MK TIN MARIETT A ENERSY SY 5 TEMS LiBRARIES ¥ § ] . ] i ] : y ' 1 | wih 1 1 ORNL 1h95 This document consists of 23 pages. Copy 4 ‘of 353 copies. Series A. : Contract Ho. W-"fit-()fi-—eng«-?é ATRCRAFT NUCLEAR PROPUISION DIVISION GENERAL INFORMATION CONCERNING HYDROXTDES Mary E. Lee DATE TSSUED QMKRBE@ mmxamu,memflmmw Operated by CARBIDE AND CARBON CHEMICALS COMPANY _ A Diviesion of Union Carbide and Carbon Corporstion i Oak Ridge, Tennessee % 3 HHSE DBEBELE;& ORNL 1ho5 Chemistry INTERNAL DISTRIBUTION 1. C. E. Center 36. D. D. Cowen 2. Biology Library 37-40. M. E. ILee 3. Health Physics Library 41, E. S. Bettis 4-5. Central Research Libf&ry ho, A. P. Fraas 6. Reactor Experimental = k3., L. A, Maxn Engineering Library - Wh-h5, H, F. Poppendiek T-12. Central Piles W6, H. W. Savage 13. C. E. Larscn W7, W. K. Ergen 14, W. B, Humes (K-25) 418-53. W. R. Grimes 15. L. B. Emlet (Y-12) -~ 54.55, F. Kertesz 16. A. M. Weinberg 56. M. A. Bredig 17. E. H, Taylor 57T. W. D. Manly 18. E. D. Shipley 53. E. G. Bohlmann 19. R. C. Briant 59. J. L. English 20, F. C. Vonderlage 60. C. D. Susano 21. J. A. Svartout 6l.. Frauces Sachs 22, 8. C, Lind 62. Blizabeth Carter 23. F. L. Steahly 63. C. H. Secoy 24k, A. H. Snell 64, E, Wischhusen 25, A. Hollaender 65. J. Courtney White 26. M. T. Kelley 66. J, P. Blakely 27. G. H. Clewett 67. G. M. Adamson 28. K. Z. Morgan 68. W, K. Anderson 29. J. S. Pelton 69, W. L. Harwell 30. A. S. Householder T0. G. P, Smith 31. C. S. Harrill Ti. d. V. Cathosrt 32. C. BE. Winters . T2, D. €. Vreeliand 33. D. W, Cardwell T3. E. E. Hof{man 3k, E. M., King Th~97. ANP Reports Office 35. A. J. Miller EXTERNAL DISTRIBUTION 98-101. T. W. Laughlin, AEC, Osk Ridge 102-353, Given distribution as shown in TID-4500 under Chemistry Category. imcmssnflm : - ABSTRACT This report is an addition to ORNL-1291. It includes abstracts taken from Chemical Abstracts (Bec. 4, 1952, through Sec. 22, 1952) containing information concerning the hydroxides of barium, calcium; cesium, lithium, megnesium, potassa.umj, ru'bldlum, sodium, a.nd strontium. UNCLASSIFIED b UNCLASSIFIED CA Lk, 3780g Ethanol-Alkaline Hydroxide-Water Systems Giorgio Peyronal (Univ. Milano, Italy) Gazz. chim. ital. 79, T92-9(1949) The zones of immiscibility of ag. alc. solns. of KOH and NaGH at 17°, 309, 60°, and 90° wers studied. KOH and NaOH showed considerably different behavior. 1In the aqg. stratum, NaOH showed at satn. at all temps. a greater degree of hydration than did KOH. This is contrary to their behavior in pure aq. solns., and is explained by traces of EtOH, which break the mol. assocn. of the NaOH. In pure satd. ag. s0lns., these bonds between NaOH - 2 HoO groups are stable at room temp. At 179, satd. solns. of NaOH are in equil. with the phase 3 NaOH - (3) EpO + EtOH, where only the No. (3) of the HpO mols. is uncertain. Correspondingly zatns. of KOH are in equil. with the phase KOH - 2 Hp0. 1In the upper alc. strata, there is for NaOH an extension of the zone of the immiscibility whieh increases with rise in temp. for both systems, but more strongly for NaOH than for KOH. This is explain- ed by a breaskdown of the NaOB-EtOH assocn., which is affected more by temp. than is the EtOH-KOH assocn. However, with KOH, this scission takes place at 60°, because solid KOH - 2 EtOH m. at this temp. and forms 2 strata. Between 60° and 90° no further dissocn. is evident 2 whereas, with NaOH, dissocn. continues progressively from 60° to 90°. The results explain the different behaviors of NalOH and KOH in coned. solns. contg. org. compds. with COO groups or OH groups, and the grester tendency of NaOH to form addn. compds. CA Uk, UEU1g Correlating Viscosities. Caustic Soda Solutions Donald F. Othmer and Salvatore J. Silvis (Polytech, Imst., Brooklyn, N.Y.) Ind. Eng. Chem. 42, 527-8{1950) \ When the viscosity of NaOH solns. is plotted against the viscosity of a reference material (water) at the same temp. on log paper, straight lines are obtained. A nomograph is constructed from this plot which permits detg. the viscosity of NaOH solns. from 0-50% by wt. and from O to 100° in temp. Ca hh, L46lke Solutions Containing Sodium Hydroxide N. V. Koninklijke Nederlandsche Zoutindustrie Brit. 632,081, Nov.. 16, 1949 See Dutch 61,090 (Ca 42, 472kb) UNCLASSIFIED CA b, 5201h fAeat Content of Anhydrous Sodium Hydroxide Richard E. Hulme Chem. Zng. 57, 139uhlf1950) Results of a survey of farexgn