Accuracy of the chemical data evaluated from one-atom-at-a-time experiments

Studies of chemistry of the transactinoid elements, which are available only as single atoms, by gas (thermo)chromatographic techniques can provide the adsorption enthalpies of the atoms or molecules. These values serve the ultimate goal—to characterize bulk volatility of the species in terms like sublimation enthalpies. The paper attempts an in-depth discussion of the statistical significance of the adsorption enthalpies derived in such experiments. Usually, the counting statistics are very poor and one faces nonstandard problems in evaluating the confidence intervals for the values of parameters. Here, a most efficient way seems to be the Bayesian approach, realized, when necessary, by Monte Carlo simulations of the counting results. Necessarily, the adsorption enthalpy is not evaluated based on the second law of thermodynamics but through accepting an a priori value of the adsorption entropy. More additional assumptions about the mechanisms and parameters involved are needed. This may produce systematic errors in the quantitative conclusions; the analysis of some recent works with elements 106 and 108 corroborates this concern. Despite such problems, it is possible to reveal qualitative differences in the adsorption behavior of a transactinoid and its expected known congeners as well as to use chemistry for an independent assignment of the atomic numbers of transactinoid nuclides.