5160 1D, D. Winutsats, J. A. GRAND AND R. R. MILLER: Vol. 78 [Corsainmios rroxt Cusaesiay Div The Reactions of Molten Sodium Hydroxide with Various Metals! By D. D, Winttans, J. A. Graxp anp R. R. MILLER ‘Rocrave Marea 15, 1058 Under the conditions ofthe system geornetry andl at temperatures up to 100°, the priaary reaction of som hydroxide with the investigated metals appeacs te follows pattern iustrated by the general equation (A) NAOH + Metal =r NusO “= Rietal Oxide (or Sodium Mfetalte) + Hy. The various metals difer only in rate of reaction and valeyce state ofthe cot bined metal esct tending to form its ost stable or common oxile. ‘The secondary reactions gress, with ouly those metals having easly seluced o unstable ondes reaching s scady-seate condition, Hence, cxrorim, rom, Gtaninn, beryl, ‘utalisn, manganese aad ferrous alloys exhibit snly reaction (A). Nicks, coppes’ Monel, guid and probably silver an fobalt exhibit oue or more ofthe following sccandary reaction leuding to a “steudy-sate™ condition. (8) Mecal Oxia > Hy Metal $1.0. (C) NigO = fll NaOH “+ Na; (D) HO Na NaOH + fal, Tarte presence of nickel oopes, Monel and probably cobalt, reactions (B) and (C) are reveruble. In the eres of gold and probably silver, rence {How (C) is mot reveralbla by reason of the fermiation of an alloy betweea the uoble metal and te produved scdeam metal For the same reason and because of the stability of the alloy formes, reaction (D) is prevented. Therefore. oaly nickel, ‘copper, and ther alloys and probably cobalt will produce detaite equiibrim sine the summation of equations B, Cand Dis the caact reverse of the primary equation A. Only ehese metal aze pevterted hy hydrogen aditons pris to heating IW getion & praceads to comsletion, ita tae hyiragen eoastantly removed by evucuacin, sad if there ean exces a acting metal gresent, all of tue vacate investigated Wl react further withthe sodium oxide fraction ofthe primary esction prodaet () Naso SMetal = Nctal Oxide © 2Na “Keaetion F proceeds completely co the right only if provision is made fp removs the metallic sou feom the tesco sone, elthat by duthiaton ar alloy formation ‘The application of guid materials 4s high tem. peratare heat transfer media ia Reld of growitg importance. Current zesearch has extended the fea of interest beyond liguie metals molten salts" among the obvious requizetnents for auch shaterials are thermal stability and inerinens with Feapect to the container material Ube wor ov going on ie a study of reactions of aults ard con finer taterals {or posible use a She igh te pecuture fel Ore of the lower selling and more theemlly stable materials is sodiuan ivdroxide. White he shovnial hus long buco adie as 0 Liquid near its tnelting point, Mile fs icin of its bebavior at shore elevated temperatures.” The most significant {lata in the literature were published by Le Blane Sind Bergman," whose appeasal of thee own work Stipulated the ‘sted for further study. More re feitly, an ingenious comrosion sty by Lat and Sitnont nus delimeated serious phoma of sass transport in AT systemsemploying sod hydrve fein nickel Thetr data show nickel to be resist fant, thougi not inert, to attack by Hquid hyo ite. “This paper presents chemical zeaction data on rnetal sodium hydroxide systems which explain Corrosion and mass (rassfer in such systems, Experimental Apparatus —With the work of Le lass and Berguane agin putes in apparatus war eontricteg, the simples of ‘whieh aided in the soterpeecatioa of tse data, The appara Tis consisted ofa verueal cceed-ond reaction tube mate of ‘he metal to be studied anda alas calipated polume ad rereury maviometer. A siopeock as lovated betwen the Fesclon cube di mainder of the eter, A cold trad ‘Was uaed io check for condemable gises: "Temperatures trate Fecorded andl contaed by a Brown Electron po Tentiometer eaulpped ‘with a Be, PicRh thermocouple {Ealing was sveouplied throug the glass and metal bal Joint Between the reaction tube and the glae system wile jurgig throogh «stopcock sees ‘connected to gh a, ev sre ov vacuum manifold. Gas pressres were determined to the Searest mn. and were calculated