literature g1v1ng data, fcr the flrst time in English, on the sp. heat of solid and molten NaQH. = CA 45, shéhn The Practical Calculation of the Heat~Transmission Laefflclent of quulds J. Boehm (German Tech. Univ., Prague) Arch, ges. Warmetech. I, 209-14(1950) Formilas are derived that permit more exact calens. for heat exthangers and similar app. and take into sccount the Reynolds, Nusselt, Prandtl, Peclet, and Grashof nes. The heat transm 581on for prautlcal conditions can be expressed by a factor 2 = K(Recp YB/A B he values of the guantities on the right side are given in curves as function of temp., and 7 was detd. for szeveral liguids used industrially; these values are (av. values): Ho0 1760, CaClp soln. (29.9%) 1360, MgClp soln (20. 9%) 1345, NaCl soln. (23%) 1520, Nap(0O3 soln. (200 g./1.) 1785, NaOH soln. g25o g./1.) 1905, 1375, HoSOy (60% S03) 1000, MeCl 540, Freon 12,300, acetone 235, cgfig 210, BulH 220, Heag (100% 285, and EtOH floa% 220, The heat transmission in keal./sq.m.hr.degree is then caled. from & = Z{1/ve-R)yhan-1l. yhere 7 is the value given sbove, v is the kinematic viscosity in sqg. m./br., and 4 is the diam. in m, nlamd n are constsn v is the velocity in m. /hr. ~ CA L5, 6036e Low-Temperature Heat Capacities of Inorganic Solids. VII. Heat Capacity and Thermodynamic Functions of Lithium Oxide. Thermodynamics of the Lis0-H,0 Bystem. | H. L. Johnston and T. W. Bauer J. Am. Chem. Soc. 73, 1119-22(1951) The heat capacity of Lin0 was meaaured over the temp. range 16 to 3049K. Graphic integration of the heat-~capacity curve yielded 9. 06 + 0.03 cal. / wole/degree for the entropy at 25°. When the entropies of LiOH and of stesm were also considered, the curve yielded a AS° value of 33.70 + 0.12 e.u. for the dissocn. reaction 2 LiOH = Lis0 + HpO {(gas). This latter value is in pgovd agreement with the vaive 33.85 cbiained from the disscen. equil. snd confirms the spplication of the 3rd law of thermo- dynamies to LipO. A itsble of thermodynamic functicns for Lin0 was prepd. for smoothed values of temp. Heats and free energies of formation were CA b5, 6036e (Contrd) computed for LiOH, LiOH * Ho0, end Lip0, by combining their entropies with heat-of-soln. and vapor pressure data. Values of AF8g are: -105,676 + 130, -163,4%37 + 160, and -133,965 + 210 cal./mole, resp.; of AHZ5 are: -116,589 + 90, -188,926 + 120, and -142,567 + 160 cal./ mole, resp. The standard-state entropy of the Li ion at 25° was calcd. as 2.46 + 0.34 e.u. and the standard electrode potentisl of Li as 3.0383 + 0.0010 international volts. Ca 45, 8353 Investigation of the Hydrogen Bond of Aqueocus Solutions of Hydroxides by the Method of Combination Scattering of Light M. I. Batuev Doklady Akad. Nauk S.5.5.R. 59, 715-18(1948) In the spectra of highly concd. ag. solns. of KOH and NsOH (40 wt.-%) there appears on the short-wave edge of the wide HoO band e sharply prominent, although somewhat broadened line at 3630 cm.-l. This line gradually fades with decreasing concn. (down to 0.5 wt.-%) and dis- appears. In its place a faint band appears at about 3950 cm.-t. These findings indicate that the quasicryst. structure is present in concd. solns. and is destroyed with increasing diln. and dissocn. The OH ion forms H bonds even in cryst. and quasicryst. lattices; therefore, it is not a free ion. The high-frequency OH™ band is gbsent in the spectrum of pure, distd. water kept in quartz vessels. The different chen. nature of the OH groups of acids and of bases is spparent from the fact that the optical evidence of the H bond appears at a higher fre- guency in bases (4200-3600 cm.~1l) then in acids (3600-2800 cm."1). ca 46, 80v Stress Corrosion Cracking in Alkaline Solutions. Report of Technical Practices Committee SC--Subsurface Corrosion by Alksline Sclutions H. W. Schmidt, P. J. Gegner, G. Heinemann, C. P. Pogacar, and E. H. Wyche Corrosion 7, 400 (1951) cA b6, 82¢ The P3551vat1ng Characterlstics of the Stainless Steels W. G. Renshaw and J. A. Ferree Corrosion T, #00-1 (1951) In all of the expts. relating to air passivation, specimens were held in air except at the instant when potential measurements were made. Where passivation in HNO3, H3POL, or NaOH soln. was involved; specimens vere. continuously held in these solns. after gctivation. Potential measure- ments do not necessarily reflect practical experience in every case. The measuring equipment used