J. Inorg. Nucl. Chem., 1964, Vol. 26, pp. 965 to 980. Pergamon Press Ltd.

Printed in Northern Ireland

STABILITY OF SOME I N O R G A N I C A N D O R G A N I C
COMPLEX C O M P O U N D S OF ZIRCONIUM
AND HAFNIUM
D. I. RYABCHIKOV, I. N. MAROV, A. N. ERMAKOV and V. K. BELYAEVA
Vernadsky Institute of Geochemistry and Analytical Chemistry, Academy of Sciences, U.S.S.R.
(Received 16 May 1963)
THE chemical properties of hafnium and zirconium are very similar. This explains
the discovery of hafnium 133 years later than that of zirconium in spite of the fact that
hafnium and zirconium are always present together.
Despite the fact, that interest to the chemistry of zirconium and hafnium has
increased during the last years, little is known about complex formation. There are
only a few determinations of the composition and stability constants of zirconium
compounds. Analogous data for hafnium are not available.
Such a situation results first of all from the complexity of behaviour of these
elements in solutions. Because of the high charge and small radius, zirconium and
hafnium have a great tendency to undergo hydrolysis with the formation of poly-
nuclear compounds. Investigation of the reactions involved in complex formation,
which are competitive with the reactions of hydrolysis and formation of polynuclear
compounds, is very complicated on account of the simultaneity of the several
processes.
New methods of investigation, namely, solvent extraction and ion exchange,
make it possible to approach the investigation of complex formation by zirconium
and hafnium with various substances in solutions in a more profound way.
The present review sets forth the results of a number of our investigations of
equilibrium reaction in the complexing of ions of Zt a+ and H f 4+ with inorganic
and organic addends. (1-6) The behaviour of these elements in sulphate, nitrate and
chloride solutions was investigated. Oxalic acid and a number of carboxylic and
hydroxycarboxylic acids were selected as organic complexing agents.
To determine the compositions and stability constants of the complex com-
pounds of zirconium and hafnium, we have used the method of ion exchange.
EXPERIMENTAL
The choice of conditions for complex formation of zirconium and hafnium. Methods of the experiment
To investigate the equilibrium reaction of complex formation, we chose conditions under which
zirconium and hafnium exist in the solution in the form of monomeric, non-hydrolysed, ions, i.e.,
~1~A. N. ERMAKOV,V. K. BELVAEVA,I. N. MAROVand M. K. CHMtrrovA,Zh. Neorg. Khim. 4, 493
(1959).
t~ D. I. RVAaCmKOV,A. N. EmaAKOV,V. K. BELVA~VAand I. N. MAROV,Zh. Neorff. Khim. 4,
1814 (1959).
~3~D. I. RVABCl-nKOV,A. N. ERMAKOV,V. K. BELYAEVAand I. N. MAROV,Zh. Neorff. Khim. 5,
1051 (1960).
~4~1. N. MAROV,V. K. BELYAEVA,A. N. ERMAKOVand D. I. RVABCmKOV,Zh. Neorff. Khim. 5,
2844 (1960).
~s~ I. N. MAROV, M. K. CHMtrrovA, Zh. Neorg. Khim., ed. 12 (1961).
ce~ D. I. RYAaCmKOV, A. N. ERMAKOV, V. K. BELYAEVAand I. N. MAROV, Yao-ke-min. Zh. Neorg.
Khim. 7, 69 (1962).
965
966 D.I. RYABCH1KOV,I. N. MAROV,A. N. ERMAKOVand V. K. BELYAEVA

Zr 4+ and HP +. This is accomplished when the concentration of the element is less than 5 × 10 -4 M
at high hydrogen ion concentrations; 2 M perchloric acid is used as electrolyte to maintain a
sufficiently.high acidity.
Concentration of Zr (IV) in the experiments was generally 5 × 10£e M or less. This concentra-
tion range permits experiments in linear part of the sorption isotherm. The distribution coefficient
of the element did not depend either on the concentration at 5 × 10-4 M and lower, or on ratio of
the volume of solution to the quantity of resin. In addition, the distribution coefficients in the
sorption step were identical with the distribution coefficients in desorption.
Soviet ion exchanger, the cation exchanger KY-2 and anion exchanger ~J~Okl01-I, were used in
the work.
The experiments were carried out under static conditions.
The solution under investigation was shaken together with the resin to attain equilibrium.
The concentration of elements in the solution (or in the resin phase under investigation was
fixed radiometrically by ~,- and fl-radiation of 9sZr and lSlHf isotopes used as radioactive indicators.
One parameter, e.g. addendum concentration, was changed in each series of experiments, other
conditions remaining constant. The experiments were carried out at a fixed ionic strength and
hydrogen ion concentration.
The distribution coefficient Ks is defined as the ratio of the equilibrium concentration of the
element under investigation, in the ion exchanger phase CMR,and the equilibrium concentration in
the solution phase, C~, i.e.,
C~,R
Kd=--
CM
K~ is calculated from the equation:
100 per cent - per cent of the element in solution V ml
K a == per cent of the element in solution m' g

where V is the solution volume (ml), m is the quantity resin of (g), and per cent of the element in
solution refers to the element concentration in the solution as a percentage of the initial concentration.

