594 LARRYc. THOMPSON AND
JUDITH
LA. LORAAS
Inorganic Chemistry
formation function for each metal with values of fi calculated (circles and dots) from experimental values of [P’] and the over-all conditional formation constants.
Acknowledgment.-The authors wish to express their thanks to Dr. J. C. Sullivan of Xrgonne National Laboratory for providing the I B l I 704 program for the least squares treatment of potentiometric titration data.
CONTRIBUTION FROM
THE
DEPARThfENT O F CHEMISTRY, U X I V E R S I l Y 01’ 18, A‘fIYNESOTA
h ~ I S N E S o T AAT I)DLUTH, DCLVTH
Complexes of the Rare Earths. VI. N-Hydroxyethyliminodiacetic Acid BY LARRY C. THOMPSOS
ASD
JLTIITH
LOR.-lXS1
Received February 4 , 1963 The formation constants of the complexes between the rare earth ions and S-hydroxyethyliminodiaceticacid ( H I M D A J have been investigated a t 25’ and p = 0.1 (KXC,). Both 1: 1 and 2 : 1 chelates of unusually large stability were found. Trends in the formation constants are discussed and it is shown that the data can be explained by assuming that the IIJ-droxyethyl group is coordinated in both the 1: 1 and 2 : 1 chelates. The data also indicate that the rare earth ions have a coordination number larger than six in these species.
In connection with the project underway in this Laboratory in which the basic complexing tendencies of the rare earths are being investigated, the formation constants for the rare earth-N-hydroxyethyliminodiacetic acid (HIMDA) chelates have been measured and are reported herein. This ligand is of particular interest for several reasons. First of all, i t has been rather extensively and carefully studied and the formation constants for a large number of HIMDA-metal chelates have been d e t e r m i ~ ~ e d .Comparison ~’~ of these data with the corresponding formation constants for the rare earth chelates should be useful in obtaining information relative to the factors influencing the coordination of the rare earth ions. A second reason for investigating this ligand is the opportunity t o compare these complexes with the corresponding complexes of iminodiacetic acid (IMDA).4 Of primary interest here is the inductive effect of the N-hydroxyethyl group and the possibility of coordination through the hydroxy group. In addition, since HIMDA contains four potential donor sites, it is possible that in the 2 : 1 complexes the central rare earth ion has a coordination number larger than six. The only previous studies with the, rare earth complexes of HIMD.4 appear to be an investigation of some mixed complexes with X-hydroxyethylethylenediaminetriacetic acid,5 a study of the hydrolysis of the lanthanum chelate,6and a study of the ligand as an eluent in the ion-exchange separation of the rare earth^.^ The structural formulas of HIMDA and the other (1) Xational Science Foundation Undergraduate Research Participant, 1961-1962. (2) G . Schwarzenbach, G. Anderegg, U’. Schneider, and H. Senn, Helo. Chim. A c t a , SB, 1147 (1955). (3) S. Chaberek, Jr., R . C . Courtne)., and A. E . Martell, J . A m . Chef??. Soc., 74, 5067 (1962). (4) I,. C. Thompson, J n o ~ g C . h e m , 1, 490 (19112). ( 6 ) L. C. Thompson and J. A. Loraas, ibid., 2 , 89 (1813). (6) R. C. Courtney, R. I,. Gustafsnn, S.Chaberek, Jr., and A . E, hlartell, J . A m . Chem. Soc., 80, 2121 (1868). (7) L. Wolf and J. hlassone. 1 . P i n k f . Chrin., 6, 2x8 (lCK-3), and references therein.
