Tnn AMERrcex M TNERALocIST JOURNAL OF THE MINERALOGICAL SOCIETY OF AMERICA Vol 25 JULY, 1940 No. 7 CRYSTAL CHEMISTRY OF THE PHOSPHATES,ARSE- NATES AND VANADATES OF THE TYPE A.zXO+(Z) War,r,acBE. RrcHuoNr HaraardUniversity TeelB on CoNrBNrs Page L lntroduction M2 1. Statement of problem M2 2. Criteria for mineralogical classification M2 A. Chemical criteria 442 B. Crystallographic criteria 4M II. Data for the type AzXO{Z) 445 1. Chemistry 445 A. Phosphates, arsenates,vanadates 445 B. Sulphates M5 Lanarkite 445 Dolerophanite M5 C. Silicates .M6 Andalusite 446 Sillimanite. M6 Cyanite. 446 Sphene M8 Datolite. 448 2. Crystallography. .49 A Orthorhombic Section 449 a. Libethenite group 452 Libethenite and adamite 452 Olivenite .. 453 b. Adelite group Adelite 455 Higginsite Austinite. 457 Duftite 458 Descloizite. 459 Descloizite series 459 Pyrobelonite. 460 c. Effectoftheionsin the AA and AB positions 461 B. Monoclinic Section . 462 a. Tilasite group. 464 Tilasite 464 Durangite 465 442 II/ALLACE E. RICHMOND Page b. Sarkinitegroup 466 Sarkinite. +ot Triplite. 468 Triploidite 469 Wagnerite(Cryphiolite) . 470 Cryphiolite. 47r Herderite A'N C. Triclinic Section Amblygonite . 473 Amblygonite series 475 Tarbuttite 475 III Minerals previously classified with members of this type . 476 Cornetite 477 Araeoxen 477 Brackebuschite... .. 477 Spodiosite 477 Calciovolborthite (Tangeite) 477 Pseudotriplite +77 Allauaudite 477 Sarcopside +77 Xan t hoarsenite Melanchlor 478 Morinite and soumansite .. 478 IV. Acknowledgments 478 V. References 478 I. INTRODUCTION 1. SrarnnnNT oF PRoBLEM This investigation was undertaken to determine the extent to which minerals of a single chemical type are related, and whether their chem- ical and physical properties permit their arrangement in a simple classi- fication. The chemicaltype chosenfor this researchis expressedby the general formula A2XO4(Z), which assumed no prior knowledge of the atomic structure. Another formula (AZ)(AXO4), in usein current litera- ture, presupposesa clear perceptionof the structure, which, the writer believes,has not been adequately demonstrated. 2. CnrrBnrn loR MTNERALocTcALCressrlrcerroN A. ChemicalCriter'io. The newapproach to the crystallochemical classi- fication betweenspecies has been hereattempted (Berman, 1937).When minerals are assumedto belong to a chemical type, it implies that their crystal structures may be related through similarities in the relative numbersand sizesof the atoms, the type of bonding betweenthem, and their polarization properties (Stillwell, 1938). In simple chemical com- pounds,these properties are well known, sincemany structural analyses CRYSTALCHEMISTRY OF THE TYPE A,XOA(Z) M3 have been made (Stillwell, 1938).However, in the type AzXO4(Z),Uttle is known concerningtheir structure becauseof their complexity. Never- theless,it is possible to recognizecertain fundamental structural proper- ties which must belong to all minerals of this type. The minerals of the type ArXOa(Z) rrlay be divided into two families, one with a general formula AAXOa(Z), the other ABXO+(Z). This im- plies, in the first formula, that the two ,4 positions are equivalent and must, therefore,be occupiedeither by identical atoms or by unlike atoms whoseionic radii are similar in size and may therefore substitute for each other. When these positions are occupied by identical atoms, simpler compoundsare formed, e.g. libethenite CugPO+(OH)which is typical of a simple salt of this type. If the positions are occupied by different atoms similar in size,a seriesusually results in which the ratio between the two atoms is variable, e.g. triplite (Fe,Mn)2PO*(OH). In this paper, those minerals forming mixed crystals are said to be isomorphous,using the term in its restrictedand classicalsense (in Ber- man, 1937).Further examplesof this relationshipwill be seenunder the discussionof the sarkinite group. The positionsAA, assumedto be equivalentin the family AAXOa(Z)' becomenon-equivalent in the family ABXO+(Z). The AB positions are occupied by unlike atoms whose ionic radii are different, and therefore form double salts in which the ratio between these atoms closely ap- proaches1:1, e.g.adelite CaMgAsOr(OH). Thesecation positionsAA or AB are not necessarilyoccupied by atoms of equal valence,but the sum of such valencesequals four in the phos- phates,arsenates, vanadates and sulphatesand six in the silicates.This is shown in adelite Ca++Mg++Aso+(oH), durangite Na+Al+++Ason(oH) and andalusiteA1+++Al+++SiOr(O). The major division within a chemical type is the family, which is again basedon chemistry. The individual speciescomprising the families do not necessarilyform isomorphousseries with eachother, but they are united by ties of similar cell size, cell edge lengths, axial ratios, optical, chemical