RESULTS AND DISCUSSION

Taking into consideration that under the experimental conditions used in this
work, zirconium a n d hafnium are present in the solution as monomerie, non-
hydrolysed ions Me(H~O)~ 4+, the equilibria involved in the complexing reactions
can be represented schematically by the equations:

Me 4+ + j L - ~ MeLj ~-j

[MeLj4--q
/~ = [Mea+][L_],
L - ~ N O a - and C1- concentrations.
Some complexing substances are weak acids, and in highly acidic medium they
exist practically in a non-dissociated state. Their corresponding equilibria are ex-
pressed by the equations:
Me ~- + HaL ~ MeH~_,,L + n H +,

[MeH~L][H+] ~
Keq. = [Me4+][H~L] ,

where H~L = HzC204, HsCsOT, HsC4Os, HsCsOT, etc.

I n a general case, providing the presence o f the element under investigation in the
solution in microconcentration, the dependence o f the distribution coefficient K a on
 Stability of some inorganic and organic complex compounds of zirconium and hafnium 967

the concentration HxL is expressed by the equation:

1 + Elj[H~L] s
Kd= KOo Keq j
1+ ~ [HxL] j

where/(do is a distribution coefficient in the absence of L-ion; lj is a term, which

takes into account of the sorption of a positively charged complex ion by the cation
exchanger.
Calculation of the constant and the determination of the compositions were
made by the methods of FRONEUS and SCHUBERT.
For substances which are weak acids, the values of
Keq.
K~-- [H] nj
were first calculated.
In order to obtain values of equilibrium constants, Keq., it was necessary to know
the number of hydrogen ions that originate from the molecule H~L in the course of
interaction with Me 4+. In the case of the sulphate system, by analogy with the data
for Th a+ and other tetravalent elements it was assumed that the reaction proceeds
according to the equation:
Me 4+ + j H S O 4- ~- Me(SO4)~4-2j + j H +,
[Me(SO4)~4-2q [H+] j
Keq.j = [Me4+][HSO4_]j
For oxalate complexes values of KIj at two different hydrogen ion concentrations
(2.0 and 4.0 mole/1.) were obtained, though at different ionic strengths. If we assume
that in complex formation two hydrogen ions are dissociated from the molecule
H~CzO4 then the calculated values of Keq. coincide. This provides evidence that the
reaction takes place according to the equation:
Me 4+ + j H 9 C 2 0 4 ~ Me(C~O4)~4-2j + 2jH +
Ks = [Me(C204)~4-~][H]ZJ
[Me4+][H~C204] ~
The determination of hydrogen ions which are dissociating in the cause of complex
formation was made on the system Hf 4+ -- HeC4Oe as an example. If we analyse the
function of Ka = f[HxL] at constant ionic strength but at different [H+], we obtain
K
Ko =f([H+]), where Kt -----[H+]n--------
7 . From this, log Kt ---- log Keq. -- n log [H+]. From
this last equation we find n, the number of hydrogen ions originating from the molecule
HxL ii~ the course of interaction with Me 4+.
In the interval [H +] = 2.0 -- 1.2 mole/l, hafnium forms a complex of 1:1 type
with tartaric acid (Fig. 1). In the region of hydrogen ion concentration [H+] =
2-0 -- 1.6 mole/1, one hydrogen ion dissociates from the tartaric acid, and the reaction
Hf 4+ + H 2 Tart ~ Hf H Tart 3+ + H +, K1 = 98
takes place, whereas at [H+] < 1.6 mole/l, two ions of hydrogen are dissociated:
Hf 4+ + H2 Tart ~ H f Tart S+ + 2H +, K 1 = 150.
968 D. ]. RYABCH1KOV,I. N. MAROV,A. N. ERMAKOVand V. K. BELYAEVA

2'0

1.9

0
FIG. 1.--The dependence of Kr on the
1.8 hydrogen ion concentration.

,-7 ~ 9 2

I I I I
)-6 o., 0.2 0.3 0.4
log [H+ l
Since citric, tartaric, malic and trioxyglutaric acids have values o f Kldi~ocn o f
the same order o f magnitude, it is assumed that during complex formation o f zir-
conium and "hafnium with the enumerated oxyacids at [H +] = 2.0 mole/1, the dis-
sociation o f one hydrogen ion from the organic acid molecule takes place, i.e.
Me 4+ + HnL ~ MeHn_IL 3+ + H +
K = [MeH~-ILS+][H+]
[Me4+][H.L]
TABLE 1.--DIssOCIATION C O N S T A N T S OF SOME O X Y A C I D S

Acids K1 Kz
Malic
HOOC--CH--CH2--COOH 3.9 × 10-4 7'8 × 10-e
\
OH
Tartaric
HOOC---CH--CH--COOH 6 × 10 -~ 1"53 × 1 0 - 5

/ I
• OH OH
Lactic
HOOC--CH---CH3 1"4 × 1 0 - 4
I
OH
Citric
OH
\
HOOC--CH2--C--CH 2--COOH 8"4 × 10-' 1"8 × 10-s
/
COOH
Trioxyglutaric
HOO C--CH---CH--CH---COOH 8"4 × 10-4 6"1 × 10-6
/ I \
OH OH OH
 Stability of some inorganic and organic complex compounds of zirconium and hafnium 969

Let us now examine the results obtained on the composition and stability of some
zirconium and hafnium complex compounds.
Owing to their chemical similarity zirconium and hafnium form complex com-
pounds of an identical type. The composition of the chloride compounds is MeC1a+,
MeCI~~+, MeCla+, MeC14 (Table 2). The information available in the literature(7) on

TABLE 2 . - - V A L U E S OF STABILITY CONSTANTS flj OF CHLORIDE COMPLEXES OF ZIRCONIUM

AND HAFNIUM

# = 2.0 /~ = 4.0

Zirconium Hafnium Zirconium Hafnium

fll 0"95 4- 0"05 1"1 4- 0"05 0"94 + 0"06

f15 0"12 4- 0"05 0"21 4- 0"05 0"18 4- 0"05
fls 0"070 4- 0"010 0"05 4- 0"01 0"08 4- 0"02
f14 0"080 4- 0"005