to volume at STP. Upon completion of-= nu, solid. non-volatile products were be fined by cutting the reaction tbe at the melt fine, ard Solaile products sick gs metallic sodium were to be found Condensed on the cooler upper portion of the reaction tube ‘Thus, jn given run, the existence and, is some cass the extent, of a feuetion cold be shown by press tessares feat alone. Ia additom, the enable of pseudo ‘equlibriuin oc a “steady-state” (since the system wast Kebthermnal) yas made apparent i consecutively teprodace ie coustaat pressares were obtainer: These comecties Headings were Sbained by seccessive collection and vac Ho ot tha gas, easions wich gave "steadprstace™ con ‘Stioas woul be driven to completo by suet incremental {gag rembrid ts well ne by conta cwncistom “Moot of te stats seated did uot nckieve a “stead state” oondition ine sontinae to react unt the reaceanes ‘vers conmtics or mnt pevtectiveconting of reaction prot lusts soolated the esctats, Tineae motals were studied, thercfore, on a bast of reaction product valeaca seate by Allowing & relatives small known weight sf themmeral so react completely with an eneest of Hpurovite. The gaseous 910 {fdeges) as calsable to ols cme Valence State for he Material —The cosiwmn invdeowie used jn the tests way ACS reget NuCO,, plus the ustul impurities, the "The elect of the carbonate impurity was considered neg- Higblefuasmuch ag 0 reaction eas observed wha the metals studied were fused in pure sodium eatoonate. In addition fo this evidence, the carbonate wat always cesovered seats fly unchanged, in he aoldied melts,” Ta the following data, al welgnt of crigiaal charges and reaction products {rave een corrected for exonate content. he ater nasFomoved eo al chagges by evagation at 308 prior to higher temperature studies, inthis comme dion, should noted Gang water id Semuctosly by lien hydrosile below 4005, even wader reasonably high ‘Sodium Hydroxide-Nickel Reactions —¥ of commercially avaiable nickel metal ranging in Duty. from "A!" nicl to electrolrtie and vacuum case pure nekel were sed fa this investigation. Little or no ference as Rounds remands the prime, nickel-idrosde reaction, Some surface laching of tmpares Was found, but ths had idle ecco the fal reaction mechanism For this at son. all eke! ria are eneped getter witht regard to ‘nor addilvos nr “insults,” ‘Qualitative reas reseed in Sve establishaent of te exst- cece of the temperature and. presse sensitive “steady State” condition showwa in ig, 1, Figure 2 isa plot showing Fate of pressure develop fr three temparacures, Test Dressuecs ure iadeperest af the sas of the ee space in 6 Epstenn aad Valles being beamed with the elibrated ade pellets assaying 8.0% NaOH, 00% ati of uit wa ows gradeset. 20, 1956 volume being 2000, 1000 and 250.ee., High vacuum, MeLeed Gage rans established the fact that intial reaction occurred Stboue #75", but the siguiseant magnitude off am. prese fucearbitrarly sed inthis study was not reached until 739°. ‘The ras phase. consisted of hydrogen. and water vaper? while the daidied mele contained crystals of metalic nickel {nd black, green or brown nickel containing compound that Slded aligiine flemter ana black preciptatee upon hy Hetyas Some melt which had ean aapieted toe ‘ated cvacuations or profonged exposure to steady-state” onion, velded sodium rostel deposits on the Upper 129 100 | 8 AE = Sao reer er Stew -ave eo ener goo E go Ew Temp, °C, ig. 1 Steady-state pressure over NaOH-NIg By sepeated evacuation a a given temperature aboxe 725°, te Histhiometric removal of the ‘hydrogen coneined ia the orginal Rydroxde charge was demoattated. ‘Sct coudtions varied ‘nthe early runs, particularly vith rapect to fie, the reside welts didnt exit con Stent er iterpresuble analytical reults, It way deter fined, Someverr that neither the stendy-aage presare nor Feremientl hydrogen yells were accurate measure of fe ‘Tu mont fepoducible step through which the reaction coud be driven as the pitt of complete hydrogen removal. ‘This was accomplished by the continuous evacuation of & ‘eke! tube containing Rydrotide at a temperate above Tos". ‘Aare drying