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61.
提出了一个广谱测定强酸、强碱溶液浓度的方法。用铂电极作工作电极,电位溶出法对溶液酸碱性产生响应。通过调节沉积时间和沉积电位,利用电位溶出法可以检测溶液酸、大致 的浓度范围为2.5mol/L H^ -1.0mol/L OH^-。详细研究了不同测定范围的实验条件,以及溶出过程的响应机理。在不同酸碱性溶液中电沉积产生的氢吸附于电极表面,溶出过程中被溶液中的氧氧化成氢离子,从而产生电位平台。该平台的出现还与随后的电极表面金属/金属氧化物电对电位值有关。 相似文献
62.
Danilov A. I. Molodkina E. B. Polukarov Yu. M. 《Russian Journal of Electrochemistry》2004,40(6):585-596
The oxidation of polycrystalline platinum in 0.5 M H2SO4 is studied by cyclic voltammetry at potential scan rates of 5–500 mV s–1 while varying the potential cycling range. The scheme, which is proposed for explaining the observed acceleration and deceleration of oxygen sorption at 0.75–1.0 V, accounts for the presence of oxygen in the subsurface layers of platinum (Oss) and the formation of a barrier layer comprising complexes Oss–Pt
n
–SO4. Cycling platinum secures certain steady-state contents of Oss at 0.01–1.35 V. In an anodic scan, Oss accumulates at E > 0.85 V (slow post-electrochemical stage) due to exchange of platinum and oxygen atom sites. In a cathodic scan, the desorption of most oxygen gives way to the adsorption of anions, which prevent residual Oss from appearing on the surface. The residual Oss disappears at E < 0.1 V after a sufficiently complete desorption of anions and the destruction of stable complexes Oss–Pt
n
–SO4. Varying the potential cyclic limit leads, after a delay, to other steady-state Oss contents. 相似文献
63.
R. A. Manzhos B. I. Podlovchenko Yu. M. Maksimov 《Russian Journal of Electrochemistry》2006,42(6):658-664
Transients of the open-circuit potential, which are observed when formic acid is interacting wit adsorbed oxygen (Oads) preliminarily accumulated on polycrystalline “smooth” platinum (pcPt), are measure in an aqueous solution of sulfuric acid. It is shown that, as with platinized platinum (Pt/Pt), at large coverage by adsorbed oxygen (θO = 1?0.8), adsorbed oxygen interacts directly with molecules of formic acid from solution. In the region of medium coverages (θO = 0.8?0.2), on the other hand, a mechanism of “conjugated reactions” is realized. It is established that, in the case of pcPt, the direct interaction of Oads with molecules of HCOOH from solution proceeds slower by nearly three times and the interaction via the mechanism of “conjugated reactions,” faster by about three times, as compared with Pt/Pt. 相似文献
64.
B. Michalkiewicz 《Chemical Papers》2006,60(5):371-374
The reactions taking place during methane esterification in oleum were investigated. It was found that the primary products
were methyl bisulphate and formaldehyde, which was subsequently oxidized to carbon dioxide. The catalyst, Pd or PtCl4, was needed to activate methane and for its oxidation to the primary products. The formation of CO2 was not a catalytic process. It was found that the addition of either carbon dioxide or ester into the reaction mixture did
not slow down the reactions. Methane oxidation in oleum is an irreversible process, during which water is produced and subsequently
consumed to give sulphuric acid by the reaction with sulphur trioxide.
Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May
2006. 相似文献
65.
The hydrogenation of benzene and toluene was investigated over US-SSY, -Al2O3, and Ha1-MCM-41 supported platinum catalysts. The acidity of catalyst supports was measured by IR spectra of pyridine adsorption. On the Brönsted acid supported catalyst, both the hexacyclic saturation product and the pentacyclic one, the hydroisomerization product, were observed, and these two products were revealed to be primary reaction products. The two products were proposed to be formed competitively on Brönsted acid sites with carbonium ions as the reaction intermediate. By contrast, no hydroisomerization product was found on Lewis acid supported catalysts. It was inferred that the electron-deficient reaction intermediate formed on Lewis acids could not undertake any skeletal isomerization process to give a pentacyclic saturation product. 相似文献
66.
Pt电极上吸附原子对仲丁醇电催化氧化性能的影响 总被引:1,自引:0,他引:1
运用电化学循环伏安和石英晶体微天平研究了HClO4溶液中仲丁醇在Pt电极及以Sb和S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的电催化氧化过程 .从电极表面质量变化可以看出 ,仲丁醇的氧化与电极表面的氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子可在较低的电位下吸附氧 ,明显提高仲丁醇的氧化活性 .与Pt电极相比 ,Sb吸附原子修饰的Pt电极使仲丁醇氧化的峰电位负移约 10 0mV .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制仲丁醇的氧化 .从电极表面质量变化提供了吸附原子电催化作用的数据 相似文献
67.
