Spectrophotometric determination of zinc in copper-base alloys with TAN

TAN reacts with zinc(II) forming a red complex with composition 1:2 Zn(II)-TAN and absorption maximum at 582 nm. Zinc can be determined with this reagent in the presence of Triton X-100, in the pH range 6.20-8.00 with a molar absorptivity of 4.5×10⁴ l/mol/cm Beer's Law was obeyed up to least 1.55 g/ml. Copper interference was eliminated with a mixture of thiosulfate and ascorbic acid and nickel separated by precipitation with dimethylglyoxime. The proposed method was used for zinc determination in several copper-base alloys and the results of analysis in comparison with certified values indicated that the procedure was accurate and precise. A derivative procedure is also proposed, allowing zinc determination with high sensitivity (5-400 ng/ml).     

Intersections of random walks and Wiener sausages in four dimensions

Let {S ₁ (n)} _n0and {S ₂ (n)} _n0be independent simple random walks in Z ⁴ starting at the origin, and let % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiabfc6aqnaaBaaaleaacaqGPbaabeaatCvAUfKttLearyqr1ngB% Prgaiuaakiab-HcaOiaadggacaGGSaGaamOyaiab-LcaPiabg2da9i% ab-Tha7Hqbciab+Hha4jabgIGiolab+PfaAnaaCaaaleqabaGaaGin% aaaakiaacQdaieGacaqFtbWaaSbaaSqaaiaabMgaaeqaaOGae8hkaG% Iaa0xBaiab-LcaPiabg2da9iab+Hha4baa!5761!\[\Pi _{\rm{i}} (a,b) = \{ x \in Z^4 :S_{\rm{i}} (m) = x\]for the some % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaGqaciaa-1gacqGHiiIZtCvAUfKttLearyqr1ngBPrgaiuaacqGF% OaakcaWGHbGaaiilaiaadkgacqGFPaqkcqGF9bqFaaa!4936!\[m \in (a,b)\} \]. Let two integervalued sequences {a _n}_n0and {b _n}_n0be given, such that the limit lim_n a _nexists and lim _n b _n=+. In this paper, it is shown that the probability of % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiabfc6aqnaaBaaaleaacaaIXaaabeaatCvAUfKttLearyqr1ngB% Prgaiuaakiab-HcaOiab-bdaWiab-XcaSiabg6HiLkab-LcaPiabgM% Iihlabfc6aqnaaBaaaleaacaaIYaaabeaakiab-HcaOiaadggadaWg% aaWcbaGaamOBaiaacYcaaeqaaOGaamyyamaaBaaaleaacaWGUbaabe% aakiabgUcaRiaadkgadaWgaaWcbaGaamOBaaqabaGccqWFPaqkcqGH% GjsUieaacaGFydaaaa!5904!\[\Pi _1 (0,\infty ) \cap \Pi _2 (a_{n,} a_n + b_n ) \ne \O \] is asymptotic to % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaamaalaaabaGaaGymaaqaaiaaikdaaaGaciiBaiaac+gacaGGNbWe% xLMBb50ujbqeguuDJXwAKbacfaGae8hkaGIae8xmaeJae83kaSIaam% OyamaaBaaaleaacaWGUbaabeaakiaac+cacaWGHbWaaSbaaSqaaiaa% d6gaaeqaaOGae8xkaKIae83la8IaciiBaiaac+gacaGGNbGaamOyam% aaBaaaleaacaWGUbaabeaaaaa!5364!\[\frac{1}{2}\log (1 + b_n /a_n )/\log b_n \] if it tends to zero as n, and the probability of % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% qaaiabfc6aqnaaBaaaleaacaaIXaaabeaatCvAUfKttLearyqr1ngB% Prgaiuaakiab-HcaOiab-bdaWiab-XcaSiabg6HiLkab-LcaPiabgM% Iihlabfc6aqnaaBaaaleaacaaIYaaabeaakiab-HcaOiaadggadaWg% aaWcbaGaamOBaaqabaGccaGGSaGaamyyamaaBaaaleaacaWGUbaabe% aakiabgUcaRiaadkgadaWgaaWcbaGaamOBaaqabaGccqWFPaqkcqWF% 9aqpieaacaGFydaaaa!583C!\[\Pi _1 (0,\infty ) \cap \Pi _2 (a_n ,a_n + b_n ) = \O \]is asymptotic to % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiGc9yrFr0xXdbba91rFfpec8Eeeu0x% Xdbba9frFj0-OqFfea0dXdd9vqaq-JfrVkFHe9pgea0dXdar-Jb9hs% 0dXdbPYxe9vr0-vr0-vqpWqaaeaabiGaciaacaqabeaadaqaaqGaaO% abaeqabaaabaGaam4yaiaacUfaciGGSbGaai4BaiaacEgatCvAUfKt% tLearyqr1ngBPrgaiuaacqWFOaakcaWGHbWaaSbaaSqaaiaad6gaae% qaaOGaey4kaSIaamOyamaaBaaaleaacaWGUbaabeaakiab-LcaPiab% -9caViab-XgaSjab-9gaVjab-DgaNjab-HcaOiaadggadaWgaaWcba% GaamOBaaqabaGccqGHRaWkcaaIYaGae8xkaKIae8xxa01aaWbaaSqa% beaacqWFTaqlcqWFXaqmcqWFVaWlcqWFYaGmaaaaaaa!5BAC!\[\begin{array}{l} \Pi _1 (0,\infty ) \cap \Pi _2 (a_n ,a_n + b_n ) = \O \\ c[\log (a_n + b_n )/log(a_n + 2)]^{ - 1/2} \\ \end{array}\], for some constant c, if it tends to a finite constant (1) as n. These results extend some results obtained by G. F. Lawler about the intersection properties of simple random walks in Z ⁴. By using similar arguments, we also get corresponding results for the intersections of Wiener sausages in four dimensions. In particular, a conjecture suggested by M. Aizenman, which describes nonintersection of independent Wiener sausages in R ⁴, is proven.Partly supported by AvH Foundation.     

An Efficient and Simple Entry to N-Substituted beta-Enamino Acid Derivatives from 2-Alkyl-2-oxazolines and 2-Alkyl-2-thiazolines

Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/3-21+G) have been carried out on several representative examples (1e, 1p, and 1l) in an attempt to support and provide the correct geometry of these derivatives. Structural considerations among the possible isomers of compounds 1 are discussed. From these studies it was concluded that the theoretical calculations agree with the experimental results. In addition, a very simple one-pot procedure for the preparation of masked N-substituted alpha-alkylated beta-enamino acid derivatives 2 from 6, 7, and different alkyl halides (R(3)Y) is described.