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15. ZENCHELSKY, S . J. and SEGATTO, P. R . , Analyt. Chem. 2 9 , 1856 (1957). 16. PERCHEC, H . and GILOT, B . , Bull. Soc. Chim. France, 619 (1964). 17. BARK, L , S . and DORAN, K . , Unpublished results. 18. POPPER, E . , ROMAN, L . , Talanta 1 1 , 515 (1964), 19. TYSON, B . C . , MCCURDY, W . H . Jr. and BRICKER, C . E , , Analyt. 3 3 , 1640 (1961). Chem. APPARATUS 20. 21. 22. 23. 41 KEILY, H . J. and HUME, D . N . , Analyt. Chem. 3 6 , 5 4 3 ( 1 9 6 4 ) . , LEGRAND, M . , and PARIS, R . Α . , Compt.

One serious disadvantage of such a highly-sensitive derivative circuit becomes apparent when dealing with reactions in which the rate of attainment of equilibria is of the same order as the rate of titration. The shape of the thermometric curve for such a system is as shown in Fig. 8; the pronounced curvature over the end point region B-C is characteristic of such a reaction. e. the ñrst derivative of the voltage vs. time, if the sensitivity of the derivative circuit is arranged such that the burette is switched off immediately a change in the rate is discerned, the end point indicated by the titrator corresponds to the volume at Ε whereas extrapolation of the straight line portions AB, DC, indicate a stoichiometric equivalence point at a volume corresponding to F ml.

Since this must generally be done by a calorimetric study, the disadvantages probably outweigh the NEUTRALISATION IN AQUEOUS SOLUTIONS 45 advantages. The empirical approach is analytically much simpler and one may well remember the work of those earlier workers such as Paris et al/^^ who successfully titrated very weak acids and bases using much less sophisticated apparatus than is now available. One of the earliest reported uses of thermometric titrimetry was the titration of citric acid with ammonium hydroxide/^^^ since then, weak organic acids such as sahcylic acid and formic acid have been successfully t i t r a t e d .

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