Composition and Stability of Iron and Copper Citrate Complexes

in Aqueous Solution
TERRENCE
B. FIELD,
JANETL. MCCOURT,AND W. A. E. MCBRYDE

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Departnzent of Chetnistty, Utzir,ersit) of Wuterloo, Wuterloo, Ontario N2L 3GI

Received March 7, 1974

JANETL. MCCOURT,and W. A. E. MCBRYDE.

Can. J. Chem. 52,3119
TERRENCE
B. FIELD,
(1974).
The acidity constants of citric acid and the stability constants of the citrate complexes of
copper(lI), iron(II), and iron(I1I) have been measured at 25 "C in 0.1 M KNO, background.
The measurements were based o n mass balances o n hydrogen ions, supplemented in the case
of Cu(I1) and Fe(lI1) complexes by measurements of free metal concentration with a solid-state
copper-ion-sensitive electrode and a redox electrode respectively. The data required the
assumption of a binuclear copper complex, but all complexes characterized were of 1 : 1
stoichiometry.
TERRENCE
B. FIELD,JANETL. MCCOURTet W. A. E. MCBRYDE.Can. J. Chem. 52,3119
(1974).
On a mesure, a 25 'C et en presence de KNO, 0.1 M, les constantes d'acidite de I'acide
citrique et les constantes de stabilite des complexes de citrate avec le cuivre(II), le fer(I1) et le
fer(II1). Ces mcsurcs sont basees sur les balances dcs masses des ions hydrogene auxquels
s'ajoute dans le cas des complexes du cuivre(I1) et du fer(I1I) des mesures de concentration
d'ions metalliques libres en utilisant respectivement une electrode sensible aux ions cuivre et
une electrode redox. Les donnees recueillies necessitent que l'on fasse l'hypothese que les complexes de cuivre sont binucleaires mais que tous les complexes sont caracterises par une stoi[Traduit par le journal]
chiometrie 1 : 1.
or potassium hydroxide solutions were stored and used
Hn&oduction
under nitrogen to limit contamination by carbon dioxide.
Citrates have been traditionally used as mask- Volumetric
glassware for preparation, dilution, or transing agents for various metal ions and as eluting fer of solutions was Class A grade. Small amounts of
agents in ion exchange chromatography. Re- acid or alkaline solutions were delivered from an Agla
centlv citrate has been considered as a i-~~ssible syringe equipped with micrometer drive, the delivery of
by direct weighing.
subsljtute for polyphosphates added to s h d de- which was
The cell used for tltratlons, measurements of pH, etc ,
appllcations are based On 'Ormatergents.
consisted of a jacketed upper and lower colupartment
tion of stable complexes with metal ions, but through
- which water thermostatted at 25 o -+ o 1 c was
examination of the literature discloses some un- circulated (2). Measurements of DN or cell e.1n.f. were
certainty regarding the composition and stability made with an Orion Model 801 meter. All p H readings
were converted to hydrogen ion concentrations by the use
of some of these, especially those of copper(I1) of
a n empirical factor measured in the appropriate salt
and iron(1lH). This investigation was undertaken background (3, 4). A solid-statc copper(1l) ion sensitive
to try to clarify this situation for the last-named electrode (Orion 794-29) was used in conjunction with a
complexes. Two facilities, novel for the study of reference eiectrode (Orion $90-01-00) for measurements
citrate complexes, were appiied: first, a solid- of copper(I1) ion concentration. This electrode was calibrated for this purpose with solutions of known concenstate electrode was able to furnish data on the trations of copper(I1). A platinum electrode, used to
concentration of copper ion in equilibrium with measure redox potential, was similarly calibrated with
complexes; second, the experimental data were solutions containing known concentrations of iron(l1)
interpreted by the computer program COGS and iron(II1) in the background electrolyte used.
Spectrophotometric measurements were made on a
(I), which is of particular value when, as in this Carji
Model 14 spectrophotometer with carefully matched
case, protonated, deprotonated, or polynuclear 1 cm cells. In view of the known sensitivity of iron citrate
species are involved.
solutions toward light (5), these were prepared and titra-

Experimental
All solutions were prepared from reagent grade chemicals and standardized by conventional methods. Sodium

ted in wrapped glass vessels. Also, in view of the marked

sensitivity of the copper ion electrode to illumination, all
measurements with it were made in a shrouded titration
vessel.

