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Abstract
The theory of pH-stat chelatometric titrations recently developed [Anal. Chim. Acta 456 (2002) 313] is experimentally
substantiated here. The titrations of four representative doubly charged cations having different behaviour (copper, zinc,
calcium, magnesium) are taken as examples. Copper is titratable between pH 3 and 5, zinc between 3 and 6, calcium
between 6 and 10, and magnesium between 7 and 10. The shapes of the titration plots agree well with the theory, accounting
for simultaneous equilibria involving proton exchange. The technique yields accurate and precise results, which compare
favourably with those of other instrumental techniques, in particular photometric titrations.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Titrimetric analysis; Chelatometric titrations; pH-stat titrations; Calcium(II); Copper(II); Magnesium(II); Zinc(II)
0003-2670/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 3 - 2 6 7 0 ( 0 2 ) 0 0 6 9 1 - 8
278 C. Macca et al. / Analytica Chimica Acta 470 (2002) 277288
skim milk) has so far been described [10]. In the third electrode with encapsulated Ag/AgCl reference elec-
paper of this series [11], the fundamentals of pH-stat trode in 3 M KCl and sleeve junction (Ingold, Urdorf,
chelatometric titrations have been developed, and the Switzerland, type 405.60.88.E) was measured with a
criteria for optimising the experimental conditions resolution of 0.1 mV or 0.01 pH. The Stat program
have been discussed. Accordingly, such titrations are allowed choosing either mV or pH as the controlled
expected to attain good accuracy and high precision. operational parameter.
The purpose of the present work is to substanti- The measured solution was contained in a 20
ate those favourable anticipations by implementing 90 cm3 jacketed cell Metrohm (Herisau, Switzerland)
experimental procedures for some representative type 6.1418.220 and stirred with a PTFE-coated mag-
determinations. netic bar. It was thermostated at 25.0 0.1 C and
fluxed with carbon dioxide-free nitrogen.
titration cell was filled with 20 cm3 of 0.1 M sodium erated either in the absorbance or transmittance mode.
perchlorate solution containing a suitable buffer at Very small (10 l) additions were made, and a strict
low concentration (generally (12) 103 M) and a stability criterion (signal drifting less than 1 mV in
volume of standard solution of the metal cation con- 10 s) was chosen, in order to reach the best precision
taining approximately 50 mol of cation was added. and accuracy even when the signal change at the end
A preliminary adjustment of the solution pH to a value point was abrupt or the complexation reaction was
slightly more acidic than the operating value was slow.
made either by addition of some drops of diluted acid
or (if the standard solution of cation was too acidic)
by a preliminary end-point titration with strong base. 3. Results and discussion
The exact operating pH value was reached by tem-
porarily activating the Stat function. Finally, the Stat 3.1. The pH-stat titration plot and the choice of
operation and the record of the titration plot were operating pH
simultaneously started and, after a known time delay
(30 or 60 s which allowed to control the stability of In pH-stat chelatometric titrations of metal cations,
pH), the primary titrant addition was begun. Constant the addition of primary titrant (EDTA or another suit-
volume (2448 l) stepwise additions at fixed time able chelating agent) is accompanied by the addition
intervals (30 s2 min), or continuous additions (min- of the auxiliary titrant (a strong base solution) at a rate
imum rate 0.05 cm3 min1 ) were carried on until the suitable to maintain the pH constant at a pre-selected
added primary titrant was 1.52 times the equiva- value by neutralising the acidity delivered by EDTA.
lence volume (usually corresponding to 0.5 cm3 ). The The titration plot shows the added volume of strong
numerical titration report (displaying time, measured base, VOH , against the volume of EDTA, VY . When
pH or mV, auxiliary titrant volume, single volume the chelation of the titrand cation is complete, the
increments, temperature) was printed during opera- delivery of acidity by EDTA does stop or change
tion at 10 s intervals. The graphical report (auxiliary rate, depending on the operating pH. Therefore, in
titrant volume versus time) was printed after ending the correspondence of the equivalence point the titra-
the titration. The true titration plot was recalculated tion plots slope also changes. If the conditions are
by using as the abscissa the primary titrant volume VY suitable, it is expected that the change of slope is easily
and as the ordinate the volume of auxiliary titrant VOH appreciable.
required to reach stationary conditions (pH constant The dependence of the titration plots shape on the
in time at the operating value within the resolution of nature of the reactants and on pH has been discussed
the pH-stat system, i.e. 0.01 units). in detail [11]. Two main aspects of the titration plot
The equivalence volume of the primary titrant, Ve , do condition the feasibility of a titration: the extent of
was determined by least-square analysis as the ab- slope change and its sharpness. The extent of slope
scissa of the intersection between two straight-line change depends on the difference between the net
segments. Data was treated with SigmaPlot scien- number of protons delivered by EDTA before and af-
tific graphing software (Jandel Scientific, Erkrath, ter the equivalence point. Its sharpness, in turn, de-
Germany). pends on the quantitativity of the chelation reaction.