iz described, & wiring diagram is given for the vacuum tube voltmeter, and further detalls of the tests. For general corrosion resistance there is no better passivating agent than air, but the surface must be clean and free from scale before passivation. This is secured by the usual pickling treatment or by trestment with 20% warm HEO3 soln. Stainless steel is not usually recommended unless the corYoO -~ sive medium handled is capsble of promoting and maintaining & passive surface on the metal during service. CA k6, 3184 The fidsorptlon of Molecules of Sodium Hy&roxiae, Sodium Chloride, and Sodium Citrate by Sodium Montmorillonite F. Kayser, J. M. Bloch, and G. Gommery Bull. soc. chim. France 1951, 462-5 Montmorillonite previously satd. with ¥a adsorbed approx. 75 millimoles of NalH per 100 g. of the mineral clay. The NaOH iz removed by repeat- ed washing with doubly distd. HpoO, and is held by van der Waals forces, Nall and.fla citrate are nol adsorbed by the cl&y : : CA 46, 1726e ‘Sodlum Hydroxide from Sodium Sulfate by‘Using Iron Oxide or Hydroxide Catalyst Yoshihiko Qkae - Japan. 180,137, Sept. 6, 1949 An equiv. smbt. of C to reduce NapSOL to NaoS is heated with FeO or Fe(OH)g while superheated steam is passes through fcr the reaction Nap3 + FeO + HQO~—47 FeS + 2 NaOH. CA U6, 23508 Dialysis of Caustic Soda Solutions R. D. Marshall and J. Anderson Storrow (Coll. Technol., Manchester, Engl.) Ind. Eng. Chem. 43, 2934-42(1951) Concn. distributions were measured in the continuous countercurrent dialysis of 20 wt.% NsOH in order to asdess 'the mass transfer in terms of dialysis coeffs. appropriate to specific positions along the contact path. For design purposes it is adequate to use an over-all coeff. based on the logarithmic mean of the terminal conen. differences between the lye and water cells. It was shown that the reduction of relative resistance to transfer in the liguor films and in the membrane will inerease the over-zll dialysis coeff. o CA 46, 24314 Caustic Alkall by Electrolysis G. Passelecqg Fr. 963,354, July 6, 1950 Chlorides of alkslil metals, made as pure as possible; are electrolyzed in ag. soln. in an app. comsisting of a small cell (A) having graphite snodes, an anode of Hg-Na amalgam having at least 1% Na, and an ag. s0ln, of the pure chloride as electrolyte, and a much larger cell which is divided into two parts, (B) and (C). An anode of graphite in ag. chlorides is in (B), and an Fe cathode in NaOH soln. is in (C), which is 2, 3, or 4 times larger than (B). The amalgam passes by gravity from (&) to (B) to (C), a weir lying between (B) and (C) so that (C) gets an amalgem of the highest Na content, and the amalgam in (C) is spread over as large an area as possible. A pump passes the amalgam from (C) to (A). The cell (B-C) runs at 10,000 amp. and 2.8-2.9 v.; (C) at 300-500 amp. and % v. CA 46, 2763¢g Caustic Soda from Lime and Sea Water Yoshio Okayama Japan. 172,643, May 9, 1946 Ca0 300 g. is hydrated with 500 ml. HoO at 50°, and HoS 1s passed in for 10 hrs. to obtain Ca(SH)o (I), (450 ml. 41%). I 200 ml. is mixed with 300 g. Na zeolite (II) at 50-6Q° for 2-3 hrs., filtered, and the filtrate is treated with the same amt. of II. The filtrate contains oh.5% NaSH (III). To 100 ml. IIT 60 g. Fe(OH); and 6 g. powd. AlpO3 are added with agitation at 30-60° for 30 min.; and the mixt. is filtered to yleld 90 ml. 11.2% NaOH. The ppt. of FepS3z iz washed free 9 CA 46, 2763g (Gont'd) of alkali, made slightly acid, and boiled with water to recover Fe(OH)3 Ca zeolite is regenerated to II by Passing sea water through it. ca hé, 27631 Treatmént of Caustic Soda Cell Liguor Vernon A. Stenger (to Dow Chemicel Co.) U.8. 2;575’238'9 NOV@ 13, 1951 BElectrolytic-cell NaOH liquor is treated with either BaO, Ba(OH)o, or BaCly in an amt. sufficient to ppt. the sulfates and carbonates present and provide s Ba-ion comcn. of 0.2% in the effluent when the ppt. is removed. The effluent may then be coned. to a colorless product. Ca 46, 2931n The Formation of Hydrcxides Euring the Electralysis of Nlckel A. L. Rotinyan and V. Ya. Zel'des J. Applied Chem. U.S.S.R. 23, 75?-63(1950)(Engl translation) See CA 4k, 8748a. CA 1;6, 33581 Water Absorption by Melting Oxides "H. v. Wartenberg (Univ. Gottingen, Ger.) Z. anorg. u. allgem. Chem. 264, 226-9(1951}; z Elektrochem. 