THE HYDROLYSIS AND POLYMERIZATION OF CYANOGEN CHLORIDE IN THE PRESENCE OF HYDROGEN CHLORIDE

1947 ◽  
Vol 25b (5) ◽  
pp. 430-439 ◽  
Author(s):  
A. B. Van Cleave ◽  
H. E. Mitton

Cyanogen chloride reacts quantitatively with water in the presence of hydrochloric acid according to the equation: CNCl + 2H2O → CO2 + NH4Cl. As the percentage of hydrochloric acid is reduced towards zero, the rate of hydrolysis at 30 °C. becomes exceedingly slow. The rate of hydrolysis, as indicated by the pressure increase, shows an increase with time which is particularly marked when the concentration of hydrogen chloride is less than 1%. This apparent autocatalytic effect is not due to the accumulation of solid ammonium chloride. A polymerization reaction, the rate of which is increased by the addition of dry hydrogen chloride, proceeds simultaneously with the hydrolysis reaction. Pure cyanogen chloride shows little or no tendency to polymerize at 30 °C. Carbon dioxide has been shown to be quite soluble in liquid cyanogen chloride and an explanation has been suggested for the form of the pressure vs. time curves obtained in studying the acid catalyzed hydrolysis and polymerization of cyanogen chloride.

1913 ◽  
Vol 17 (2) ◽  
pp. 132-151
Author(s):  
Harold Lindsay Amoss

Weichardt claims to have demonstrated the presence of an organic body in the expired air. He allowed the exhaled breath to pass through hydrochloric acid solution, evaporated the resulting solution to dryness on a water bath, and obtained a weighable residue which charred on ignition. If he neutralized the acid solution and concentrated it under reduced pressure, he obtained a solution which inhibited the bluing of the guaiacum indicator by blood. By exposing calcium chloride in a room in which the air had been vitiated, he claimed also to have obtained a substance from the air which prevented the bluing of the guaiacum indicator by blood. The experiments here recorded show that a variable amount of matter is retained by weak hydrochloric solution when exhaled breath is passed through it, and that this matter is volatile on ignition. Contrary to the findings of Weichardt, there is no charring or blackening. Nesslerization shows the residue to consist mainly, if not wholly, of ammonium chloride. This ammonia is believed to have come from the decomposition of food particles about the teeth. In one case the person (S.) had smoked just before the experiment, so that a small amount of the ammonia from the tobacco smoke may have been held temporarily by the saliva and food particles in the mouth and been given off gradually during the experiment. Weichardt's experiments on the inhibition of the guaiacum test for blood by means of the substances retained when exhaled breath is passed through hydrochloric acid or over calcium chloride crystals are not corroborated. It is further shown that the guaiacum indicator is unreliable for these tests in view of the fact that a small amount of free acid or free alkali will inhibit the guaiacum test for blood. This fact is offered as a probable explanation of Weichardt's results. Calcium chloride alone gives a deep blue color with the guaiacin indicator. Weichardt used this salt to collect from the expired breath certain unknown substances which he claims inhibit the oxidation of guaiacum by blood. His results are therefore inconclusive. The phenolphthalin test for blood has been studied in this connection and further light has been thrown on this reaction. The sodium salt of phenolphthalin is colorless in alkaline solution, and is readily oxidized by minute quantities of blood to phenolphthalein which gives a characteristic deep purplish red color in alkaline solution. It has been found that the presence of calcium chloride and ammonium chloride in small amounts retards and, in large amounts, prevents this reaction. It is believed that any salt composed of a weak base combined with a strong acid will have the same effect. This is discussed in the text. It has also been shown that the presence of calcium chloride or ammonium chloride decreases the depth of color of phenolphthalein in sodium hydroxide solution. Carbon dioxide also prevents the oxidation of phenolphthalin by blood. Of course this does not mean that carbon dioxide prevents the action of the oxidizing ferments generally. In this particular case the substance to be oxidized, namely phenolphthalin, was not allowed by reason of the presence of the carbon dioxide to combine with the alkali and thereby assume a state in which it could be easily oxidized. The results of one experiment seem to indicate a relation between the amount of dissolved oxygen in the solutions and the percentage of oxidation. Sodium chloride either alone or with the aid of hydrogen peroxide is able to bring about the oxidation of phenolphthalin in alkali to a very slight extent (3.5 to 5 per cent. in twenty-four hours). Therefore phenolphthalin as a test for oxidizing ferments should not be used in the presence of an appreciable amount of inorganic salts or carbon dioxide. Complete dialysis is recommended in these cases. It is also to be noted that the great delicacy of the test allows considerable dilution. Liquids were obtained from the expired breath by passing this through weak hydrochloric acid or by condensing the moisture in it by conducting it through cooled Drechsel bottles. Attempts were then made to prove the presence in these liquids of some substance which inhibits the oxidation of phenolphthalin by blood, but all were unsuccessful. Moreover attempts to concentrate these liquids by evaporation under reduced pressure or by the passage of a direct current (colloidal travel) were also unsuccessful. It is planned to improve upon the apparatus used to concentrate colloids by the passage of a direct current, and to test the effect of expired breath products on the rate of oxidation of phenolphthalin by blood.