Both are strongly influenced by pH [11].
2.3.2. Photometric titrations According to the primary reaction:
Photometric titrations were performed on a mea- Mm+ + H2 Y2 MYm4 + 2H+ (1)
sured volume of standard solution of the analyte cation
diluted with 25 ml of buffer at the required pH and con- the slope of the titration plot before the equivalence
taining a suitable indicator. The programmable titrator point ideally corresponds to 2 mol of strong base per
was operated in the inflection point titration mode mole of EDTA. However, competing reactions in-
with constant volume additions. This mode allowed volving proton exchange, whose extent depends on
printing and plotting the complete titration record. The pH, can decrease this ratio [11]. The slope after the
input signal was taken from the photometric probe, op- equivalence point, ideally null after the completion of
280 C. Macca et al. / Analytica Chimica Acta 470 (2002) 277288
reaction (1), is dictated by the degree of protonation ing value caused by unbalanced titrants ratio. In the
of the unreacted ligand at the operating pH. At pH absence of any buffer, EDTA addition, particularly
increasing over about 5, the prevailing form is HY3 ; when discontinuous, could cause sudden and large pH
at still higher pH it is Y4 . Therefore, a finite and changes, hindering the pH-static control. A too high
increasing amount of base is consumed to deproto- buffering power would instead cover the titrants ac-
nate the excess titrant, H2 Y2 ; the relative amount tion. Both effects cause large random errors [8]. With
gradually approaches the maximum value of 2 mol of synthetic samples, optimum conditions are realised by
auxiliary titrant per mole of primary titrant in excess. adding a suitable buffer pair.
In consequence, the change of slope at the equivalence The approach to the choice of the instrumental pa-
point vanishes at a pH is larger than about 11.5 [11]. rameters is similar to the one discussed in detail for
In turn, the quantitativity of the chelation reaction acidbase pH-stat titrations [8]; in the present instance,
depends on the conditional stability constant of the however, it is much more dependent on the nature of
chelate complex KMY in the reaction medium. This the chemical system involved. Indeed, an important
quantity is heavily conditioned by the dependence of peculiarity of chelation reactions is that they are more
the degree of protonation of EDTA anion on pH [16]. or less appreciably slow, at variance with neutralisa-
Competing ligands decreasing the free-cation fraction tion, which is generally fast.
of the unreacted metal may also have an appreciable When the reaction is fast, the practical rate-
effect. The overall trend is towards a decrease of KMY determining stage can be, alternatively, the mixing of
on decreasing pH. As the reaction becomes less and reactants, the electrode response, or the ability of the
less quantitative, the slope change occurs in a larger pH-stat device to keep pace with the acidity change.
and larger interval around the equivalence point, thus This last is mostly conditioned by the instrumental
impairing the sharpness of the equivalence point. parameters set. By acidbase titrations, it was quite
For every analyte cation, a compromise value of pH generally possible to operate with continuous, al-
for the two contrasting effects must be found. This op- though moderately slow, addition of titrand (which in
timum value can be accurately forecast if the stability acidbase titrations operationally takes the place of
constant of the chelate complex and the equilibrium the primary titrant). In contrast, preliminary experi-
constants of the competing reactions are known with ments did show that complexometric reactions with
sufficient accuracy [11]. continuous additions, although yielding apparently
It must be noted that pH does not need to be known satisfactory linear segmented plots, were frequently
with the greatest accuracy, as long as it lies in the affected by appreciable systematic errors. These were
wanted range and is kept rigorously constant during removed by operating with constant additions at
each single titration. For quantitative determinations, fixed time intervals. With this procedure, the plot of
calibration of the measuring cell with usual pH stan- auxiliary titrant volume against time together with
dards is quite acceptable. the numerical record of both quantities and pH (see
Section 2.3) allowed to verify point by point the time
3.2. Choice of the instrumental and other necessary to reach equilibrium conditions (Fig. 1).
experimental parameters The size of the added aliquots (1/20 to 1/10 of the
equivalence volume), and thus their number, was cho-
The experimental parameters to be set at the be- sen to satisfy the somewhat contrasting requirement
ginning of each titration are either of chemical or of efficient pH-stat control, good least-squares evalu-
of instrumental nature. The chemical parameters are ation of data and reasonable total titration time. The
operating pH and buffer power of the supporting time between two subsequent additions, set after the
solution. The instrumental ones are addition rate, results of a preliminary titration, was just long enough
equilibration time and control band [8]. to allow the reaction to reach equilibrium after each
The choice of pH is dictated by the criteria dis- addition (Fig. 1).