tube was pind “indie” to detec he neaour the mates content St the evelved gee Tae fuss were stopped by quotehing the system Just as the of “apor pump ithe wast line Sepun to enperae smooth er having been flowed by gas evolution The tube maa ‘hen cut at the melt lie, weighed leached in water and the Empty tube dried and rewesgeed. The wav obeamed & ‘Stople the dey welent of Which. was known, The Bydror [jae prodct was feral and washed, te trate utrated or abtulaiey and he reidve analyaed gravimetrically (a imetilelystne) for mike. ‘Thee results ealesieted aa ‘arious posse compounds (ondes) of sodium aad wicket ‘which evald conselvaaly have resaled from aa NaOH ‘action were compared fo the dry weight of the sample ‘Te combination ol a sofium eomijound and a whckel com ‘oud the agreed withthe engine! weight was thus stows fvbe the probable molecular specs of the melt. The ‘red desing tube was wig fort check on water contest, {ind the opper partion of fhe teuetion tbe waa checked fot telalle sodium by hydrolysis ia a fasometric erste. “When the reaction drives rapidly to completion by cou stant evacuation, no water, godlum ital or alkel etal Sppear in the teaction producta, Tm addition, the said Felfacs antes eomsteatly to be an equimolar mixture of Sodium end cke! monoxide. ‘There was no way of deter Se en ted hy ri es ten wero ke product say be'a soda nckelive ( ors ‘hited oxides. The NO fraction is removed realy by dry, aid, a wil be shown later, the NiO portion f fquanetatively converted to Ni(OH) bir the Eame process Semmes of the sold residue were subiected fo Xfy a Fenctun, tut the lites were too alias fer Hentigeatio twa the opinion of the operator that the mater Was Smnorpats,Tevepecive of these doubts as to actual prod Ets Poe ata stow the pee NaOH NT reaction 8 be ‘Reactioy oF Mouren opium Hyproxipe wri Misrats » 2 * a See pn 5 Ea *- : 316 2 0 2 6 0 8 t00 ‘inwe (eninutes) Fig. 2—-Raue of pressure development over NaQH-Ni system. 120 49 160 2NaOH + Ni—> NaO + NiO (or NaNiO) + Ha (2) Te igen mene thee and previo run, wee the lengeh of time hydrogen remained tm comtact with the elt, end, i some caves, the extended ime of heating after complete hydrogen removal, Ie follows at the appear Sc of water, mck crystals ad codiumn metal must be fe- feted to hese diferences. To cheek ese points, the op between the reaction tube and the eaibrated volume Bion fand.a vacauan line conueetion above the manometer. The fella residuce from reactions in this apparatus were sub- Sested to magnetic analyst on a Gouy magnetic balance Fil lace ice ost ns, stcrnine paramegnet. as qualitative tgol for detecung traces of ft Bickel in Ue provenee of notferromagnetie materi “The runt were made fx tie folowing tanaers Sodium hydroxide wa placed in te Toaction tube and dehydrated “Wider vacuuan 400°." Toe sjstem was then solated fra ‘he wos maniola ‘and the temperature rated tao Shedieve” Aifevolved gas passed over the tared “iodine eying tube. “Thus, hyfogen was detected by pressure and ‘water"by tie tard dorccast, Sold products were e=09- red, afer quenching, by cutting the geuction tube aad fusking the’ mele EMG crunbed sample was wunslerred {ora tated glas tube for welghing bot in and out-of the Iognete Ae of the Gouy balance. The rests of these ingave shown fn Tale Ie ‘Tame L ‘Macsusie Muasunuatents of NaOM-Ni Reaciton Pravvcrs BEE ae TEP eating owe ewueu5152 ‘Table UL shows the typeof deflection characteristic of as, paras and ferromagnetic materia These data deze fasteate that te very stall ackel containing fraction of the melts in Table had co conta «dispersed feromagnetic ‘terial (sickel) in ordet to here prodused positive Geen ‘dons of tne magnitude shown, ‘Tame at ‘Turteat Maowarie Dartzcrions Ko, (80%) Ease 0-008 NiO rs) 1878 NaOH aii = “0079 Ni 00008 * * Unaighable—pailed to poe piece and stuck. Analy Table I, itt shown that ay detectable reaction sedulted at O00"; runs gt 800 and 88)" hve produced hy ‘Grogen and some solid tesdue but no wate? or snetalic hicks in ten minutes, Runs at 900, 920 and 989" extend the time element, and water and nickel appear simaltance fously. The long run at WO)" C240 