GERMANIUM, TIN, AND LEAD Germanium, tin, and lead complete the members of Group 14 (IV A) elements, and

the change from nonmetallic properties in carbon to weakly metallic properties in lead is readily obser able! A. Occurrence, Preparation, and Uses Germanium minerals are not abundant, and the element is usually reco ered from coal ash or the flue dust of "inc ores, with which germanium often occurs! #eco ery of germanium is effected by preparing the tetrachloride (bp, $%&'), distilling, hydroly"ing to Ge(), and reducing with charcoal* Ge'l4 (l) + ),)((l) - Ge() (s) + 4,'l Ge() (s) + )' (s) - Ge (s) + )'( (g) .he cooled germanium crystalli"es with a diamond structure and, when highly purified, finds its greatest use in transistors! It is a brittle, gray/white metalloid! 'assiterite, 0n(), is readily reduced by hot carbon, a process known to the ancients and still employed in the pyrometallurgy of the element* 0n() (s) + )' (s) - )'( (g) + 0n (s) .in e1ists in two allotropic forms* a gray form and a white metallic form! .he white or metallic form (density, 2!%1 g3cm%) is stable from the melting point, )%)&', down to 1%&', at which temperature it changes to crumbly, grayform with a diamond structure (density, 4!24 g3cm%)! .his transformation from the shiny metallic allotrope to the crumbly form was known in the past as 5tin pest6 or 5tin disease!6 7ecause tin is rather e1pensi e, it is rarely used alone8 howe er, it finds wide application in coatings, in platings, and in solders and alloys (bron"e and pewter), in which it can be e1tended by use with a less e1pensi e metal! 9ead, like tin, is a metal with which the ancient world

was familiar! .he rather simple pyrometallurgy permitted easy reco ery of lead from the mineral galena, :b0! ):b0 (s) + %() (g) - ):b( (s) + )0() (g) :b( (s) + '(s) - :b (l) + '((g) :b( (s) + '((g) - :b (l) + '() (g) .he largest use of lead is in storage batteries, from which more than $;< is reco ered and recycled! 9ead is also used in ethyl gasoline and in paints, but both uses are being phased out! 9ead is also found in certain types of solders and pipes! .he to1icity of lead is well known, but its congeners, tin and germanium, ha e not been shown to be poisonous! B. Hydrides Germanes, the hydrides of germanium, are somewhat similar to silanes in their chemical and physical properties! .he general formula Gen,e)n+) (n =1/4) recalls that of 'n,)n+) for alkanes and that of 0in,)n+) for silanes! Germanes are less olatile and flammable than silanes and are somewhat less reacti e toward alkali! .he two known stannanes, 0n,4 and 0n),>, are much less stable than silanes8 and the one plumbane, :b,4, decomposes readily! In fact, its e1istence is still ?uestioned! . Ha!ides 9ead, tin, and germanium form two distinct series of halides, @A) and @A4! .he dihalides are more ionic and ha e higher melting points and boiling points8 the tetrahalides are generally co alent with a tetrahedral geometry! 0n'l) is a colorless, crystalline solid that dissol es in water, melts at )4>&', and boils at >)%&', whereas 0n'l4 is a colorless olatile li?uid that dissol es in nonpolar hydrocarbon sol ents, melts at B%%&', and boils at only 114&'! .he stability of dihalides follows the order GeA) < 0nA) <:bA)8 that of tetrahalides is GeA4 >0nA4 > :bA4! .he lead dihalide :b'l) is much more stable than

:b'l4! .he latter is e1plosi e when warmed to 1;4&'8 howe er, :b'l) can be heated to 4;;&', its melting point, and then up to C4%&', at which temperature it boils without decomposition! D. O"ides All three elements, lead, tin, and germanium, form both a mono1ide and a dio1ide! .he order of stability for mono1ides is Ge(<0n(<:b(8 that for dio1ides is Ge() > 0n() >:b()! :b() functions as the positi e plate of lead storage batteries! A mi1ed o1ide of lead, :b%(4, is called red lead! It is used as a pigment and primer and as an additi e to leaded glass! E. Or#ano$eta!!ic o$pounds .etraethyllead, :b('),4)4, is added to gasoline to reduce knocking8 howe er, its use will continue to decline as a switch is made to other, less en ironmentally ha"ardous antiknock agents! In terms of the number and ariety of industrial applications, organotin deri ati es are the most aluable of any organometallic compounds! :oly inyl chloride plastics are readily degraded by heat and light unless stabili"ed by the addition of dioctyltin compounds! (ther organotin compounds function as curing agents for another important type of polymer, the silicones! 'ertain triorganotin deri ati es ha e been found to function as highly selecti e, ersatile pesticides! .hese pesticides ha e additional ad antages8 they are safe and readily biodegradable! %I. MULTIPLE&BOND OMPOUND' 'onsiderable progress in the determination of ?uantitati e alues for bond strengths in silicon compounds has been reali"ed! .hese thermochemical data gain additional significance in light of the continuing success with syntheses of stable silicon compounds containing multiple bonds! In fact, startlingly rapid ad ances in the doubleDbond chemistry