1953 ◽  
Vol 31 (10) ◽  
pp. 923-936
Author(s):  
L. E. Bodnar ◽  
A. B. Van Cleave

A series of hydrogen chloride catalyzed reactions involving cyanogen iodide as the starting material have been investigated in dioxane and in aqueous solution at 30°and 45 °C. The course of the reaction was followed by determining the decrease in the number of oxidation equivalents present. Reaction products identified were: iodine monochloride, iodine, ammonium chloride, and carbon dioxide. A possible reaction mechanism has been suggested.


1979 ◽  
Vol 44 (3) ◽  
pp. 912-917 ◽  
Author(s):  
Vladimír Macháček ◽  
Said A. El-bahai ◽  
Vojeslav Štěrba

Kinetics of formation of 2-imino-4-thiazolidone from S-ethoxycarbonylmethylisothiouronium chloride has been studied in aqueous buffers and dilute hydrochloric acid. The reaction is subject to general base catalysis, the β value being 0.65. Its rate limiting step consists in acid-catalyzed splitting off of ethoxide ion from dipolar tetrahedral intermediate. At pH < 2 formation of this intermediate becomes rate-limiting; rate constant of its formation is 2 . 104 s-1.


1985 ◽  
Vol 50 (4) ◽  
pp. 845-853 ◽  
Author(s):  
Miloslav Šorm ◽  
Miloslav Procházka ◽  
Jaroslav Kálal

The course of hydrolysis of an ester, 4-acetoxy-3-nitrobenzoic acid catalyzed with poly(1-methyl-3-allylimidazolium bromide) (IIa), poly[l-methyl-3-(2-propinyl)imidazolium chloride] (IIb) and poly[l-methyl-3-(2-methacryloyloxyethyl)imidazolium bromide] (IIc) in a 28.5% aqueous ethanol was investigated as a function of pH and compared with low-molecular weight models, viz., l-methyl-3-alkylimidazolium bromides (the alkyl group being methyl, propyl, and hexyl, resp). Polymers IIb, IIc possessed a higher activity at pH above 9, while the models were more active at a lower pH with a maximum at pH 7.67. The catalytic activity at the higher pH is attributed to an attack by the OH- group, while at the lower pH it is assigned to a direct attack of water on the substrate. The rate of hydrolysis of 4-acetoxy-3-nitrobenzoic acid is proportional to the catalyst concentration [IIc] and proceeds as a first-order reaction. The hydrolysis depends on the composition of the solvent and was highest at 28.5% (vol.) of ethanol in water. The hydrolysis of a neutral ester, 4-nitrophenyl acetate, was not accelerated by IIc.


1986 ◽  
Vol 73 ◽  
Author(s):  
Bruce D. Kay ◽  
Roger A. Assink

ABSTRACTHigh resolution 1H NMR spectroscopy at high magnetic fields is employed to study the reaction kinetics of the Si(OCH3)4:CH3OH:H2O sol-gel system. Both the overall extent of reaction as a function of time and the equilibrium distribution of species are measured. In acid catalyzed solution, condensation is the rate limiting step while in base catalyzed solution, hydrolysis becomes rate limiting. A kinetic model in which the rate of hydrolysis is assumed to be independent of the adjacent functional groups is presented. This model correctly predicts the distribution of product species during the initial stages of the sol-gel reaction.


1984 ◽  
Vol 62 (1) ◽  
pp. 74-76 ◽  
Author(s):  
R. A. Burt ◽  
Y. Chiang ◽  
A. J. Kresge ◽  
S. Szilagyi

The acid-catalyzed hydrolysis of the nine-membered ring cyclic vinyl ether, oxacyclonon-2,8-diene, occurs with a normal isotope effect, [Formula: see text], which indicates that this reaction proceeds by the conventional vinyl ether hydrolysis mechanism involving rate-determining proton transfer to carbon. The specific rate of this reaction, [Formula: see text], may then be used to show that there is no significant ring-size effect on the rate of hydrolysis of a vinyl ether group in a nine-membered ring. The previously noted unusually great reactivity of the vinyl ether group in 9-methoxyoxacyclonon-2-ene, for which an unorthodox reaction mechanism has been claimed, must therefore be due to some other cause.


1981 ◽  
Vol 85 (26) ◽  
pp. 4106-4108 ◽  
Author(s):  
Joseph S. Francisco ◽  
Jeffrey I. Steinfeld ◽  
Keith D. King ◽  
Robert G. Gilbert

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