min.) demonstrates that Iyutogen sdded prior ‘to heating completely wsppressed reaction; apd. the last fun shows agate that continuous ‘concuation has prodced only hytrogen and = nostlerror Stagucti ei aecordace wl CGuaion, "Bhs p _tayseem which allows the evolved hydrogen to “equilibrate” ‘withthe melt, the following secondary resction oocsts S10 + Hy —> Nit HO. @ 1m these experiments, reaction 2 is driven to the right by thedifsion of water vapor itn te fee apace ofthe system. Earlier work at this Laboratory establisied the fact that nytyogea and sodium monoxide react at temperatures up to 580" producing sodium hydroxide and sodium hydride, A ‘repetition of this experiment at TO) and 900" was made in fed to demonstrate a source of mctalie sodium ft the SaOHNI reaction. ‘The runs were made, inthe apparatus frst desenibed, by placing dry codiura monoxide tn the Fe Action. tube, purging. fing the calibrated. volume with ‘arious pressures of hydrogen and Teating to temperature before opening the stopeoce between tie reaction table and ‘theapparatine The dats on the vate of reaction ake ow 0 60 120 180 280 800 ‘ios (xionter). Fig. Rate of reaction between NayO and Ht. ‘The data in Table Land Fig. 3 show that the solid reaction rodict from equation | will equllorace wath the hydrogen Srodiuced by the same fexcthons The NiO portion of the Droduet react readily asin equation 3 with the production Ef meta nicks ant water Vapor. The NayO partion of the residue reacts to produce NaOH and metalic wxaien ‘au 420 even Laburtory Mey Rept #93, Ja 1052 1D. D. WiutaaMs, J. A. GRAND xo RR, MiLceR Vol NaO + Yilly—> NAOH + Ne) ‘Roth reactions tend toward the right in the systems used ly ‘hese ‘studies, equation 2 by reason of the distillation of Water and equation by dintlation of tmetalse sodium iat the coaler parts of the system. Analytical results contra the, stalchiomeuy of equation 3, Evidendy sodium y= ‘ride didnot Fort nder the conditions of tse experiment Inthe gl tube rut, the reastion proceeds ready t0 co pletion since the sodium preduced tmmedlatay alloys with {he god tebe. Fro the nickel rune, flows, than steadystate ce equilibrated nyatern ia whisi equations > ‘Ste progressing, their products would reat farther HO + Ne—> NaOH + Yitht "The sum effect of senctious 2,8 and 4 is the exact reverse cf reaction 1, thus establishing the mechanssm of equilib tion in the son-isethermal, state system used for these ex: PeNBdiRoal proof af eguiriu in the NeOH-N system was demonst/aced by isothermal capsule runs. Tie espe Sele were made by nee age welding Sn lenge of SI fcke! tubing after ting half Fall ck predves hydroxide ‘The Tee apace ithe cape wan filed wth argon. These capsules were heated in a mule furnace four tics and at feinperatores. vrespanding to. complete atic “under acum conditions. The realty ate ows io Table {11 ‘taste 1 argue: Tess nr NaOH 1 Nese NaOH, Tepe. Tie, lefty xing Ene eh TG Tet BRE 20a 500120 ois O03 $170 1000120 ne) 2710 $0 oer 10 ‘These data (Table {11) show that isothermal conditions ith al ce space etl in United stack The ate Is probably dependent upon the rate of eilusion of hydrogen thfuagh the mks) ee “The effet of ateiosphere control op the NaQH-Ni system was also investigated. Tse rans were made in t30 origina lpparatis, nnd dn erucibles equipged with close fitting lis ‘Sovenning inlet and outlet tubes, The data arein Tabk IV Tame 1 Anaoseuenz Cowrnor, He 700950) H 480880, o 20 oa a rT a 90 1000 7 SN; 780800 Bt 1882 a ne | 682 ne 185 Mie 700 80 +201 Gas flowing over suet i covered crucible ‘Table IV demonstrates that initially added hydrogen, i ‘an amoaut in excess of the "steady-state pressure reguired iors given temperature (Hg, 1), wal aiibit NaOH-Nt Fe ‘ction. Inert gh is so peatctive effet. Further Reactions of the NaOH-Ni Reaction Products.—The solid residue produced by equa- tion 1 exhibits at least two further reactions of interest. Of primary concern to an analyst ‘wrestling with these materials is the fact that the Na,O-NiO residue is stoichiometrically hydrolyz. able, thus NAO + NiO + 21,0 —> BNUOM + NKOHOct. 