a n a l y t i c a c h i m i c a a c t a 6 2 8 ( 2 0 0 8 ) 181189

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Experimental verication of the modied Gran methods applicable to redox systems

Maja Ponikvar a , Tadeusz Michaowski b, , Krzysztof Kupiec b , Sawomir Wybraniec b , Maciej Rymanowski b
a b

Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia Department of Inorganic Chemistry and Technology, Jozef Faculty of Chemical Engineering and Technology, Cracow University of Technology, 31-155 Krakw, Poland

a r t i c l e
Article history:

i n f o

a b s t r a c t
This study describes the application of the modied Gran I and II methods for determination of equivalence volume in redox titrations and for calibration, i.e. for determination of the correct slope of the redox indicator electrodes, which appears to be a major problem in using these electrodes. The four new versions of the Gran II method, denoted as MG(II)B, MG(II)C, MG(II)D and MG(II)E methods, in which the problem of calibration and determination of equivalence volume are considered simultaneously are suggested and compared with MG(I)S and MG(II)A methods known hitherto. All the methods are experimentally tested and discussed. 2008 Elsevier B.V. All rights reserved.

Received 17 June 2008 Accepted 4 September 2008 Published on line 11 September 2008 Keywords: Potentiometry Gran methods Redox titration Redox indicator electrode Calibration

1.

Introduction

The primary (original) Gran methods of the equivalence volume (Veq ) determination, specied later as Gran I [1] and Gran II [2] methods, and denoted later as G(I) and G(II) methods (for brevity), are commonly perceived as linearization methods, where a part of sigmoidal (S-shaped) titration curve E = E(V) or pH = pH(V), is transformed into linear form, intersecting Vaxis at equivalence volume (Veq ); V is the volume of titrant added from the start for the titration, where potential E or pH are measured. The G(I) and G(II) methods are applied, among others, for alkalinity measurements [3]. However, the Gran methods do not provide accurate results for Veq , particularly in potentiometric redox titrations, as were stated both in earlier literature [46] and in the papers issued recently [79]. This opinion is particularly referred to the G(I) method, that was practically discarded, despite some trials done, among others, by the Gran itself [10]. In effect, the eponym Gran method has

been perceived later as one tantamount with the G(II) method. Nonetheless, one can still indicate some papers issued lately, e.g. [11], where G(I) method was cited. The Gran methods, in their original and modied versions, were extensively described in the previous papers [79], where the problem of accuracy of algorithms involved with these methods has been raised. The inaccuracy of G(II) method in redox systems is caused by different reasons. First, the related plots are non-linear (bended). It makes difcult to locate the equivalence point by extrapolation. For such reasons, the Gran methods were perceived as ones non-applicable to redox systems and the related papers are scarcely met in literature. Generally, this state of the matter resulted from the fact that the equilibria in redox systems were perceived only from the viewpoint of the stoichiometric redox reaction notations, see e.g. [12]. A new quality was provided by the generalized approach to electrolytic systems (GATES) devised by Michaowski, which

Corresponding author. Tel.: +48 12 628 21 77. E-mail address: michalot@o2.pl (T. Michaowski). 0003-2670/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.aca.2008.09.012

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between the variables Nomenclature D E RIE T V V Veq Veq0 titrand (solution titrated) potential redox indicator electrode titrant volume of T added into D portion of T equivalence volume obtained from calculations theoretical equivalence volume = (V, ) = V 10E/ (2)

and V, occurring at = c . For this purpose, some useful criteria of choice of the c value are suggested. We refer also to the MG(I)S method [9]; its further (simple) modication, denoted as MG(I)B method is suggested.

2.

