TOPICS IN INORGANIC AND GENERAL CHEMISTRY ‘A COLLECTION OF MONOGRAPHS EDITED BY P. L ROBINSON Emeritus Professor of Chemistry inthe Univeristy of Dushare an the University of Newcastle upon Tyne MONOGRAPH 11 Other tits in the clletion: 1 The Chemistry of Berylium by D. A. Evenesr 2 Inonanie ton Exchangers by C. B, Awpuert 3 Imiroduetion to the Atomic Nucleus 4y J. G, Cuxiicnams 4 3 ‘The Chemisty of the Rare-Earth Elements by N, E. Torr ‘The Chemistry of Gallium by I A. Suaxa, IS. Cavs and TT, Mirvuneva 6 ‘The Chemistry of Technetium and Rhenium by RD. Peacock 7 The Chemistry of Setenium, by KW. BAGNALL 10 The Chemistry of Niobium and Tantalum 6p F, PaIRBROTHER In preparation. ‘The Chemistry of Noble Gases by N, Banrtrr Reactions in Liquid Ammonia by G. W. A. Fowtss and D. NicHous (Carbons: Their Structure and Properties by H. Hanxcen and H, MaRsmt Active Carbon by M, Swix and 8, Cunns Fused Sats by G. J, Hints and D. Keaniooe ‘Chemistry and Technology of Uranium by E. H. P, CoxDruNKe THE CHEMISTRY OF TITANIUM AND VANADIUM An Introduction to the Chemistry of the Early Transition Elements ty R.J.H. CLARK M.Sc, (N.Z.) Ph.D. (Lond) University College, London (Great Britain) ELSEVIER PUBLISHING COMPANY AMSTERDAM / LONDON / NEW YoRK 1968@ Preface Some aspects of the chemistries of titanium and vanadium are very old, but only in the last decade has the complex chemistry of ‘hese elements been studied in any detail. This advance has come low oxidation states, m show a number of fies to one another, and, especially in the +-3 and lower nn states, to chromium. It therefore seemed desirable to the two elements together in a monograph in order to bring these 5, at the same time drawing attention to th the related heavier transition elements, zirconium, iobium and tantalum. It is thus hoped that much furt be stimulated, for it ins true that considerably less work has been done on the he reactions and properties of the halides and oxyhalides of the + because these are the most frequently used starting \crials for new reactions. Emphasis has also been laid on the ictures of compounds, especially those determined by X-ray raction, and extensive discussion of the electronicand vib a of various species and of the magnetic properties inds are included, Alloys and detailed metallurg ly treated. compounds.va PREFACE A fairly extensive bibliography to each section is included, but in order to keep t have frequently been ci Journals have been scanned up to mid-1967, but many papers published in late 1967 haye also been included, The major source- books on the older Tam indebted to W. P. Grirrira, and to Professor P. L, Roninson. I am also very grateful to Dr. A. E. Comyns and his associates at British Titan Products Co. Ltd., Billingham, Co. Durham, for their comments and for granting me access to th J am also grateft lowing journals for permission to p ly modified forms, diagrams from their journal rca Scandinavica, Angewandte Cheinie, Inorganie Chemistry, Journal of the American Chemical Society, Journal of Chemical Physies, Journal of the Chemical Society, Journal of the Physical Society of Japan, Nature, Journal of Polymer Seien organische und Allgemeine Chemie, Reference to the source is made with the captions to each figure. Edgware, 1968 RIHC Contents troduction References hoptr 3 Compre of anum( IY), Vena HAV) and Y) CChtoro- and brorao-compiexes ofttanium(l¥) Complexes of vanedium tetrachloride Complexes of titanium tetraiogide esablo and rated metal comple References Canter 4, Comers of erent Tana at Yond{ x CONTENTS CONTENTS xI References... ities a ‘Canter 5. Comper of Tanta end anaCHAPTER 1 Discovery, Isolation, General and Elementary Properties of Titanium and Vanadium Discovery, isolation and properties of titantum metal Introdu ‘Titanium is a relatively common clement which has been known over 170 years. It is the ninth most abundant element in the 's crust, being twenty times as abundant as carbon, and out iked only by