of silicon and phosphorus, as well as other members of Groups 14 and 14 (IVA and VA), ha e created a need for increasingly reliable thermodynamic data to pro ide coherence and direction for further work! (nly a few years ago, students were taught that silicon and germanium formed no multiple bonds to anything! .e1tbooks emphasi"ed that these elements, as well as other, hea ier main group elements, were simply not able to selfDlink through double bonds to yield stable compounds analogous to those of alkenes, the important family of unsaturated hydrocarbons with ' ' bonds! Eow the facile synthesis of multiple bonds in hea ier main group elements is routinely reported, and doubtless the detailed thermochemistry will keep apace! (ne of the reasons for the lack of success in early attempts to synthesi"e multipleDbond compounds of hea ier elements can be attributed to the failure to recogni"e that two single bonds (two bonds) are more stable than one double bond (one and one bond)! #ather than remain doubleDbond monomers, the hea ier elements form cyclic oligomers* If, howe er, sufficiently bulky # groups are present, their steric re?uirements will preclude oligomeri"ation and will effecti ely shield the double bond! 0ome of the stable compounds that ha e been synthesi"ed include the following* :roof that a double bond is present is best illustrated by the reactions of a germanium phosphorus compound, an orange crystalline solid! If treated with ,'l, ,(,, or ',%(,, the compound undergoes an addition reaction similar to alkenes, and its orange color is discharged as it forms a saturated colorless product*

I(. AR'ENI , ANTIMON), AND BI'MUTH Arsenic, antimony, and bismuth are the last three members of Group 14 (VA)! .he first two members of the family, nitrogen and phosphorus, are decidedly nonmetallic8 howe er, arsenic is a metalloid, antimony is partially a metalloid, and bismuth is definitely a metal! Arsenic and antimony, like phosphorus, e1ist in allotropic modifications! Arsenic, antimony, and bismuth occur in nature in both the free state and combined states, usually as sulfides! .he principal ores of arsenic are realgar (As)0)), orpiment (As)0%), and arsenopyrite (FeAs0)8 the principal ore of antimony is stibnite (0b)0%)8 and the maGor ore of bismuth is bismuthinite (7i)0%)! Eone of the elements is abundant in crustal rock8 the partsDperDmillion alue of arsenic is 1!$, that of antimony is ;!);, and that of bismuth is only ;!;;$! In terms of abundance, the rankings among all elements are fiftyDfirst for arsenic, si1tyDsecond for antimony, and si1tyDninth for bismuth! .he pyrometallurgy of all three elements is similar8 the sulfide is first roasted and then reduced with carbon (H = As, 0b, 7i)* )H)0% + C() - )H)(% + >0() H)(% + %' - )H + %'( A considerable amount of bismuth is reco ered as a byproduct of the processes in ol ed in refining the metals lead, "inc, and copper! Arsenic is a gray crystalline solid that does not melt at atmospheric pressure but simply olatili"es to gi e a dense, malodorous yellow apor! Its main use as an element is to harden lead/antimony alloys, for e1ample, those in storage batteries or lead shot! Arsenic compounds are highly to1ic8 hence, many ha e been used as potent herbicides and insecticides! Antimony, more metallic than arsenic, is an opa?ue,

lustrous, tin/white, brittle solid! 7oth the element and its compounds are poisonous! 9ike arsenic, antimony is used to impro e the properties of lead alloys! As e1pected, bismuth is more metallic and more lustrous than either arsenic or antimony!Abrittle, white metal )4 @ain Group Hlements with a slight reddish tint, bismuth is one of the few substances that e1pands on free"ing! @ost bismuth is used to prepare lowDmelting alloys composed of bismuth, tin, and lead! #oseIs metal, which contains 4;< bismuth, )4< lead, and )4< tin, melts at C4&'8 and JoodIs metal, in which half the tin is replaced with cadmium, melts at only >4!4&'! .hese remarkably lowDmelting alloys are used in automatic sprinkler systems and fire alarms! A minor use of bismuth, which has not been demonstrated as being poisonous, is its application in pharmaceutical compounds! A. Hydrides .he three hydrides of arsenic, antimony, and bismuth are arsine (As,%), stibine (0b,%), and bismuthine (7i,%)8 all are thermally unstable and ha e high positi e enthalpies of formation* 1>>, 144, and )2$ kK3mol, respecti ely! .he three hydrides are colorless, poisonous gases that decompose on heating to gi e the elements! .he decomposition temperatures for As,%, 0b,%, and 7i,% are about )4;, %;, and B44&', respecti ely! B. Ha!ides 7oth trihalides and pentahalides are known for arsenic, antimony, and bismuth! .he 1) possible trihalides, all of which are known are as follows* AsF% 0bF% 7iF% As'l% 0b'l% 7i'l% As7r% 0b7r% 7i7r% AsI% 0bI% 7rI%

(nly fi e pentahalides are known, and one of these, the thermally unstable As'l4 (decomposition temperature, about B4;&'), was not synthesi"ed until the mildD1C2;s! .he fi e known pentahalides are the following* AsF4 As'l4 0bF4 0b'l4 7iF4 Eo pentaiodides or pentabromides for any of the three elements ha e been prepared!