Basic formulae

Greek letters slope of indicator electrode c and 0 correct and Nernstian values for , respectively

All the formulae presented in this paper are referred to V < Veq . In ref. [9], the general relationships: E = E0 c + c log V c log Veq 1 V Veq

(3)

has been widely applied [9,13]. The central role in the theoretical considerations on redox systems within the GATES approach is ascribed to the generalized electron balance (GEB), presented in the papers [79,12,1419] for different redox systems. Essential modication of the G(I) method [20] caused its reactivation, also for redox systems purposes. This modication, denoted in [9] as MG(I)S method, is based on the approximation [79,20] ln(1 + x) = 1 1 + x 2
1

= G2 (Veq V ) exp( V ) where =+V

(4)

(5)

were derived; and in (5) are constant values in the titration. Assuming = 0 in (4) [9], the formula valid for G(II) method is obtained and the resulting regression equation has the form j = P2 G2 Vj + j (6)

that appeared to be useful for calibration of redox indicator electrodes (RIEs) [9]. The difculties in calibration of RIEs, which is of primary importance in potentiometric measurements performed in redox systems, were probably the main reason for generating the opinion on inapplicability of the Gran II (G(II)) method for determination of equivalence volume (Veq ) in redox titrations [79]. This problem has been recently exposed in [9], where inaccuracy of the results obtained according to G(II) method at greater discrepancies between true (correct, c ) and preassumed () slope values, |c | for RIEs has been proved. It was also stated that the error in Veq can be substantially decreased, even at greater |c | values, if the modied Gran II method in its accurate version (MG(II)A) proposed in [9] is applied. In other words, the error in Veq obtained according to MG(II)A method is smaller than the error obtained for G(II) method at higher |c | value. Nonetheless, the problem of calibration of RIEs is still of interest from the scientic viewpoint. As stated above, the MG(I)S method [9], suggested in [20], appeared to be more appropriate for determination of c value than the original Gran I method, denoted as G(I) method. In the current paper we tried to examine appropriateness and validity of some new modications of Gran (II) method, denoted as MG(II)B, MG(II)C, MG(II)D and MG(II)E method designed for determination of c and Veq values. The basis for these methods is the linear relationship = G2 (Veq V ) (1)

where j = Vj 10Ej / . Applying the least squares method, we get Veq = P2 G2 (7)

The assumption exp( V ) =1+V is the basis for MG(II)A method, valid for ||Veq (8) in Eq. (4), we get the regression equation [9] j = B2 Vj2 B1 Vj + B0 + j (8) 1. Applying

(9)

After the least squares method is applied to Eq. (9), Veq is calculated from the formula [9] B1 (B2 1 4B0 B2 ) 2B2
1/2

Veq =

(10)

3. Novel modications of the G(II) and G(I) methods

The problem of c determination according to the modied G(II) methods, suggested in this paper (Fig. 1), is immediately related to the determination of Veq value and the two problems are considered simultaneously. If the value Ej corresponds to the total volume Vj of the titrant added from the outset of the titration, a set of experimental points {(Vi , Ei )} is obtained,

a n a l y t i c a c h i m i c a a c t a 6 2 8 ( 2 0 0 8 ) 181189

183

Fig. 1 The relationships between original (G(I), G(II)) and modied Gran methods in the light of the formulae (1) and (2), referred to V < Veq ; Approx 1: ln(1 + x) = x; Approx 2: ln(1 + x) = (1/x + 1/2)1 [9].

whose subset {(Vj , Ej )|j = 1, . . ., N} is chosen for calculation of c and Veq values.

3.1.

MG(II)B and MG(II)C methods

Another alternative, named as MG(II)C method, is the application of Lagrange polynomial interpolation method; dE/dV and d2 E/dV2 in Eq. (12) are then obtained, successively, by differentiation of the function E = E(V). Then the values: dE = dV dE dV and d2 E = dV 2 d2 E dV 2

Both methods are based on the second derivative of the function (2). For the linear relationship (1), we have d/dV = G2 = const and d2 /dV2 = 0. The rst and second derivatives are: ln 10 dE d = 10E/ 1 V dV dV d2 E dE ln 10 d2 E/ ln 10 = 10 V +2 V dV dV 2 dV 2 dE dV
2

Vj

Vj

were inserted in the formula (12) and thus the j = (Vj ) values were calculated.

3.2.