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3120

C A N . J . C H E M . V O L . 5 2 . 1974

Treatment of Data
Acidity constants were calculated as protonation constants, Pi0, and used as concentration
quotients applicable to the particular medium in
which measurements were consistently made,
namely 0.1 M potassium nitrate solution. It is
worth calling attention to the fact that conventional thermodynamic acidity constants, particularly for citric acid, differ from these conditional
constants owing to the appreciable effect of multiple ionic charges on the activity coefficients.
The data from p H titrations (except those
which included simultaneous measurement of
copper-ion concentration in some cases) were
submitted to processing by the powerful computer program SCOGS (I), which finds best fit
values of acidity constants or metal-complex
stability constants. In using this, one postulates
a set of plausible species to describe the composition of the solution throughout the range of the
p H titration; tentative stability constants are
assigned to these, and the computer adjusts these
until a minimum is found in the standard deviation of titre (s.d.t.). The most probable of several
alternative sets of postulated constituents is that
yielding the smallest s.d.t., though it is wise to
recognize that this criterion cannot be regarded
as proof for the preferred selection of species.
The program will also reject a particular constituent by failing to give convergence in the refinement of a constant for it, so that the inappropriateness of certain species or groups of species
is thus signalled.

to apply to citric acid and to sulfosalicylic acid.

C,

121

[A]F1

+ [MA]

In the absence of citrate

This contains the quantity K,, the first-stage hydrolysis constant of iron(I11); at the p H and prevailing concentrations in these experiments this
adequately compensates for hydrolysis; the value
of K, used (6) was 2.5 x
It had been established from p H and potentiometric titrations subsequently to be described
that the citrate complexes apparently present
were MHL, ML, and MOHL. Therefore with
citrate and sulfosalicylate present together
[41 CM= [MI(]

+ KhI[HI) +

[MA1

+ [MHL] + [ML] + [MOHL]

[5] C,

[L]FO

+ [MHL] + [ML] + [MOHL]

The concentrations of the citrate complexes may

be expressed in terms of their stability constants
designated P,, for M,H,L,.
[6] [MHL]

+ [ML] + [MOHL]

= X

= [MI[HI[Ll (PI,,

+ Bioi[HI-'
+ P1.11[Hl-2>

There is a reliable method for evaluating E,,

the molar absorptivity for MA ( 7 ) , so from the
measured absorbance [MA] can be determined.
There is sufficient information in eqs. 2 and 3 to
enable PI for MA to be evaluated under these
experimental conditions. With this information
x, the concentration of iron(1II) in citrate complexes could be found in any solution by means
of eq. 4, and hence [L] from eq. 5. It is seen from
eq. 6 that x is pH-dependent. However, if values
of x/[M][H][L] were plotted against l/[H], all
data fell on a smooth curve (Fig. I). Either by
standard curve-fitting routines or by solutions of
equations in X, values of the required B's could
be obtained.

Spectrophoton~etricCompetitive Method
Within the p H range 1.5 to 2.5 iron(II1) will
react with sulfosalicylic acid (H2A) or with citric
acid (H,L), or will undergo some hydrolysis. The
sulfosalicylate complex under these conditions is
MA and has an intense purple color. In the
presence of citric and sulfosalicylic acids together the intensity of this purple color is diminished. Apart from a uniform reduction in absorbance the visible spectral characteristics of
these solutions are in no way altered from those
of MA, and so it may be assumed that no mixed
complex has been formed by the two ligands
Results
together.
The mass balances and other relationships apMost investigations published in the past
plying in these solutions are given by the follow- twenty years have shown 1 : 1 stoichiometry in
ing equations.
the reactions of copper(11) and iron(II1) with
citric acid, and this has been confirmed by the
results in this study. Also in agreement with
The symbols Po and F' will be used respectively several previous studies, it was observed that up