55, 4l5.6 (1.951} | BeO, AlpO3;, and LapO3 absorb HpO when melted and release it with eruption upon solidification. The technique for the manuf. of artificial rubies prevents HoO from interfering with the process in this manner. The same phenomenon occurs slightly with ZrOp, but not at all with a mixt. of | PrpoO3, Ndp03, and YbpO3 or with CaO, MgO, or Th0z. Since the temp. is above 2000°, the Ho0 must be chemically bound to the oxide; consequently g8se0us hydrnxide and hydroxide in soln. in the oxide melt must be % present. The heat of formation of gaseous Be(OH)p and the heat of volatilization of Be(0OH), aré caled. to Be approx. -47 kcsl. and -60 keal.; resp., from the data of Hutchison and Malm on the volatilization of BeO in the presence of HpO vapor (CA 43, 5321h). Alp03 is more volatile in the presence of HoQ vapor than in dry air, so gaseous AltOH}3 is also stable. 10 CA 46, 33691 The Solubllity of Copper, Zinc, Nickel, and Cobalt Hydroxides in Caustic Alkalil end Awmmonisa M. I. Arkhipov, A. B. Pakshver, and N. I. Podbornova {(Ivanovo Inst. Chen. Eng.) J. Applied Chem. U.5.3.R. 23, 685-91 (1950) (Engl. translation). See CA 4l; 87hon. CA 46, 3835e The Kinetics of the Absorption of Carbon Dioxide by Solutions of Sodium Hydroxide in a High~-Speed Propeller Agitator J. K. Kishinevskii and M. A. Kerdivarenko (Kishinev State Univ.) J. Applied Chem. U.5.S.R. 24, 449-56(1951) (Engl. translation) The rate of abgorption of COs in NaOH was studied by recording prassure loss from the vapor phase over the system. An equation was derjived that defines the kinetics of the absorption process over the temp. range from 4.2 to 59.4°, The activation energy of the reaction between COp and OH groups was detd. CA 46, 4i11p Catalytic Oxidation of Alkaline Chromites to Chromates with Oxygen at Low Temperature Rolando Rigamonti and Elena Spaccamela (Polytech., Turin, Italy). Atti acced. sci. Torino, Classe sci. fis. mat. e nat. 85, 364-79(1950-51) The oxidation, with gaseous 0 of Cr(OH)z in alk. media, represeanted by Cr(0H)3 + 3 NaOE == Cr{ONa)3 + 3 Hy0 (%), and 2 Cr(ONa)3 + 1.5 Op +-Hp0 —> 2 NagCrOy + 2 NaOH (II), vas studied with several metallic hydroxides present as catalysts. The efficiency of Mn{OH)o as a catalyst was detd. by varying the temp., the Op pressure, the velocity of agitation, the excess of NaOH, and by adding colloids and coloring matters. The be- havior as catalysts of Ma, Fe, Ag, Cu, Co, and Ni hydroxides with respect to the method of pptn. either separately or in binary mixt. was studied. It was concluded that the efficiency of the catalysts resulted from two opposite effects: one tending to favor II and the other tending to hamper I. 11: CA 46, hohii Studies in the Oxidation of Metallic Hydroxides. I. Nickel Hydroxide N. R. Dhar and Nand Kishore (Univ. Allshabad) , Proc. Natl. Acad. Seci. India 19A, 12-14(1950); cf. CA 46, 514 Oxidation of Ni(OH)p by a current of air in the presence of NapSOj increases with the amt. of NapS0g added up to a certain limit, sbove which there is no further increase of the percentage of oxidation. The pgreater the quantity of RapB80q used, the longer 1s the time requir- ed for initiating the oxidation. Variation of the concn. of Ni(OH)s does not vary the percentage of oxidation; hence, some definite compd is formed Glucose retards the oxidation; sucrose, even more. CA k6, 5794 Alkali Metal Hydroxides Dow Chemical Co. , Brit. 662,314, Dee. 5, 1951 A method of producing an alkali metal hydroxide(I), e.g., NaOH, soln. from Ca(0OH)s and an alkali metal halide (II), e.g., NaCl, by excha.nge of ions comprises passing an ag. soln. of Ca{0H)p into contact with a halide of a HpO-insol., strongly basic, anion-exthange resin (III) to absorb OH ions and then tresting (IIT) with an ag. soln. of II of at least 10 wt.% concn. to effect displacement of the absorbed OH ions with formation of an ag. soln. of 5-15 Wt.