t h o d for s u c h p u r p o s e s 3°. F i n a l l y , ZIMAKOV et al. 1~1 h a v e u s e d t h i s m e t h o d t o d e t e r m i n e q u a n t i t a t i v e l y all of t h e i o n s of Ce, Y, St, Zr, Nb, R u , a n d Cs in a s o l u t i o n of fission p r o d u c t s . B y c a r r y i n g o u t e l e c t r o m i g r a t i o n in 0,I N HC1, 0.I N N a 0 H ,

and 2 % K4Fe(CN)s electrolyte

solutions, a n d u s i n g s t a n d a r d i z e d t e c h n i q u e s for m e a s u r i n g v a r i o u s s e c t i o n s of t h e strips, o n e c a n o b t a i n q u a n t i t a t i v e e s t i m a t e s of e a c h of t h e s e s u b s t a n c e s r a p i d l y . I2. MISCELLANEOUS T h e s e p a r a t i o n of i s o t o p e s b y e l e c t r o m i g r a t i o n p r o c e d u r e s h a s b e e n s t u d i e d b y a n u m b e r of w o r k e r s . T h i s h a s b e e n t r e a t e d in a r e c e n t r e v i e w b y CHEMLA122, a n d will n o t be d i s c u s s e d f u r t h e r . MAK1123 h a s u s e d t h e z o n e l e n g t h t o g i v e a m e t h o d of q u a n t i t a t i v e l y e s t i m a t i n g B a a n d A1. W i t h p r o p e r s t a n d a r d i z a t i o n , t h e e s t i m a t i o n was a c c u r a t e t o w i t h i n 1 0 % o v e r t h e r a n g e of 150 t o 1 5 0 0 / ~ g of Ba, a n d 25 t o 5 0 / ~ g of A1. O t h e r s h a v e e l u t e d t h e s e p a r a t e d s u b s t a n c e s f r o m t h e s t r i p for a n a l y s i s b y s t a n d a r d m e t h o d s . SCHUMACHER also h a s a d a p t e d his t e c h n i q u e for q u a n t i t a t i v e a n a l y s i s ~. REFERENCES I E. 8LASIUS, Chromatographische Methoden in der analytische~ und prdparativen anorganischen Chemie,Ferdinand Enke, Stuttgart, 1958. 2 H. J. McDONALD, Ionography, Year Book Publishers, Chicago, 1955. 3 O. MANECKE, Naturwiss., 39 (1952) 62. 4 E. SCHUMACHERAND H. J. STREIFF, Helv. Chim. Acta, 4° (1957) 228. 5 E. SCNUMACHXRAND H. J. STREIFF, Helv. Chim. Acta, 4 ° (1957) 234. e E. SCHUMACHERAND H. J. STRXlFF, Helv. Chim. Acta, 41 (1958) 824. ? E. SCHUMACHERAND H. J. STREIFF, Helv. Ghim. Acta, 41 (I958) 1771. 8 E. SCHUMACHERAND R. I~LUHLER, Helv. Chim. Acta, 41 (1958) 1572. 9 G. GRASSlNI AND M. LEDEEER, J. Chromatog., 2 (1959) 326. 10 D. GROSS, Chem. and Ind. (London), (1957) 1597; values tabulated in Chromatog. Data, i (I958) XVl. 11 M. LEDERER, Anal. Chim. A eta, 17 (1957) 606 ; values tabulated in Ghromatog. Data, I (1958) xvI. la G. 8. BELLING AND R. E. UNDERDOWN,Anal. Chim. Aeta, 22 (196o) 203. 13 G. CETINI, A tti accad, sci. TotinG, Classe sci. ]is., mat. e nat., 91 (1956-57) 171 ; values tabulated in Ckromatog. Data, 2 (1959) D26. la M. MAKI, Japan Analyst, 4 (1955) 156. 15 G. DE ANGELIS, P. IPPOLITI AND A. PUPELLA, Rass. chim. per chim. e ind., IO, No. 3 (1958) I3. 16 S. YASUNAGAAND O. SHIMOMURA,J. Pharm. Soc. Japan, 74 (1954) 66. 17 o. SCHIER, Angew. Chem., 68 (1956) 63. xs D. GRoss, Nature, 18o (1957) 596. 19 S. HARASAWAAND T. SAKAMOTO,J. Chem. Soc. Japan, Pure Chem. Sect., 74 (1953) 862. 10 C. 8ERGAMINI AND G. I~.API,Ann. chim. (Rome), 49 (1959) 39 TM 21 G. H. EVANS AND H. H. STRAIN,Anal. Chem., 28 (1956) 156o. 22 S. NAKANO,J. Chem. Soc. Japan, Pure Chem. Sect., 73 (1952) 912. la H. SEILER, K. ARTZ AND H. ERLENMEYER, Helv. Chim. Aeta, 39 (1956) 783 • 24 A. K. MAJUMDARANn 8. R. SINGH, Anal. Chim. Acta, 2o (1959) 275. 25 M. MAKI, Japan Analyst, 4 (1955) 74. 28 T. R. SATe, W. P. ~2q-ORRISAND H. H, STRAIN,Anal. Chem., 27 (1955) 521. 27 M. MAKI, Japan Analyst, 4 (1955) 304 • 18 E. OHARAAND H. NAGAI, J. Chem. Soc. Japan, Pure Chem. Sect., 73 (1952) 92411 T. R. SATe, W. P. NORRIS AND H. H . STRAIN, Anal. Chem., 26 (1954) 267.

SEPARATION OF INORGANIC IONS BY ELECTROMIGRATION

175

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