The partial molal volume of two nickel chelate complexes

Y . K. SZE
Wllitesllell Nlrclecrr Re~etrrc.17E~tcrblh11t~~errt,
Ato~nicEtrergy of Carlcrrlrr Ltrl.,
Pirlait'a, Man., Cnr~n(inROE ILO
AND
W. A. E. MCBRYDE
Drpartrnerit of Chemistry, Ur~i~;ersity
of Watrrloo, Waterloo, Orlt., Carlada N2L 3GI
Received September 5, 1979'

Y. K. SZEand W. A. E. MCBRYDE. Can. J . Chem. 58, 1795 (1980).

Partial molal volumes have been determined for the nickelfll)complexes of ethylenediaminetetraacetic acid (tj~orrocomplex) and
methyliminodiacetic acid (bis complex). The formation of these is accompanied by appreciable increases in volume, greater in the
case of the second ligand. The observations are discussed in terms of reduced electrostriction of water by the complexes, and the
different volume increases are accounted for by structural features of the complexes which are partially confirmed by spectral
measurements.

Y. K. S z t et W. A. E. MCBRYDL. Can. J . Chem. 58, 1795 (1980).

On a determine les volumes molaires partiels des complexes entre le nickel(I1) et les acides ethylenediaminetetraacetique
(complexe simple) et methyliminodiacetique (complexe double). La formation de ces composes s'accompagne d'une augmentation
importante de volume et elle est plus elevee dans le cas du deuxieme ligand. On discute de ces observations en fonction d'un
Clectrostriction reduite de I'eau par ces complexes et on attribue les differentes augmentations de volume a des caracteristiques
structurales des complexes que les mesures spectrales confirment.
[Traduit par le journal]

Introduction tween the two complexes is the absence of one

hi^ investigation was prompted by the idea that
volume changes which occur during formation of
metal complexes might provide some evidence
concerning the accompanying uptake or exclusion
of solvent m 0 l e ~ ~ l e S
The
. Concept of Solvent ex-
clusion has moved to be of some value in accounting"
for changes in stability constants observed as a
result of changes in solvent composition (1,2). The
apparent molal volume of a solute at infinite dilu-
tion, obtained from measurements of the densities
of solutions of graded concentrations, can be con-
ventionally divided into partial molal volumes of
ions, and from the latter, volume changes that ac-
company formation of a given complex may be
derived. However, the interpretation of such vol-
ume changes appears to be limited to systems
where the formation of complex from the reactants
appears to be essentially complete.
We have selected for initial study the complexes
of nickel(I1) formed bv ethvlenediaminetetraacetic
acid (EDTA) and methylimhodiacetic acid (MIDA),
the molecule of the latter being very 'lose to
that of the These ligands yield very
complexes with nickel(II), the bis complex of the
latter being of the same charge as the mono com-
plex the former. The difference be-
'Revision recelved May 17. 1980.
0008-40421801I7 1795-04$01 .OO/O
@ 1980 National Research Council of CanadaIConseil national de recherches du Canada
chelate ring in the methyliminodiacetate case.
Experimental
Prc,parritiO,,o ~ s o ~ l r r i o ~ l s
Five series of solutions were studied, the preparation ofwhich
is described as follows.
Series I. NazNiEDTA. 2NaCI0,
A stock solution was prepared by refluxing NiO (Baker
Analyzed) with HCIO, (Baker Analyzed) for 24 h. Disodium
EDTA dihydrate (Baker Analyzed) and NaOH (Baker analytical
concentrate) in amounts slightly less than stoichiometric for
Na,NiEDTA 2NaCI0, were added and refluxing continued. A
small amount of NiO remaining undissolved was removed by
filtration through a tared sintered-glass crucible. Its mass was
determined to be about 0.5% of the NiO taken, and the concen-
tration of the solution calculated from the mass of NiO actually
dissolved. More Na2EDTA. NaOH, and HCIO, were added to
provide the exact stoichiometry represented by the above for-
mula. When cooled, the solution was transferred to avolumetric
flask, diluted to the mark, and stored at a temperature close to
25°C. More dilute solutions were prepared by weighing portions
of the stock solution and mixing with water in a volumetric flask.
s ~ r l e 2.
s KzNiEDTA .2KNO3
T h ~ s solution was prepared by direct weighing from
Ni(NO,)< 6 H 2 0 (BDH Analar, dried over anhydrous CaSO,),
EDTA (Baker Analyzed), and KOH (BDH concentrated vol-
umetric solution).
Series 3. Nn,Ni(MIDA):. 2NnCI0,
Prepared from stoichiometric proportions of Ni(NO,),.
6 H 2 0 , methyllminodiacetic acid (Aldrich Analyzed 99%), and
NaOH.
1796 C A N . J . CHEM. VOL. 58, 1980