TABLE 3 . - - V A L U E S OF STABILITY CONSTANTS flJ NITRATE COMPLEXES OF ZIRCONIUM

AND HAFNIUM

# = 2-0 # = 4-0
~J
Zirconium Hafnium Zirconium

fll 0"92 4- 0'07 0"90 4- 0.07 0"88 4- 0"1 0.60 + 0-05

f12 0"46 4- 0"08 0"55 4- 0.08 0.14 4- 0"08 0.12 4- 0.04

TABLE 4.--THE VALUES OF THE EQUILIBRIUM CONSTANTS K j AND STABILITY CONSTANTS OF

SULPHATE COMPLEXES OF ZIRCONIUM AND HAFNIUM

Element: K1 fll x 10-3 K2 x 10-5 f15 x 10-5 K5 × 10-e f13 × 10-s

Zr 466 4- 23 5-6 4- 0"27 3'48 4- 0"32 5-0 + 0"46 3.92 4- 0"63 6"8 4- 1.1
Hf 130 + 5 1.56 4- 0.06 2"1 4- 0"1 2"1 4- 0-1 3-02 4- 0-14

the strong adsorption of these elements by anion exchangers from hydrochloric acid
solutions, which occurs beginning with [HC1] = 8 mole/L, apparently can be
explained by formation of anion form complexes of the MeC15- and MeCle~. The
Complexes of the type MeNOa~- and Me(NOs)~2+ are found in nitrate solutions
(Table 3). There is very limited information as to the formation of Zr (NOs)a+ and
higher nitrate complexes.
With sulphate ions, zirconium forms compounds ZrSO42+, Zr(SO4)z and
Zr(SO~)a~. Formation of HfSO42+ and Hf(SO4)2 is observed for hafnium (Table 4).
The complex Hf(SO4)az- apparently is formed under the conditions of much higher
concentrations of H S O c ion.
(7) The Structure of Electrolytic Solutions (Edited by W. J. HAMER), Wiley, New York (1959).
(s) A. S. SOLOVKIN,Zh. Neorg. Khim., ed., 3, 611 (1957).
5
970 D.I. RYABCHIKOV,I. N, M.,~ov, A. N. ERMAKOVand V. K. BELYAEVA

The formation of the cation and neutrat oxalate complexes MeC~O42+ and
Me(C20~)~ (Table 5) is established by the method of cation exchange. The anion
complexes Me(C2Oa)3z- and Me(C~Oa)~*- are formed even in strongly acid media
when [H+] = 2 mole/l, and are strongly sorbed by anion exchangers. In nearly
neutral media (pH 5.8--6.2) with a large excess of the oxalate-ion, Zr ~- and H f ~- form
the complex Me(C~O4)n 6--.
At [H +] -----2.0 mole/l, zirconium and hafnium form with oxyacids the follow-
ing complexes: lactates MeLact 3+, Me(Lact)a2+; malates, M e H M a l ; tartrates,

TABLE 5 . - - T H E VALUES OF EQUILIBRIUM CONSTANTS K j OF OXALATE COMPLEXES OF

ZIRCONIUM AND HAFNIUM

# = 2"0 (mole/l) p = 4-0

Element Method
K1 × 10-5 K2 × 10-9 K3 × 10-11 K4 × 10-14 K4 × 10-b

Zr Cation 3.16 + 0.3 4.8 -4- 1.6 4.0 :~ 0.6

Hf Cation 1.48 -4- 0.36 5.3 + 1.8 1-4 ± 0.3
Hf Anion 0.28 1"6 6.4 1'28

TABLE 6.~THE COMPOSITIONOF COMPLEXES~ (IV) AND Hf (IV) WITHOXYACID$AT

[H+] = 1.0-O'125 MOLE/I.

Complex Concentration of hydrogen ions (mole/l.)

Me(IV):H3Cit = 1:1 1.0 -- 0.125

Me(IV):H~Tart = 1: 1 1-0
Me(IV):H2MaI = 1: 1 1.0
Me(IV):HzTart = 1:1 1:2 0.5 -- 0.125
Me(IV):H2MaI = 1:1 1:2
Me(IV):H2Tog = 1:1 1:2 1.0 -- 0.125
Me(IV):HLac = 1:1 1:2

MeHTart; citrates MeH2Cita+; trioxyglutarates, M e H T o g*+ and Me(HTog)22+.

Investigation shows (Table 6) that in the concentration range [H +] ----2.0-0.125
mole/l, the composition of citrates complexes is 1:1 (with the exception of
hafnium citrates in 0.125 mole/1 H +, where an additional complex 1:2 is formed);
lactates and trioxyglutarates, M e : H , L = 1:1 and 1:2. The composition o f
tartrates and malates is M e : H ~ L = 1 : I, [H-] = 1 mole/1, 1 : 1 and 1:2, [H+] =
0.5-0.125 mole/1. It should be noted, that despite the identical ratio of M e : H ~ L at
different concentrations of hydrogen ions, the composition of the complexes can be
different. This may occur, firstly, because with decrease in acidity, the hydrolysis of
zirconium and hafnium increases, resulting in the formation of M e O H 3+, Me(OH)a s+
and other species; and, secondly because different number of hydrogen ions dis-
sociate from the organic acid, as was shown in the example of the tartaric complexes
of hafnium.
The similarity of zirconium and hafnium becomes apparent not only in the forma-
tion of an identical type, but in the stability of these compounds. Stability constants
 Stability o f s o m e inorganic a n d organic c o m p l e x c o m p o u n d s o f z i r c o n i u m a n d h a f n i u m 971

