Platinum selectivity

We will use the built-in optimizer to optimize the molecule in a stepwise fashion. As Momec3 does not yet automatically assign atom types, please remember to set the atom type for each added atom manually. The list of defined atom types for the current force field can be found in the project-molecule-forcefields section the comments appended to the atom type normally give an indication of the use of the atom type. Atom types for all atoms in the tutorial are present in the standard force field. For platinum, select PT2, for the aliphatic nitrogen atoms the NT atom type, for the aliphatic carbon atoms CT, for the hydrogen atom H, and for the chlorine atoms CL. 

Khuhawar, M. Y., Sarafraz-Yazdi A., Seeley). A. and Uden P. C. (1998) Platinum-selective capillary gas chromatographic determination with microwave-induced plasma atomic emission detection, 824 223-229. 

I.U. Urasa, VD. Lewis, J. DeZwaan, and S.E. Northcott. Characterization and purity determination of trans-( )-l,2-diaminoliquid chromatography with a platinum selective detector. Anal. Lett., 22(3), 579 (1989). 

A pletliora of different SA systems have been reported in tire literature. Examples include organosilanes on hydroxylated surfaces, alkanetliiols on gold, silver, copper and platinum, dialkyl disulphides on gold, alcohols and amines on platinum and carboxyl acids on aluminium oxide and silver. Some examples and references can be found in [123]. More recently also phosphonic and phosphoric esters on aluminium oxides have been reported [124, 125]. Only a small selection out of tliis number of SA systems can be presented here and properties such as kinetics, tliennal, chemical and mechanical stability are briefly presented for alkanetliiols on gold as an example. 

Cyclopropane rings are opened hydrogenolytically, e.g., over platinum on platinum dioxide (Adam s catalyst) in acetic acid at 2 - 4 bars hydrogen pressure. The bond, which is best accessible to the catalyst and most activated by conjugated substituents, is cleaved selectively (W.J. Irwin, 1968 R.L. Augustine, 1976). Synthetically this reaction is useful as a means to hydromethylate C—C double bonds via carbenoid addition (see p. 74f. Z. Majerski, 1968 C.W. Woodworth, 1968). 

Common catalyst compositions contain oxides or ionic forms of platinum, nickel, copper, cobalt, or palladium which are often present as mixtures of more than one metal. Metal hydrides, such as lithium aluminum hydride [16853-85-3] or sodium borohydride [16940-66-2] can also be used to reduce aldehydes. Depending on additional functionahties that may be present in the aldehyde molecule, specialized reducing reagents such as trimethoxyalurninum hydride or alkylboranes (less reactive and more selective) may be used. Other less industrially significant reduction procedures such as the Clemmensen reduction or the modified Wolff-Kishner reduction exist as well. 

Pla.tinum. Platinum catalysts that utilize both phosphine and tin(Il) haUde ligands give good rates and selectivities, in contrast to platinum alone, which has extremely low or nonexistent hydroformylation activity. High specificity to the linear aldehyde from 1-pentene or 1-heptene is obtained using HPtSnClgCO(1 1P) (26), active at 100°C and 20 MPa (290 psi) producing 95% -hexanal from 1-pentene. 

Catalytic dewaxiag (32) is a hydrocrackiag process operated at elevated temperatures (280—400°C) and pressures, 2,070—10,350 kPa (300—1500 psi). However, the conditions for a specific dewaxiag operatioa depead oa the aature of the feedstock and the product pour poiat required. The catalyst employed for the process is a mordenite-type catalyst that has the correct pore stmcture to be selective for normal paraffin cracking. Platinum on the catalyst serves to hydrogenate the reactive iatermediates so that further paraffin degradation is limited to the initial thermal reactions. 

Several processes are available for the recovery of platinum and palladium from spent automotive or petroleum industry catalysts. These include the following. (/) Selective dissolution of the PGM from the ceramic support in aqua regia. Soluble chloro complexes of Pt, Pd, and Rh are formed, and reduction of these gives cmde PGM for further refining. (2) Dissolution of the catalyst support in sulfuric acid, in which platinum is insoluble. This... 

Reduction. Quinoline may be reduced rather selectively, depending on the reaction conditions. Raney nickel at 70—100°C and 6—7 MPa (60—70 atm) results in a 70% yield of 1,2,3,4-tetrahydroquinoline (32). Temperatures of 210—270°C produce only a slightly lower yield of decahydroquinoline [2051-28-7]. Catalytic reduction with platinum oxide in strongly acidic solution at ambient temperature and moderate pressure also gives a 70% yield of 5,6,7,8-tetrahydroquinoline [10500-57-9] (33). Further reduction of this material with sodium—ethanol produces 90% of /ra/ j -decahydroquinoline [767-92-0] (34). Reductions of the quinoline heterocycHc ring accompanied by alkylation have been reported (35). Yields vary widely sodium borohydride—acetic acid gives 17% of l,2,3,4-tetrahydro-l-(trifluoromethyl)quinoline [57928-03-7] and 79% of 1,2,3,4-tetrahydro-l-isopropylquinoline [21863-25-2]. This latter compound is obtained in the presence of acetone the use of cyanoborohydride reduces the pyridine ring without alkylation. 