20, 1956 However, if the NaO-NiO residue be heated for some time beyond the point of complete hydrogen removal (equation 1) and in the presence of an ex: cess of nickel metal, a further reaction occurs Which leaves a non-hydrolyzable residue of crystal- line NiO. ‘The reaction involves the NaO por- tion af the residue and proceeds as NaO + Ni—> Nio + 2Na @ ‘The reaction goes completely to the right only if time and temperature allow for the complete dis- tillation of the metallic sodium produced. ‘Table V is a compilation of the results of tests leading to the establishment of equation 6. The analyses in Table V are based on the hydrogen ‘yield from the upper portion of the reaction tube ‘when hydrolyzed in a gasometric analysis system, Tame ¥ Reacrio oF NaO-NiO Mixrure win Exeuss Nrcesn, REACTIONS oF MoLtEN Soptum HypRoxips wir METALS ‘Total hydrogen diffusion through the tubes used, at an arbitrarily selected average tem- perature of 900° and internal pressure of 12 mm., amounted to less than 0.5 mm. per hour. While this amount could have e decided long range effect, the times involved in the experiments herein re- ported make diffusion effects of minor import. No evidence could be found of a reaction be- tween NaOH and commercial NiO. 'No evidence could be found of @ reaction be- tween Na,CO, and nickel at temperatures up to 1000". Reaction 6 can be simulated by the use of separ rately prepared NajO in a Ni tube. Reaction times and temperatures are identical to. those shown for the NaO-NiO mixture from equation 1. Capsule tests involving NaiO in Ni show the exist: ence of an equilibrium tending toward the left of the equation, Jess than 10% reacting in two hhonrs at 950 to 100°, x Ns, Nao, The role of certain reactive elements present in . ‘ond, regi, commercial nickel was investigated slightly. Car- osm oe bon and iron, and probably all other impurities oo 48. except copper and cobalt, are selectively leached ae from the surface of nickel by sodium hydroxide, ae «8 The effect on the reaction of NaOH with nickel is 8 so slight as to be undetectable; however, itis prob- re able that corrosion data would find rate differences, SS depending upon impurity concentration and depth tor of leaching, me az 28 The Reaction of Copper and Monel with NaOH. Chemical analysis of residues from the last two runs in Table V confirm the percentage of reaction shown. ‘Table VI presents data on the hydrolysis of residues from equation 1 and equation 6 Tn ad- dition, data are given for commercial crystalline ~The runs with these metals were performed ex: actly as were the ones with nickel. The copper used was commercial tubing and the Monel was BGN:-B2Cu-2Fe. ‘With one exception, these metals exhibit the ‘same reactions found for NaOH-Ni. ‘The "steady- state” pressures shown in Fig. 1 apply to both the copper and the Monel systems. Taste VI Hyonousaie oF NaOH-Ni Reaction Resipves ‘The one exception Source of sumples Bragiaiee S852 ES oe aoe NO-NO from eg 1 HO 6.0861 0.1108 0.1209. 0.1032 NiO from eg, 8 #0 Nowe 7825 7800." 7600 NiO from e9. 8 10% NaOH Tssae[saa0 “fant Si0(Comm. 1o%e Nsom a7 14703 Lares NiO(Comm) fm NeOH (fused) HO 120 [tas “us The solid hydrolysis product of equation 5 was pyrolyzed in a semi-micro train equipped with, tared tubes containing P.O, LiOI and PO, hot CuO, and hot Cu for determining H.0, COs, Hy and Ox respectively. No COs, Hor O: was detected. “rhe weight gain of the water absorption tube ‘was nearly identical to the weight loss of the sample at 500°, The chemical analysis of the pyrolysis residue established it to be NiO. These runs sub- stantiate the data in Table VI and show the prod- uct to be NICO). Certain tests were performed to check variables in the material and equipment used in the preced- ing experiments. For the sake of what litde brevity can be salvaged they will be mentioned ‘without accompanying data. is the valence of the copper compousd formed by Snitial NaOH-Cu reaction, Ta the case of pure copper, the oxide formed is CiyO, since this i the Stable oxide inthe presence cf excess copper metal! "The prime reation, hence, i 2Ns0H + 20a —> 40 + a0 (or NACHO) + He CP In the case of Monel, the