ligands which are mentioned in this paper are given below. /CH*CooH
I-TOCHlCHZN
\
CH2COOH HIMD.1
FT s/cH*cOO1-r
\
cErlcooII
I M D.l
/CH*Cool*
S -CH?COOH
\
CHzCOOH NTAl
Experimental Solutions.-The HIMDA was obtained from the Dow Chemical Company and was purified by two recrystallizations from water. An approximately 0.005 J J solution was prepared by dissolving the required amount of acid in de-ionized water and was standardized by potentiometric titration both in the presence and absence of copper(I1) ions. The preparation and standardization of the 0.005 J J rare earth nitrate* and 1.000 ,\I potassium nitrate solutions have been described p r e ~ i o u s l y . ~ ,4 solution 0.005 .!If in tren.3HCI (tren is 2,2’,2”-triaininotriethylamine) was prepared by dissolving the required amount in de-ionized water and was standardized by potentiometric titration in the presence of copper(I1) nitrate. All other metal ion solutions were prepared from the analytical reagents and standardized complexometrically. For the measurements using the copper amalgam electrode a 0.05 ;vl HIMDA solution was prepared so that the total ionic strength was 0.1 using potassium nitrate as the inert salt. Copper(I1j Amalgam.-The liquid copper amalgam, 2.00%; by weight, was prepared by electrolyzing a solution of copper( 11) sulfate with pure mercury as the cathode. The amalgam was stored under dilute nitric acid and an atmosphere of nitrogen. Experimental Procedures.-( a ) pH method : In those cases where the 1: 1 complex was not too stable (log K1 < 9), the direct titration procedure described previously4 was used with solutions containing HIMDrl and the rare earth ion in the ratio 1: 1 , 2 : 1 , (8) T h e rare earth materials were generously supplied by I.ind.;ay Chemical Division, American Potash and Chemical Corporation, Weit Chicago, J 11in o i s,
RAREEARTH-N-HYDROXYETHYLIMINODIACETIC ACID COMPLEXES595
VoZ. 2, No. 3, June, 1963
or 3: 1. (b) tren method: The procedure consisted of a potentiometric titration of a l : l : l : l solution of the rare earth ion, copper(II), tren.3HC1, and HIMDA using the same apparatus and technique as in the direct titration procedure. (c) Copper(11) amalgam: The apparatus used in this procedure consisted of a 200-ml. Berzelius beaker and a stopper which contained holes for the glass and calomel electrodes, the nitrogen inlet tube, the copper amalgam electrode, and the buret. The calomel electrode was modified by coating the inside with a thin layer of agar prepared so that it was 0.1 M in potassium nitrate. The copper amalgam electrode consisted of a Sargent S-30438 Reilley electrode with the amalgam placed in the annular cup. The potentials of the amalgam-calomel assembly were read with a Leeds and Northrup type K-3 potentiometer. The cell is described by
Cu, Hg glass
I experimental solution I
p = 0.1
(Ki\o3)
I/
0.1 M KN03
I1 satd. KCl
Hg,Clz, Hg (25’) The concentration of copper(I1) in the solution was found from 0.02958 log [Cuz+]. The value of ED’was determined in solutions where there was little reduction to copper( I ) and was found to have the value 0.3348 v. Solutions containing a known concentration of copper(I1) and rare earth ion in a medium of p = 0.1 (KNO2) were titrated with the 0.05 M HIMDA solution a t a constant pH of 3.20 (maintained by the addition of 0.1 M KOH). The potential of the cell was read after each addition of HIMDA and base. Calculations.-(a) pH method: The acid dissociation constants were determined 6s outlined by Chaberek and Martell.g Since both 1: 1 and 2: 1 chelates were formed, the method of Block and McIntyre’O was used to solve the sets of simultaneous equations. The lanthanum system also was solved using the comThe puter program developed by Professor 2 2 . Hugus, Jr.ll agreement between the two methods of computation was excellent. (b) tren method: The usual calculations12were carried out and values for the formation constants of some of the 1: 1 chelates were obtained. (c) Copper amalgam method: This method has been discussed in detail previously13and only the relevant features are mentioned here. In the region in which [HIMDAIt > [Cu2+]tfor solutions containing only copper(I1) and HIMDA, eq 1-3 hold and the copper-HIMDA formation constant is easily
E = EO’
+
[CuZ+It = [CUXI
X = HIMDA2-
(1)
The free ligand concentration is found from the values of [Cu2+], Kcu/cux,and [CuX]. Since [Cu2+]is