% or more of I. III, which is a quaternary ammonium base or a salt thereof, may be prepd. by the reaction of a halomethylating agent (IV), e.g., chloro--or bromo-methyl methyl ether, and the normally solid CgHg-insol. copolymers of monovinyl aro- watic compds. (V), e.g., styrene, ar-methyl., ar-chloro-, or ar- dimethylstyrenes, or vinyl-, or ar-methylvinylnaphthalenes, and a polyw vinyl aromatic compds. (VI), e.g., divinylbenzenes, or -naphthslenes, ar-divinyltoluenes, -Xylenes, or ~ethylbenzenes, which co-polymers may contain 0.5-20% by wt. of VI chemically combined, e.g., interpolymerized with V. Then the halomethylated vinyl aromatic resin is treated with a tertiary amine (VII), prefersbly a tertiasry mono- or dialkyl N-substituted alkancl or alkanediol amine by dispersion in a liquid, e.g., Ho0D, acetone EtOH, at 25-100° for 4 hrs. to form s quaternary ammonium halide, which is washed with HpO0, or preferably with an org. liquid, e.g., acetone, EtOH, or dioxane, and then with HpO. VII may be dimethylethanolamine, methyldiethanolamine, dimethylisopropanolamine, methyldiisopropanclamine, and l-dimethylamino 2,3-propanediocl. The halomethylating reaction may ‘be carried ocut at room temp. or above in the presence of a catalyst, e.g., ZnClo, Zn0, SnCly, AlCl3, Zn, Suo, or Fe, while the copolymer is swollen by, or dispersed in, an org. liguid, e.g., an excess of IV, that is less reactive with IV than is the polymer. The method also may be used to cone. weak (0.1-3%) ag. NaDH or KOH and to recover more cancd. NaOH from waste liguor from pulp and pesper industries. CA 46, 57974 Magnesium Hydroxide Jean C. Seailles U. 8. 2,587,001, Feb. 26, 1952 The process for prepg. Mg(OH)2 from brine consists of mixing the brine with enough H3POL4 to decomp. all the bicarbonates, sepg. the CO2 thus liberated from the soln., mixing the previously pptd. Mg{OH)o into the soln., and mixing the soln, with Ca(OH)o in an amt. sbout equal to the Mg salts present to ppt. Mg{OH)2. The wet or dry Mg{(OH)> ppt. may be dispersed by placing it in an aq. suspension and adding a small amt. of H3POh4 80 as to obtain after settling a new ppt. having a vol. about 2.6 times greater. This ppt. will be less milky and less unctuous than that prior to the dispersion. Cf. CA 45, 8321, CA 46, 5798z Debydration of Sodium Hydroxide Solutions Dow Chemical Co. Brit. 664,023, Jan. 2, 1952 NaOH liquors (70%) ere evapd. at 380° and 20 in. of Hg. A small amt. of sucrose is added to destroy any €103~ and 0. The molten product contains more than 1% Ho0 and is free from 0%03', CA W6, 64674 Solubility in Acetone of Some Salts of Barium, Strontium, Calcium, and Magnesium Manuel Font Altaba (Inst. “Alonso Barba,” Madrid). Rev. real acad. cienc.; exact., fis. y nat. Madrid 4%, 271-346(1951) The aim is to provide more sccurate soly. data for the pharmacopeia. Measurements were made over the range 09 to 502, The following are insol. within the error of measurement: MgO, Cal0, Sr0, Bald, Mg0o, Calz, Sr0o, Balp, Mgi{OH}o, Ca(OH)s, Sr{0H)o, Ba(OH)o, MgFy, CaFo, SrF2, BaFp, MgSiFg, CadiFg; SrSiFg, BaSiFg, MgClo, MeClp - 6 HoO, CaClp, CaClz ° 2 Hp0, SrClp, SrClp - 6 HpO, Ballp, BaClp - 2 HoO. The s0ly. in g. per 100 g. of solvent at 20° isg: Mglo 5.946 + 0.009, Calo 88.337 + 0.0038, Srio 42.006 + 0,0038, Cally ° 6 Hy0 0.005 + 0.008, MgBro 0.533 + 0.008, CaBr, 2.746 + 0.003, SrBrs 0.621 + 0.0025, SrBrp ° 2 HpO 1.94%6 + 0.0038, SrBrp ° 6 Hs0 1.031 + 0.009, BaBrp 0.0265 + 0.00104, BaBrp - 2 HoO 0.0288 + 0.0010%. The soly. of MgBro, Mglo, Calp, and hydrated Callo increases with increasing temp.; that of SrBro, BaBrp and Srlo decreases. CaBrp has a min. soly. at about 25°° 13 CA 46, Thhoi Hydroxytrifluoroborates - I. G. Ryss and M. M. Slutskaya (Dnepropetrovsk Met. Inst.) Zhur, Obshchel Khim (J. Gen. Chem.) 22, hl~8(l952) (1) KHFp, 0.1 mnle, was added to 4.1 g. soln. contg. O. 1 mole BF, the gsoln. was cooled to 0°, and 0.1 mole H3BO3 was added with stirring. The yield of KBF0H was 1l. 6 g. The salt can be recrystd., contrary to the statement of Wemser (CA 42, Lk30i). It is insol. in, and is not decompd. by, EtOH or iso-AmCH, (2) fiaBF3OB cannot be prepd. by this method with an adequate yleld and sufflciently pure. To obtain better products, mix ag. NaHFp = 2:1 moles at 0°, with 50-100 ml. HoO per mole H3 BOE Evap. the fil ra e from the small amt. of NaF in Vacuo or ppt. with a fold vol. of EtOH. Mean yields are sbout 50% of the theory. NaBFz0E is easily sol. in H,0, very little sol. (0.3%) in EtOH, and is not decompd. by the latter. This compd. is very different from the alleged NeODH-EF3 described by Meerwein snd Pannwitz (CA 29, 1060-1). (3) On standing, the acidity of ag. KBF3OH solns. decreases. The decompn. can be 3 BF0H™ == 2 BFY” + H3BO3 + F~(I} or 2 BF3OH" == BFp(OH)s + BFy (II). é‘he equil. yield of BF),~ increases slightly with the diln., particularly in the cancn, range 0.33-0.11 M:; this is taken to indicate a prevalence of the process I. The yield of BF)~ also increases slightly with the temp. The calcd. heat of reaction I is 4.2 keal.; for II, the calcd. heat of the reaction is less than 1.4 kcel. The order of the formation of BFy~ is somewhat lower than lst. (&) The soly. of KBFJ0H in HpO cannot be detd. with accuracy on account of the slow decompn. of the solns. | C‘A 46, T2kt Magnesium Hydroxide f Arthur W. Vettel and R. D. Isrsel (to Kaiser Aluminum and Chemical Corp.) U. 8. 