MG(II)D and MG(II)E methods

(11) respectively. Zeroing the second derivative (11) gives = ln 10 V (dE/dV ) V (d

2 2

E/dV 2 ) + 2 (dE/dV )

(12)

A change in value affects the arrangement of the points in co-ordinates (V, ). At sufciently high Ca0 values, the nearly linear arrangement occurs only at = c . Then the coefcient of linear regression, expressed by R2 value, attains maximal value, i.e. the difference 1 R2 is minimal. The minimal value for 1 R2 is the basis for searching the c value according to MG(II)D method, in the coordinates (, 1 R2 ). Analogously, in MG(II)E method, the minimal value of the sum of squares
N

The rst and second derivatives on the right side of Eq. (12) can be approximated by differential quotients = ln 10 V ( E/ V ) V 2 ) + 2 ( E/ V )
2

SS =
j=1

(P2 G2 Vj j )

(14)

V(

2 E/

(13) has been applied as the criterion of choice of the c value. The formulae related to particular methods specied in Sections 3.1 and 3.2 will be considered in experimental part of the paper.

referred to MG(II)B method. For the experimental points {(Vj , Ej )|j = 1, . . ., N 1} we have: V = Vj+1 Vj , E = Ej+1 Ej , and
2E V2

( E/ V ) V

3.3.

MG(I)B method

Both differential quotients are set at Vj = (Vj + Vj+1 )/2 [79,20]. Then the j = (Vj ) values were calculated from the formula (13).

This method is a simple modication of MG(I)S method, where Veq = Veq0 is assumed to be known on preparatory step of the

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Fig. 2 The points (Vj , 0j ) and the corresponding lines plotted on the basis of titration curves E = E(V, ) related to different values and tted to the lines obtained according to (a) classical G(II) method; (b) MG(II)A method for pre-assumed value = 0 = 59.1 mV, V = 1.00 mL.

analysis. For this purpose, the regression equation [9] Yj = G1 (Veq0 Vj ) + j where Yj = 1 Vj+1 Vj Vj Ej+1 Ej ln 10 Veq0

4.

Initial assumptions

G1 =

can be rewritten into the form Yj = G1 Zj + j (15)

The theoretical approach will be formulated on the basis of simulated titrations of V0 = 100.00 mL of the solution containing FeSO4 (C0 = 0.0100 mol L1 ) + H2 SO4 (Ca0 mol L1 ) with V mL of C = 0.0200 mol L1 KMnO4 ; Veq0 = 0.2C0 V0 /C = 10.00 mL is the reference equivalence volume value in the theoretical considerations. The assumptions concerning the experimental part and D and T composition are specied in Section 6.1. Let Veq be the equivalence volume value obtained from calculations referred to theoretical or experimental data. In both instances, the value Veq 1 Veq0

where Zj = Veq0 Vj . Applying the least squares method to Eq. (15), we get c = ln 10 G1 Veq0 (16)

= (Veq ) = 100

[%]

(17)

expresses the relative error in Veq evaluation.

5.

Effect of the slope on Veq value

Fig. 3 The (%) (Eq. (17)) vs. (mV) relationships plotted for G(II) and MG(II)A for c = 56 mV.

In titrations made in electrolytic redox systems, the potential E is monitored with RIE [21], made of noble (usually Pt) metal, combined with a reference electrode, immersed in an electrolytic redox system. Preceding calibration of indicator electrode is required for the determination of the correct slope value ( = c ) [2232]. Major difculties involved with electrode calibration are cleaning, soaking, and conditioning of the electrode. This is often more troublesome than the measurement itself and usually accounts for most of the error. Accordingly, the Nernstian slope, 0 = 59.1 mV at 25 C, or more rounded value, 60 mV, is set as the pre-assumed value, = 0 in Eq. (4) in most papers dealing with application of the G(II) method for potentiometric titrations in redox systems. A particular value used in Eq. (2) imitates the correct slope ( = c ) for real indicator electrode applied in the

a n a l y t i c a c h i m i c a a c t a 6 2 8 ( 2 0 0 8 ) 181189

185

Fig. 4 The effect of the choice of value on the ordinate at c equal: (a) 53 mV, (b) 55 mV.