oxygen, silicon, aluminium, iron, magnesium, icium, sodium and potassium, in that order. The average tita- 1m content of the lithosphere is 0.63% by weight. Yet is century, that the element has developed any tential, partly because of difficulties associated with its refine- tt by Hunter! by eduction of the tetrachloride with sodium, In 1925, van Arkel and de Boer? obtained a very pure form of the metal by dissociation the ide. Nevertheless, the tit olves reduction of the tetrachloride with magnesium. The p properties of titanium which recommend it to metallurgists and neers are its low density, strength and resistance to cor- ion, The most important industrial use the dioxide (rutile or anatase) as a white pigment in the paint s outstanding property is its opacity or covering power: together with jts relative chemical inertness, have is in the form Aeteences p172 DISCOVERY, ISOLATION, PROPERTIES 1 Discovery (now known tobe ilmenite), which had been sent to im for analysis, from the Menacchan valley in Corn the sun, in stars and in meteorites. In the Ear the principal ores are ilme important deposit of ilm hhad been mined there for discarded; it was not until the end of the nineteenth century that ‘the titanium was first recovered and used in very small amounts (<1%) to refine the crystal structure of some steels and aluminium alloys. Imenite is widely distributed as a black sand on many imenite-producing 1965 production figures, are Canada, , Norway, Malaysia and Finland. Rutile is less common, but is produced commercially in Australia and Sierra Leone. Some other minerals of (Ba, Sr, K) Na (Ti, Fe) Ti Sis (O, OH, F)s, benitoite te (Mg, Fe)sTiBsOs, osbornite TiN, and lographic details for all these minerals perovskite CaTiOs. Cr have been tabulated, Preparation of the metal It is not possible to obtain titanium metal by the usual method of reduction of the dioxide with carbon, because a very stable carbide is formed. Moreover the metal is reactive towards nitrogen PREPARATION OF TITANIUM METAL 3 .ygen at elevated temperatures, and hydrogen at 900°C only cs TiOs as far as TiyOs. Reduction of the di ing metals, e.g. Na, Al, Ca or Mg, seldom scems to yield a pure ct; the most common contaminants,and in some cases the products, are lower oxides of titanium, Reduction of the loride is thus the basis of the preferred methods. ‘A successful laboratory method is reduction of the dioxide with 1g the he first general method for the ion of the metal involved reduction of the tetrachloride sodium! In-+ 4 Na>Ti +4 NaCl AG? = —226,200-+ 65.27 (calm) “ion, which is very exothermic, is carried out at 700-800 °C steel bomb under an inert atmosphere, The method, which es very careful control of the temperature, is capable of jum metal with a purity of 99.9%, It is also possible wepare the metal by hydrogen reduction® of the tetrachl ~2000°C: TiCl, + 2 Ha» Ti+ 4 HCI AG? = 87,100 —358T —(cal/m) diffcutties of removing hydrogen from the metal, and the high peratures required, make the method impr: ‘nother important way of producing the met 1338 in which magnesium is the reducing agent. is by the Kroll TiC + 2 Mg->Ti +2 MgC AG* = 19,2004 457 (eal/m) rnces ITeter: 4 DISCOVERY, ISOLATION, PROPERTIES 1 ‘The magnesium is contained in a molybdenum-coated iron crucible in an atmosphere of argon at 850-950°C; the TiC is added drop by drop. Towards the end of the addition the temperature is slowly raised to a maximum of 1180°C, that is, to slightly above the! point of magnesium. After cooling the crucible in argon, the magoesium and magnesium chloride are extracted with water and alternatively, these materials may be removed by above 1000°C. The process is clearly expensive, ‘because it involves the prior preparation of the tetrachloride from ilmenite or rutile, followed by fractionation of the TiCl, to remove any FeCls. Some electrolytic methods are also available (mainly for the recovery of titanium from scrap metal), and these have been the subject of extensive research particularly