Transformation series parakeldyshite-keldyshite: mechanism of transformation, chemical formula revision and crystal structure of keldyshite

Мұқаба

Дәйексөз келтіру

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Аннотация

A holotype sample of keldyshite has been studied and found to consist of aggregates of partially protonated, Na-deficient parakeldyshite (which is predominant) and keldyshite itself. A series of laboratory experiments on the hydrolysis of parakeldyshite was conducted, leading to the clarification of the crystal structure of keldyshite formed during this process. An idealized refined formula for keldyshite, (Na□)ZrSi2O6(OH), has been obtained. As a result of the protonation of the oxygen atom at position O5 and the formation of strong hydrogen bonds (with an O5...O5 distance of 2.458 Å in keldyshite), a series of hinge transformations occurs, causing significant distortion of the Zr–Si–O framework within the crystal structure. The existence of the transformation series from parakeldyshite to keldyshite in nature has been confirmed. The mechanism for keldyshite formation can be described by the reaction scheme: Na+ + O2‒ → □ + (OH)‒. It is likely that the substitution reaction of parakeldyshite by keldyshite occurs via a transition from single crystal to single crystal.

Толық мәтін

Рұқсат жабық

Авторлар туралы

T. Panikorovskii

Kola Scienсe Centre of the Russian Academy of Sciences

Хат алмасуға жауапты Автор.
Email: t.panikorovskii@ksc.ru
Ресей, Apatity

G. Samburov

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Ресей, Apatity

A. Nikolaev

Apatite Museum and Exhibition Centre

Email: t.panikorovskii@ksc.ru
Ресей, Kirovsk

A. Bazai

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Ресей, Apatity

O. Goychuk

Kola Scienсe Centre of the Russian Academy of Sciences

Email: t.panikorovskii@ksc.ru
Ресей, Apatity

I. Pekov

Moscow State University

Email: t.panikorovskii@ksc.ru
Ресей, Moscow

S. Krivovichev

Kola Scienсe Centre of the Russian Academy of Sciences; St. Petersburg State University

Email: t.panikorovskii@ksc.ru
Ресей, Apatity; St. Petersburg

Әдебиет тізімі

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Қосымша файлдар

Қосымша файлдар
Әрекет
1. JATS XML
Жүктеу
2. Fig. 1. Sample No. 9518: parakeldyshite (1) and snow-white pseudomorph of keldyshite (2) after it in association with aegirine (3), eudialyte (4), nepheline (5) and murmanite (6). Umbozero mine, Alluaiv town, Lovozero.

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Метадеректер
3. Fig. 2. SEM images of samples MVC No. 465 (a, b, d) and No. 9518 (c), obtained in the backscattered electron detection mode: parakeldyshite (1), keldyshite (2), phase M-34 (3), catapleite (4), hydroxynatropyrochlore (5).

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4. Fig. 3. X-ray phase analysis of the initial parakeldyshite (1) and phases after treatment for seven days with an acid solution at 20 (2) and 70°C (3). The calculated diffraction pattern of the M-34 phase (4), experimental diffraction patterns of keldyshite (01-072-1944) (5) and parakeldyshite (00-029-1293) (6) are shown.

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5. Fig. 4. Projections of the crystal structures on the (100) plane of the original parakeldyshite No. 9518 (a), parakeldyshite MVC No. 465 (b), keldyshite obtained during the hydrolysis of sample No. 9518 (c), and keldyshite (d) described in [9].

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6. Fig. 5. Projections of the zirconium silicate framework of parakeldyshite MVC No. 465 on the planes (100) (a) and (010) (b); similar projections of keldyshite obtained during hydrolysis of sample No. 9518 (c, d).

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7. Fig. 6. Bond lengths in the coordination polyhedra of Zr, Na1 and Na2 (a–c) in the structures of parakeldyshite MVC No. 465 and keldyshite obtained during hydrolysis of sample No. 9518 (d–e).

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8. Fig. 7. Fragments of the crystal structures of parakeldyshite MVC No. 465 (a) and keldyshite obtained during hydrolysis of sample No. 9518 (b). The arrows indicate the formation of a hydrogen bond between the O5…O5 atoms.

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