APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .2. A THEORY OF QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS

The analytical expressions of quasi-first and second order homogeneous catalytic reactions with different diffusion coefficients at ultramicrodisk electrodes under steady state conditions are obtained by using the reaction layer concept. The method of treatment is simple and its physical meaning is clear. The relationship between the diffusion layer, reaction layer, the electrode dimension and the kinetic rate constant at an ultramicroelectrode is discussed and the factor effect on the reaction order is described. The order of a catalytic reaction at an ultramicroelectrode under steady state conditions is related not only to C(Z)*/C(O)* but also to the kinetic rate constant and the dimension of the ultramicroelectrode; thus the order of reaction can be controlled by the dimension of the ultramicroelectrode. The steady state voltammetry of the ultramicroelectrode is one of the most simple methods available to study the kinetics of fast catalytic reactions.

APPLICATION OF ULTRAMICROELECTRODES IN STUDIES OF HOMOGENEOUS CATALYTIC REACTIONS .3. THE CONDITION FOR QUASI-1ST AND 2ND-ORDER HOMOGENEOUS CATALYTIC REACTIONS AT ULTRAMICRODISK ELECTRODES IN THE STEADY-STATE

The conditions for quasi-first and second order homogeneous catalytic reactions and their variation with each other at an ultramicrodisk electrode in the steady state are discussed in this paper. The order of reaction can be controlled by changing the dimension of the ultramicroelectrode: the second order reaction can be changed to quasi-first by decreasing the dimension of the ultramicroelectrode. An example of this is given. The main factor effect on the reaction order is the dimension of the ultramicroelectrode. The K4Fe(CN)6-aminopyrine system is selected to confirm the theory, the experiments showing that the system is a second order reaction at a 432 mum microelectrode, and a quasi-first order reaction at a 19 mum ultramicroelectrode. The kinetic constant of the system can be determined by applying the previous theory of homogeneous catalytic reaction.

SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF [EU(ETA-6-C6ME6)(ALCL4)2]4 - THE 1ST CYCLOTETRAMERIC LANTHANIDE(II) COMPLEX WITH A NEUTRAL PI-LIGAND

The reaction of EuCl3, AlCl3 and C6Me6 in toluene gives the Eu(II) complex [Eu(eta-6-C6Me6)(AlCl4)2]4; X-ray crystal determination shows the molecule to be a cyclotetramer, in which the four Eu(C6Me6)AlCl4 units are connected via four groups of eta-2-AlCl4.

Apocryffa Si?n Cent

Bryant-Quinn, M. (2004). Apocryffa Si?n Cent. Cyfres Beirdd yr Uchelwyr, 26. Aberystwyth: Canolfan Uwchefrydiau Cymreig a Cheltaidd Prifysgol Cymru.

Investigating the Interhemisphere 14C Offset in the 1st Millennium AD and Assessment of Laboratory Bias and Calibration Errors

Past measurements of the radiocarbon interhemispheric offset have been restricted to relatively young samples because of a lack of older dendrochronologically secure Southern Hemisphere tree-ring chronologies. The Southern Hemisphere calibration data set SHCal04 earlier than AD 950 utilizes a variable interhemispheric offset derived from measured 2nd millennium AD Southern Hemisphere/Northern Hemisphere sample pairs with the assumption of stable Holocene ocean/ atmosphere interactions. This study extends the range of measured interhemispheric offset values with 20 decadal New Zealand kauri and Irish oak sample pairs from 3 selected time intervals in the 1st millennium AD and is part of a larger program to obtain high-precision Southern Hemisphere 14C data continuously back to 200 BC. We found an average interhemispheric offset of 35 ± 6 yr, which although consistent with previously published 2nd millennium AD measurements, is lower than the offset of 55–58 yr utilized in SHCal04. We concur with McCormac et al. (2008) that the IntCal04 measurement for AD 775 may indeed be slightly too old but also suggest the McCormac results appear excessively young for the interval AD 755–785. In addition, we raise the issue of laboratory bias and calibration errors, and encourage all laboratories to check their consistency with appropriate calibration curves and invest more effort into improving the accuracy of those curves.