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AN OPTIMAL CALIBRATION DESIGN FOR pH METERS

Christos P. Kitsosa; Konstantinos G. Kolovosb a Department of Mathematics, T.E.I. of Athens, Athens, Greece b Department of Civil and Construction Engineering Educators, School of Pedagogical & Technological Education (ASPETE), Athens, Greece Online publication date: 27 October 2010

To cite this Article Kitsos, Christos P. and Kolovos, Konstantinos G.(2010) 'AN OPTIMAL CALIBRATION DESIGN FOR

pH METERS', Instrumentation Science & Technology, 38: 6, 436 447 To link to this Article: DOI: 10.1080/10739149.2010.514158 URL: http://dx.doi.org/10.1080/10739149.2010.514158

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Instrumentation Science and Technology, 38:436447, 2010 Copyright # Taylor & Francis Group, LLC ISSN: 1073-9149 print/1525-6030 online DOI: 10.1080/10739149.2010.514158

AN OPTIMAL CALIBRATION DESIGN FOR pH METERS

Christos P. Kitsos1 and Konstantinos G. Kolovos2 1 Department of Mathematics, T.E.I. of Athens, Athens, Greece 2 Department of Civil and Construction Engineering Educators, School of Pedagogical & Technological Education (ASPETE), Athens, Greece
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& Routine pH measurements are carried out with pH meterglass electrode assemblies. The use of these electrodes is subject to various effects, described in this article, producing uncertainties of unknown magnitude. Therefore, the measurement of pH requires a suitable calibration by certified standard buffer solutions traceable to primary pH standards. This article addresses the optimal experimental procedure for the calibration problem to common pH meters, under D- and c-optimality criteria. The relevant calibration data analysis and the results are also presented in detail. Keywords calibration, glass electrode, metrology, optimal designs, pH meter

INTRODUCTION pH Measurement in Chemical Analysis With the availability of inexpensive glass pH electrodes and pH meters, the determination of pH is one of the most common and frequent quantitative analytical measurements in chemical analyses. The potentiometric determination of pH, however, is not without complications, several of which are discussed in the following section. The conventional definition of pH as the negative logarithm of the concentration of hydrogen ions [H] in solution at 25 C was first introduced in 1909 by Danish chemist Sren Peder Lauritz Srensen at the Carlsberg Laboratory, namely: pH log[H]. The pH of a solution, however, is defined by the response of an electrode to the H ion, and, therefore, is a measure of its activity aH. Thus, calculating the pH of a solution only approximates the true pH, as pH log aH .
Address correspondence to Konstantinos G. Kolovos, Department of Civil and Construction Engineering Educators, School of Pedagogical & Technological Education (ASPETE), 141 21 N. Heraklion, Athens, Greece. E-mail: kolovosk@gmail.com

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Although this definition has been superseded, pH measurement is based on potensiometry, if an appropriate electrode is calibrated with solution of known hydrogen ion concentration. Several methods leading to the determination of the sample concentration Ci of an ionic species i exist. In the presence of a buffer solution for total ionic strength adjustment, which can fix the pH, as Ecell E 00 0:0591 log Ci z 1

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For a monovalent ion at 298 K, the slope factor S, that represents the term 2.303 RT=F is equal to 0.05916 V (the theoretical slope). This is also the value of the gradient factor per pH unit for a glass electrode, where E 00 is the potential difference (PD) between the ion selective electrode (ISE) and the internal membrane surface (constant, as fixed by its design), R is the ideal gas constant (R 8.3145 J=K mol), F represents Faradays constant (F 96485 C=mol), T is the temperature (in K), z is the charge carried by the target ion i to be measured, and 2.303 is the logarithmic conversion factor. Complications and consequent errors in pH experimental determination, besides the temperature, the hydration of glass, and equilibration time (as it takes about 30 s for an electrode to equilibrate with a solution) are mainly concerning the following:[1,2] . Standard buffers: A pH measurement cannot be more accurate than the standard buffers, which are typically 0.01 pH unit. . Junction potential: A junction potential exists at the porous plug. This effect gives an uncertainty of at least $0.01 pH unit. . Junction potential drift: A compensation for this error can be achieved by recalibration of the electrode every 2 h. . Sodium error: When the concentration of H is very low and the concentration of Na is high, the electrode responds to Na and the apparent pH is lower than the true pH. . Acidic error: In strong acid, the measured pH is higher than the actual pH, perhaps because the glass surface is saturated with H and cannot be protonated at any more sites. Measurement of pH differences between solutions can be accurate to about 0.002 pH unit, but knowledge of the true pH will still be at least an order of magnitude more uncertain. A standard error of 0.02 pH unit corresponds to a standard error of 0.05 in aH. Glass electrode calibration in proton activity has been widely studied.[25] Although the measured potential follows a linear relationship with the