by the U.S. Bureau of Mines (published in a series of reports). The metal is normally formed as a sponge by the above methods, and this may be fused in an atmosphere of argon or aan electric arc, and cast into ingots. Extremely pure titanium on a laboratory scale may be prepared by the method of van Arkel and de Boer; in this, impure titanium is allowed to react with iodine at 150-200°C and the resulting tetraiodide vapour is decomposed into the elements on an in- candescent tungsten filament®.7 at ~1300°C. The methods used for the preparation of titanium have been reviewed in detail by Brauer”, Pr of the metal im is dimorphic with a transformation temperature of 882 4. 5°C. Below this temperature, the metal is hexagonal (Den!-— (Cb6|mme, Z = 2) with lattice parameters at 25°C ofa = 2.9504 A and c= 4.6833 A (a-form)'s8, The second (8) form is cubic (04° — Im3m, Z = 2) with the cell parameter? of 3.3065 A at 900°C. The two forms are isomorphous with the corresponding forms of zit- ductile metal with important industrial Jess dense than iron, much stronger than PROPERTIES OF TITANIUM METAL 5 ium, and almost as corrosion-resistant as platinum. Ale is unlikely ever to be as cheap as steel, its rare combination. pertics makes it ideal for a variety of uses, particularly in » aircraft frames, some marine equipment, in industrial ind in laboratory equipment. Certain properties may be ed by alloying it with aluminium, 'e metal has a tremendous affinity for oxygen, nitrogen and gen at elevated temperatures, but only in the case of hydrogen ‘bsorption reversible. Moreover, titanium dust is explosive and evena fresh surface of the metal will ignite spontaneously ‘ygen at 25 atmos. Traces of oxygen or nitrogen render the very brittle and hence of little utility. The kinetics of oxidation We metal in the range 850-1050 °C have been studied®*, It is icked by mineral acids in the cold or by hot aqueous alkali, issolves in HF, hot HCI, hot HNOs and hot concentrated 1. It reacts with many metals and non-metals forming inter- oF interstitial compounds, e.g. with Al, Sb, Be, Cr, Fe id B. Other properties of the metal are sum in Table 1, id detailed metallurgical aspects are available in three text. Discovery, isolation and properties of vanadium metal Discovery ‘The discovery of clement 23 was fist claimed in 1801 by del jo, 8 professor of mineralogy in the University of Mexico, who lered it to be present in a lead mineral. He gave it the name mn account of the variety of colours of its derivatives id media. Although these observations were reported by von lt in 1803, in the fo ‘tion, that the mineral was a basic chromate of lead, ‘The element was unequivocally discovered in 1830 by the Swede in an iron ore from Taberg, Sweden, He gave it the name lium, after Vanadis, a name of the Scandinavian goddess Keterences 9176 DISCOVERY, ISOLATION, PROPERTIES 1 TABLE 1 [PROPERTIES OF THE ELEMENTS Property ‘Tania Vanadium Blectronie structure ust sate 451@ 60-616 42) 1668 1919) 2282 3400 Magnetic susceptibility 108 7, (casu) 153 21 (atomic, 25°C) ‘Metalic radius (A) 147 733 “163 037 Heal of atomisation (Keal/g. atom) 1126 * Redox couples in aqueous acd solution ex: ® VI. Vepexevey, LV. Guavics, V. N. KONORAT'YEy, ¥. A. MEDVEDEV AND Y. 1, Frawxevicn, Bond Energies, Ionization Pte ‘Amol, London, 1966, and Electron Afiniie, recognition of the richness of the colours ofits derivatives. lentified vanadiumas the original erythronium indeed itis now known that the original mineral was the vanadium ore, vanadinite!