titration. This way, the sets of points {(Vj , Ej )} were generated and the subsets {(Vj , Ej )|j = 1, . . ., N} not loaded by random errors, covering the V-interval (mL) 1.0, 9.0 with volume increment ( V) of 1.00 mL, was the basis for plotting the lines in co-ordinates (V, ), where 0j = (Vj , 0 ), i.e. = 0 = 59.1 mV, according to regression equations: (6) in Fig. 2a or (9) in Fig. 2b. As we see, the points (Vj , 0j ) are arranged along curved lines; the degree of curvature (bending) increases with the increase of |c 0 | value. The points {(Vj , j )|j = 1, . . ., N} are arranged along concave (at c < 0 ) or convex (at c > 0 ) lines. At c = 0 , the points are arranged along the straight line. As we see, the points {(Vj , 0j )|j = 1, . . ., N} adhere more tightly the line obtained from Eq. (9) (MG(II)A method) than the line obtained from Eq. (1) (G(II) method). The degree of adherence affects the errors (Veq ) in Veq value. At greater |0 c | discrepancies, the theoretical errors (Veq ) calculated according to MG(II)A method, are many times smaller than the ones referred to the G(II) method (Fig. 3).

Let us consider the formula (3), valid for V < Veq . After dividing this equation by , and transforming it we get 10E/ = 10E0 / 10 Veq V V
c /

(18)

By multiplying the sides of Eq. (18) by V, we get (see Eq. (4)) = [10 (Veq V )]
c /

V 1c / 10E0 /

(19)

For = c and = 0 ( = = const), Eq. (19) can be rewritten into linear form = (Veq V ) (20)

where = 10E0 / (21)

Fig. 5 The vs. V plots at = c equal (a) 53 mV, (b) 55 mV and different concentrations of sulphuric acid (Ca0 , mol L1 ) indicated at the corresponding curves.

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MG(I)S

Table 1 Results for c and Veq determinations found from results of 12 experiments according to different modied Gran I and Gran II methods

10.09 0.03

Veq (mL)

55.3 0.7

(mV)

MG(I)B

56.0 54.5 55.5 55.0 55.2 54.5 56.2 54.7 54.9 56.0 56.4 55.0

55.5 0.8

(mV)

56.2 54.6 55.6 55.1 55.4 54.6 56.6 54.5 54.8 56.3 56.8 55.3

10.06 0.06

Veq (mL)

10.08 10.04 10.05 10.06 10.08 10.04 10.13 9.95 9.95 10.12 10.13 10.12

MG(II)E

10.03 10.10 10.11 10.12 10.12 10.12 10.13 10.06 10.04 10.06 10.09 10.06

Fig. 6 An effect of Ca0 on (%) value (eq. 17) in G(II) and MG(II)A; V-interval 1.0, 9.0 , = 0 = 59.1 mV, V = 1.00 mL.

54.1 0.5

(mV)

MG(II)C

10.13 0.08

Veq (mL)

10.15 10.02 10.12 10.18 10.24 10.01 10.19 10.04 10.12 10.08 10.16 10.25

If any of the pre-assumptions is not valid, the vs. V relationship is nonlinear. The plots in Fig. 4a and b are valid for the case = 0, i.e. = const, assumed in G(II) method; this assumption is acceptable at relatively high concentration (Ca0 ca. 1 mol L1 ) of H2 SO4 [9]. As we see, the curvature of the lines is more distinct for greater differences | c |. At = c , the relationship between and V is linear (Eq. (20)). The course of curves in Fig. 5, plotted at = c , is inuenced by the change of with V value (Eq. (5)) [9]. As we see, the degree of curvature enhances with lowering the Ca0 value; it affects the error (Veq ) (Eq. (17)) in Veq value (Fig. 6). This effect is much smaller in MG(II)A than in G(II) method. It should be noticed, however, that too low Ca0 values are not recommended in practice, due to the possible reaction MnO4 + 4H+ + 3e = MnO2 + 2H2 O that collapses the reduction of permanganate to Mn(II) species. Therefore sufciently high Ca0 is the prerequisite to assure that the system is buffered [8]. Referring again to Veq determination, one can state that G(II) method assumes linear relationship in co-ordinates (V, ), see Eq. (1). This assumption is reasonable when the assumptions: = c and = const are fullled simultaneously. Otherwise, one should choose one of the following options:

53.9 53.7 54.6 54.2 54.2 54.0 55.0 53.8 53.8 54.0 54.8 53.4 9.99 10.02 10.00 10.00 10.01 10.02 10.03 9.92 9.94 10.01 10.02 10.07 53.5 53.0 53.7 53.1 53.3 53.1 54.1 52.5 52.9 53.5 54.2 53.4 54.9 53.0 54.7 54.7 55.2 53.0 55.5 53.6 54.5 54.1 55.4 55.0 10.11 10.16 10.13 10.15 10.13 10.17 10.18 10.10 10.12 10.14 10.16 10.25 54.6 54.2 54.8 54.4 54.3 54.4 54.4 54.1 54.5 54.7 55.4 55.0

MG(II)D

MG(II)B

54.6 0.4

(mV)

10.15 0.04

Veq (mL)

54.5 0.9

(mV)

53.4 0.5

(mV)

10.00 0.04

Veq (mL)

Experiment no.

10.04 0.03

Veq (mL)

10.01 10.06 10.06 10.06 10.06 10.07 10.07 9.99 9.98 10.03 10.06 10.08

(a) apply the MG(II)A method [9], where the error in Veq value (Eq. (10)), obtained from resolution of parabolic regression Eq. (9), is less sensitive on mist of value (Fig. 3) or (b) apply the procedure where accurate values for both Veq and c are desired.

MG(II)A

The approach based on the correlation coefcient applied for curvilinear regression analysis based on Eq. (9) (MG(II)A method) is less applicable, because the error in Veq is less sensitive on the value and depends also on other, indenite factors. It should be noted, however, that the assumption of variability of (Eq. (5)), is inherent in the MG(II)A method.

Mean s

1 2 3 4 5 6 7 8 9 10 11 12

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187

6.2.

Apparatus

Fig. 7 The vs. V plots for the experiment 1.

An Orion 960 autochemistry system with a temperature sensor and combined Pt redox indicator electrode with Ag/AgCl reference electrode (Sentek model 0.1/Pt band/coil) were used for automated titrations. The temperature during titrations was kept constant at (25.0 0.05) C using a thermostat. Standardisation of the stock solution of iron(II) was conducted by potentiometric titration using digital voltmeter (Iskra pH-meter MA 5740) with platinum indicator electrode (Radiometer P 101) and calomel reference electrode (Metrel 40563), the dosing device (Metrohm 775 Dosimat) with burette (Metrohm 806 Exchange unit). The temperature of the system was monitored using Pt 100 sensor (Iskra). The value Veq0 = (10.06 0.01) mL has been obtained from the standardisation made from preliminary (reference) tests, performed within 3 days with use of comparative method based on location of maximal slope of the titration curve (rst derivative).

6.3.

Procedure

6.
6.1.

Experimental part
Reagents

All reagents were of analytical purity grade and all solutions were prepared with use of doubly distilled water. Standard solution of KMnO4 (titrant) with C = 0.02000 mol L1 was prepared by diluting Titrisol (Merck) to 1000 mL with water. Stock solution of iron(II) (titrand) was prepared by dissolution of 5.5603 g (0.02 mol) of iron(II) sulfate heptahydrate (Merck) in water, followed by addition of 111.4 mL of conc. H2 SO4 (Carlo Erba) and dilution to 2000 mL with water (Ca0 ca. 1.0 mol L1 for H2 SO4 ). C0 of this solution, obtained by standardization with 0.02000 mol L1 KMnO4 , was 0.01006 mol L1 and Veq0 = 10.06 mL is considered as the reference value for equivalence volume.

The volume V0 = (100.00 0.12) mL of Fe(II) solution used as titrand (D) was transferred into the titration cell. The titrant (T) was added in equal volume increments ( V) of (1.002 0.001) mL. The electrode potential was registered at the drift smaller than 0.5 mV min1 and the titration continued to the maximum titrant volume of 10.023 mL. A series of 12 experiments was conducted (see Table 1) at (25.0 0.05) C, in thermostated system.

7.

Results and discussion

The results of calculations based on 12 sets of experimental values are collected in Table 1. For all the methods consid eq sVeq (sVeq , standard ered, the mean Veq values, written as V deviation for Veq ) are close to Veq0 = 10.06 mL, considered as c sc the reference value. The mean c values, written as

Fig. 8 The collected vs. V plots for indicated experiments, related to (a) MG(II)B method and (b) MG(II)C method.

