Overview on the Gran and other linearisation methods applied in titrimetric analyses.

The paper provides some linearisation methods presented in modified (Gran I method), extended (pH-static titration) and generalised (Ni method) or corrected versions. Particularly, the modified Gran I method, based on the approximation ln(1+x) congruent withx/(1+x/2), enables (a) significant error inherent in the original Gran I method of equivalence volume V(eq) evaluation to be avoided, (b) greater portions of titrant to be added and (c) the points more approached to V(eq) to be involved in calculation of V(eq), according to the linear model applied. Moreover, prior determination of the real slope of the (pX, E) characteristics for X-selective indicator electrode (inherent in Gran II method) is thus avoided. The modified Gran I method is particularly useful in potentiometric titrations where electromotive force (E) is measured. The pH-static titration has been extended on some complexometric and precipitation titrations. Among others, two new methods of cyanide determination and a three-component precipitation pH-static titration have been suggested. A new criterion, involved with accuracy of pH and volume measurements in pH-static titrations, is suggested. The data were obtained, according to simulating procedure based on iterative computer programs involving all attainable data related to a system in question and widely accepted physicochemical data related to the systems considered. This way, any analytical prescription performed according to titrimetric mode can be fully reproduced and none simplifying assumptions in calculations made for this purpose are required. The Ni method, confined primarily to mixtures of weak acids, has been extended to acid-base systems involving salts of different type; to apply a kind of 'homogenisation' in formulae related to such systems, the Simms' constants were introduced.

[1]  D. Midgley,et al.  Improved linear titration plots for weak-acid titrations. , 1974, Talanta.

[2]  F. Ingman,et al.  Graphic method for the determination of titration end-points. , 1966, Talanta.

[3]  J. Yan A Method for the Determination of Equivalence Point in Potentiometric Titrations Using Unequal Volume Increments. , 1965 .

[4]  G. Gran,et al.  Equivalence volumes in potentiometric titrations , 1988 .

[5]  G. Gran,et al.  Automatic titration by stepwise addition of equal volumes of titrant. Part VII. Potentiometric precipitation titrations , 1981 .

[6]  Y. Ni,et al.  Simultaneous determination of halide and thiocyanate ions by potentiometric precipitation titration and multivariate calibration , 1999 .

[7]  Ebbe Still,et al.  Determination of the equivalence point in potentiometric titrations with gran's first method used to test the electrode response , 1979 .

[8]  T. Michałowski Some new algorithms applicable to potentiometric titration in acid-base systems. , 1992, Talanta.

[9]  S. Reis,et al.  Calibration of pH glass electrodes by direct strong acid/strong base titrations under dilute conditions , 2000 .

[10]  Marilda Rigobello-Masini,et al.  Application of modified Gran functions and derivative methods to potentiometric acid titration studies of the distribution of inorganic carbon species in cultivation medium of marine microalgae , 2001 .

[11]  J. Kochana,et al.  Extended Gran method and its applicability for simultaneous determination of Fe(II) and Fe(III) , 2001 .

[12]  F. Ingman,et al.  Acid-base titrations by stepwise additions of equal volumes of titrant with special reference to automatic titrations-I Theory, discussion of the gran functions, the hofstee method and two proposed methods for calculating equivalence volumes. , 1976, Talanta.

[13]  T. Michałowski Calculation of pH and Potential E for Bromine Aqueous Solution , 1994 .

[14]  C. Maccà pH-stat techniques in titrimetric analysis , 2002 .

[15]  J. W. Clayton,et al.  Determination of pKa values of acid components in atmospheric condensates by linearization of segmented titration curves , 1977 .

[16]  A. Dickson The development of the alkalinity concept in marine chemistry , 1992 .

[17]  C. Maccà Gran plots and rigorous linear plots for weak acid titrations: the “chemical” rationale , 1990 .

[18]  C. Maccà,et al.  Potentiometric characterization of weak acids by multiple sample addition-I. Linear equations and intrinsic performance of the method. , 1994, Talanta.

[19]  T. Michałowski,et al.  Acid-Base Titration Curves in Disproportionating Redox Systems , 1994 .

[20]  G. Gran Determination of the equivalence point in potentiometric titrations. Part II , 1952 .

[21]  C. Maccà,et al.  pH-stat techniques in titrimetric analysis: IV. pH-stat monitoring of chelatometric titrations , 2002 .

[22]  Toshihiro Suzuki,et al.  Development of a method for estimating an accurate equivalence point in nickel titration of cyanide ions , 2003 .

[23]  O. Godinho,et al.  Potentiometric study of acid-base properties of humic acid using linear functions for treatment of titration data , 1992 .

[24]  B. Hofstee Nonlogarithmic Linear Titration Curves , 1960, Science.

[25]  Y. Ni Simultaneous determination of mixtures of acids by potentiometric titration , 1998 .