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logarithm of the activity of proton, the experimental slope obtained usually departs from the Nernstian value. A straight line is calculated in the calibration with the two buffers, and the pH of the unknown solution is calculated assuming linearity between pH and potential. If non-Nernstian slope response is accepted in pH measurements, this fact should also be taken into account when calibration of electrode is done in proton concentration.[3] Statistical Theory for the Calibration Problem Various methods for different (linear or not) models have been adopted concerning the statistical calibration problem. In practice, most of the models attempt to face the simple linear calibration technique. Eventually a nonlinear function needs to be estimated as well as possible, although the underlying model is linear. When the variance of the measurement is due to many sources of variability, different techniques are followed, while a robust approach might be more appropriate.[6] In the following section, the theoretical background of the calibration problem, linked with the pH meters, is discussed in detail. Consider the simple regression model: n E y j u h0 h1 u; u 2 U 1; 1 2

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where U is the (transformed) design space, y is the response, and u is the input variable. Our target is to estimate the value of u u0 given that n C, i.e., u0 C h0 =h1 3

The most well known competitive estimators of u0 when y0 is provided are  Sxy y y the so-called classical predictor, C(u0) x Sxx _ 0 , and the inverse P Sxy   _   _ predictor, I(u0) x Syy y0 y, with Str ti t ri r , whereby y0 we mean the possible average of the possible k observations taken at the prediction stage (or experimental condition) and y as usual.  The comparison of C(u0) and I(u0) is based on the values of n and jr= h1j under the assumption that u0 belongs to the experimenter area.[7] The main difficulty is the construction of confidence intervals[8] as the variance of u0, Var(uo 0), does not exist, which provides food for thought for an optimal design approach to the calibration problem. For the one-stage design, either D-optimality or c-optimality is applied for estimating u0 as well as is possible. Under c-optimality, thanks to Elfvings theorem, we can construct a locally optimal two-point design geometrically,[7] in the sense that the proportion of observations at the end points can be defined as a function

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of the calibrating point u0. Hence, we minimize the variance of the estimate uo 0, obtained due to the c-optimality approach. We can proceed consider ing u0 as a function of h0 and h1, and therefore: ru0 1=h1 u, where u 1; u0 T Then, ^ Varu0 h2 u T Varhu ^ 1 4

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^ ^ with u0 C h0 =h1 . ^ The optimal design measure either under D-optimality or c-optimality defines a percentage of p and 1p observations at the end points. Following the work of Kitsos,[7] the design matrix M (mij) has elements m11 m22 1 and m12 m21 2p 1. We are interested in minimizing the quantity v(p), vp nh2 1 u T M 1 u, i.e., 1 1 2 vp 4nh2 p1 p u0 2u0 1 2p 1 1 5

Under D-optimality we allocate half observation at the end points 1 and 1. That is, p 1 p 1=2, and from Equation (5), the corresponding VD for example, is
2 VD nh2 1 u0 1 1

The locally c-optimal design can be obtained,[7] and then the design measure or the weight of the observations at each point can be evaluated according to Elfvings theorem, for ju0j < 1, and ju0j > 1. It can be proven[7] that the proportions of the observations at the end points are as follows: & p u0 1=2 u0 1=2u0 & 1p 1 u0 =2 u0 1=2u0 ifju0 j < 1 otherwise ifju0 j < 1 otherwise

Therefore, under the c-optimal criterion the optimal v(p) value as in Equation (5), for example VC, is & VC nh2 1 1 2 nh2 1 u0 1 ifju0 j < 1 otherwise 9