2,595, 314, May 6, 1952 | Mg(OH)g with increased d. 5 improved settllng and filtering characteristics, and high purity is obtained by admixing sea water or dil. Mg salt soln. with spent sea water or a soln. from a previous treatment {0.5-1.5 times the vol. or rate of flow of the incoming soln.) and Mg(OH)p seed crystals (3-15 times the wt. of Mg(OH), being produced), adding calcined dolomite {particle size not less than 290 mesh), agitating the mixt. in a re- action zone, withdrawing an underflow enriched in impurities, e.g., Si0Og, Fe, Al, and Ca oxides, and as overflow a suspension of Mg(OH)o in spent sea water or soln. A portlan(of the settled underflow is recycled; ‘the balance is discarded, 1k CA b6, 79061 Hydroxide Formation under Conditions of Electrolysis of Nickel A. L. Rotinyan and V. Ya. Zeltdes J. Applied Chem. U.S5.S8.R. 23, 991-5(1950) (Engl. translation) See CA 46,6013n CA 46, 83374 Lithium Salt Yasumichi Chya Japan. 1126(50), Mar. 31 Li ore or its compds. in powd. form is heated in an autoclave with the oxides or hydroxides of alk. earth and a suitable amt. of water. The * LiOH is sepd. by filtration, and the L1 in the filtrate is pptd. as the carbonate; which is used to prep. various Li salts. cA 46, 8u66a Behavior of a Mixture of Negatively Charged Colloidal Iron and Chromium Hydroxides E. H. Daruwalla and G. M. Nabar (Univ. Bombay) Kolloid-Z. 127, 33-8(1952) The stability of Fe(OH)o, Fe(OH)z, and Cr(OH),, prepd. by reaction of FeS0y, FeCl3, Crp(SOy)3 with definite amts. of NaOH, was detd. in the presence of nanelectroiytes, (peptizing agents, sugar, glycerol) and electrolytes (pptg. agents, NapSO, MgSOy, Alg(SOL,) ). For peptizing a metal hydroxide, sufficient nonelectrolyte must be presant tefore the alkali is added to the metal salt. Also an excess of alkali, above that needed theoretically for pptn. of the hydroxide, is necessary to obtain the metal hydroxide in colloidal soln. When the NaOH concn. is increased progressively, the min. ambt. of nonelectrolyte required to peptize a given amt. of Fe(0H),; decreases gradually to a const. value. Glycsrol is unsuitaeble for peptizing Fe(OH),, but it can peptize Cr{CH), even at relatively high concns. Eowever, Fe(OH)g can be easily peptizéd by glycerol in the presence of Cr(OH)3 The min. gquantities of NaOH and sugar required for peptization of a mixt. of Fe(OH)3 and Cr(OH)3 greater than the sums of these reagents necessary to peptize like amt . of the individual metal hydroxides. The mixed colloidal hydroxides are more stable to ppin. by dialysis than are the individual hydroxides. These observations point to the possibility of formation of a complex when a mixt. of 2 metal hydroxides is peptized. 15 CA 46, 8473f A Rectilinear Representation of Isotherms of Separating Mixtures of Aquecus Solutions of Alkalies and Certain Organic Solvents Marie Jeanne Duhamel and Pierre Alfred Laurent Compt. rend. 234, 2069-72(1952) Ag. solns. of LiDH, NaOH, and XOH up to satn. were mixed with water-sol. splvents such as dioxane, MeoCO, and pyridine and the amt. of solvent sepg. at 25° was detd. Plotting x, moles of solvent/{moles of solvent + zoles of HoO), against y, moles of alkali per 100 cc. soln., gives a hyperbola. Plots of x against z (2 = x}/(yo - ¥), where y, is soly. of alkeli in pure HoO give straight lines of the form z = ax + b. The relation of moles of solvent per 100 g. of soln. (Mg), moles of HpO (Mg, and moles of alkali in 100 g. of satd. soln. (Myp) is expressed by MS/ME = K((MQA/Hgy - 1), where K is 2 const. having a value of 0.013, independent of solvent or alkali. ‘ ’ CA 16, B483b Solution Kinetics of Aluminum in Sodium Hydroxide G. P. Bolognesi (Univ. Perrars, Italy) Alluminio 21, 27-41(1952) The speeds of soln. of Al of 99.5% and 99.99% purity in NeOH of different conens. (from 0.1 N to 10 N) with either Hg present or not, were measur- ed by the H generated. The results show that Hg in 4il. NalH soln. (0.1- IN for Al 