Joseph Grobe Duc Le Van Franz Immel Marianne Hegemann Bernt Krebs Mechtild Lge 《无机化学与普通化学杂志》1996,622(1):24-34
Reactive E = C(pp)π-Systems. XLII [1]. Novel Coordination Compounds of 2-(Diisopropylamino)-1-phosphaethyne: [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}], [(Ph3P)2Pt{η2-(iPr2NCP)}], and [Co2(CO)6{η2-μ2-(iPr2NCP)}] 2-(Diisopropylamino)-phosphaethyne iPr2N? C?P ( 2 ) reacts with the Ni(0)-complexes [Ni(1,5-cyclooctadiene)2] and [Ni(CO)3(1-azabicyclo[2.2.2]octane)], respectively, to give the novel complex [{η4-(iPr2NCP)2}Ni{η2-(iPr2NCP)}] ( 5 ), with the 1,3-diphosphacyclobutadiene derivative and 2 (side-on) as π-ligands. The molecular structure of 5 determined by X-ray diffraction on single crystals proves the spin systems and rotational barriers deduced from NMR-data (1H, 13C-, 31P). The PC distances of the four-membered ring of 1.817(2) and 1.818(2) Å – as expected – are considerably longer than the PC bond of the η2-coordinated phosphaalkyne 2 [1.671(2) Å]. – In the reactions of 2 with [(Ph3P)2Pt(C2H4)] or [Co2(CO)8] the ligand properties of 2 resemble those of alkynes affording the complexes [(Ph3P)2Pt{η2-(iPr2NCP)}] ( 7 ) with side-on coordinated 2 and [Co2(CO)6{η2-μ2-(iPr2NCP)}] with 2 acting as a 4e donor bridge in quantitative yield. In attempts to prepare copper(I) complexes of the aminophosphaalkyne 2 by reaction with CuCl or CuI the only isolable product formed in reasonable amounts under the influence of air and moisture is the 1 λ3, 3 λ5-diphosphetene (iPr2N) ( 10 ) (isolated yield: ca. 20%). The crystal structure analysis of 10 indicates a strong structural relationship to the diamino-2-phosphaallyl cation [Me(iPr2N)]+ ( 12 ), the 1,3-diphosphacyclobutadiene ligand (iPr2NCP)2 in the binuclear complex [{η1, μ2-(iPr2NCP)2}Ni2(CO)6] ( 3a ) as well as to the heterocycles (dme)2LiOE2′ (E′ = S, 11a ; E′ = Se, 11b ) prepared by Becker et al. [11b, 35]. 相似文献
68.
D. N. Kravtsov V. M. Pachevskaya A. S. Peregudov E. I. Fedin 《Russian Chemical Bulletin》1995,44(7):1311-1315
A number of compounds of the type oftrans-4-FC6H4Pt(PAr3)2SC6H4F-4, where Ar is a substituted phenyl group, have been prepared starting from the corresponding chlorides. By exchange reactions oftrans-4-FC6H4Pt[P(C6H4F-4)3]2SC6H4F-4 with the above-mentioned compounds or Ar3P,trans-4-FC6H4Pt[P(C6H4F-4)3][PAr3]SC6H4F-4 have been generated in solution. For the latter compounds, the effect of Ar3P oncis- andtrans-ligands has been studied by the19F NMR technique. It has been shown that thecis- andtrans-effects of Ar3P run parallel and are well described by pK
a
values and ionization potentials of the unshared electron pair in Ar3P, as well as by 0 constants of the aryl groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1359–1363, July. 1995. 相似文献
69.
A. V. Makarycheva-Mikhailova S. I. Selivanov N. A. Bokach V. Yu. Kukushkin P. F. Kelly A. J. L Pombeiro 《Russian Chemical Bulletin》2004,53(8):1681-1685
Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN)2] (R = Me, CH2Ph, Ph) with 1,2- and 1,4-PhS(=NH)C6H4SPh in CH2Cl2 afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The latter were isolated in 75—90% yields and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and 1H and 13C1H NMR spectroscopy. The temperature dependence of the 1H NMR spectra of the model [PtCl4{NH=C(R)N=SPh2}2] complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to -70 °C demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40 to -10 °C. The activation free energy of this process was calculated.Published in Russian in Izvestiya Akademii Nauk.
Seriya Khimicheskaya, No. 8, pp. 1618–1622, August, 2004. 相似文献
70.
V. V. Gritsenko O. A. D'yachenko P. Cassoux A. I. Kotov E. E. Laukhina C. Faulmann E. B. Yagubskii 《Russian Chemical Bulletin》1993,42(7):1149-1151
A neutral metal complex, [Pt(dddt)2]° (1), has been obtained by oxidation of the [Pt(dddt)2]– anion with excess (Bu4N)AuBr4 in nitrobenzene. Crystallographic data for 1a=17.854(9) Å,b=18.409(9) Å,c=4.717(5) Å, =68.83(2)°, space group P21/n,Z=4,d
calc=2.55 g/cm3. In1 two independent centrosymmetric [Pt(dddt)2]° molecules are packed in stacks that form layers parallel to the (110) plane. The molecules of1 in the layers have shortened S...S contacts 3.491(9) Å, and 3.594(10) Å. The average bond lengths Pt-S 2.242(7) Å, S-C 1.71(2) Å and C=C 1.40(3) Å, together with the square-planar coordination of Pt in PtS4, suggest considerable conjugation in the metal cycles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1207–1209, July, 1993. 相似文献