The Rare Earths: Their Occurrence, Chemistry, and TechnologyLevy, Stanley Isaac
Science
The Rare Earths: Their Occurrence, Chemistry, and Technology
Levy, Stanley Isaac
Rare earths
The _hydroxide_ is of doubtful individuality, since on drying it loses
water progressively as the temperature is raised, no definite stable
compound being known; in this respect zirconium resembles titanium. When
heated to 100°, its composition corresponds approximately with that
required by the formula ZrO₂,H₂O, but the percentage of water varies
with the history of the specimen. When precipitated by alkalies in the
cold, it forms the so-called α or ortho modification, which, like the
analogous titanium compound, is readily soluble in dilute acids, and
glows when heated. By precipitation at the boiling point, the β form is
obtained; this is less soluble in acids, and does not glow when heated.
The differences between the two forms are by no means sharply marked;
they are rather the limiting forms of a continuously varying series than
distinct chemical individuals, and the properties of any hydroxide
precipitate depend very largely on the conditions under which it is
thrown down.
The hydroxide is insoluble in water, but can be obtained in colloidal
solution after it has been repeatedly heated with dilute acids, which
serve to break down the molecular complexes; it can be also readily
obtained in colloidal solution by dialysis of the nitrate, chloride, or
acetate. In these solutions it is positively charged; electrolytes
precipitate it with great ease. The gel has a very high power of forming
adsorption products. When thrown down from solution by soda or potash,
it carries down considerable quantities of alkali, to which it clings so
tenaciously that the most careful washing cannot entirely remove them.
If the gel be placed in contact with an ammoniacal solution of a cupric
compound, it removes the cuprammonium complex entirely from the
solution, becoming itself deep blue in colour, and leaving the liquid
quite clear and colourless. In colloidal solution it forms adsorption
compounds with negatively charged colloids, especially metals, the gels
obtained from such solutions containing both colloids.
In the presence of hydrogen peroxide, ammonia throws down an hydrated
peroxide, which is also obtained[463] by electrolysis of a brine
solution in which the hydroxide is suspended, oxidation being effected
by the sodium hypochlorite formed. This reaction is expressed by the
equation:
Zr(OH)₄ + NaOCl = Zr(OOH)(OH)₃ + NaCl
[463] Pissarjewski, _Zeitsch. anorg. Chem._ 1900, ~25~, 378.
It is an endothermic compound, and is very unstable, losing oxygen on
standing; by the action of acids it gives hydrogen peroxide. It
dissolves in alkalies containing hydrogen peroxide; from such solutions,
alcohol precipitates salts of the formula R´₄Zr₂O₁₁,9H₂O.
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