99.5% to 5N for Al 99.99%) inhibits, wheress with higher comen. {1-GN for Al 99.5 and sbove 58 for the Al 99.99%) it aids H generation. Moreover, the soln. potentials as a function of the Hg content, the Hy generated, and wt. losses to the cgthode and ancde, are detd. by apply- ing an e.m.f. to two 99.5% Al electrodes in NaOH 0.2N soln., with Hg present or not. 41 references. | o CA 46, Bugbe ' Ternary Reciprocal System of Alkalies and Nitrates of Lithium and Potagsium ? | f : ' G. G. Diogenov {Irkutsk Med. Inst.) | Doklady Akad. Neuwk $.5.5.R. 78, 697-9(1951) The system K, LifOH, NO3 was investigated by the visual polythermal method. Studies of the system LiOH-LiNO3, the only one of the binary systems not previcusly investigated, showed a eutectic at 40.5% LiOH, m. 183°, and the compd. LiOH * LiNOg, decompg. at 195°, 484 LiOH. In the ternary system the Li0OH-KNO3 diagonal is stable. In a cigar-shaped region slong this disgenal, two liquid layers are formed between 5 and 95% LiOH. There are 10 regions of crysth. with the following phases and percentages of total area: LIOE, 63.47; 2 LiOH * KOH, 13.29; LiNO3, 10.88; KOH (including 3 16 CA 46, 8hoBe (Cont'd) polymorphic modifications), 5.65; KOH - KNOL, 3.7, KNO3, 2.66; LiOH - LiNC3, 0.35. There are 5 nonvariant points with the following values for temp., %L1, ¥NO3, and with solid phases in equil., resp.: 2 eutecties: 107, 47.5, 95, LiOH, LiNC3, KNO3; 180, 17.5, 21.0, KOH, KOH - KNO3, 2 LiOH - KOH; 3 transition points: 155, 92.5, 64.5, Li0H - LiNO3, LiNWO3, LiOH; 21.0, 4.5, 58.0, 2 Li0H - KOH, KOH - KNO+3, KNO3; 266, fEQS, 63.0, LiCH, 2 LiOH - KOH, KNO3. The low-melting mixts. could be used as heat-exchange fluids in the catalytic crack- ing of petroleum. CA 46, 85401 The Cathodic Corrosion of Iron and the Formation of Crystallized Ferrite at the Anode during Blectrolysis of Molten Sodium Hydroxilde M. Doderoc (Inst. electrochem., Grenoble, France) J. chim. phys. 49, €210-13(1952) The electrolysis of molten NaOH between 500° and 750° leads under certain conditions to c¢cathodic corrocsion and deposition of Na ferrite on the anode. The cathodic corrosion is explained by assuming the formation of FeOoH- ions and by a transfer of electrons from the soln. to the cathode, opposite to the usual transfer. The formation of ferrite was assumed to result from the secondary reaction which occurred after transfer of electrons from the OH" and FeOoH™ ions to the anode. No corrosion occurred when as.c. was used. CA 46, 85434 Investigation of Anodic Oxidation of Ferrochromes. I. Generslities. Oxidation in NaOH Solution Jean Besson and Yung Chao Chu Bull. soc. chim. France 1951, 510-15 Anodic oxidstion of ferrochrome was carried out with a cylindrical shest cf Fe, about 1 cm. awsy, as cathog+. The bath was maintained at counst. temp. Yield is defined as W = Cr® actuaslly formed /Cr®" thecretically formed. By using NaOH es electrolyte, » has a max. value (T70%) arcund 4.5 N, and & min. value of conens. from 0.1 to 0.5N. The anode 1s generally covered with a& thin film, but the film does not appear in dil. or concd. solns. at high current d.; under these conditions alkali ferrates are formed. Yields are best around 80°. With a c.d. of & am./ sg. dm., the energy, W, required for the formation of 1 kg. of NasCrOy, is about 3 kw. hrs. 17§ cA 46, 85434 {Contvd) II. Oxidation in KOH Solution. Ibid. 763-8 Yields are higher with KOH than with NaOH, with a max. of 72% for 3-8 N solns. A film of Fe203 forms, but not beyond 1O0N. Values of W are lower with KOH than with NaOH because of better yield and greater cond. At all concns. of alkali there is present in the electrolyte bath a substance, HpOp, capable of reducing the chromsie in an acid medium° About 5% of the Cr exists as Cr3+. | | IVQ Prolonged oxidation in alkaline solutlona Practical productiofi of - chromate and dlchromate¢ Canclusionv Ibid. 95-9 123.7 Prolonged exid&tion results in lowered production of KQCPGh as the free alkali content decreases. For best results the follGW1ng conditions should be used: the energy must be & min.; 4-5N NaOH, 4-8% KOH, 5-6N KgCOgO a c.d. of k-5 amp./sq. dm.; and the bath temp. is maintained at CA 46, 85h8h Eleetrolytmc Pollshing of Iron or its Alloys with,Alkali as the Electrolyte : Jun Ohkoshi, et al. (to Sc:entific Research Institute, Ltd, ) Japan 324 ('50), Feb. 8. The electrolyte consists mainly of NaOE, KOH, or KQCO3 with KQCr203,or KCN and C3H5(0E)30 Electrolysis is with a.c. or d.c. CA 46, 8558 The Hydroxides and the Salts of Magnesium. III. A Light Basic Magnesium Carbonate Obtained by the Reaction between Magnesium Hydroxide and Carbon Dioxide Hiroshi Murotani ({Tokyo Inst. Technol. ) ' J. Chem. Soc, Japan, Ind. Chem, Sect. 23, h5.7(1950); cfu CA 46, 8335h Ppts. baving various proportions of MgO, COn, and EQO-uere obtained by vassing COp into Mg(OH)p suspension at various temps. The ppt. 2 Mg0 - 1.1 €03 < nHoQ, obtained at 90° is very light, the interior part is 2 ¥g0 « CO2 ° nHp0, and the surface layer has a grester COo content. 