®.12,12, The greatest contributor to the early chemistry of vanadium was H. B. Roscoe, who in a series of papers over the period 1868— 1871 laid the foundations for most of the subsequent work. ‘The element in the combined state is distributed widely in the Earth's crust to an extent variously estimated as between 0.01 and 0.05%. There are over sixty vanadium ores, the most important of which is patronite, the polysulphide VSs, found in association with sulphur 2s well > sulphides. Other important ores are vanadinite 3Pb,(VO,)2 * PbCle (which has the same structure as luorapatite and chlorapatite), carnotite K(UOs) (VO.) “15 HO, roscoelite, a vanadium-bearing mica, mottramite (Pb, Ca, Cu)a(VOo)s, descloizite (Pb,Zn)s(VO.)a and tyuyamunite, uranium- and calcium-bearing vanadate, Ca(UOp - VOi)e - 430. PREPARATION OF VANADIUM METAL, 7 clement has been identified in the sun, in stars and in mete- es, and also in low concentration in a large number of plants ‘animals in which it appears to play an important role, United States is the largest producer and consumer of 'um, the bulk of the output being a by-product of the accel- erated uranium production programme in operation!? between 6. At the present time, it continues to be a co-product carnotite ores being mined for their uranium content. ‘The leading producers of vanadium in the Western World ind and South Africa, although several other potentially erable deposits are known to exist in other countries, The deposits of asphaltte in Peru are now depleted. ‘The principal use of vanadium is as an alloy with steel which it oughens; high-speed stccls may contain a much as 4-5°% of snadium. The metal is believed to remove oxygen and nitrogen the steel to give a more uniform grain size, reparation of the metal Vanadium is most commonly prepared in the form of ferro- adium, which may contain anything from 35-95%, of vanadium, method involves reduction of the oxide or the vanadate with and fei 2V2Os + 5Si->4V + 5Si02 SiOz + CaO > CaSiOs very difficult to prepare, principally because it mbines readily with carbon, nitrogen, hydrogen and oxygen and th some of the products. Three principal ‘thods have been used forits prepa reduction of chlorides, ion of the diiodide. i to the first method, the tetrachloride may be reduced metal by sodium, by hydrogen over magnesium heated to ; by sodium hydride, or apparently best (99.95% pure) by rogen in argon at 680-700°C. The pure metal may also be ved by reduction of the trichloride with hydrogen at 900°C, h P Kotioonoee m1?8 DISCOVERY, ISOLATION, PROPERTIES 1 ‘or with magnesium turnings at 750-800 °C. The dichloride is also reduced to the pure metal by these reducing agents!®. Clearly, ‘oxygen and nitrogen must be carefully eliminated in ‘methods; any hydrogen associated with the metal can us removed by heating in a vacuum, ‘The second general method involves reduction of the pentoxide with a suitable reducing agent such as mischinetall, a mixture of lanthanide metals (principally cerium). Probably the purest vana- dium arises from reduction of the pentoxide at 900-950 °C in an jods are also available involving the reduction of the sesquioxide VaOs. Another method, due to van Arkell, is the dissociation of the on an incandescent tungsten filament. Impure metallic um and iodine are sealed in a silica tube containing the filament under vacuum, and heated to 900-1000°C. The vanadium is transported as the difodide to the filament and decomposed there vanadium as for the Group IV metals. Very high pu ‘metal (99.95%) can also be prepared by electro-refining caleium- reduced vanadium in either bromide or chloride electrolytes2®, Properties of the metaf® Iver metal which crystallises in a body- centred cubic lattice with a unit cell length#3® of 3.0282 A. It is be- lieved to undergo a phase transformation at 1550 °C. The pure metal is malleable and ductile, and can be cold-worked into i ies such as hydrogen are brittle, and to modify its other properties ‘Thus the hardness of the metal has been variously ‘The purest metal is so soft that it can be cut with a knife2 ‘The density of the metal, at ~6, lies between that of titanium IsotoPES 9 ‘on, while its thermal conductivity is similar to that of measurements of the melting point gave values in ity of 1700°C, bi ‘measurements. (1952) the figure at 1919 -i2°C. The metal is wealdy paramagnetic (see Tabi in the massive state, the metal is not attacked by air, water, alkalies oF