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Thermometric titration : ウィキペディア英語版
Thermometric titration

A thermometric titration is one of a number of instrumental titration techniques where endpoints can be located accurately and precisely without a subjective interpretation on the part of the analyst as to their location. Enthalpy change is arguably the most fundamental and universal property of chemical reactions, so the observation of temperature change is a natural choice in monitoring their progress. It is not a new technique, with possibly the first recognizable thermometric titration method reported early in the 20th century (Bell and Cowell, 1913). In spite of its attractive features, and in spite of the considerable research that has been conducted in the field and a large body of applications that have been developed; it has been until now an under-utilized technique in the critical area of industrial process and quality control. Automated potentiometric titration systems have pre-dominated in this area since the 1970s. With the advent of cheap computers able to handle the powerful thermometric titration software, development has now reached the stage where easy to use automated thermometric titration systems can in many cases offer a superior alternative to potentiometric titrimetry.
The applications of thermometric titrimetry discussed on this page are by no means exhaustive. The reader is referred to the bibliography for further reading on the subject.
== Comparison between potentiometric and thermometric titrations. ==
Potentiometric titrimetry has been the predominant automated titrimetric technique since the 1970s, so it is worthwhile considering the basic differences between it and thermometric titrimetry.
Potentiometrically-sensed titrations rely on a free energy change in the reaction system. Measurement of a free energy dependent term is necessary.
: Δ''G''0 = -''RT'' ln''K'' (1)
Where:
: ΔG0 = change on free energy
: ''R'' = universal gas constant
: ''T'' = temperature in kelvins (K) or degrees Rankine (°R)
: ''K'' = equilibrium constant at temperature ''T''
: ln is the natural logarithm function
In order for a reaction to be amenable to potentiometric titrimetry, the free energy change must be sufficient for an appropriate sensor to respond with a significant inflection (or "kink") in the titration curve where sensor response is plotted against the amount of titrant delivered.
However, free energy is just one of three related parameters in describing any chemical reaction:
: Δ''H''0 = Δ''G''0 + ''T''Δ''S''0 (2)
where:
: Δ''H''0 = change in enthalpy
: Δ''G''0 = change in free energy
: Δ''S''0 = change in entropy
: ''T'' = temperature in K
For any reaction where the free energy is not opposed by the entropy change, the enthalpy change will be significantly greater than the free energy. Thus a titration based on a change in temperature (which permits observation of the enthalpy change) will show a greater inflection than will curves obtained from sensors reacting to free energy changes alone.

抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)
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