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FIELD E T AL.: ON IRON AND COPPER CITRATE COMPLEXES

3121

vided the pjO are known; but if q # 0, this relationship is alone insufficient to define [L] and
must be combined with other conservation
equations to secure information on [MI and [L].
The solution of the necessary equations containing experimental quantities is less precise and
can also lead to a number of possible sets of p,
q, and r values (i.e., alternative sets of possible
complex species) which satisfy the data roughly
as well. It is undoubtedly for this reason that
somewhat different assignments of compositions
and stabilities have been made in the case of the
metal citrates by various investigators.
Acidity Constants
From p H titrations at 25 "C in a background
solution of 0.1 M potassium nitrate the following
conditional proton-association constants were
obtained: log PI0 = 5.70 & 0.02; log P,O =
10.06 & 0.02; log p , O = 12.87 & 0.08.
Copper Complexes
When p H titrations were carried out with
FIG.1. Variation of x;[M] [HI [L] with l/[H] for iron- copper(11j present at various ligand: metal ratios,
(111) citratc complexes; x is the total concentration of
the results could be fitted reasonably well by the
iron(1II) present as citrate complexes.
assumption that the complex species present
t o four protons were displaced through complex were MHL, ML, and MOHL. A second set of
formation per metal ion or per molecule of citric titrations was then performed in which pointacid reacting. It is not yet proven whether the by-point the copper ion concentration was
fourth proton is displaced from the carbinol measured as well as the pH. The p H titration
group of the citric acid or from the remainillg data were analyzed by SCOGS according to the
coordinated water ~noleculesassociated with the above choice of constituents, with print-out of
central metal ion. It is also clear that the proton the theoretically related concentrations of free
balance observed in formation of these com- metal ion. The latter were then compared with
plexes indicates the presence of two or more the measured copper ion concentrations. The
species differing in degree of protonation. Thus comparison revealed a significant discrepancy
if citric acid is represented as H,L, mono- between these values in the range of occurrence
nuclear metal complexes may form from among of the species ML, the difference increasing and
the series MH2L, MHL, ML, and MOHL.
decreasing in much the same way as the conIt is advisable to point out that systems of this centration of this species. A marked improvesort stretch the capabilities of the Calvin-Bjerment in fit to the data was obtained by assuming
rum pH-titration method of establishing the that the species present were MHL, M2L,, and
formation of metal complexes because the pro- MOHL, and allowing the computer to seek the
ton balance, which is normally the basis of cal- best values for the corresponding formation conculating the concentration of free ligand, must stants. There were thus two criteria for best fit of
additionally define the extent of protonation of the data to assumed species and derived equilibthe series of metal complexes. This is demon- rium constants: the standard deviation in titre
strated by the relationship
(volume of base), and minimum deviation between calculated and observed metal ion conC
H
[HI
[OH]
=
[7]
centration. For these two criteria together the
~qP,,,[MIPIHlq[Llr+ ~jPj"[HIj[Ll above choice of species gave the optimum fit to
in which CH is the total net concentration of the data.
A number of other combinations of species
ionizable hydrogen at any point. If q = 0
throughout, [L] is immediately available pro- were tried out, particularly those suggested by

C A N . J . C H E M . V O L . 5 2 , 1974

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FIELD ET AL.: ON IRON AND COPPER CITRATE COMPLEXES

the work of other investigators (see Table 2), but

in all cases these either yielded stability constants that failed to give convergence in the computer treatment, or they did not give as good
agreement with observations on the basis of the
two criteria mentioned. For instance, the species M2(OH),L, has been identified in similar
solutions by other workers, but assumption of
its presence made worse the fit to the observed
concentrations of metal ions.
Calculation of stability constants from our
data could be done in either of the two ways: (i)
the values and their standard deviations determined by the SCOGS program; (ii) values obtained by the solution of simultaneous linear
equations. Conservation equations such as 171, or
others based on C,-[MI, can be set up with
simultaneous values of [MI, [HI, and [L], and
solved for the appropriate values of P,,,. For this
particular choice of constituents only
An IBM computer subroutine CLLSQ conveniently handles the solution of the equations,
yielding values of the P,, and standard deviation
of these. The results of five titrations of this sort
gave the values shown in Table 1. The lack of
agreement between two estimates of PMZk2based
on the same data illustrates the difficulty In fixing
values of equilibrium constants unambiguously,
especially for polynuclear species.
Iron Cotn~lexes
The direct determination of formation constants for the iron(II1) citrate complexes proved
to be unsatisfactory. The complexes are so stable
that at all hydrogen ion concentrations which
can be measured precisely with a p H meter [MI
or [L], according to which reactant is not in
excess, cannot be fixed precisely by the experimental data (8). The difficulty can be overcome
in the presence of excess ligand if an independent
probe is available to measure [MI. For this
purpose the authors employed Fe3+/Fe2+redox
electrode in the presence of a fixed concentration
of iron(I1).
It was first necessary to determine the formation constants of the iron(I1) citrate complexes.
This was done by a direct p H titration carried
out in triplicate at each of nine different metal
and ligand concentrations. The results obtained
are included in Table 1. Their magnitude is such
that under the conditions of low p H applying to
the study of the iron(II1) complexes very little