non-oxi weds other than HF at room mperature. However, it does dissolve in concentrated sulphuric id, nitric acid and aqua regia. At high temperatures it combines h most non-metals. In air, itis oxidised via the lower oxides to ‘20s, and on heating with the Group VBelements, the compounds VN, VP, VPs, VAs and VsAs are produced. A variety of products sre formed with carbon, silicon and boron, e.g. VC, VSi, VsSi, »mpounds with non-metals are non- Both nitrogen and carbon raise the ‘Halogens react with vanadium to give ides, the precise product depending upon the temperature and pressure in the reaction vessel. ‘The metal alloys or forms definite compounds with a number of 'et metals, and in particular forms a solid solution im. It also displays catalytic propert iety of chemical reactions. Isotopes of titanium and vanadium ‘um has five naturally occurring isotopes with mass numbers 1g from 46 to 5 ‘measured nuclear spins of the various nuclides, half-lives, and some details of the modes of decay, the ms emitted and their energies (in MeV). Where different les of decay are possible, they are listed in order of decreasing dance, if this information is available®2.1, esorences 01710 DISCOVERY, ISOLATION, PROPERTIES 1 TABLE 2 ‘sotopie Nuclear ‘Half —Decay modem Neclde — % ase in ie rations, ‘nerses ee er ps8 wm | = a3997 tae ey “T ga95813, 2 3.08h BL OR Ey “Ta some om a8 4695165 em 1394 asap em S51 agoane? 72 wn 534 ap.sucre9 en = S096 = p2itiy eee 7 Be vy = ase * ey = agpsaeg = 189: “v= ome 08: av = agomasn a Ec ey om apaTi6s ty BOA ECs ay 99.76 so94978 © ey = Simo 26:9 sy > Rear B25: ee S aay 5 = second; m= minute; h- hour; y ~ years EC = eleciran expture; particle energies in MeV. *P.E, Monitann and D. Hevwanny, J. Trorg. Nucl. Cem. 27 (1965) 493. ‘The atomic weight of titanium is 47.90 (on the 140 scale) as determined by the ratio TiCU/4Ag and TiBr/4Ag. That of ‘vanadium on the same scale is 50.95, based on the ratio® VOCIs/ 3Ag, The atomic weight of titanium based on the 1C scale is also given as 47.90, whereas that of vanadium on this scale is 50.942. Slight sep. titanium isotopes is possible in the extraction of itanium by ether from aqueoussulpl mn factors®® are Ti:**Ti = 1.006, #*Ti:4°Ti = 1.008 and S°Ti:4*Ti ~ 1.014. PROPERTIES OF GRoup TV ELEMENTS General properties of the Group IV elements tunium is the rst member of the 3d transition seties and has our valence electrons, 34s. The most stable and most comma ion state of four involves the loss of all these electrons nwever, the element may also exist in a variety of lower oxidatien, , most importantly as Ti, but algo ia the 2, 0,—Land 9 s. The last two of these, Known only in compounds such ae ipy)ol"~ (Chapter 5), may not be genuine oxidation states of metal, but may involve reduction of the ligands. Zirconiuen sa similar range of oxidation states, but the tervalent stare less stable relative to the quadrivalent: titanium. Little work has been done on hai ter- and quadrivalent states, but in gener splay a remarkable similarity to those of zirconiu ‘The ionisation potentials ofthe Group TY elements are given in TABLES IONISATION POTENTIALS OF GROUP 1V ELEMENTS (RV)12 DISCOVERY, ISOLATION, PROPERTIES 1 on passing down the group, this being associated with the altemna- tion in the screening constants and hence with the effective nuclear charges (Z*) of the different atoms. In particular, the third member of a group (Ge in this case) first suffers the transition-metal con- traction associated with the poor screening of the underlying d'° shell, and the fifth member (Pb) first suffers the double contraction shell. Consequently these elements have higher ionisation potentials ‘than might otherwise have been expected. The elements of Group IVA (Ti, Zr, Hf) have uniformly lower ior those of Group IVB, and former achieve high coordination numbers with greater Facility than the latter. inverse, as the inversely proportional to the radius. This is clear from Fig. 1, in which the M-Cl bond lengths for the tetrachlorides are shown. ‘The energy required for the removal of the four valence electrons of titanium is so high that the nor do the Zr‘ and Hf‘ ions, but Tat is known. Ti radii of Ti and Sn). For instance TiOs (rutile) is isomorphous with TABLE 4 IONIC (\") AND COVALENT RADII OF THE GROUP IY BLEMENTS c on uSi 04, 1.1) nGe 053, wSn O71, nro 0h a7 Properties of Grour IV ELEMENTS 13 25) 2] M=cl Distance (A) 20.40 6080 ‘Atomic Number big. Metal-chlorine (M-C) bond lengths ‘There are also series of hexahalo-anions such as TiFe~, Goofs? TiClet, SnCle?