cussed in Section 3.1. The buffering power of the mea- The size of additions also has a role in dictating the
sured solution regulates the sensitivity of the pH-static instrumental parameters specific of the pH-stat oper-
response, i.e. the deviation of pH from the operat- ational mode, i.e. equilibration time and control band
C. Macca et al. / Analytica Chimica Acta 470 (2002) 277288 281
experiments described here was seen to increase only plexes involved (cation-EDTA and cation-indicator).
negligibly its contamination as an effect of the nec- In practice, the location of the equivalence point may
essary manipulations. In preliminary experiments, become rather subjective, although less than in visual
solutions at the usual level of carbonate contami- titrations. With computerised photometric titrators,
nation (about 2%) were used without appreciable the accuracy depends on the algorithm chosen.
inconvenience. An alternative automatable technique, the poten-
tiometric titration, is convenient only if an electrode
3.4. Selected titration systems selective for the analyte cation is available (proce-
dures involving the use of electrodes responding to an
When discussing the theory of pH-stat complex- auxiliary cation, e.g. mercury(II), are not of current
ometric titrations [11], summarised in Section 3.1, use in the analytical laboratory). Even in this instance,
we took those of copper(II) and magnesium(II) with it can suffer some limitation due to the relatively high
EDTA as examples representative of the main features lower response limit of the sensor.
of the technique. Owing to their diverse properties, All titrations were performed using primary stan-
these systems are also very suitable for introducing dard solutions of cations. In order to favour a direct
the experimental application of the pH-stat technique, comparison among all series of titrations, the results
while confirming the theoretical deductions. In addi- were expressed by calculating the titre CY of the
tion, we report here the results of investigations on two EDTA solution (Table 1).
other cations of great analytical relevance, calcium(II)
and zinc(II). 3.5. Copper
For comparison with other well-established tech-
niques, we have considered only volumetric methods The chelatometric titration of copper(II) can be
based on chelatometric reactions. Indeed, the most performed either in acidic solution at pH not exceed-
common instrumental determination technique of ing 5, above which precipitation occurs, or at pH
metals in solution, atomic absorption spectrometry, near to 8 [12,13]. We have tested the determination
measures concentration in a much lower range and of Cu(II) in the acid pH range from pH 5 to 3, where
with limited precision, with the inconvenience of re- the chelate is still strong enough (log KCuY 8.3)
quiring a specific lamp for every element. Direct po- [16] to form quantitatively even in the proximity of
tentiometry also requires a specific electrode for each the equivalence point and assign the titration a good
determinand cation and has only moderate precision. intrinsic [17] precision.
When higher precision determinations are required, Typical pH-stat titrations plots of 2.4103 M cop-
the choice is usually chelatometric titration (even in per(II) (48.64 mol in approximately 20 cm3 of sup-
preference to gravimetry, which is too time consum- porting solution) at various pH values are represented
ing). Visual titrations are performed after adding a in Fig. 2A. The buffers were, respectively, 2 103 M
suitable indicator. The procedures can be automated chloroacetate at pH 3 and 2 103 M acetate at pH 4
and their precision improved by using photometric and 5.
titrators. Therefore, in order to state whether the new It is known that the chelation of Cu(II) is moder-
technique offers any advantage in an automated ana- ately slow. The speed increases with increasing pH. At
lytical laboratory, we have compared pH-stat titrations pH 3, reaching stationary conditions required at least
of each investigated metal cation with corresponding 45 s as shown in Fig. 1; with increasing pH, 3015 s
indicated photometric titrations. However, it must be became sufficient. With additions of primary titrant
stressed that a photometric titration can hardly be aliquots corresponding to approximately 1/10 of the
considered an accurate reference method. Indeed, the equivalence volume (48 l), titrations lasted not more
shape of the titration curve (let it be absorbance A, than 1215 min and yielded satisfactory results. Some
or transmittance T, against titrant volume V), and by experiments performed by halving the aliquot volume
consequence the procedure for locating the equiva- (24 l) yielded identical results, with an only moderate
lence volume, are strongly dependent on the values improvement in the statistical evaluation of the linear
of the conditional stability constants of the com- parameters and the drawback of longer duration.
C. Macca et al. / Analytica Chimica Acta 470 (2002) 277288 283
284 C. Macca et al. / Analytica Chimica Acta 470 (2002) 277288
3.6. Zinc
In comparison, photometric titrations can reach com- preparation of the computer program for timed discrete
parable precision only at the cost of longer duration; additions is gratefully acknowledged.
indeed, in our experiments, they required smaller ad-
ditions in the proximity of the equivalence both when
the end point was interpolated (with sigmoidal titra- References
tion plots) or extrapolated (to identify a discontinuity).
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