Chromium chloride solution

Reactions with salts. This procedure is more limited and is illustrated by the use of chromium chloride solutions under reflux for partial dealumination of Y and X zeolites (19), as well as of erionite (20). It is assumed that in this case a partial substitution of chromium for aluminum takes place, leading to the formation of Si-O-Cr bonds in the framework (19). Up to 40 percent of aluminum was removed by this method. Zeolites can also be dealuminated with solutions of ammonium fluorosilicate (107). 

Colorimetric comparisons have also been made with green chromium-chloride solutions, and it is found that, in general, the sensitiveness is similar to that of potassium chromate solutions. 

The Behaviour of Chromium Chloride Solutions m presence of added Neutral Salts... 

In the present work, UV-Visible spectroscopy coupled with electrochemistry were used to analyse the influence of oxygen on the chromium chloride solution properties. 

Product Specification. Sodium chlorate can be shipped either as soHd crystals or preblended chlorate—chloride solution. A typical specification for technical-grade sodium chlorate is NaClO, 99.5 wt % min NaCl, 0.12 wt % max moisture, 0.20 wt % max and 5 ppm chromium. 

The residue (12 g) which contains the 18-iodo-18,20-ether is dissolved in 200 ml of acetone, 5 g of silver chromate is added Note 3) and after cooling to 0°, 11.8 ml of a solution of 13.3 g of chromium trioxide and 11.5 ml of concentrated sulfuric acid, diluted to 50 ml with water is added during a period of 5 min. After an additional 60 min, a solution of 112 g of sodium acetate in 200 ml of water is added and the mixture diluted with benzene (400 ml), filtered and the benzene layer separated. The aqueous phase is reextracted with benzene, washed with half-saturated sodium chloride solution, dried and evaporated to yield 11.2 g of a crystalline residue. Recrystallization from ether gives 7.2 g (72%) of pure 3/5, 1 la, 20/5-trihydroxy-5a-pregnan-18-oic acid 18,20 lactone 3,11-diacetate mp 216-218°. 

Butler, G., Stretton, P. and Beynon, J. G., Initiation and Growth of Pits on High-purity Iron and its Alloys with Chromium and Copper in Neutral Chloride Solutions , Br. Corr. J., 7, 168 (1972)... 

Imoi, H., Saito, Y., Kobayashi, M. and Fujiyama, S., Pitting-corrosion-resistant Chromium Stainless Steel , Japan Kokai 7300, 221 (1973) C.A., 79, 22569a Sato, E., Tamura, T. and Okabe, T., Aluminium Anode for Cathodic Protection. 7 Pitting and Corrosion Potentials for Gallium in Sodium Chloride Solutions , Kinzoku Hyomen Gijutsu, 24, 82 (1973) C.A., T9, 12792d... 

Table 2.25 Breakdown potentials for 316S12 stainless steel (cold worked), high nitrogen stainless steel (cold worked), titanium-6Al-4V and cast-cobalt-chromium-molybdenum alloy in continuously aerated aqueous acidified chloride solution 0.23 m [C1 ] pH 1.5 at 25°C. ...

Ferric chloride solutions are particularly aggressive to high-chromium irons. Rates of attack greater than 12 mm/y have been recorded for a 25% solution at 20°C. The useful resistance of the alloys to mine waters which contain this salt is probably because the concentration involved is very much lower than this. 

The occurrence of stress-corrosion cracking in the martensitic steels is very sensitive to the magnitude of the applied stress. For instance, a 13% chromium martensitic steel tested in boiling 35% magnesium chloride solution (125.5°C) indicated times to failure that decreased abruptly from more than 25(X)h to less than 0.1 h as the applied stress was increased from 620 MPa to about 650 MPa (Fig. 8.25). However, the effects of stress on time to failure are not always so dramatic. For instance, in the same set of experiments times to failure for a 17Cr-2Ni martensitic steel gradually decreased from more than 800 h to about 8 h as the applied stress was increased from 500 MPa to 800 MPa. 

Fig. 8.30 Effect of nickel content on the susceptibility to stress-corrosion cracking of stainless steel wires containing 18-20% chromium in a magnesium chloride solution boiling at 154°C...