— and PbCle?~, some of the salts of which are isomorphous. The tetrahalides of zirconium and hafnium are chlorine-bridged mers and hence are not soluble in non-coor theless, they possess strong acceptor properties and many logous and even isomorphious Ti, Zr and HF compounds have order is Ge UFe > MoFs > WFe > NbFs = TaFs. Although the crystal structure of the pentafluoride has not yet ‘been determined, the volatility of the compound in relation to that of the other vanadium fluorides suggests that it is a polymer of hexacoordinate VFs units, each sharing two fluorine atoms with adjacent octahedra®. The standard heat of formation of vanadium pentafiuoride has recently been determined® from measurements of the heat of hydrol lute sodium hydroxide solution. It is —352 Keal/m. Vanadtum oxytrifluoride ‘Vanadium oxytrifluoride may be prepared by the action of oxygen on the trifluoride at red heat in a platinum apparatust or by treatment of the pentoxide with fluorine? or bromine trifiuoride®. Itis an extremely hygroscopic yellowish-white solid which attacks lass especially when warm. Its chemistry has been little investigated. ‘Although it was originally reported? to melt at 300°C and 480 °C, Trevorrow*# has since found that it sublimes QUINQUEVALENT STATE 23 ic vapour state, infrared measurements (Table 51, p. 188) have ly demonstrated that the molecule, like POFs, is monomeric ith Cop symmetry. im oxytrichloride jium oxytrichloride may be synthesised by the action of jorine on the oxides VsOs or V2Os' at 600-800°C, but tures of 500-600 °C are adequate in the presence of charcoal sulphur. It may also be made by passing hydrogen chloride gas oxide at 150-400 °C; the enthalpy of reacti 5 150°C but 9 Keal at 400°C per 2 moles ofthe pentoxide. Above 400 °C reduetion takes place, Other chlorinating agents such ‘onylchloride!® and acetyl chloride will react with the pentoxide produce the oxytrichloride and it may also be synthesised by oxygen. The liquid mn in the presence of mally purified by fractional 1m oxytrichloride is a liquid which is hydrolysed bonds pressure is 4.4 mm at 0°C; the expression for the vapour ‘essure as a function of temperature? ® is given in Table 9. Many -- physical properties of this molecule have been measured: ides. It is completely miscible with many hydrocarbons les such as CCl, TiCly, SoC and dissolves o' polar solvents le to form addition compounds. jeed, on most metals, but it reacts with caesium ‘ubidium at 60, potassium at 100 and sodium at 180°C.» HALIDES AND OXY HALIDES, 2 Vanadium oxytribromide ‘Vanadium oxytribromide has been little investigated since Ros- ‘coel4 in 1870 carried out the original synthesis by passing bromine vapour at red heat over vanadium sesquioxide V2Os. It may also be synthesised by passing bromine vapour over a mixture of the pentoxide and carbon. It is a deep-red hygroscopic liquid which is decomposed slowly ‘and bromine; this react nis violent and complete at 180°C. Vanadium dioxyfiuoride "This compound was first prepared in 1966 by fluorination of the Gioxychloride!§*, Vanadium dioxyehloride ‘Vanadium dioxychloride, reported only very recently by Deh- nicke!