Series 4. Nu, EDTA . 2 N u O H

Prepared from stoichiometric proportions of Na,EDTA.
2 H z 0 and NaOH.
Series 5. Nu,MIDA. N u O H
Prepared from stoichiometric proportions of methylimino-
diacetic acid and NaOH.
Detlsity Meusuretnents
Densities of the solutions were measured by a vibration-tube
flow densimeter (Sodev Model 0.1 D) under flow conditions
(0.1 cm3 min-I for liquid and ca. 3 cm3 min-I for nitrogen). The
resonance period of the vibrating tube was measured with a
Hewlett Packard digital electronic counter (Model 5245 L). The
densimeter was calibrated several times during each run with
dried, filtered nitrogen gas, preheated to 25 f 0.0l0C, and with
filtered, deionized, distilled, and degassed water (3). The con-
sistency of the densimeter was checked with absolute methanol
(Baker Photrex Reagent).
The temperature of the vibrating tube in the densimeter was
maintained by water pumped through insulated tubing from a
precision thermostat. The temperature of the water in the latter
was controlled by a precision controller (Tronac Inc., Model
PTC-1000) equipped with anticipating and proportioning de-
vices and an integrator circuit to minimize temperature fluctua-
tion. Cooling water for the precision thermostat was supplied
I I I I I I
from a n auxiliary thermostat maintained at 24.5 f 0.05"C
through brass coils immersed in the former. 0 0.1 0.2 0.3 0.4 0.5 0.6
The temperature of the precision thermostat was set at 25'C 1/2 1/2 -3/2
by means of a thermometer with 0.IoC subdivisions and cali- (concentration) /mol dm
brated against an NBS-certified master. A Beckmann differential
FIG. I. Apparent molal volumes in aqueous solution. A,
thermometer (O.OI°C subdivisions) was used t o note variation in
K , N i E D T A 2 K N 0 3 ; B, Na,Ni(MIDA), 2NaC10,; C, Na,-
temperature of the bath (to 0.0002"C). The latter was also moni-
N i E D T A 2NaCI0,.
tored with a probe consisting of a thermistor in series with a
metal-film resistor forming one arm of a Wheatstone bridge VZ0,of the solute are obtained. The VZ0values for
circuit. Alternatively the ratio of the resistances of the thermis-
tor and the metal-film resistor was measured with a Hewlett K2NiEDTA. 2 K N 0 3 and Na2NiEDTA.2NaC10,
Packard ratiometer. In either arrangement the output of the are (258.8 f. 0.5) cm3 mol-I and (242.9 f. 0.7) cm3
circuit was connected to a recorder the signal of which indicated mol-I respectively. These two systems have
that the temperature was contolled to within 0.000IoC during NiEDTA2- 2 s a common constituent. The differ-
each day and rarely varied by more than 0.0002"C between days.
Densities (p) are related to the resonance period (7) of the
ence in the VZ0values for the two systems, namely
vibrating tube by the equation 15.9 cm3 mol-I, can be accounted for in terms of
the other constituents in the solutions. From the
literature, VZ0(KN0,) = 38.0 c q 3 mol-I ( 3 ,
in which A and B a r e constants found by measuring the densities V20(NaC10,) = 42.9 cm3 mol-I (6), V2O(KC1O4)=
of two pure fluids, nitrogen gas and water.
Apparent molal volume, +.,was calculated by the equation 55.2 cm3 mol-I (7). Hence
[I] -) VZ0(Na+)
VZ0(~+
in which p is the density of the solutionlg c w 3 , p0 is the density = VZ0(K~10,) - V20(~a~l~4)
of pure waterlg c w 3 , C is the concentration of the solu-
tion/mmol ~ m o -r mol~ dm-3, and M, is the molar mass of the = 55.2 - 42.9 = 12.3 cm3 mol-I
solute.
[2] V Z 0 ( ~ N o -
3 )V 2 0 ( ~ a ~ =
l ~38.0
4 ) - 42.9
Spectroscopic Meusurernet~ts = -4.9 cm3 mol-I
Visible spectra were recorded with a Cary 118 spec-
trophotometer at 25°C and in 1-cm cells. From [I] and [2]

