The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution. — John Shaqi
The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.Stieglitz, Julius
Science
The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.
Stieglitz, Julius
Chemistry, Analytic -- Qualitative
The fact that ‹all solvents› and ‹all solutes› are included in this
hypothesis, with the sole limiting condition that the solution must
be dilute, is one of great significance and of greatest practical
importance, as we may use any suitable solvent for determinations.
When molecular weights are determined in this way, a very large
number of compounds give the same molecular weight by the solution
method as by the gas method. For instance we have:
Substance. Mol. Wt. Mol. Wt. Solvent.
Gas Method. Sol. Method.
Chloroform, CHCl_{3} 119.5 119.5 Benzene
Carbon bisulphide, CS_{2} 76 76 Benzene
Methyl (wood) alcohol, CH_{4}O 32 32 Water
Ethyl (ordinary) alcohol,
C_{2}H_{6}O 46 46 Water
Ether, C_{4}H_{10}O 74 74 Acet. Acid
Further, the molecular weight of glucose is found in aqueous
solutions to be 180, conforming to the formula C_{6}H_{12}O_{6}, and
agreeing with the molecular weight as obtained by a chemical study of
compounds derived from glucose.
While there are, then, very many agreements in the molecular
weights determined by the solution and by the older methods, it was
recognized, at the outset,[58] that there is also a large number of
apparently ‹abnormal› cases, in which, in particular, ‹much lower
molecular weights› are obtained by the solution methods than by the
gas method,—lower even than the weights consistent with the accepted
atomic weights of the elements in the compounds in question.[59]
For instance, we find 36.5 to be the molecular weight of hydrogen
chloride in the gas form, but in ‹aqueous› solution its apparent
molecular weight, as determined on the basis of van 't Hoff's
hypothesis, is not even a constant; it is found to be less than
36.5 and approaches the limit 18.25, the more dilute the solution,
[p038] the lower being the apparent molecular weight.[60] For sodium
chloride, the formula weight, corresponding to the formula NaCl, is
58.5. This would also represent its smallest molecular weight in gas
form, consistent with the accepted atomic weights for sodium and
chlorine. In ‹aqueous› solution, again, the apparent molecular weight
of sodium chloride is found to be less than 58.5, and more than
29.25, the value found depending on the concentration of the solution
used. For zinc chloride we have, likewise, in aqueous solution values
much less than 136 and tending toward the limit 45, whereas the
formula weight for ZnCl_{2} is 136.
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