[Back]

A.B. Koudriavtsev, W. Linert:
"Do Experimental Errors Really Cause Isoequilibrium and Isokinetic Relationships?";
MATCH-COMMUNICATIONS IN MATHEMATICAL AND IN COMPUTER CHEMISTRY, 70 (2013), 7 - 28.

Numerical experiments simulating spectroscopic determination of equilibrium constants
with normally distributed random noise in spectral amplitudes and temperatures have shown
that the `statistical´ correlation between estimates of H0 and S0 only appears when
measurements are performed on systems with H0 and S0 varying within an interval smaller
than two standard deviations ( ) of their estimates, i.e. when the precision of an instrument or
a method is insufficient for studies of such small variations of chemical reactivity. Random
variations of H0± H and S0± S completely destroy statistical correlation. This means that
in properly designed experiments the experimental errors cannot be the origin of the observed correlations between H0 and S0. This has been proven by numerical experiments on
reaction series exhibiting compensation effect. When analysing experimental data of
unknown precision the Exner-Linert method can be advantageously used to distinguish the
`statistical´ compensation effect.

Isokinetic relationships, Enthalpie Entropie Compensation,