copper compound formed is bivalent, evidently because the copper remaining in the ‘alloy is not readily available Monel reacts exactly as would be predicted for a mixture of nickel and copper (©) J. W. eon, “A Comprehensive Trentne on Inreane end icin Chenin WO Lesgmn. Ge ad Gnji) + 28001 —> (hao /iCx0) + NO + He) “The iron portion ofthe alloy reacts ageoring to the equation developed later for pure iron. The total elect is a uniform reaction ‘throughout the alloy, with little ot no sign of pitting. : IR “the temperatures. eiployed 700-900"), both Monel and ‘copper exited ‘deep non” Protective external oxidation, ‘he alloy exidtacs Soichionetrially and uniformly, with severe Salling occuring apo cool ‘The Reaction of Gold with NaOH. —Tn the work of Le Blane and Bergmann, god was presumed to be nourreacive with NaOH se cts TO" iy spite of the recovery of macro quantities of geld fakes from ‘ther-melis'and. cera unexplained gold Hating effects on the metals tested fe gold. "The Frese investigation fotnd go toe reatant but nopimert to Naor. “The ruas were made osactly as hasbeen described fon the niche syste, Gold a fod to ce tabish a steady state” presse of hydrogen ond Water vapor somewhat lower than nickel and cop- Pets Alp, the proportion of water was couse NOD ighet that ie case of ickal” “The data trestown in Fig. 4. Another important diference tras that te presse developed dependent upon The site of the See space inthe system, whereas it the ease of nickel at copper no such dependence tras found. Hence, the presures show fa Fag = Bpply only tora aOb.cee hee spaces This effect or doubt relate to the prevominance of water apor in the guserus progcts, ato the sokbaity of Feaction products in thea » — 20) BES snd ace cies ‘e00 woo 1100 Teap., °C. Fig, Steady-state pressure over NaOH-Aw system, ‘The results of representative NaOH-Aw reac- tions are shown in Table VIL ‘The data in Table VI show that water, hydrogen and gold compounds occur nearly. simultaneously under all test conditions, except the run_at 750° which was below the temperature of significant a tack (see Fig. #) and the run in on isothermal sealed capsule, It should bo noted that two runs produced reaction products even under an excess of added hydrogen in contrast to the nickel and copper reactions ‘The solid residues resulting from hydrolysis of the melts were subjected to analysis by pyrolysis, swith subsequent chemical analysis of this residue, In addition to the hydrolysis residue, a consider- able fraction of all the total reacted gold was found fs a soluble salt in the alkaline filtrate from the hydrolyzed melt. This compound separated as neutrality was approached during the titration of the filtrate with acid, The small weight involved D. D. WituiaMs, J. A. Geax ano R. R. MILL Val 78 ‘ram VIE NuOH.Aw Reactron Paouvers + Combined and metallic gold and the preponderaice of gold in, the compounds prevented exact identification, ‘The meager data Indicated, Rowever; thatthe reaction Bau + HO (or AO —> PAu + 1/s0y nd Hs + ¥40;—> HO) (10) NaO + VF—> MOH Na (1) Na + Au —> Na-Au Alloy (3) ‘The prime reaction, number (9), is similar to the nickel and copper reactions. However, reaction, 10 is not reversible and the reverse of reaction 11 is, prevented by reaction 12. Thus, the "steady- State” system is not as predictable as in the case of nickel and copper, as, indeed, was found to be the fase, particularly with respect fo hydrogen inhibition. Reaction of NaOH with Fe, Cr, Ti, Ta, Be Mn, ‘Ag, Co and Ferrous Alloys.——LExcept for silver andOct. 