of chloride complexes of Zr 4+ and Hf ~- are identical (Table 2). There are some
distinctions, however, though extremely small, at ionic strength # = 4-0. In a
number of studies {~-n) it is noted that the sorption of hafnium by the cation ex-
changer is not as good as that of zirconium, at a [HC1] concentration of 6 Mol/1
which may indicate high stability of the higher chloride complexes of hafnium.
The stability of Zr(NOa) a+ and Hf(NOa)s+ as one can see from Table 3, is approx-
imately the same, and the complex Zr(NOa)a2+ is a little less stable then (NOa)~+/
at/~ = 2.0 mole/1. Practically the same degree of zorption of zirconium and hafnium
by the cation exchangers from nitrate solutions was observed by other workers. {ga°)
However, there are considerable differences in complex formation with sulphate ions.
The complex ZrSO4~- is approximately three times more stable then Hf SO4z+, and
the complex Zr(SO4)a is about 1"5 times more stable than Hf(SO~z° (Table 4). In
addition, zirconium forms Zr(SO4)3~. The oxalate complex ZrC~O4~+ is two times
TABLE 7.--EQUILIBRIUM CONSTANTS K~ OF ZIRCONIUM AND HAFNIUM COMPLEXES WITH
OXYACIDS AT H + = 2"0 MOLE/1.

Hafnium Zirconium
Acids Kxzr/Klrt~
K1 Ka K1 K2

Lactic 108 4- 8 108 4- 60 190 i 10 350 ± 150 1-75

Malic 67.5 4- 5.0 -- 172 + 17.2 -- 2.5
Tartaric 97"2 4- 2-4 -- 310 4- 24 -- 3.1
Trioxyglutaric 530 4- 40 (16 4- 4.0) × 104 2580 4- 100 (25 4- 4.6) x 104
Citric 348 4- 43 -- 2600 4- 432 -- 7-5

more stable than the corresponding complex of hafnium (Table 5). The values of
Keq.~ for oxalate complexes of zirconium and hafnium are approximately the same.
Thus, the biggest differences in complexing of these elements with C~O4~- ion exist in
the first stage of the process.
The differences in the stability of zirconium and hafnium complex compounds for
various oxyacids are considerable (Table 7). Zirconium malates are 2.5-3 times
stronger than those of hafnium. Zirconium tartrate, formed in 1 M HCIO4, is five
times more stable than that of hafnium.
Increasing the [H+] up to 2.0 mole/1, leads to a decrease in differences in the tart-
rates stability of zirconium and hafnium complexes. In the case of trioxyglutaric acid,
the situation is reversed, since the zirconium complex, formed at [H+] = 2-0 mole/L,
is 4"7 times more stable than that of the corresponding hafnium compound; decrease
of [H+] to 1 mole/l, leads to a decrease in the ratio Kizr/K1m.
Compounds with citric acid have the greatest differences. Zirconium citric acid
complex is approximately seven times more stable, than hafnium citrate. A general
regularity becomes apparent for all investigated complexes, with the exception of
chloride and nitrate, namely: zirconium complex compounds are more stable than
the corresponding hafnium compounds. In the case of chloride and nitrate complexes
this regularity is very indistinct. The lower stability of the hafnium complex
{9~ R. A. J. LISTER, J. Chem. Soc. 3123 (1951).
{10~j. T. BE~DICT, W. C. S ~ , C. D . CORWLL, J. Amer. Chem. Soc. 76,.2036 (1954).
{Xl~ K. STREET, G. T. SEAeORO, J. Amer. Chem. Soc. 70, 4268 (1948).
972 D . I . RYABCHIKOV,I. N. MAROV,A. N. ERMAKOVand V. K. BELYAEVA

compounds is apparently connected with the somewhat greater size of the Hf 4+ ion
and its 4fa4 electron shell.
The stability of complex compounds formed both by zirconium and hafnium with
inorganic ligands decreases in the order of
O H - > F - > SO42~ CI- ~> NO3-.