Results and Discussion

Molar Volumes
+,
Values found for are shown plotted against Cli2
for the five series of solutions in Figs. 1 and 2. The
plots in general support Redlich and Rosenfeld's
equation (4). Only in the Na2NiEDTA2NaC104
series is some curvature apparent. By extrapola-
tion to infinite dilution the partial molal volumes,
This value is sufficiently close to the experimen-
tally measured value, 15.9 cm3 mol-I, to support
the supposition that the partial molal volume of
the constituent, NiEDTA2-, is independent of
background ions in the solution.
 SZE A N D McBRYDE 1797

more reliable than others because it leads to better

i~ternal consistency among derived values of
VZo(ion)(9- 12).
The following can be obtained from Table 1:
I . Reactions represented by

show considerable increase in volume. This may be

attributed in part to a neutralization effect, and also
to the fact that in the product the charge is distri-
buted inside the complex entity with little interac-
tion with water. These two factors lead to a
significant decrease in electrostriction, with a con-
sequent increase in volume (9).
2. The partial molal volume of Ni(MIDA)22-
(176.6 cm3 mol-') is larger than that of NiEDTA2-
(170.3 cm3 mol-I). This difference in volume is be-
lieved to be statistically significant, and may be
interpreted as follows: (a) The packing in the five-
membered ring in NiEDTA2- should require less
space than that required for Ni(MIDA)22- where

(concentration )'I2 / m 0 1 ' / ~

FIG. 2. Apparent molal volumes in aqueous solution. D,
Na4EDTA. 2NaOH; E. Na2MIDA. NaOH.
this ring is lacking. (b) In NiEDTA2- the nitrogen
TABLE1. Apparent and partial molal vol- donor atoms are cis to one another, whereas in
umes
Ni(MIDA),'- the trans isomers are the likely
Solution vz0/cm3 configurations (see discussion of spectral observa-
tions). The consequent larger over-all dipole mo-
ment in the case of N i E D T A Z would cause a
larger electrostriction of solvent, and may be re-
sponsible for its smaller volume. (c) The additional
chelate effect (13) in NiEDTA2- results in stronger
metal-ligand interactions with shorter Ni-0 and
Ni-N distances compared to those in
Ni(MIDA)22-.

