Properties of Chlorides

A particularly troublesome property of chlorides is their sensitivity to moisture and their tendency to undergo hydrolysis. Titanium tetrachloride, when exposed to normal (humid) air even at room temperature, fumes-it undergoes hydrolysis  

Similar are the behaviors of aluminum trichloride, zirconium chloride and many other chlorides. There are, however, chlorides like sodium chloride, which do not undergo hydrolysis readily. Only at 600 to 900 °C does the reaction 

It is clear that when the formation of a higher chloride, by the interaction between a lower chloride and chlorine is difficult, the reverse reaction, i.e., the decomposition of the higher chloride to a lower chloride and chlorine, occurs easily. For example, vanadium tetrachloride decomposes, on heating at its boiling point (148.5 °C) to the trichloride and chlorine  

However, heating vanadium trichloride (VC13) above 400 °C causes its disproportionation according to the reaction 

The conversion of a higher chloride to a lower chloride by hydrogen reduction has been mentioned earlier in connection with the formation of the relatively less volatile ferrous chloride from ferric chloride. This type of reaction is more general and is widely used. Vanadium trichloride can be reduced to the dichloride by hydrogen at temperatures higher than 500 °C  

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Noborn [30] has studied the dynamic properties of chloride selective electrodes and their application to sea water. An Orion 94-17 electrode was used in these studies. 

The value of A, < 1 for this Cr(II) reduction, as with the reactions of Eu(II), indicates that the substitution of bridging F by I" is unfavorable in the bridged trrmsition complex in both cases. The two sets of reactivity patterns noted above thus disappear. It has been noted that K < 1.0 when both metal centers are hard acids, whereas AT, > 1 when one reactant is soft e.g., Cu+. These relationships have been rationalized. The much better bridging properties of chloride than water are shown by the data in Table 5.7 and Table 5.9. 

Information regarding the physical and chemical properties of chloride dioxide and sodium chlorite is located in Table 4-2. Table 4-2 lists important physical and chemical properties of chloride dioxide and sodium chlorite, but is not intended to be all inclusive. 

Table 14 Luminescence properties of chloride-bridged dinuclear complexes3... 

Additional properties of chloride solutions have been studied, namel the characteristics of constant boiling hydrochloric acid solutions zirconyl chloride 206) and activity coefficients of zirconium oxychlorii solutions 319). The ultraviolet spectra of hydrochloric acid solutions zirconium and hafnium have been recorded by a variety of investigatoi but no assignments of the spectra have been made to specific species solution 312, 353, 465, 537). 

Interpretation of the results shown in Fig. 10 suggested the following contributions to the understanding of chloride ion-acceptor properties of chlorides of the representative elements, 46,... 

Properties of chloride, MCI4 Liquid, boiling point less than 100 C Liquid, boiling point 86°C... 

The formation and properties of chloride of nftrogen may be also exhibited in tbe following wi. ... 

The presence of CN in the solution shifts the standard potential of the Au/Au electrode by -2.28 V. Therefore Au may be oxidized by oxygen in cyanide solutions, which is used to extract Au from minerals. Table 1.8 summarizes several other examples. Au may be also dissolved by a mixture of hydrochloric and nitric acid. Even the oxidizing power of concentrated nitric acid is not sufficient to oxidize Au to Au. The complexing properties of chloride helps to shift the standard potential from Eau = 1.42 V to = 0.994 V, which is... 

The paper discusses the application of dynamic indentation method and apparatus for the evaluation of viscoelastic properties of polymeric materials. The three-element model of viscoelastic material has been used to calculate the rigidity and the viscosity. Using a measurements of the indentation as a function of a current velocity change on impact with the material under test, the contact force and the displacement diagrams as a function of time are plotted. Experimental results of the testing of polyvinyl chloride cable coating by dynamic indentation method and data of the static tensile test are presented. 

Fig. XIII-9. The dependence of the flotation properties of goethite on surface charge. Upper curves are potential as a function of pH at different concentrations of sodium chloride lower curves are the flotation recovery in 10 M solutions of dodecylammo-nium chloride, sodium dodecyl sulfate, or sodium dodecyl sulfonate. (From Ref. 99.)...

A century ago, Mendeltef used his new periodic table to predict the properties of ekasilicon , later identified as germanium. Some of the predicted properties were metallic character and high m.p. for the element formation of an oxide MOj and of a volatile chloride MCI4. 

The tribromide and triodide of both boron and aluminium can be made by the direct combination of the elements although better methods are known for each halide. The properties of each halide closely resemble that of the chloride. 