The OH-group and F-ion are placed in this series in accordance with literature
data for zirconium. ~s'm As for hafnium, there are only calculated value Of Klhyd.
Apparently, HfOH 3+ and HfF a+ are less stable than the corresponding zirconium
compounds. Perch/orate ion, to all appearances, has a very small tendency to complex
formation with Zra+ and Hf ~. The absence of complex formation with C104- ion with
various cations was postulated in many papers; however, formation of FeCIO4~ and
CeCIO4 ~ was pointed out. t13,14J Recently, it was shown, t15~ that Nd a+ forms a
complex with C104- ion only at high concentration of perchloric acid (8 M and
higher). Among the dicarboxylic acids, oxalic acid gives the most stable complex
compounds with zirconium and hafnium. The homologues of oxalic acid, malonic
(0.03 M), succinic (0.2 M) and glutaric (0-1 M) acids do not change the distribution
coefficient of Zr 4+ and Hf 4+ on a cation exchanger in an 0.125 M solution of HC104;
this provides evidence for the lack of noticeable complex formation in these systems.
The sharp decrease in the stability of complex compounds in the order of
oxalic >~ malonic, succinic, glutaric acids
corresponds to the decrease in the stability of rings during transition from five to six,
seven, and eight membered rings. An analogous order is found for tin, t16~ Cu~, ttT~
Mn2+. t~8~ Maleic (0.05 M) and glutamic (0.1 M) acids do not form complexes with
zirconium and hafnium at [H+] = 0.125 mole/1 and higher.
Equilibrium constants of zirconium and hafnium complexing reactions with
different oxyacids diminish in the series trioxyglutaric > citric > tartaric > lactic >
malic acids.
Deviation from this sequence takes place only in one case: the hafnium lactate
equilibrium constant Keq.1 is greater than that of hafnium tartrate.
Calculation of stability constants of complex compounds is unreliable because of
lack of data on dissociation constants of oxyacids at ionic strength/~ = 2.0 mole/1.
It should be pointed out that the order of stability constants can differ from that of
equilibrium constants of reactions involving zirconium and hafnium complex
formation with oxyacids.
In a number of chemical properties, zirconium and hafnium are identical to other
tetravalent elements---Th ~-, Pua+, U ~-, Np ~-, Cea+. Let us compare the tendency of
<12) R. E. Co~rlCK and W. H. McVEY, 3. Amer. Chem. Soc. 71, 3182 (1949).
~la) R. H. Strrc~'EE and J. R. WEBER, Trans. Faraday Soc. 52, 1225 (1956).
~4) j. StrrroN, Nature, Lond. 169, 71 (1952).
~6) p. KRtnC~OLZ, J. Phys. Chem. 63, 1313 (1959).
(~e) DAY, Univ. Allahabad Studies, Chem. See., 1946, 7; Chem. Abstr. 41, 6169 (1947). Cited from
book J. B.~J..Av (Editor) Chemistry of Coordination Compounds, p. 192. Foreign Languages
Publ. House, Moscow (1960).
(~7) H. L. RILEY,J. Chem. Soc., a) 2985 (1928); 1307 (1929); 1642 (1930).
t~8) N. C. LI, W. M. WESTZALL,A.. LINBERNBAUM,J. M. WHITE and J. SCHUBERT,J. Amer. Chem.
Soc. 79, 5864 (1957).
 Stability of some inorganic and organic complex compounds of zirconium and hafnium 973

these elements to hydrolysis. In Fig. 2 we see logarithm values of equilibrium con-

stants of the reactions Me4+ 4- HzO ~ MeOH a+ + H ÷

[MeOHS+][H+]
K1 hya = [Me4+]

The theoretical value of g I hyd', calculated by KASPER'S method, txgj in the series
Zr ~-, Hf ~-, Pu4+, Ce~-, Np 4+, U 4+ and Th 4+ diminishes, as follows from the values of
the ionic potentials. (The experimental values of/(1 hyaCe4+, in our opinion, is wrong.)

f Ce4+
-I

Z
a ,\
~u0
-2 o

-3

II Pu4"
I 1 -4
00.80 0.90 1.00
rMe4÷
Fie. 2.--Dependence of KMeSo4z+ and K1 hyd. the radius of some tetravalent metals.

The tendency of tetravalent elements to undergo hydrolysis in the series Zr~-,

Hf ~-, Pu4+, U ~-, Np ~- and Th 4+ diminishes in this order. So, among the enumerated
ions, Zr~- and H P + are most susceptible to hydrolysis, as expected from their radius
values.
The change of hydrolysis and equilibrium constants in the formation of sulphate
complexes of Me4+ ions is not monotonic; the change in values of lg Kx~eso,,+ and
lg K 1hyd have the same regularity: the stability of complexes MeSO~2+ (Fig. 2,
curves 1 and 2) diminishes with the decrease in the tendency to undergo hydrolysis.
Apparently, such a non-monotonic dependence of both hydrolysis and complex
formation with sulphate-ion upon the radius is conditioned by the influence of the
cation electronic shell structure on the compounds formed by them. The value
~t,~ j. KASPER, Ph.D. Thesis. The Johns Hopkins University (1941). Cited from the book Actinide
Elements, pp. 627, 257. G. SEASORGand J. KATZ (Editors). Foreign Languages Publ. House,
Moscow (1955).
~0~ T. J. HARDVvaCI(and E. ROnERWSON,Canad. J. Chem. 29, 818 (1951).
974 D. I. RVAaCHIKOV,I. N. MAROV,A. N. E ~ o v and V. K. BELYAEVA

TABLE 8 . - - T H E VALUES fl~ OF OXALATE COMPLEXES OF TETRAVALENTIC METAL

Element fll f12 f13 f14 References

Th 4+ 3'05 × 10 ~4 42
U ~+ 4"07 × l0 s 7"93 × 1016 5 × 1022 5 × 1027 43
N p 4÷ 3"5 × l0 s 3"2 × 1017 1 × 10 ~4 2'5 × 1027 44
Pu 4+ 5"5 × l0 s 8 × 10 TM 2"5 × 1028 3"2 × 1027 43, 45
t-If4+ Cat. 1"97 × 101° 1'12 × 102° 46
H f 4+ Anion. 4"1 × l0 s 3"38 × 1019 1"95 × 10 ~7 5"65 × 103e 47
Zr 4+ e x c h a n g e 4.3 x 10 TM 1 × 1020 46
Note: When calculating flj o f oxalate complexes o f zirconium and hafnium the values o f dissociation
constants o f oxalic acid, given in the Reference (41) are used.