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interval 2.00, 8.00 . The results are presented in Fig. 8a and b, for a few experiments chosen randomly. Examples of the curves related to MG(II)D and MG(II)E methods are presented in Figs. 9 and 10. The related plots assume nearly parabolic shape, e.g. y = p0 + p1 + p2 2 , where y = 1 R2 or SS, with minimal value at = 0.5p1 /p2 , considered as c value. By comparing the results obtained with different methods: MG(I)S, MG(II)B, MG(II)C, MG(II)D and MG(II)E one can state that all suggested methods provide comparable values for c and Veq . The MG(II)A method can be applied for determination of Veq value at the pre-assumed slope = 0 = 59.1 mV (if c is not too distant from 0 ) and the MG(I)B method is applicable for determination of c under the assumption that the equivalence volume is known accurately, Veq = Veq0 .

8.
Fig. 9 Illustration of MG(II)D method for indicated experiments from Table 1.

Conclusions

(sc , standard deviation for c ) are within the interval 53.4, 55.5 . These values differ distinctly from the value of 58.2 mV calculated for the Nernst slope at 20 C or 59.1 mV at 25 C. This difference signicantly affects the Veq value, by several (ca. 8%) percents, under assumption that Ej and Vj values are determined correctly, with zero errors (see Fig. 3); it means that the error will exceed this value in real titrations. This discrepancy |c 0 | in -value seems to be insignicant for MG(II)A method, however. The arrangement of the set of points {(Vj ,j )|j = 1, . . ., N} exemplied by the data obtained from experiment 1 and presented in Fig. 7 is similar to ones illustrated in Fig. 4a and b. As results from Fig. 7, the line plotted at ca. 54 mV assumes nearly linear shape. The data j obtained according to MG(II)B and MG(II)C methods were applied for the data (Vj , Ej ) taken from the V-

Four new methods of simultaneous determination of c and Veq values, based on the assumption of linear relationship (Eq. (1)) occurred only at = c , were suggested. The curvature of the lines = (V, ) depends on the difference | c |. The methods proposed are based on: (1) zeroing the second derivative of the function = (V, ). The derivatives were determined with use of the nite differences method (MG(II)B) and the Lagrange polynomial interpolative method (MG(II)C) and (2) the linear regression equation to the points {(Vj , j )|j = 1, . . ., N} obtained from experimental data {(Vj , Ej )|j = 1, . . ., N}. The t is characterized by the linear correlation coefcient R (for MG(II)D method) or by the sum of the least squares value SS (for MG(II)E method). In both cases, the minima of the related functions: 1 R2 vs. or SS vs. (approximated by parabola) are searched. In the Gran methods it is assumed that the = c value is constant within the concentration range, covered by the points {(Vj , Ej )|j = 1, . . ., N} considered in calculations made according to the Gran methods, applied for results of potentiometric redox titrations. However, this assumption can be valid with respect to the fact that, in the Gran methods, the points {(Vj ,Ej )|j = 1, . . ., N} cover ca. one or (at most) two orders of magnitude of analyte concentrations interval. Within such narrow range, involving higher concentrations of the analyte (assuming normal mode of titration procedure), the assumption of linearity is valid, as a rule. This viewpoint contradicts the principle of the rst derivative ( E/ V) method, involving the region in the immediate vicinity of equivalence point, where a dramatic change in the analyte concentration occurs. The G(II) method gives accurate results for Veq only under assumption that the accurate -value, c , for the indicator electrode is known beforehand. The problem of non-linearity of the related plots, raised in earlier papers [79], was explained on the basis of generalized approach to electrolytic systems (GATES). Thee MG(I)A method is more prone to errors, owing to the iterative procedure applied for determination of parameters of the system examined.

Fig. 10 Illustration of MG(II)E method for indicated experiments from Table 1.

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189

Acknowledgements
One of the authors (M.P.) gratefully acknowledges the Slovenian Research Agency (ARRS) for nancial support of the present study within the research program: P1-0045 Inorganic Chemistry and Technology.

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