Chromium ratios

Figure 10. Vanadium/chromium and vanadium/nickel ratios of the top and central portions of the bed. Numbers 1-9 indicate samples taken from localities shown in Figure 9. Solid line are vanadium/chromium ratios, dashed line vanadium/nickel ratios. Stipled areas of columnar samples were not analyzed...

The polymerization of butadiene to 1.2 polymers with anionic Ziegler type catalysts has been studied by Natta and co-workers (46). They have shown that isotactic 1.2-polybutadiene can be produced by the use of catalysts which are made up of components which have basic oxygen and nitrogen structures such as triethylaluminum with cobalt acetylacetonate or with chromium acetylacetonate. Natta and co-workers have shown that either syndiotactic or isotactic structures are produced depending on the ratio of aluminum to chromium. Syndiotactic structures are obtained at low aluminum to chromium ratios while isotactic polybutadiene is obtained at high ratios. The basic catalyst component is characteristic of syndiotactic catalysts. Natta, Porri, Zanini and Fiore (47) have also produced 1.2 polybutadiene using... 

The spectra of successively collected portions of the effluent were found to be qualitatively identical, with well-defined absorption maxima located at 427 and 335 m/i, having absorbancy indices of 110 and 50.0/ mole cm S respectively. The determination of cyanide-to-chromium ratios in the various fractions gave values between 4.0 and 4.2, consistently. These values are probably within experimental uncertainty of 4.00, considering that small amounts of free cyanide not removed by purging with nitrogen gas might have some tendency to adsorb on the anion-exchange column and would, therefore, be eluted with sodium perchlorate. 

In Table 2, a comparison is made of the red cell plasma chromium ratio in rats given soluble Cr(VI) by three different routes of administration. The fraction of absorbed chromium entering the systemic circulation as Cr(VI) declines in the order intravenous > intestinal > oral administration. If... 

Cr(VI) enters the red cell rapidly while Cr(III) does not, the red cell. plasma chromium ratio at any single time point after administration should decline in the same order. As Table 2 shows, this is in fact the case. In addition. Table 2 shows that the red cell plasma chromium ratio increases with time after administration, and suggests that the fraction of an intratracheal dose of Cr(VI) entering the systemic circulation as Cr(VI) may fall between the values for fractional absorption from intravenous and intestinal doses. 

The dichromate ion oxidises iron(II) to iron(III), sulphite to sulphate ion, iodide ion to iodine and arsenic(III) to arsenic(V) (arsenate). Reduction of dichromate by sulphite can be used to prepare chrome alum, since, if sulphur dioxide is passed into potassium dichromate acidified with sulphuric acid, potassium and chromium(III) ions formed are in the correct ratio to form the alum, which appears on crystallisation ... 

Chromium compounds decompose primary and secondary hydroperoxides to the corresponding carbonyl compounds, both homogeneously and heterogeneously (187—191). The mechanism of chromium catalyst interaction with hydroperoxides may involve generation of hexavalent chromium in the form of an alkyl chromate, which decomposes heterolyticaHy to give ketone (192). The oxidation of alcohol intermediates may also proceed through chromate ester intermediates (193). Therefore, chromium catalysis tends to increase the ketone alcohol ratio in the product (194,195). 

Reforming is completed in a secondary reformer, where air is added both to elevate the temperature by partial combustion of the gas stream and to produce the 3 1 H2 N2 ratio downstream of the shift converter as is required for ammonia synthesis. The water gas shift converter then produces more H2 from carbon monoxide and water. A low temperature shift process using a zinc—chromium—copper oxide catalyst has replaced the earlier iron oxide-catalyzed high temperature system. The majority of the CO2 is then removed. 

Most chromium-based catalysts are activated in the beginning of a polymerization reaction through exposure to ethylene at high temperature. The activation step can be accelerated with carbon monoxide. Phillips catalysts operate at 85—110°C (38,40), and exhibit very high activity, from 3 to 10 kg HDPE per g of catalyst (300—1000 kg HDPE/g Cr). Molecular weights and MWDs of the resins are controlled primarily by two factors, the reaction temperature and the composition and preparation procedure of the catalyst (38,39). Phillips catalysts produce HDPE with a MJM ratio of about 6—12 and MFR values of 90—120. 

The width of molecular weight distribution (MWD) is usually represented by the ratio of the weight—average and the number—average molecular weights, MJM. In iadustry, MWD is often represented by the value of the melt flow ratio (MER), which is calculated as a ratio of two melt indexes measured at two melt pressures that differ by a factor of 10. Most commodity-grade LLDPE resias have a narrow MWD, with the MJM ratios of 2.5—4.5 and MER values in the 20—35 range. However, LLDPE resias produced with chromium oxide-based catalysts have a broad MWD, with M.Jof 10—35 and MER of 80-200. 

HTS catalyst consists mainly of magnetite crystals stabilized using chromium oxide. Phosphoms, arsenic, and sulfur are poisons to the catalyst. Low reformer steam to carbon ratios give rise to conditions favoring the formation of iron carbides which catalyze the synthesis of hydrocarbons by the Fisher-Tropsch reaction. Modified iron and iron-free HTS catalysts have been developed to avoid these problems (49,50) and allow operation at steam to carbon ratios as low as 2.7. Kinetic and equiUbrium data for the water gas shift reaction are available in reference 51. 