and physical properties. The minerals whose properties show this similarity may be said to be homologoas.This term, in mineralogical classifications,should be restricted to the general relationships between families or groups, not to the more intimate relationships between species or series. The family itself may be further divided into groups and specieson the basis of crystallography and other physical properties. In the classification which is given below, each family AAXO+(Z) and ABXO4(Z) containsthree crystallographicsections, orthorhombic, mon- oclinic and triclinic. For purposes of clarity and to avoid repetition, the WALLACE E RICHMOND discussionof the groups and specieswill be given under their appropriate crystallographic sections. This arrangement of the discussion will also bring out certain relationships between the orthorhombic specieswhich would otherwise be lost. B. Crystallographic Criteri.a. The general crystallographic constants from the morphology and r-ray study must be in simple relation. fn many casesthe morphological constants do not coincide with the r-ray constants. This disagreement may lie in the adopted morphological orientation, in the choice of the unit form or both. When such discrep- ancies occur, the morphology is changed in this paper to conform to the T,q.nr,n 1. Cl,lssrFlcnrroN or rrre Pnospn.Lrns, Ansnx,lrns aNo V.q.nlomus ol rnr Cnurrclr- Typn ArXOr(Z) Family AAXOa(Z) Orthorhombic Section Libethenite group Libethenite Cur POr (OH) Olivenite Cu: AsOq (OH) Adamite Znz AsOr (OH) Monoclinic Section Sarkinite group Sarkinite Mnz Asor (OH) Triplite (Mn, Fe), POa (F) Sarcopside (Fe, Mn, Ca)2 POr (F) Pseudotriplite (Fe, Mn)z POr (F) Triploidite (Mn, Fe)g POa (OH) Wagnerite Ms, (Ca,P)Or (F) Triclinic Section Tarbuttite Zn, POr (OH) Family ABXOa(Z) Orthorhombic Section Adelite group Adelite MgCa AsOr (OH, F) Higginsite CuCa AsOr (oH) Calciovolborthite CuCa vor (oH) Austinite ZnCa AsOr (oH) Duftite CuPb AsOr (OH) Descloizite (Cu, Zn)Pb vor (oH) Araeoxen ZnPb (V, As)Or(OH) Pyrobelonite MnPb vor (oH) Brackebuschite PbMn vor (oH) Monoclinic Section Tilasite MgCa AsOr (F, OH) Durangite NaAl AsOa (F) Herderite CaBe PO+ (OH, F) Triclinic Section Amblygonite (Li, Na)Al POr (F, OH) CRYSTAL CHEMISTRY oF THE TYPE AzXoI(Z) structural crystallography. This change is commonly advantageous since the new morphology usually gives simpler indices. A full discussion of the orientation adopted here will be given later' These crystallographic constants, when properly adjusted, may then be used as a basis for arranging the speciesin an orderly manner within their crystallographic sections. The major criteria for a mineralogical classification have now been given. It is, therefore, advisable at this point, before discussingthe de- tails of the data, to present the suggestedclassification. This is given in Table 1. This classification may be compared with that of Dana (1892). The major outline of both classificationsis essentially the same, since both are based on the same principles. Because Dana did not recognize the family, as used here, his arrangement is somewhat difierent. This is due in large part to the fact that the new r-ray technique was not available to him. The classificationsgiven by H:intze and by Doelter are essentially the sameas Dana's with more emphasisplaced on chemistry, which accounts for the somewhat different arrangement. II. DATA FOR THE TYPE ArXO4(Z) 1. CnpnnsrnY A. Phosphates,arsenates, vanailates. No new chemical analyses have been made for this study with the exception of wagnerite, which will be discussedin its proper place. The chemical composition of the members of the type is well known and generally accepted so that a detailed de- scription of each speciesfrom this point of view is unnecessary. B. Sulphotes. Two sulphates, lanarkite, PbzSOr, and dolerophanite, Cu2SOb,may be considered as possible members of the chemical type, since their formulae may equally well be written PbrSOa(O)and CuzSOa- (O), respectively. The r-ray examination of these two minerals in con- junction with their chemical and physical properties shows no relation- ship with the correspondingpropeities of any members of the type. The- study of these minerals has already been published by Richmond and Wolfe (1938,1939). The following table summarizesthese results. Lanarkite DoleroPhonite Comp. PbzSOs CugSOs Ao 13.73 9.39 bo ).06 6.30 Co 7.07 7.62 r asibnics 2.417: | :| 245;A : 116013' 1.490:1: 1 .209; B : l)2o41t Vo 494 380 446 WALLACE E. RICHMOND Lonarhi.te Dolerophanite SpaceGroup Cza3-C2/m' Czn3-C2fm H 2-2.5 3 D 6.92 +. rt Optics X 1.928 1.715 Y 2.007;Y:b 1.820;Y:b Z 2 O36;Z\c:30" 1 .880; 27\ :6 - 19' A comparisonof theseproperties with those shown in Table 4 under the tilasite group indicatesthat