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We use the efficiency measure, Eff(c, D) for example, to assess the efficiency of the D-optimal design relative to the local c-optimal design. & Eff c; D VC =VD
2 u0 11 2 2 u0 =u0 11 u0

ju0 j < 1 otherwise

10

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A plot of Eff(c, D) versus u0 indicates that the efficiency at the end points 1 is 50%. Moreover, the D-optimal designs at any other points in the interval (1, 1) have a greater efficiency. The efficiency also increases outside the end points (Figure 1). It would be interesting to investigate the maximumminimum efficiency design for this particular problem.[7] That is, we choose the design whose minimum efficiency is greater than that of any other design. The minimum values of the corresponding proportion are p, 1p, and 4p(1p).[8] Therefore it is easy to see that the maxmin value occurs when p 1=2. Thus, it is proven[8] that for the calibration design problem currently under discussion, the maxmin efficiency design turns out to be the D-optimal design. This article deals with the assessment of different calibration procedures, such as the two-point calibration with D- and c-optimal designs, as well as with the multipoint calibration of pH electrodes, thereby using certified reference buffer solutions traceable to primary pH standards. Since the calibration of pH-meters has attracted a lot of interest,[915] an optimal design approach is developed in this article. Attention is also given to the assessment of measurement uncertainties and to certified reference buffer solutions, such as ready-to-use buffer solutions, frequently in use for the calibration of pH electrodes. Moreover, we investigate the limitation of the calibration procedure beyond the common

FIGURE 1 Efficiency of D-optimal design.

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pH range of 210. Adoption of the c-optimal design for the extrapolated values (beyond the [1, 1] interval) is also discussed.

EXPERIMENTAL Apparatus and Reagents A WTW Inolab 7300 pH meter with serial interface, including a SenTix 82=81 glass electrode, was used in all conducted experiments (range for measured pH values: 1 to 17), along with WTW standard buffers at pH 2.00 0.02 (299.6 0.2 mV, respectively), 4.00 0.02 (181.8 0.3 mV, respectively), 7.00 0.02 (2.8 0.2 mV, respectively), and 10.00 0.02 (171.1 0.5 mV, respectively) values. Additionally, the pH of aqueous solutions of varying proton activities required to operate the ECN-2 and ECP-2E processes for Kodak Eastman motion picture color films were also measured.

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Calibration Procedure A two-point calibration procedure (bracketing calibration) was performed, with the use of two standard buffers with pH values of 2.00 and 10.00 at 25 C, following the WTW instructions. The WTW model we used was equipped with a temperature compensation feature that allows the pH meter to correct the measured pH for any change in temperature. The pH electrode was immersed in the first buffer, and the calibration control was adjusted until the pH meter read the correct pH value. Then the electrode was placed in the second buffer and adjusted to the second buffers pH. After the calibration procedure was completed, a second measurement of the pH value and electrode potential (in mV) of each one of the two standard buffers at the same temperature was conducted, and the pH values were recorded. Additionally, a measurement of the pH value of the standard buffer of pH 7.00 was also recorded for further evaluation of uncertainty. Data sets of 2164 coupled values for pH and electrode potential in mV of each one of the two standard buffers (pH 2.00 and pH 10.00) were recorded and are presented in detail[9] at the following Web site: http://www.teiath.gr/stef/math/articles.php? mid=811&lang=el. Apart from the two-point optimal calibration proposed, a regression equation with the use of four standard buffers (not five, as is generally recommended[1,2]), with pH values of 2.00, 4.00, 7.00, and 10.00 at 25 C, was estimated for comparison.

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RESULTS AND DISCUSSION In two-point and multipoint calibration, an electrode system is calibrated against several pH standard solutions, and the mV readings are transferred into a calibration line by ordinary least squares regression. From Nernsts Law, a linear relationship is expected: ES E 0 k 0 pH S 11