TABLE 9.--TrlE VALUES flf OF CHLORIDE COMPLEXES OF SOME TETRAVALENT IONS

Element fll flz f13 f14 /~ References

Th 4+ 1"21 0'1 0"2 -- 2"0 48

1"70 0"14 : 0"1 0'018 4"0

U 4+ 1"21 1'14 -- -- 2"0 49

Pu 4+ 1"38 0"67 -- -- 1"0 50

1"4 1-2 0"1 -- 4"0 51

TABLE 10. - - T H E VALUES flj OF NITRATE COMPLEXES Th 4+, Pu 4+

Element fl~ fl~ f18 f14 /~ References

4.73 0,15 52
Th 4~- 2.83 1.41 5,97 53
6 5:0.5 13 -~ 1 10 :~ 0.5 5-5 ± 0.5 2,0 54

2.9 ± 1.6 2.0 55

Pu 4+ 4.7 6.0 55
3,48 -4- 0.05 1.0 55
5.5 ± 0.2 23.5 ± l 15 ~ 10 4.0 51

(41) L. E. DROBKINA, A. I. MOSKVIN and A. D. GEL'MAN,Zh. Neorg. Khim. 3, 1934 (1958).

(4~) M. Bose and D. CHOWDHURY, d. Indian Chem. Sue. 31, 111 (1954); 32, 673 (1955).
(4a) F. A. ZArd-IAROVAand A. I. MOSKWN, Zh. Neorg. Khim. 5, 1228 (1960).
(") P. I. KONDRAT'EV and A. D. GEL'MAN, Radiokhimiya 2, 315 (1960).
(4~) A. I. M o s K v ~ , MSc. Thesis, Institute o f Physical Chemistry A c a d e m y o f Sciences o f the U S S R
(1957).
t,6) I. N. MARov and D. I. RYASCRIKOV, Zh. Neorg. Khim. 7, ed. 5 (1962).
(47) A. N. ERMAKOV, V. K. B~LY,~VA and I. N. MAROV, Proceedings of the Commission on analytical
chemistry; v. I X (XII), 171 (1958).
(48) W. C. WAC_,OEr~R and R. W. STOUtmrON, J. Phys. Chem. 56, 1 (1952).
~4,) R. A. DAY, R. N. WlLma~ and F. D. HAMILTON, J. Amer. Chem. Soc. 77, 3180 (1955).
(50) S. W. RAamEAtm, L. S. ASPRY, T. K. KEEr,mN and T. W. NEWTON, R e p o r t N 2247 at the Geneva
conference on peaceful usage o f atomic energy (eit. o n 45) (1958),
(51) j. GRErrrrm and B. NOREN, Acta Chem. Scand. 14, 2216 (1960).
cs~) R, A, DAY and R. W. STOOOn'rON, J. Amer. Chem. Soc. 72, 5662 (1950).
(ss) E. L. ZEBROSrd, H. W. ADER and F. K. NEtJ~r~-N, 3". Amer. Chem. Sue. 76, 5646 (1951).
rs4) V. V. FoMrN and E. P. MAIOROVA, Zh. Neorg. Khim. 1, 1703 (1956).
(ss) G. T. SEASORO and J. J. KATZ, Chemistry o f Aetinide Elements, Atomizdat, M o s c o w (1960),
 Stability of some inorganic and organic complex compounds of zirconium and hafnium 975

Kx hrd and Kmeso ,+ for Ce e+ obtained in reference (20) are doubtful. It is interesting to
point out one more fact: the differences in the tendency to hydrolysis between Z r t+
and Th e+ are very great, whereas the differences in the stability of ZrSOe~ and
ThSOe 2+ are small.
Zirconium and hafnium form more stable oxalate complexes than Th a+, U 4+,
Np e+ and Pu 4+ (Table 8).
The values of the stability constants of the chloride complexes Th 4+, U e+, Pu e+,
Hf ~- and Zr4+ are given in Table 9, which shows that the stability of the complexes
MeC13+ is approximately the same. Table 10 gives fl~ values of nitrate complexes of
Z # +, Hf a+, Pu ~- and The+; the complexes ZrNOz 3+ and HfNO3 a+ are the least
stable. Apparently, the stability of nitrate complexes increases with increase of ionic
radius.
Analogous phenomena are observed with the alkali (Li+-Cs +) and alkaline earth
(Mg~+-Ba2+) metals/v) and in the series Ce3+-pua+-Ama+-Cm3+. ~2t) The increase in
stability with decrease in the radius of the hydrated cation is known also for some
other ligands, e.g., C1Oa-, BrO3-, SOu2-, S~Oa2-. According to the theoretical concepts,
the increase in complex stability with increase of the radius is to be observed with
large ligands, ta2)
Let us consider briefly the relation between the stability constants of known
complexes. At the present time, three different equations, determining the connection
between stepwise instability constants, can be set forth, tin-25) The most satisfactory
coincidence of experimental and calculated data is observed when we use the equation
pK,, = pK 1 -- 22(n -- 1), suggested by VAN PANTHALEONVANECK.t~5~ In it Kn = step-
wise instability constant and 2 = constant.
Stepwise constants for fluoride complexes of zirconium and hafnium satisfy this
equation well (Fig. 3). Fig. 4 shows the change of stepwise equilibrium constants
K for the sulphate complexes of Z # +, Hf 4+ and Pu ~ . In the case of zirconium and
plutonium, K3 > ~c~. Analogous phenomena are observed for sulphates o f INS+,t~)
Cea+, ~zT~and UO2~.t~s)
The values Ka for zirconium, hafnium, thorium chlorides is also greater than
K2 (Fig. 5). It is rather difficult to analyse the relation of K~.for the oxalate complexes,
of hafnium because approximate values of stability constants were determined by
anion exchange.
Probably, the irregular change of stepwise stability constants can be explained in
the following way: in aqueous solutions cations exist in the form of aquo-complexes.
Combination of ligands during complex formation takes place, molecules of water
being substituted in aquo-complexes by ligands gradually. This can proceed in
t2x~I. A. LEBEDEV,S. V. PIROZHKOVand G. N. YAKOVLEV,J~adioehimiya 2, 549 (1960).
c22~K. B. GmNBERQand K. B. YATSIMIRSKY,Izv. AN SSR, OKhN, N 2, 211 (1952); K. B. YATSI-
MIRSKY,Zh. Olsch. Khim. 27, 1948 (1957); K. B. YATSIMIRSKYand V. P. VAS]LYEV,Instability
constants of complex compounds, AN SSSR, Moscow (1959).
t2a~A. N. BABKO,Physico-chemical analysis of complex compounds in solutions, Kiev (1955).
~24~j. BJERRUM, Metal ammine formation in aqueous solutions, Copenhagen, Haase (1957).
t25~C. L. VANPANTHALEONand VAN ECK, Rec. Tray. Chim. 72, 529 (1532).
tz6t j. BJERRUM,G. SCHWARZENBACHand L. G. SILLEN,Stability Constants, Part I, II, London,
Chem. Soc. (1958).
tz7~S. FRONAEUS,Svensk Kern, Tidskr. 64, 317 (1952); 65, (2), 19 (1953); 65 (1) 7, 21-31 (1953).
t2,~S. AI-IRLAND,Acta Chem. Scand. 5, 1151 (1951).
976 D.I. RYABCH1KOV,I. N. MAROV,A. N. ERMAKOVand V. K. FIELYAEVA