3123

formation of iron(I1) complexes occurs. The

actual extent of such complex formation can,
however, be calculated.
Iron(II1) complexes were studied by titrations
with p H and redox electrodes enabling the determination of [HI and [MI, point by point. Corresponding values of [L] could be deduced as before, though allowance had to be made for hydrolysis of free iron(II1) as mentioned previously.
The experimental results were processed by solution of linear conservation equations based on
C,-[MI, as in the second method for copper(l1)
complexes mentioned previously. The values of
stability constants obtained in this way are given
in Table 1. In order to have a cross check on the
foregoing work, the spectrophotometric competitive procedure described earlier was applied.
These results are also included in Table I .

Discussion
A comparison of the results in Table 1 for
copper(I1) citrates with a selection of other published results shown in Table 2 reveals that the
values for MHL and MOHL are in reasonable
agreement with those obtained by other workers
who have postulated these species. The variety
of different assumptions apparent in Table 2
concerning which complexes are or are not
present illustrates the difficulty mentioned previously concerning interpretation of p H measurements. For instance, our data when fitted to
the complexes MHL, ML, and MOHL gave log
Pill = 9.1, log PI,, = 5.8, and log PI-,, =
1.6. But, taking into account the measured
values of [MI, we were led to replace ML by the
dimer and to assign the relatively high value of
log P,,, shown in Table I . This value is appreciably larger than those for the same species
proposed by Lefebvre (9) and by Rajan and
Martell (10).
The formation of a dimeric complex of copper(1I) is consistent with the e.s.r. spectra and
magnetic susceptibility measurements of Dunhill
et al. (20). These authors have deduced that in
solutions at low and high p H copper citrate
exists as a chelate monomer, whilst over an intermediate range of p H a dimeric species is
formed. This is qualitatively in agreement with
our findings, though these authors worked with
ranges of concentration very different from ours,
and did not evaluate any equilibrium constants;
they regarded their dimeric species as deprotonated, e.g., M,(OH),L2. This matter clearly requires further study.

C A N . J . C H E M . V O L . 5 2 , 1974

3124

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09

FIG. 2. Distribution of copper(I1) among citrate complexes according to stability constants reported in this
M.
M, CH3, = 2.0 x
paper. C,, = 1.0 x

FIG. 3. Distribution of iron(II1) among citrate complexes according to stability constants reported in this
paper. CE, = 1.0 x
M , CHBL
= 2.0 x
M.

The data for iron(II1) citrate complexes in

Table 1 are in fair agreement with those of other
workers for ML (see Table 2). The formation
along with this of a protonated species of pK
1.2 is revealed by the experiments conducted at
fairly low pH. Formation of the deprotonated
species MOHL has been reported previously;
nothing in our observations, which included
measurements of [MI, suggested formation of a
dimer as reported by Timberlake (17), but this
may simply be a consequence of working in
more dilute solutions.
Species distribution diagrams for copper(I1)
and iron(II1) citrates, calculated with the constants of Table 1 , are shown in Figs. 2 and 3.

The authors are obliged to Dr. V. Cheam, Canada

Centre for Inland Waters, Burlington, Ontario, for providing facilities for and assistance with the measurements
with the copper-ion-sensitive electrode; also to W. J.
Reynolds for preliminary experiments with the spectrophotometric method described. The work was assisted by
a grant from the Inland Waters Directorate, Department
of the Environment, Government of Canada.
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