where E(S) is the electron potential of the cell in pH standard S, E0 is the standard electron potential of the cell, and k 0 is the slope factor of the cells electron potential. The slope factor k 0 of a glass combination electrode is usually larger than the theoretical slope factor (Nernst slope) for thermodynamic reasons and, hence, is called the practical slope factor.[14] Thus, the calibration data must be interpreted according to the model described by Equation (2) as ESi E 0 k 0 pH Si ei ; (i 1,...,n), where pH(Si) is the pH of the i-standard, E(Si) is the corresponding mV reading of the pH meter, and ei represents the i-th residual. Various values of n were considered (n 1000, 100, 50, 20, 10; see Tables 14), and therefore the number of proportions for the observations at the end points were considered, under D and c-optimality, according to Equations (7) and (8). Inconsistencies encountered by the two-point calibration as described above are minimized if more than two standards are used for the calibration. The multi-point calibration allows assessment of the uncertainty associated with an individual pH measurement by the statistical concept of ordinary least squares regression. Multipoint calibration is recommended when minimum uncertainty and maximum consistency are required over a wide range of sample pH values. The ordinary least squares regression is applicable only to that range of pH values in which the calibration function is linear. Deviations from linearity are caused, for example, by the so-called alkali error of the electrode. By solving Equation (11) with respect to pH(X), we conclude that 0 pH X E EX , which is in accordance with Equation (3), from the k0
TABLE 1 N 1000 100 50 20 10 D-Optimal Design for Two-Point Calibration h0 51.92 51.71 52.34 52.14 52.76 h1 215.79 215.28 214.16 214.60 215.91 Adjusted R2 0.9985 0.9983 0.9985 0.9983 0.9975

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TABLE 2 n 1000 100 50 20 10 Linear Regression Data for Multipoint Calibration (4 Points) h0 51.70 51.59 51.16 50.65 51.82 h1 217.79 217.26 217.74 218.64 218.66 Adjusted R2 0.9979 0.9978 0.9977 0.9979 0.9983

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statistical point of view. This is the dominant reason we followed the described theoretical framework. The additional information we obtained by using the multipoint regression is actually very restricted, as one can see by comparing Tables 1 and 2. Consequently, multipoint calibration is recommended only when minimum uncertainty and maximum consistency are required over a wide range of pH values; otherwise a D-optimal (two point) design is suggested.

D-Optimal Design for Two-Point Calibration Table 1 presents the D-optimal approach for the calibration of pH meters, with sample size of 1000, 100, 50, 20, and 10 observations. The data were measured for the standard buffers of pH values 2.00 and 10.00 (more often used in experimental practice), where the assumption of linearity between pH and E is still valid. The corresponding transformed values were 1, 1 after each two-point calibration procedure under the D-optimality approach. D-optimality was based on devoting half of the observations at the converted end points. For example, for 1000 observations, 500 coupled data for pH and E were selected for pH 2 and 500 coupled data for pH and E were selected for pH 10, and an ordinary least squares method was conducted based on Table 1. Due to symmetry, the design points in [1, 0] coincide with those in [0, 1]. The results presented in Table 1 suggest that optimal regression line can be obtained with the D-optimal two-point calibration design. Values of adjusted R2 are of the same magnitude and do not differ significantly.

Multipoint Calibration Table 2 presents part of the regression data performed with sample size of 1000, 100, 50, 20, and 10 observations (measured values of each one of the four standard buffers after each multipoint calibration procedure). As can be easily seen, all regressions produce values of the adjusted R2 coefficient that are very close to the value of 0.9978, implying strong linear

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TABLE 3 c-Optimal Design for Two-Point Calibration, ju0j < 1 u0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 P 0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 0.95 0.90 0.85 0.80 0.75 0.70 0.65 0.60 0.55 N 1000 h0 52.420 52.011 51.935 52.021 51.987 52.026 52.063 52.067 51.911 52.278 52.555 51.856 51.897 52.765 52.335 52.382 52.534 52.288 56.611 52.059 51.883 52.458 51.932 51.681 52.012 51.504 52.010 53.761 55.550 52.825 54.058 50.937 50.934 51.174 51.667 52.153 54.425 56.655 54.194 55.001 52.764 53.448 53.464 55.557 53.955 H1 215.50 215.90 216.02 215.97 215.99 215.91 215.89 215.75 215.87 215.08 214.86 215.48 215.62 214.55 214.83 215.13 215.12 215.11 210.50 215.02 215.44 214.84 215.45 215.35 214.78 215.26 214.70 211.57 209.71 212.39 211.42 213.99 214.45 214.82 213.88 213.40 212.58 211.00 213.89 212.44 215.91 217.04 217.16 217.80 215.24 Adjusted R2 0.9956 0.9975 0.9981 0.9983 0.9985 0.9985 0.9986 0.9986 0.9986 0.9952 0.9973 0.9980 0.9983 0.9985 0.9985 0.9985 0.9985 0.9985 0.9948 0.9970 0.9978 0.9982 0.9983 0.9984 0.9986 0.9986 0.9985 0.9960 0.9978 0.9981 0.9984 0.9978 0.9981 0.9983 0.9983 0.9983 0.9983 0.9990 0.9988 0.9988 0.9975 0.9975 0.9972 0.9961 0.9926