I0

I i I
0 I 2 3
n

Fie. 3.--The change of stepwise instability constants on the number of

added ligands for fluoride complexes of thorium and zirconium.

Zt

c Hf/

I I I
0 I 2 3

FIG. 4.--The change of equilibrium constants (for Hf ~+, Pu t+) for stepwise stability
constants depending on the number of added ligands for sulphate complexes of some
metals.
@ - - H f ++, G - - Z # +, © - - P u 4+, [~--Ce 3÷, I~--In 8+, x - - U O ~ ~+.
 Stability of some inorganic and organic complex compounds of zirconium and hafnium 977

different ways. In so doing some kinds of substitution can turn out to be "unprofi-
table", which effects the value of the stability constant. ~
As is known, in relation to oxygen, zirconium and hafnium have the co-ordination
number eight. It may be assumed that aquo-complexes contain eight water mole-
cules, Me(H20)a4+. Nitrate and chloride ions, occupying one co-ordination site form
with Zr ~- and Hf ~- complexes of the type MeLj(H20)~_-i (provided there is a definite
co-ordination number). Sulphate ion may occupy one (combining at a tetrahedron
comer) or two (combining along an edge) co-ordination sites, ta°~ At the present

-go I I I

FIG. 5.--The change of instability constants with the number of added

ligands for chloride complexes of thorium, zirconium and hafnium.
I~]--zirconium, hafnium,/a = 2.0 mole/l.
E]--torium,/~ = 2.0 (299).

time it is difficult to answer the question of how many co-ordination sites are occupied
in zirconium and hafnium complex compounds by the SO~~ group. As was pointed
out above, X-ray investigation of the crystal structure of Zr(SO4)2"4H20 showed
that the SO4~ group occupies one co-ordination site (Fig. 6). BLUEMENTAL(31) also
thinks that the group SO4~ in this compound and in the compound (NH4)4Zr(SO4)4.
4H20 occupies one co-ordination site. B~LAR ~z2~writes that the cases where the group
SO42- occupies two co-ordination sites are almost unknown.
Oxalate ion may occupy two co-ordination sites, forming a five-membered ring.
In this case, for Me~-, the composition of the co-ordinatively saturated complex must
be Me(C204)4~-; this is exactly what is encountered in reality. Under certain con-
ditions, Zr 4+, Hf 4+ and Pu4+, form a complex of the Me(C,O4)5 e- type. GEL'MANand
SOKHINA~a3~isolated and investigated complexes of the composition Mea(Pu(C20,)5).
nH20, where Me = NH4+, K +, which dissociate in aqueous solutions into seven ions.
~*~ K. 1R. YATSIMIRSKY,Zh. Neorg. Khim. 2, 491 (1957).
,ao~A. VER~R, New Views in the Field of Inorganic Chemistry, ONTI, Leningrad, 1936.
tsl~ W. B. BLt/F.~NTAL, The Chemical Behaviour of Zirconium, Toronto--N.Y.--London (1958).
~a2~j. ~ L A R (Editor), Chemistry of Co-Ordination Compounds, I.L., Foreign Language Publ.
House, Moscow (1960).
tas~ A . D . GEL'MAN, A . P. SOKHINA, Zh. Neorg. Khim. 3, 1100 (1958).
978 D.I. RYABCmKOV,I. N. MAROV,A, N. ERMAKOVand V. K. B~LYAEVA

The compound 3Na2C204.Zr(C~O4)a.H2C204.5HzOta~ is known for zirconium.

Formation of compounds where Zr:C204 = 1:2; 1: 4; 1: 6; 61 : 6; 1: 8, (28) was
determined by means of potentiometric titration of zirconium nitrate solutions with
potassium oxalate solution. To explain these results one can postulate two explana-
tions:
1. The co-ordination number of the central ion may change. Thus, for example,
according to this statement it should be assumed, that the co-ordination number
of Me ~- in the complex Me(C~O4)44- --, is eight, and in Me(C204)~~- --, etc.
2. The co-ordination number of the central ion remains permanent by the same
although the co-ordination capacity of the group C2042+ changes. In the com-
pound Me(C204)~~-, each of C20~2- groups occupy two co-ordination sites,
forming a stable five-membered ring. However, when there is a great excess of
C20~2- ion, and under certain conditions, a part of the rings may break. In
this case the co-ordination number of the central ion is increased up to eight
by entry into the inner sphere of the complex of an additional C~O~2- group.
In accordance with this view, in complexes Me(C20~)5e- and Me(C20¢)6 s-
there must be irregularly connected C20~~- groups: one part of the C~O~2-

0
group connected in a ring, and the other not.