Isoquinoline can be reduced quantitatively over platinum in acidic media to a mixture of i j -decahydroisoquinoline [2744-08-3] and /n j -decahydroisoquinoline [2744-09-4] (32). Hydrogenation with platinum oxide in strong acid, but under mild conditions, selectively reduces the benzene ring and leads to a 90% yield of 5,6,7,8-tetrahydroisoquinoline [36556-06-6] (32,33). Sodium hydride, in dipolar aprotic solvents like hexamethylphosphoric triamide, reduces isoquinoline in quantitative yield to the sodium adduct [81045-34-3] (25) (152). The adduct reacts with acid chlorides or anhydrides to give N-acyl derivatives which are converted to 4-substituted 1,2-dihydroisoquinolines. Sodium borohydride and carboxylic acids combine to provide a one-step reduction—alkylation (35). Sodium cyanoborohydride reduces isoquinoline under similar conditions without N-alkylation to give... 

Selected physical properties of rhenium are summarized ia Table 1. The metal is silvery-white and has a metallic luster. It has a high density (21.02 g/cm ). Only platinum, iridium, and osmium have higher densities. The melting poiat of rhenium is higher than that of all other elements except tungsten (mp 3410°C) and carbon (mp 3550°C). 

Oxidation of Sucrose. Sucrose can be oxidized by HNO, KMnO, and peroxide. Under selected conditions using oxygen with palladium or platinum, the 6- or 6 -hydroxyls can be oxidized to form sucronic acid derivatives (29). 

To this point the presence of ethylbenzene in the mixed xylenes has been ignored. The amount can vary widely, but normally about 15% is present. The isomerization process must remove the ethylbenzene in some way to ensure that it does not build up in the isomerization loop of Figure 8. The ethylbenzene may be selectively cracked (40) or isomerized to xylenes (41) using a platinum catalyst. In rare cases the ethylbenzene is recovered in high purity by superfractionation. 

For more selective hydrogenations, supported 5—10 wt % palladium on activated carbon is preferred for reductions in which ring hydrogenation is not wanted. Mild conditions, a neutral solvent, and a stoichiometric amount of hydrogen are used to avoid ring hydrogenation. There are also appHcations for 35—40 wt % cobalt on kieselguhr, copper chromite (nonpromoted or promoted with barium), 5—10 wt % platinum on activated carbon, platinum (IV) oxide (Adams catalyst), and rhenium heptasulfide. Alcohol yields can sometimes be increased by the use of nonpolar (nonacidic) solvents and small amounts of bases, such as tertiary amines, which act as catalyst inhibitors. 

Potentiometric Titrations. If one wishes to analyze electroactive analytes that are not ions or for which ion-selective electrodes are not available, two problems arise. First, the working electrodes, such as silver, platinum, mercury, etc, are not selective. Second, metallic electrodes may exhibit mixed potentials, which may arise from a variety of causes. For example, silver may exchange electrons with redox couples in solution, sense Ag" via electron exchange with the external circuit, or tarnish to produce pH-sensitive oxide sites or Ag2S sites that are sensitive to sulfide and haUde. On the other... 

Silver-containing catalysts are used exclusively in all commercial ethylene oxide units, although the catalyst composition may vary considerably (129). Nonsdver-based catalysts such as platinum, palladium, chromium, nickel, cobalt, copper ketenide, gold, thorium, and antimony have been investigated, but are only of academic interest (98,130—135). Catalysts using any of the above metals either have very poor selectivities for ethylene oxide production at the conversion levels required for commercial operation, or combust ethylene completely at useful operating temperatures. 

PROPERICIAZINE AS A SELECTIVE AND SENSITIVE REAGENT FOR THE SPECTROPHOTOMETRIC DETERMINATION OF MICROGRAM AMOUNTS OF PLATINUM... 

Stratifying water systems for selective extraction of thiocyanate complexes of platinum metals have been proposed. The extraction degree of mthenium(III) by ethyl and isopropyl alcohols, acetone, polyethylene glycol in optimum conditions amounts to 95-100%. By the help of electronic methods, IR-spectroscopy, equilibrium shift the extractive mechanism has been proposed and stmctures of extractable compounds, which contain single anddouble-chai-ged acidocomplexes [Rh(SCN)J-, [Ru(SCN)J, [Ru(SCN)J -have been determined. Constants of extraction for associates investigated have been calculated. 

The copper(II) flux is directly proportional to the cuiTent density up to 10 mPJcrcf. The extraction degree of platinum(IV) into the strip solution is less than 0.1 % per hour of electrodialysis. About 55% of copper(II) is removed from the feed solution under optimal conditions. The copper(II) extraction process is characterized by high selectivity. Maximum separation factor exceeds 900 in the studied system. 

The copper(II) transport rate increases, as a rule, as Cu + initial concentration in the feed solution increases. The increase of the caiiier s concentration from 10 to 30 vol.% results in a decrease of both metal fluxes and in an increase of Cu transport selectivity. The increase of TOA concentration in the liquid membrane up to 0.1 M leads to a reduction of the copper(II) flux, and the platinum(IV) flux increases at > 0.2 M. Composition of the strip solution (HCl, H,SO, HNO, HCIO, H,0)does not exert significant influence on the transport of extracted components through the liquid membranes at electrodialysis. 

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