®, may be synthesised by passing a stream of ClgO gas diluted with oxygen into vanadium oxytrichloride at room temperature, Temay also be made by passing ozo: oF by reaction of the oxytrichloride th arsenious oxide. VOCIs ++ ClO > VOsC! + 2 Cle, VOC! ++ Os + VOxCl + Clz + Or, 3-VOCIs + AsnOz -> 3 VOsCl + 2 AsCla. It is a very hygroscopic, orange, crystalline solid which dissolves ‘without obvious decomposition in weakly polar solvents such as tetrahydrofuran and acetoacetic acid, and is diethylether. Cryoscopic measurements in phosphorus oxytri ride indicate that it is a monomer. However from the o1 report it would not appear to be certai ‘phosphorus oxytrichl dioxychloride with chlorinated hydrocarbons regenerates vanadium oxytrichloride according to the equation: VOsCI + CCl, + VOCIs + COC. ‘The dioxychloride thermally decomposes®* to the oxytrichloride and the pentoxide at 180°C. The V=O stretching frequency of ‘QUADRIVALENT STATE 25 VOsCI occurs at 990 cm! suggesting that at least one oxygen in the solid state is tains some accep- ly with an excess of dry teresting that the molecule soluble in non-polar solvents; it has not been investigated further. Quadrivatent state ‘The general properties of these halides are summarised in Table 10. itanium tetraftuoride jum tetrafluoride is usually made by dropping the tetra- TABLE 10 /ROPERTIES OF THE TEPRAHALIDES OF TUFANIUM AND VANADIUM. joc AH See Kealim white colourless orange éark-brown26 HALIDES AND OXYHALIDES 2 copper of pol absence of moisture, and finally the tetrafluoride is sublimed in a copper apparatus. Gaseous HF may also be used!?—"8, + 4K -> Tika 1-4 HCI jum tetrafluoride may also be made by the action of dry HF on 700-800 °C, by the reaction of boron trifluoride le at $00°C, by direct reaction of fluorine on in non-polar solvents suggest that it is a fluorine-bridged polymer. In this regard itis similar to the tetrafluorides of tin and zirconium which ate also associated and relatively non-volatile solids, but GeF, which are highly volatile monomers. These tween the properties of the Group TV tetrafluorides are believed to be due to the greater tendencies of titanium, zirconium and tin to achieve coordination numbers greater than four (p. 63). How- ever, heat capacity data on titanium tetrafluoride indicate that it is not as highly associated as the fluorides ZrFs, ThFa, UF4, HiF and CeFs, which are isostructural, having a monociinic lattice and a probable? ‘Titanium tetrafluoride may be reduced to the metal by sodium, ‘magnesium or calcium, and it reacts with hydrogen sulphide at 800°C to give titanium disulphide. It is extremely hygroscopic, reacting with water and alcohol to give the complexes TiF1 * 2H20 and TiF; + CzHs0H. However, the hydrolysis of the tetrafluoride is complicated, a number of different species having been identified (QUADRIVALENT STATE. 2 aqueous Solutions®, 1 reacts with phosphorus oxytrichloride 30°C with the formation of phosphorus oxytrif_uoride and jum tetrachloride, but not with the chlorides S2Cle, PCls, PCls, i, CCly or AsCl or with carbon disulphide. With dry ammonia ma'8, However, if this reaction is carried only fluorotitanates are formed®, Vanadium tetrafluoride Vanadium tetrafluoride was first made by Ruff and Lickfett in by the action of anhydrous HF on vanadium tetrachloride 28°C. A purer and more homogeneous product is obtained hen the synthesis is carried out? in an inert solvent such as tri- loroflucromethane, which remains liquid at 78°C. The same 11 may be obtained by direct reaction of gaseous fluorine ith vanadium. At 200 °C, the three fluorides VFs, VFs and VEs brown powder and finally to blue paste on exposure to ure. The brown product reported by Ruff and Lickfett? was is a fluorine-bridged polymer of octahedral Wg units, each sharing four fluorines with adjacent octahedra TiF,). An analysis of the X-ray powder photograph by Cavell ‘Vanadium tetrafluoride disproportionates quite rapidly and irre- bly at 100-120°C in a vacuum to VF3 and VFs, but significant mation occurs even at room temperature if the mat in a dry glass tube at atmospheric pressure for a few days '% in ten days). However, part of the tetrafluoride sublimes iged at 100-120 °C in a vacuum; its behaviour in this con- eteences p39