20, 1956 cobalt, the above metals were found to react com- pletely with molten sodium hydroxide. The rate of reaction was dependent upon the availability of unreacted metal. These metals, therefore, were studied briefly to establish their valence state in the reaction products, Simultaneously, the absence of a “steady-state” and hydrogen inhibition was ‘established. ‘The procedure used was @ modified material balance technique in which a small weighed quan- tity of the metal reacted completely with an ex- cess of sodium hydroxide contained in a nickel tube. ‘The hydrogen yielded by the reaction was then balanced against. the original weight of metal (after a chemical check of the residue to ensure com~ plete reaction) and thus interpreted into which dxide of the metal could have resulted from the reaction. ‘The following equations summarize the results The temperatures shown are approximate points of significant reaction 6008 2Be ONIOH > FeOs + BNB,O + BU aa) 2Cr + ONO > Cros + 3Na0 4 aH (14) 225° tit arson 5 tio, + anno + 2m (15) ata + xson SP ta «9 Bo +2820 2S peo + Na+ (17) noo" Mut ANsoH “> ino, + 2NaiO + 215 (18) ‘Tue Trraxtom-HypRoceN Sysren 5155 None of the runs resulting in the establishment of the above equations gave metallic sodium of ‘water vapor as reaction products. They were, however, short time experiments. "Prolonged ex: posure to hydrogen may result in the prodaction Of some ater and sodium. All of the solid. products om the right in the above equations react with water, yielding hydrox- ides or hydrated oxides. In the ease of tantalura, the hydrolysis product is completely soluble, 0 the case of chromium, when leached in air, part of the residue forms a soluble chromate. Ferrous allgys (908 SS, $10 $8, 357%, Ni-64% Fe alloy, aad 622, Ni1T0 Ce-1Th Fe alloy) react as might be predicted trom all of the foregoing. ‘The iron and chromium fractions react completely as shown by ther individ equations, while the sickel portion appears to remain tnattacked, prob: bly by reason of the protective effect of the pro- duced hydrogen. The over-all effect on the alloy, however, is one of complete destruction, The rnechanism of attack is one of severe perctration in contrast to the more or less uniform removal {rom the surface of nickel, copper and gold eager data oa the reaction of NaOH with silver indicates a similarity to gold, One exception isthe fact that silver tubes become quite porous to mol- ten NaOH after a few fusions. Cobait, was investigated by a single test which showed “steady-state” pressires of hydrogen and water vapor identical to those showa for nickel Is further reactions are assumed to be identical Wasiexeront D.C [Gosrauauriox MoM rie KNOLLS Atomic Powe Lavonarowy,! Geneaat Euacrne COMPANY] The Titanium-Hydrogen System? By R. M, Haase np F. J. Siarxo Recerven Apa 23, 1950, ‘Tie casilbiuin pressure of lydogen over titanium-hydrogen has been messuted ot 00, 400 and 500°, Sinslar meas: urements have been tnade of Utamium-dcuterium and stanium-titium. At 800° no lsotope eect was observed. ‘The titanium-hydrogen system is one of several metal-hydrogen systems which have been studied ‘both from the practical standpoint because of the high hydrogen ceelusion obtained and from the ‘acalemie viewpoint because of the light which may bbe shed on the properties of metal systems, ‘The high hydrogen concentrations {approximately 450 ec. (STP) Hy’. titanium) obtainable in this system make itideal for many storage applications. Among these are the following: 1. Separation of hydrogen and its isotopes from other gases; 2. Transfer of large quantities of gas in a’ small volume at low pressure; 3. Preparation of materials with high hydrogen density. In the titaniuii-hydrogen system, as in the simi- (0) Thea Mamie Poneraboratcy it peated by ee Genera i) Premed ioe the Puyncal ap Ioerganie Divino the lar systems zitconium-hydrogen and hafaium— huydrogen, the occluded gas has apparently less metallic character than in the possibly unique pal- ladium-hydrogen system, but more than ia the ‘urantium-hydrogen and thoritum-hydrogen systems. ‘The dissociation pressures of the hydrides are the most convenient functions and have been exten: sively studied. Kirschfeld and Sieverts* and re cently McQuillan® have studied the Ti-H system fat pressures from 1 to 760 mim. and at tempera- tures below 1000°. Gibb, ef al,? have made measurements above 500° and at high as well as low pressures, No results have been reported, however, for the meron pressure region which in- cludes low concentrations at 500° and neatly the entire range at 400 and 300°. efyhe Re 08 A. Sere, Z ph Chem, AMA 227 (6A. D.ateguita, Pro. See (London) 406A, 3001050, pees ye dee 3 esa ae RW ree, Pe