It is possible to titrate two substances by the same titrant provided that the standard potentials of the substances being titrated, and their oxidation or reduction products, differ by about 0.2 V. Stepwise titration curves are obtained in the titration of mixtures or of substances having several oxidation states. Thus the titration of a solution containing Cr(VI), Fe(III) and V(V) by an acid titanium(III) chloride solution is an example of such a mixture in the first step Cr(VI) is reduced to Cr(III) and V(V) to V(IV) in the second step Fe(III) is reduced to Fe(II) in the third step V(IV) is reduced to V(III) chromium is evaluated by difference of the volumes of titrant used in the first and third steps. Another example is the titration of a mixture of Fe(II) and V(IV) sulphates with Ce(IV) sulphate in dilute sulphuric acid in the first step Fe(II) is oxidised to Fe(III) and in the second jump V(IV) is oxidised to V(V) the latter change is accelerated by heating the solution after oxidation of the Fe(II) ion is complete. The titration of a substance having several oxidation states is exemplified by the stepwise reduction by acid chromium(II) chloride of Cu(II) ion to the Cu(I) state and then to the metal. 

A mixture of 10 mmol of the allyl bromide and 10-15 mmol of the aldehyde, dissolved in 20 mL of THF, is added dropwise at — 5 to 0°C to the chromium(II) chloride solution in THF prepared by method A or B. The mixture is stirred for 36 h at this temperature and then 15 mL of sat. sodium hydroxide and 20 g of anhyd Na2S04 are added stirring is continued for 20 min at 201C. The mixture is filtered over a pad of Celite/Na2S04 (7 l). The filtrate is concentrated and the residue purified, usually by chromatography on silica gel with pentane/diethyl ether or hexane/ethyl acetate. 

Chromium (II) chloride solutions can be prepared by any one of several different procedures. If pure electrolytic chromium is available, the procedure of Holah-Fackler (see synthesis 4) is recommended. Some modification as noted at the end of this procedure may be desirable. If metallic chromium is not available, commercial chromium(III) chloride may be reduced electrolytically (a suitable divided cell is needed), or the reduction may be effected by zinc and hydrochloric acid. The latter procedure, which starts with the most commonly available reagents and apparatus, is described here. 

After the chromium (II) chloride solution has been transferred to flask B, the flow of ammonia through the reaction vessel should be started. The ammonia delivery tube should approach but not dip below the liquid level in flask B. If tank ammonia is used, the tank should be opened carefully to avoid spattering of liquids by a sudden burst of gas. If ammonia is to be generated, the ammonium sulfate solution should be added carefully to the potassium hydroxide in flask C. It may be necessary to cool flask C with ice at first, then to warm the generator later in order to maintain a reasonably constant flow of ammonia. The use of tank ammonia avoids these problems. If zinc was used in the reduction, a precipitate of zinc hydroxide forms first and redissolves. The violet-blue solution stirred at 0° is saturated with ammonia, then a 2- to 3-g. sample of the platinum catalyst is added rapidly to flask B. A strong countercurrent of nitrogen is used to prevent entrance of air into the system when the catalyst is added. The reaction mixture is allowed to stir for one hour while the flask is cooled with ice. 

To the chromium (II) chloride solution prepared as described in the previous section, a 75-ml. aliquot of a 65% ethylene-diamine solution is added slowly with stirring. 

If the chromium (II) chloride is prepared by the Holah-Fackler procedure from electrolytic chromium and hydrochloric acid, a three-necked round-bottomed flask may be used as a reaction vessel, and ammonia may be bubbled directly into the chromium(II) chloride solution using a T-joint in the nitrogen line. Bubbling of the ammonia through the liquid avoids the necessity for stirring. When the above procedure was used, it was necessary to centrifuge the final filtered solution at 2700 r.p.m. for 15 minutes in order to remove all the platinum catalyst. 

Another system under investigation is the iron/ chromium redox flow battery (Fe/Cr RFB) developed by NASA. The performance requirements of the membrane for Fe/Cr RFB are severe. The membrane must readily permit the passage of chloride ions, but should not allow any mixing of the chromium and iron ions. An anionic permselective membrane CDIL-AA5-LC-397, developed by Ionics, Inc., performed well in this system. ° It was prepared by a free radical polymerization of vinylbenzyl chloride and dimethylaminoethyl methacrylate in a 1 1 molar ratio. One major issue with the anionic membranes was its increase in resistance during the time it was exposed to a ferric chloride solution. The resistance increase termed fouling is related to the ability of the ferric ion to form ferric chloride complexes, which are not electrically repelled by the anionic membrane. An experiment by Arnold and Assink indicated that... 

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