Kinetic compensation effect

An anion effect is also reported for the solid-state anations of cis-[Co(en)2(py)X]Y2 (X- = Cl-or Br- Y- = Br" or I"). Experimental conditions affect activation parameters, and the kinetic compensation effect is observed (that is, a is linearly correlated with log A). However, the correlation is different for [Co(en)2(py)X]Br2 than for [Co(en)2(py)X]I2.71 This result suggests that the chemical process of importance is anion-dependent. It is proposed that the Co—py bond strength is affected by polarization effects due to the surrounding ionic halides. 

Kinetic parameters from selected publication on CO2 reactivity are shown in Table 1. A wide span of apparent activation energies is published for biomass chars, 80.3 kJ/mol -318 kJ/mol and for coal chars, 79 kJ/mol -359.5 kJ/mol Some of the discrepancy can be explained as due to different experimental procedures (such as sample load, particle size and sample preparation) and the application of different analysing equipment. Concerning the latter one, the potential role of systematic errors in temperature measurements among various thermobalances is evident. Variations might also be explained by different extraction procedures, lack of accuracy caused by the approximations used in the different computational methods and the kinetic compensation effect. 

Galwey AK, Bettany DG, Mortimer M (2006) Kinetic compensation effects observed during oxidation of carbon monoxide on y-alumina supported palladium, platinum, and rhodium metal catalysts toward a mechanistic explanation. Int J Chem Kin 38 689... 

Kappa notation, 115 3-Ketoiminates metal complexes gas chromatography, 560 Ketoxime, 2-pyridylmethyl-in gravimetry, 533 Ketoxime, 2-pyridylphenyl-in gravimetry, 533 Kinetic compensation effect ligand exchange solid state, 469... 

In order to avoid the effect of kinetic compensation effect, the Popescu non-model method based... 

From Eq(2), the integral term at certain temperature T is constant, which means the plot of the values of mechanism function G(a) versus llfi has to lead a straight line with an intercept of zero. Thus, by the calculating the values Of on each curve of different heating rate, the mechanism function can be determined by the plot of G(of) versus /p. If the plot of the values of G(of) versus llfi is a straight line with an intercept of zero, then the chosen G(or) is the mechanism function of the reaction. This method determines mechanism function with few assumption, and it also does not take the forms of k(T) into consideration, which avoids the effect of kinetic compensation effect, the analysis result has higher credibility. 

Gallagher PK, Johnson DW (1976) Kinetics of thermal-decomposition of CaC03 in CO2 and some observation on kinetic compensation effect Thermochim Acta 14 255-261... 

N. Koga, Thermochim. Acta Kinetic compensation effect, a review 244(1994)1 and 258(1995)145... 

---