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50

20

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TABLE 4 n 1000 c-Optimal Design for Extrapolated Values for Two-Point Calibration, ju0j > 1 nP 833 750 167 214 95 90 85 80 48 45 43 40 19 18 17 16 9 8 7 6 h0 51.623 51.512 51.444 51.595 49.942 50.879 50.369 50.138 50.877 49.602 49.505 50.275 54.122 50.394 51.536 50.354 57.048 52.455 50.350 50.350 h1 216.17 216.22 216.51 216.36 215.85 215.49 217.02 217.32 216.52 215.77 217.86 217.16 216.24 218.19 213.67 215.10 216.19 220.91 217.29 217.29 VC1=2 0.00022 0.00029 0.00022 0.00026 0.00069 0.00093 0.00069 0.00081 0.00098 0.00131 0.00097 0.00114 0.00155 0.00205 0.00157 0.00182 0.00219 0.00286 0.00218 0.00255 y(u0) 272.63 380.93 376.21 430.23 273.83 380.10 375.90 430.45 273.90 381.94 376.30 430.31 270.24 385.99 372.04 426.78 267.24 389.37 376.29 430.61

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U-L 0.00086 0.00115 0.00086 0.00100 0.00272 0.00364 0.00271 0.00316 0.00384 0.00514 0.00382 0.00447 0.00649 0.00858 0.00657 0.00762 0.00993 0.01295 0.00988 0.01152

100

50

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20

10

correlation. The increase of the adjusted R2 coefficient value for the 10 observations using multipoint calibration is probably due to the selection of the corresponding data, rather than another phenomenon. From the multipoint calibration, it can be said that if an analysis suggests that the calibration procedure should be repeated more than once, in order to gain better accuracy, the result would probably be the same, since all regressions do not vary significantly. c-Optimal Design for Two-Point Calibration Table 3 presents part of the regression data performed with sample sizes of 1000, 100, 50, 20, and 10 observations (measured values of each one of the two standard buffers of pH values 2.00 and 10.00), after each two-point calibration procedure under c-optimality approach, which was based on devoting a portion np and n(1 p) observation at the end points for the design points 0.1(0.1)0.9. For example, for 1000 observations and for the design point u0 0.9, the transformed value is P(u0) [0.9 1]=2 0.95 and portion np and n(1 p) equals 950 and 50 coupled data sets of (pH, E). Hence 950

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coupled data sets of (pH, E) were selected for the 2.00 pH value, and 50 paired data sets of (pH, E) were selected for the 10.00 pH value. The results presented in Table 3 suggest that optimal regression line can be obtained with the c-optimal two-point calibration design. Values of adjusted R2 are of the same magnitude and do not differ significantly as the number of observations is decreased. Even if the minimum number of 10 paired observations is used, calibration lines do not vary significantly. This is not true when we are close to zero, i.e., for u0 0.1, in respect to adjusted R2 values. Hence we can avoid the time-consuming repeated calibration procedures, as well as the relevant expenses, and that is why we recommend an optimal design approach for the pH meters. Moreover, in Table 4, for the extrapolated extreme values for pH 1, 0, and 14, the coefficients of the calibration lines are presented, as well as the estimated variance according to Equation (9). The confidence intervals for the various values of uo were evaluated, and the lengths of these confidence intervals are presented in Table 4. It is pointed out that the length of the confidence interval is of magnitude 103.

CONCLUSIONS The overall results provide evidence that the theoretical background is transferred successfully to a practical experimental problem. This is not certain in advance for all experimental situations. Therefore it is suggested that during the calibration of pH meters, adopting this procedure is easy to do, as all the design points have been examined, within the [1, 1] interval, as every [a, b] interval (experimental region) can be transformed to it. The calibration outside the [1, 1] interval was also investigated, and the results are persuaded for the valuable application of the method. In adopting an optimal calibration design, either D- or c- for easier use in the two-point calibration procedure, the experimenter can evaluate the optimal calibrating value under the optimal design procedure that he or she will adopt by applying the results from the appropriate table. In such cases, where the area of interest is of a special importance, we would recommend the c-optimal design, for the appropriate u0 value and the minimum number of observations required.

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