Significance of the solubility of hydrogen halides in liquid compounds

Abstract

The solubilities of hydrogen halides (HCl, HBr, HI), expressed as xHX moles of HX per mole of a liquid compound, have been determined for a representative selection of compounds at room temperature and below to reveal an essential pattern of behaviour to serve as a guide in operational procedures. Compared with the values predicted by Raoult's law at 0° (xHCl = 0.04, xHBr = 0.09, xHI = 0.37), liquids such as n‐heptane and carbon tetrachloride have slightly lower x values, but show increasing divergence on the low side as the temperature is lowered. Other liquids, such as toluene and alkyl halides, have values greater than those predicted by Raoult's law at 0°, and xHX remains correspondingly higher at the lower temperatures. The xHX values for many liquids can be from 2 to 6 times as great as those for water: xHCl = 0.41, xHBr = 0.49, xHI = 0.39 at 0°. From a consideration of pressure and other effects, a reference pattern of the constitution of the solutions is given. For the non‐aqueous liquids, xHX values greater than Raoult's law values are deemed to be the result of definite chemical reactions involving hydrogen bonding and dynamic equilibria. A case is presented for the desirability of the readjustment of attitudes towards acid‐base function in operational chemistry.

Preparation of the HIV Attachment Inhibitor BMS-663068. Part 3. Mechanistic Studies Enable a Scale-Independent Friedel–Crafts Acylation

“…Conversely, performing the reaction in a sealed vessel with DCE that had been saturated with anhydrous HCl completely inhibited both the desired reaction and the decomposition of 1 . Mixing AlCl 3 and pyrrole 1 in a saturated solution of anhydrous HCl in DCE did not lead to formation of complex ii but gave a different, unidentified species evidenced by a characteristic IR band at 1200 cm –1 that was indefinitely stable at RT. The dramatic difference in reaction performance observed between these two extremes attested to the strong effect of HCl.…”

Continuous Flow Synthesis of n-Alkyl Chlorides in a High-Temperature Microreactor Environment

“…As already hypothesized by Clark, 3 this effect is most likely connected to a decreased solubility of HCl in longer-chain alkyl alcohols. 13 For longerchain alkyl alcohols (for example, 1-decanol) the transfer of HCl to the alcohol phase can thus be considered to be rate limiting. Since the maximum overall pressure in our reactor system is 20 bar, full conversion for 1-decanol could not be obtained.…”

Solubility and calorimetric study of the effects of gas environment on the decomposition of o-nitrobenzoyl chloride

“…Fig. 2 shows the comparison of HCl solubility data in ortho, meta and para-xylene obtained by Ahmed, Gerrard, & Maladkar, 1970 with ours. Our solubility measurements involved slow bubbling of the solute through the solvent at constant temperature until saturation.…”

“…Although some of the data obtained do overlap with ours, higher temperatures are not covered hence the data available for the solubility of HCl in benzene and methylbenzene are also presented. The data obtained by Ahmed et al, 1970 fall on a smooth curve. Values obtained in our laboratory over the temperature range 0-20 8C are in very good agreement with those determined by Ahmed et al Solubilities between 20 and 85 8C form a smooth continuation of that curve.…”

“…Our solubility studies were performed in the temperature range K20-85 8C. Ahmed et al, 1970 studied the solubility of HCl in ortho, meta and para-xylene by bubbling HCl into the solvent in a bubbler tube at a total pressure measured by manometers (Gerrard, 1972(Gerrard, , 1976. The bubbler tube was weighed before and following the solution of the gas to determine the mass of gas dissolved in the solvent.…”