Spectroscopy
In both NiEDTA2- and Ni(MIDA),l- there are
"The pamal molal volumes of Ions were calculated uslng
the results of t h ~ sstudy and velues of convenrlonal part~dl
two N and four 0 donor atoms, and therefore the
molal volume of Ions at 25-C-(ref 96) corrected uslng Zana
and Yeager's value for H+. P ( H + ) = -5 4 at 25'C (ref 9h.
complexes must be of lower symmetry than oc-
p 542and ref 8)
tahedral. These two elements are, however, close
In Table 1 are summarized the I/,o values for to one another in the spectrochemical series, and so
Na2NiEDTA. 2NaC104, Na,Ni(MIDA), 2NaC104, to a good approximation the complexes can be
Na4EDTA-2NaOH, and Na2MIDA.NaOH to- treated as having a pseudo-octahedral geometry to
gether with those of some other ions of interest. which the rule of average environment can be
These latter values were calculated with the aid of applied (ref. 14, pp. 98, 103, 104). This is especially
VZo(ion) values based on Zana and Yeager's true for spectra of solutions at room temperature
method for VZ0(H+)(8); this method is regarded as which is the case in the present study.
1798 C A N . J. CHEM. VOL. 58. 1980
Wavelength I n m
FIG. 3. Visible spectra of complexes in aqueous solution. C,
Na,NiEDTA.ZNaClO,, 0.080mol d m 2 ; B, Na2Ni(MIDA),
2NaCI0,. 0.094 mol dm-'.
Our results show that within the range studied
(up to 0.16 mol dm-3 Na,NiEDTA. 2NaC10, and
0.125 mol dm-Wa,Ni(MIDA), 2NaC10,) the ab-
sorbance, integrated from 730 nm to 470 nm (Fig.
3), is directly proportional to concentration for both
systems. Also there is no change in band shape with
concentration. These findings suggest that there
are no shifts in equilibrium as concentration
changes. In Fig. 3 the actual spectra for repre-
sentative solutions of the two systems are shown.
The absorbances and band positions are typical for
a nickel complex with an octahedral field (15). The
peaks at 588 nm and 610 nm for the ]Val-
NiEDTA 2NaC10, and Na2Ni(MIDA), 2NaC10,
solutions respectively can be attributed to the
3A2, + 3T,,(F) transition of NiEDTA2- and
Ni(MIDA)22-. These positions lie between those
for nickel complexes with six 0 donors (e.g., ca.
700 nmfor Ni(H,O),'+) and those with six N donors
(e.g., ca. 550 nm for Ni(en),'+) (16). The solutions
containing NiEDTA2- have higher molar peak ab-
sorbance (see Fig. 3) as well as greater integrated
molar absorbance (1010 vs. 820 in units of absor-
bance x nm). This observation can be attributed
(ref. 14. pp. 105, 106) to the lower symmetry for the
NiEDTA2- complex as discussed previously.
The shorter wavelength for the peak observed
for solutions containing NiEDTA2- compared to
those containing Ni(MIDA)," confirms that
EDTA interacts more strongly with Ni than MIDA
does. Such a shift can also be caused by ligands
lying toward the stronger end of the spectrochemi-
cal series (IS), but since the donor atoms are the
same in the two systems, we attribute the shift to
the additional chelate effect in EDTA. This in-
terpretation is in accord with conclusions reached
from a study of a large number of complexes of
nickel with multidentate amines (ref. 14, pp. 105,
106, ref. 16).
Conclusions
(I) Complex formation in the two examples
studied was accompanied by a considerable in-
crease in molar volume which has been attributed
to diminished electrostriction of solvent.
(2) The chelate effect, which has been estab-
lished from stability constants of complexes, is also
evident in the present study of partial molar vol-
umes and spectra of NiEDTA2- and Ni(MIDA)?lP.
The generality of these conclusions will require
examination of other appropriate systems of corn-
plexes.
1. K. K. M U I ,W. A. E. M c B R Y D E , ~ ~NIEBOER.
~E. Can. J.
Chem. 52.2512 (1973).
2. S. H. MEHDI.D. A. B R I S B I Nand . W. A. E. MCBRYDE. J.
Soln. Chem. 4.497 (1975).
3. G. S. KELL.J. Chem. Eng. Data, 12,66(1967).
4. 0 . REDLICH and P. ROSENFELD. Z. Elektrochem. 37, 705
(1931): Z. Phys. Chem. A155,61(1931).
5. L. A. D U N NTrans.
. Faraday Soc. 62,2348 (1966).
6. H. E. WIRTHand F. N. COLLIER, JR. J . Am. Chem. Soc. 72,
5292 ( 1950).
7. E. GLNECKAUF. Trans. Faraday Soc. 61, 914 (1965); P.
MUKERJEE. J. Phys. Chem. 65,740(1961); 65,744(1961).
8. R. ZANAand E. YLAGER. J. Phys. Chem. 70,954(1966);71,
521 (1967); 71,4241 (1967).
9. ((1) F. J. MILLERO.Chem. Rev. 71, 168 (1971); ( b ) F. J.
MILLERO.It1 Water and aqueous solutions: structure,
thermodynamics and transport processes. Edited by R. A.
Horne. Wiley-Interscience, New York. 1972. Chapt. 13.
10. M. S A K U R A T I ,. KOMATSU,and T. NAKAGAWA. Bull.
Chem. Soc. Jpn. 48,3491 (1975).
11. M. S A K U R ABull.
I . Chem. Soc. Jpn. 46, 1596(1973).
12. H. HOILAND. J. Chem. Soc. Faraday Trans. 1, 71. 797
(1975).
13. S. CHABEREK and A. E. MARTELL. Organic sequestering
agents. Wiley-Interscience. 1959. p. 140.
14. C. R. HARE.It1 Spectroscopy and structure of metal chelate
compounds. Edited by K . Nakamoto and P. J. McCarthy.
Wiley-Interscience, New York. 1968.
15. F. A. COTTONand G. WILKINSON. Advanced inorganic
chemistry. 2nd ed. Wiley-Interscience. New York. pp. 881.
882.
16. C. K. JORGENSEN. Acta Chem. Scand. 10,887(1956).