The only commercial ore, chromite [1308-31-2], which is also called chromite ore, chrome ore, and chrome, has the ideal composition Fe0-Cr2 03, ie, 68 wt % Cr202, 32 wt % FeO, or ca 46 wt % chromium. Actually the Cr Fe ratio varies considerably and the ores are better represented as (Fe,Mg)0-(Cr,Fe,Al)203. Table 1 gives the classification of chromite ores. 

The final consideration for the manufacture of Cr(III) compounds is the mole ratio of acid to Cr. This ratio determines the basicity value of the product. Basicity can also be stated as the amount of positive charge on chromium (ITT) neutralized by hydroxide. For example, is 0% basic,... 

Excess NaOH is used to start the reaction and not over 35% of the chromium is added as dichromate. At the end of the reaction, the thiosulfate is removed by filtration and recovered. The hydrous oxide slurry is then acidified to pH 3—4 and washed free of sodium salts. On calcination at 1200—1300°C, a fluffy pigment oxide is obtained, which may be densifted and strengthened by grinding. The shade can be varied by changes in the chromate dichromate ratio, and by additives. 

Copper—chromium and copper—nickel—silicon—chromium alloys are also precipitation hardenable. The precipitates are nickel sdicides, chromium silicides, and elemental chromium. If conductivity is critical, the chromium—silicon ratio should be held at 10 1 so that appreciable amounts of either element are not left in soHd solution in the copper after aging. Lithium can be used as a deoxidizer in copper alloys when conductivity is important. For a discussion of the principle of age- or precipitation-hardening copper alloys, see Copperalloys,wrought copperalloys. 

Chromium is conventionally deposited from chromic acid solutions containing at least one anionic catalyst, which is usually the sulfate ion. The weight ratio of chromic acid to catalyst is important and, for sulfate-cataly2ed solutions, is maintained about 100 1. Formulations and conditions for operating hard chromium plating solutions are shown in Table 5. 

Such significant increase of accuracy may be explained on the base of analysis of the numerical values of the theoretical correction coefficients and calculated for 1, , and for analytical pai ameter lQ.j,yipj.j,jj- Changing from lines intensities for the ratios of analytical element line intensity to the intensity of the line most effecting the result of analytical element (chromium in this case) measurement enables the decreases of the error 5 or even 10 times practically to the level of statistics of the count rate. In case of chromium the influencing elements will be titanium, tungsten or molybdenum. 

C) 370/656X brittleness after exposure to temperatures between about 700 to 1. OSO-F. stainless steels. chromium stainless steels, over 13% Cr and any 400 Series martensitic chromium stainless steels low in carbon content (high Cr/C ratio). complex chromium compound, possibly a chromium-phosphorus compound. chromium steels at temperatures above about 700 F (370 C) keep carbon up in martensitic chromium steels and limit Cr to 13% max. 

Another class of complexes involves rj (N)-coordinated species of the Nl-unsubstituted pyrazoles. Chromium hexacarbcMiyl and pyrazole or 3,5-dimethyl-pyrazole form [(Hpz)Cr(CO)5] ot [(Hpz )Cr(CO)5] irrespective of the ratio of reactants. In similar circumstances, tungsten hexacarbonyl yields both [(Hpz)W(CO)5]... 

A 5% solution of chromium trioxide-pyridine complex in dry methylene chloride is prepared. The alcohol (0.01 mole) is dissolved in dry methylene chloride and is added in one portion to the magnetically stirred oxidizing solution (310 ml, a 6 1 mole ratio) at room temperature. The oxidation is complete in 5-15 minutes as indicated by the precipitation of the brownish black chromium reduction products. The mixture is filtered and the solvent is removed (rotary evaporator) leaving the crude product, which may be purified by distillation or recrystallization. Examples are given in Table 1.1. 

A silver-gauze catalyst is still used in some older processes that operate at a relatively higher temperature (about 500°C). New processes use an iron-molyhdenum oxide catalyst. Chromium or cohalt oxides are sometimes used to dope the catalyst. The oxidation reaction is exothermic and occurs at approximately 400-425 °C and atmospheric pressure. Excess air is used to keep the methanol air ratio helow the explosion limits. Figure 5-6 shows the Haldor Topsoe iron-molyhdenum oxide catalyzed process. 

The furnace scales which form on alloy steels are thin, adherent, complex in composition, and more difficult to remove than scale from non-alloy steels. Several mixed acid pickles have been recommended for stainless steel, the type of pickle depending on the composition and thickness of the scale For lightly-scaled stainless steel, a nitric/hydrofluoric acid mixture is suitable, the ratio of the acids being varied to suit the type of scale. An increase in the ratio of hydrofluoric acid to nitric acid increases the whitening effect, but also increases the metal loss. Strict chemical control of this mixture is necessary, since it tends to pit the steel when the acid is nearing exhaustion. For heavy scale, two separate pickles are often used. The first conditions the scale and the second removes it. For example, a sulphuric/hydrochloric mixture is recommended as a scale conditioner on heavily scaled chromium steels, and a nitric/hydrochloric mixture for scale removal. A ferric sulphate/ hydrofluoric acid mixture has advantages over a nitric/hydrofluoric acid mixture in that the loss of metal is reduced and the pickling time is shorter, but strict chemical control of the bath is necessary. 

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