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1.
The oxidation of iron(II) with tert-butyl hydroperoxide was investigated in the absence of oxygen in water, methanol, and the dichloromethane—methanol solvent
mixture (φr = 2:1). The oxidation rate depends on solvent polarity; measured in the presence of SCN− at constant 0.8 mmol dm−3 HCl, the rate constant increases with the polarity decrease passing from water and methanol to the dichloromethane—methanol
solvent mixture. Further, in non-aqueous solutions at this acid concentration the rate constant was higher than the rate constant
in the presence of Cl− only. The oxidation rate measured in the [FeCl]2+ complex in dichloromethane—methanol was slow in acidic medium and increased by decreasing the acid concentration. Approaching
the physiological pH conditions the rate constant attained the value of an order of magnitude of 103 dm3 mol−1 s−1, while very little alteration of stoichiometry of the oxidation reaction was observed. The rate constant measured in the
presence of Cl− strongly depends on electrolyte concentration at concentrations less than 0.5 mmol dm−3 HCl, both in MeOH and the solvent mixture. Based on these results, a possible mechanism of the influence of solvent, acidity,
and ligand type on the rate constant is discussed. We assume that the oxidation proceeds by an inner-sphere mechanism considering
that the breakdown of the successor inner-sphere complex forming reactive alkoxyl radicals is probably the rate-limiting step.
Presented at the 20th International Conference on the Coordination and Bioinorganic Chemistry organized by the Slovak Chemical
Society, Slovak University of Technology, Comenius University, and the Slovak Academy of Sciences, Smolenice Castle, 5–10
June 2005. 相似文献
2.
A. Račkauskas 《Acta Appl Math》1995,38(1):109-129
Let(X
i
) be a martingale difference sequence. LetY be a standard normal random variable. We investigate the rate of uniform convergence
相似文献
3.
Ra. Siegmund-Schultze 《Communications in Mathematical Physics》1985,100(2):245-265
It is shown that for a set of full measure with respect to any translation invariant probability distribution on the space of initial configurarations of classical particle systems on d with interaction given by a smooth superstable potential of finite range there is a solution to the Newtonian equations of motion, provided that the specific energy and the particle density of the initial configuration exist a.s. 相似文献
4.
H. Lüssi 《Helvetica chimica acta》1966,49(5):1681-1684
Vinyl interchange of vinyl phenyl ether with phenols in the presence of mercuric acetate as a catalyst gives the corresponding vinyl aryl ethers in 40–75% yields. The reaction between vinyl phenyl ether and alcohols yields isolable quantities of vinyl alkyl ethers only when this product can be removed continuously during the reaction. 相似文献
5.
The [Ru(bipy)(2)(1)](PF(6))(2) (bipy refers to 2,2'-bipyridine) complex, comprising a ruthenium(II) tris(2,2'-bipyridine) luminophore covalently linked to a di[(o-triethyleneglycoxy)phenyl]amine crown ether 1, has been synthesized and fully characterized. The photophysical properties of this metal complex have been examined in solution at ambient temperature. Luminescence from the metal complex is enhanced significantly in the presence of various adventitious cations, including protons. In particular, Li(+) cations bind to the crown ether, as evidenced by (1)H NMR and luminescence spectroscopy. Cation binding serves to decrease the rate of reductive quenching of the triplet state of the metal complex, thereby increasing the extent of luminescence. The solution-phase conformation of [Ru(bipy)(2)(1)](PF(6))(2), with and without encapsulated Li(+), has been examined by 2-D NMR and by molecular dynamics simulations. 相似文献
6.
Jean Ravez Annie Perron Jean Pierre Chaminade Paul Hagenmuller Loïc Rivoallan 《Journal of solid state chemistry》1974,10(3):274-281
Two series of phases with tetragonal bronze-like structure and composition BaxLi5?2xT5O15 (T = Nb, Ta) have been isolated in the systems BaNb2O6LiNbO3 and BaTa2O6LiTaO3. All these phases show ferroelectric-paraelectric transitions. The Curie temperature increases with the lithium content. The value of TC for Ba2.03Li0.94Nb5O15 is the highest ever observed for this type of structure: the obtained phases are potentially good materials for the harmonic generation of the 0.53-μm radiation. The optical yield of the niobate Ba2.14Li0.71Nb5O15 is about 2.5 times that of Ba2NaNb5O15 and 250 times that of the K.D.P. The crystallographic and dielectric data of the system Ba2.14Li0.71Nb5O15Ba2.14Li0.71Ta5O15 characterize three domains, which are respectively antiferroelectric, ferroelectric, and paraelectric. The Curie temperature and the optical yield decrease with increasing tantalum content. 相似文献
7.
8.
Let V
n
–1
n
be the adaptive process of self-normalized partial sums S
k
of independent random variables X
i
, defined by linear interpolation between the points (V
k
2/V
n
2,S
k
/V
n
), kn, where V
k
2=
ik
X
i
2. We prove that if the X
k
's are symmetric, V
n
–1
n
converges weakly to the Brownian motion W in each Hölder space supporting W
if and only if
V
n
–1 max
kn
|X
k
|=o
P
(1). We give some partial extension to the non symmetric case. 相似文献
9.
In this paper, we extend the Hölderian invariance principle of Lamperti [6] to the case of partial-sum processes based on a triangular array of row-wise independent random variables. As an application, we obtain necessary and sufficient conditions for the almost sure (resp. in probability) weak Hölder convergence of partial-sum processes based on bootstrapped samples. 相似文献
10.
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