The acidic properties of sulphonamides and their mono-substitution derivatives are particularly well illustrated in the alkyl ubstitution compounds, which by reason of these properties can be prepared by two distinct methods. Thus mono- and di-ethylamine, when subjected to the Schotten-Baumann reaction using benzenesulphonyl chloride, gi e benzenesulphonethylamide, and bcnzenesulphondiethylamide respectively. These compounds can also... 

Pinacol possesses the unusual property of forming a crystalline hexahydrate, m.p. 45°, and the pinacol is separated in this form from the unreacted acetone and the tsopropyl alcohol. The magnciaium is conveniently amalgamated by dissolving mercuric chloride in a portion of the acetone mercury is then liberated by the reaction ... 

The above simple experiments illustrate the more important properties of aliphatic acid chlorides. For characterisation, the general procedure is to hydrolyse the acid chloride by warming with dilute alkali solution, neutralise the resulting solution with dilute hydrochloric acid (phenol-phthalein), and evaporate to dryness on a water bath. The mixture of the sodium salt of the acid and sodium chloride thus obtained may be employed for the preparation of solid esters as detailed under Aliphatic Acids, Section 111,85. The anilide or p-toluidide may be prepared directly from the acid chloride (see (iii) above and Section III,85,i). 

The physical properties of a number of aliphatic acid chlorides are collected in Table 111,88. 

The above simple experiments illustrate the more important properties of the anhydrides of aliphatic acids. For their characterisation, the reaction with aniline or p-toluidine is frequently employed. Alternatively, the anhydride may be hydrolysed with dilute alkali as detailed under Acid Chlorides, Section 111,88, and the resulting acid characterised as in Section 111,85. 

The physical properties of a few tjrpical acid chlorides of aromatic acids are collected in Table IV, 18 7). Some acid anhydrides are also included in this Table (compare Section 111,94). 

Benzoyl chloride test. (This is an alternative to the acetyl chloride test.) Place I ml. of the compound, 0 5 ml. of redistilled benzoyl chloride CAUTION in handling) and 2-5 ml. of 10 per cent, aqueous sodium hydroxide in a small test-tube, cork the tube and shake vigorously until the odour of benzoyl chloride has disappeared. Observe the odour, density and other obvious properties of the product. 

Benzoyl chloride test (for primary and secondary amines). Place 0-5 ml. (or 0 5 g.) of the compound, 10 ml. of 5 per cent, sodium hydroxide solution and 1 ml. of benzoyl chloride (CAUTION) in a test-tube, stopper the tube and shake until the odour of benzoyl chloride disappears. Examine the properties of the substance formed. 

The most apparent chemical property of carboxylic acids their acidity has already been examined m earlier sections of this chapter Three reactions of carboxylic acids—con version to acyl chlorides reduction and esterification—have been encountered m pre vious chapters and are reviewed m Table 19 5 Acid catalyzed esterification of carboxylic acids IS one of the fundamental reactions of organic chemistry and this portion of the chapter begins with an examination of the mechanism by which it occurs Later m Sec tions 19 16 and 19 17 two new reactions of carboxylic acids that are of synthetic value will be described... 

Poly(vinyl chloride) as previously discussed in Sec. 10.3, Formulas and Key Properties of Plastic Materials, has the following structures ... 

The common physical properties of acetyl chloride ate given in Table 1. The vapor pressure has been measured (2,7), but the experimental difficulties ate considerable. An equation has been worked out to represent the heat capacity (8), and the thermodynamic ideal gas properties have been conveniently organized (9). 

The important chemical properties of acetyl chloride, CH COCl, were described ia the 1850s (10). Acetyl chloride was prepared by distilling a mixture of anhydrous sodium acetate [127-09-3J, C2H202Na, and phosphorous oxychloride [10025-87-3] POCl, and used it to interact with acetic acid yielding acetic anhydride. Acetyl chloride s violent reaction with water has been used to model Hquid-phase reactions. 

The cooled, dried chlorine gas contains - 2% HCl and up to 10% O2, both of which are removed by Hquefaction. A full scale 600-t/day plant was built by Du Pont ia 1975. This iastaHatioa at Corpus Christi, Texas operates at 1.4 MPa (13.8 atm) and 120—180°C and uses tantalum-plated equipment and pipes. Oxidation of HCl Chloride by JSHtricHcid. The nitrosyl chloride [2696-92-6] route to chlorine is based on the strongly oxidi2iag properties of nitric acid... 

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