Hydrogen chloride formation chlorine determination

If the concerted four-center mechanism for formation of chloromethane and hydrogen chloride from chlorine and methane is discarded, all the remaining possibilities are stepwise reaction mechanisms. A slow stepwise reaction is dynamically analogous to the flow of sand through a succession of funnels with different stem diameters. The funnel with the smallest stem will be the most important bottleneck and, if its stem diameter is much smaller than the others, it alone will determine the flow rate. Generally, a multistep chemical reaction will have a slow rate-determining step (analogous to the funnel with the small stem) and other relatively fast steps, which may occur either before or after the slow step. 

An account of the elaborate research of Richards and Stahler 2 on potassium chloride appeared in 1907. The salt employed was prepared by the action of hydrogen chloride on potassium nitrate purified by repeated recrystallization with special precautions. After several crystallizations, the chloride was fused in a current of nitrogen. The silver was obtained by reducing the nitrate with ammonium formate. After electrolytic purification, it was fused in a lime-boat in a current of hydrogen, and finally in vacuo. In the analyses the silver required to precipitate the chlorine from a known weight of potassium chloride was determined, and also the weight of silver chloride produced ... 

The effect of added hydrochloric acid concentration was studied in order to determine whether or not the acid had any effect on pyrite and ash removal, sulfate-to-sulfur ratio, final heat content, and possible chlorination of the coal. Coal has many basic ash constituents, so increased ash removal was expected, as well as some suppression of the sulfate-to-sulfur ratio because the reaction that results in sulfate formation also yields eight moles of hydrogen ion per mole of sulfate (common ion effect). Added acid was studied in the range of 0.0 to 1.2M (0.0, 0.1, 0.3, and 1.2M) hydrochloric acid in 0.9M ferric chloride. Duplicate runs were made at each concentration with all four coals for a total of 32 runs. The results showed no definite trends (except one-uide infra) even when the data were smoothed via computer regression analysis. Apparently the concentration range was not broad enough to have any substantial effect on the production of sulfate or to cause the removal of additional ash over that which is removed at the pH of IM ferric chloride ( pH 2). 

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