The Heats of Neutralization of Potassium, Sodium and Lithium Hydroxides With Hydrochloric, Hydrobromic, Hydriodic and Nitric Acids, at Various Dilutions

“…The potential difference between hydrogen and hydrochloric acid differs from that between hydrogen and hydrobromic acid (26). Richards and Rowe (19) found that the heats of neutralization of caustic soda and caustic potash decrease as the neutralizing acid changes from hydrochloric acid to hydrobromic acid and then to hydriodic acid. The solubility of gases in salt solutions, the heat capacity of water, the displacement of the temperature of maximum density of water, and the quenching of fluorescence in certain solutions by salts show the same general phenomenon.…”

mentioning

confidence: 99%

The Hydrols.

Bancroft¹,

Gould²

1934

J. Phys. Chem.

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Liquid water is recognized as being more or less polymerized ( 7), but very little use is made of this except to account for the temperature of maximum density of water and for its not boiling at 80-193°K. as calculated by van't Hoff, Walden, Tammann, and Sidgwick. In many thermodynamical reasonings the assumption is made tacitly that the degree of polymerization does not change. Very few people are interested in the probability of the different forms of liquid water having different properties. This is the more remarkable because we are quite used to marked changes with different metamers and polymers.We have red N02 and colorless N204; soluble and insoluble sulfur; anthracene and dianthracene; red phosphorus and white phosphorus; diamond and graphite; cyanic acid, cyanuric acid, and cyamelid; acetaldehyde and paraldehyde; oxygen and ozone; ordinary and nascent hydrogen, oxygen, and nitrogen. The enol and keto forms can be distinguished.Polymerized alcohol peptizes pyroxylin while depolymerized alcohol does not. The two forms of chromic chloride and of benzaldoxime each lower the melting point of the other. The dielectric constant of solid nitrobenzene I is nearly four times that of solid nitrobenzene II.The lyotropic or Hofmeister series of chloride, bromide, and iodide is found to hold both for true solutions and for colloidal solutions. In the case of true solutions the series holds for reaction velocity experiments (neutral salt effect), electromotive forces, boiling points, and displacements of the temperature of maximum density. Sodium chloride increases the dissociation constant ( 18) of carbonic acid one thousandfold. Sodium chloride increases the apparent strength of boric acid (16). The apparent molecular weights of sodium chloride, bromide, and iodide vary in that order. The potential difference between hydrogen and hydrochloric acid differs from that between hydrogen and hydrobromic acid (26). Richards and Rowe (19) found that the heats of neutralization of caustic soda and caustic potash decrease as the neutralizing acid changes from hydrochloric acid to hydrobromic acid and then to hydriodic acid. The solubility of gases in salt solutions, the heat capacity of water, the displacement of the temperature of maximum density of water, and the quenching of fluorescence in certain solutions by salts show the same general phenomenon.

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“…These differential heats of dilution are necessary for calculating the temperature coefficient of activity and osmotic coefficients (27,29) and are particularly useful in the calculation of activity coefficients at room temperature from freezing point data. A knowledge of the integral heats of dilution is necessary in order to make proper corrections of measured heats of precipitation (30) and neutralization (31). Where a heat of solution is to be extrapolated to infinite dilution from some finite concentration the integral heat of dilution is required; this is illustrated in the calculation of ionic entropies (32).…”

Section: Results Of Measurementsmentioning

confidence: 99%