"-22

5 1/434
.29 oi 12

3/4, ,/4~

b
I •

V'~04 l ~ x ~ ) X~
~ 3414

~ "~" -.21 ~
FIG. &--Projection of the compound structure.
Small circles-sulphur atoms
Middle circles--zirconium atoms
Large circles--oxygen atoms.

In our view, the first explanation can not be regarded as satisfactory, because
abnormally high co-ordination numbers must be attributed to the central ion.
Apparently, the second explanation, according to which the C20~~ group may occupy
one or two co-ordination sites, is correct. Pentacido-complexes are known not only
cs4~GMELINS,Handbuch der Anorgan Chem. 8, Aufl., N, 42 343 (1958).
 Stability of some inorganic and organic complex compounds of zirconium and hafnium 979

for the oxalate-ion, but for carbonate and sulphate ions as well. Such compounds
form with Th4+, Ce4+, Pu~ and U4+.{~'~'3~} However, for the time being, they are
not known as far as zirconium and hafnium are concerned.
Let us consider the question of the structure of complexes of ZP + and Hf ~- with
oxyacids. Acetic,(as) malonic, succinic (0.2 M) and glutaric (0.1 M) acids do not
form complexes with Zr 4+ and Hf ~ in strongly acidic media. However, their deriv-
atives, lactic, mesoxalic, malic, tartaric, trioxyglutaric do form strong complexes
even at [H+] = 2"0 mole/1. Introduction of an OH group into the acid structure leads
to strengthening of the acidic properties of the organic agent, which in a certain way
is conductive to complexing reactions. However, in our opinion a more substantional
factor is the possibility of ring formation of a five-membered ring when complexing
with g-oxyacids. MANDL {39) surmized, that in the citrate and tartrate complexes of
zirconium, which he obtained by dissolving zirconium carbonate in the acid salt
of corresponding oxy-acid, that the hydrogen of the OH group was replaced by the
metal. Thus, MANDL attributes the structure
0 KO 0

C--OK C
L
H--C--O O--C--H
\ /
Zr
/ \
H--C--O O--C--H
L 1
C C
S /%
O ~ONa NaO O

to the tartrate complex IC2Naz (Zr(C4H2Oe)~).

Of course, by this method of preparing compounds of zirconium with oxyacids,
it is quite possible to substitute the hydrogen of the OH group. We shall point out,
in addition, that in work (4°) on the complexing of Fe 3+ with citric acid, dissociation
of hydrogen from OH group at pH 3, i.e. in acidic medium, was observed. It is
rather difficult for such substitution to take place in a strongly acidic medium
([n +] = 1-2 mole/L].
One can assume, that formation of complexes with 0~-oxy-acids in solution of
high acidity is accompanied by closing the five-membered ring without removal of
OH group hydrogen;
O
%
C- C-
] I
O OH
\ .."

~\Me"

(35) I. I. TCHERNYAEV,V. A. GOLOV~A and A. K. MOLODKIN,Zh. Neorg. Khim. 3, edition 12 (1958).

(-) V. A. GOLOV~A, L. A. POSPELOVAand R. T. BOLOTOVA,Zh. Neorg. Khim. 5, 2204 (1960).
(8~) A. D. GEL'MAN,A. I. MOSKVIN, L. M. ZAITSEVand M. P. MEFOD'EVA,Complex Compounds of
Teansuranium Elements, AS USSR (1961).
(s6) A. M. TgOFIMOVand L. N. STEP.~qOVA,Radiokhimiya 1, 403 (1959).
(89) A. MANDL, Z. Anorg. Chem. 37, 242 (1903).
(t0) R. C. WARNERand I. WASS~R,J'. Amer. Chem. Soc. 75, 5086 (1953).
980 D . I . RYABCHIKOV, I. N. MAROV, A. N. ERMAKOVand V. K. BELYAEVA

The fact that the equilibrium constants of zirconium (hafnium) with malic,
tartaric, lactic acids differ but little, points to the presence of identical mechanism of
complex formation by zirconium (hafnium) with the above mentioned oxyacids.
The five-membered ring is formed in citric and trioxyglutaric complexes, which have
higher stability than that of the lactate and tartrate complexes. It is interesting to
note, that the smallest difference in the complex stability of zirconium and hafnium
is observed in the case of lactates, where there is a simpler complex composition, and
is increased during transition from malic to tartaric, trioxyglutaric and citric acids,
i.e. in general in so far as the composition of ~-oxyacids becomes more complicated.
This regularity holds for [H+] = 2 mole/l, and is not valid for tartaric and trioxy-
glutaric acids with smaller (1 mole/l) concentration of hydrogen ions. It is not easy
to explain the cause of the differences in the stability of zirconium complexes with
~-oxyacids. One can assume that a certain role in these differences belongs, apparently,
to a steric factor. The possibility of strong deformation of the oxyacid under the
action of Z # + and Hf a+ ions field of force is not excluded.
It is worth while noting, that at the present time a considerable amount of infor-
mation on the composition and stability constants of complexes of bi- and tri-valent
elements with oxyacids has been gathered. However information about the structure
of these compounds is not available.
The questions of the structure of Zr t+ and Hf 4+ complexes with oxyacids need a
special investigation.