18 CA k6, 8926a Structural Study of the Dehydration of Magnesium Hydroxide Julio Garrido Ton 11, 453-64(1951); ef. CA 45, 9980a Continuation of earlier work. To account for the x-ray spectra, 2 dif- ferently oriented reciprocal lattices must be postulated. These 2 lattices correspond to 2 orientations of the crystallites in which the (111) planes are common to both. The 2 systems of crystallites are characterized as orientation I with (110) of MgO parallel to (1010) of Mz(0H)s, (111} tc (0001), and (100) to (1011), and orientation IT with (110) and (111) ss in I and with (100) parallel to (1101). After dehydration at 50C°, 75-80% of the crystallites are in orientation I. Rapid dehydrstion at higher temps. (2.8, TOOO) produces supplementary spectra that do not correspond to the Mg0 lattice; these spectra are found in positions corresponding to reflec- tion with respect to the (111) plane of Mgl0. At still higher tewpsz. {20009) the supplementary spectrs disappear and only the lines corresponding to orientation I are found. The possible origins of the supplementary spactra are discussed; a mechanism based on the existence of vacant lattice sites iz considered most plausible. The product of the dehydration retains the guperficial form and size of the original crystal; the individual crystal- iites appear to be larger than 0.0001 mm., although some evidence points to sizes of the order of 50 to 100 A. The way in which the bresking of Mg=0 bonds leads preferentially to nuclei of orientation I is discussed. CA 46, 8939z The Electrolytic Disscciation of Strontium Iodate and of Stroutium Hydroxide C. A. Colman-Porter and C. B, Monk (Univ. Coll. Wales, Aberystwyth). J. Chem. See. 1952, 1312-1%; cf. CA ¥4, 2337a The conds. of dil. aq. solns. of S5r{I03)p * HpO (I) at 25° were measured. L was prepd. by adding dropwise 0.1 N solns. of SrClis, and K103 to distd. HoO at room temp. Ths solubilities of I in HpO and NaCH soln. werse weasured by packing the crystals in the saturator (ef. CA 28, k330-5) and titrating 20-ml. samples with 0.06N NspSpO7. The methods of measuring cond. wers described previcusly (cf. CA 43, 65331). From the results, a value of K = 0.10 was obtained for the dissocn. const. of the intermediate iow; Sri03*. The soly. of I in HpO and in NaOH soln. at 25° was then measured and used to derive the dissocn. const. of SrOEY, giving an av. value of 0.1, which agreed closely with that calcd. from an eguation for the strong hydroxides which assumed that interaction occcurs with the un- hydrated cations. _ 19 CA L6, 8939¢ | Electrlc Gon&uct1v1ty and Viscosity in the System.KDH-KQCOB-HoO M. I. Usanovich and T. I. Sushkevich Zhur. Priklad. Khim. (J. Applied Chem. ) 2k, 590-2(1951) The elec. cond. of KOH solns. from 18.86 to L1.59% contg. from 1 to 31% KpC03 was investigated at temps. of 259, 50° and 97°. The sp. cond. of the KOH soln. decreases as KpCO3 is added. The viscosity of RKOH solns. of two different concns. with different amts. of KpCO3 was detd. at 250 and 50°. As KoCO3 is added, the viscosity increases. The sp. cond. decreases because of the increase in the viscosity of the soln. aA 46, 9004z Reactions with Dry Alkeline-Earth Hydroxides. I. A General Method far the Preparation of the Hydrides of Sulfur, Selenium, and Phosphorus J. Datta (Sripat Singh Coll., Jiagana) J. Indian Chem. Soc. 29, 101- h(1952) Pure: HZS can be prepd by heatlng a mixt. of S and dry Mg(OH)»o powder to 2259, In which 75% of the § is converted into the hydride and the remaind- er to sulfate. HpSe of the same purity, together with selenate, can be obtained by the same procedure, but the hydride in this case is subject to appreciable gbsorption by the heated base. Phosphine can be obtained by the same method in 45% conecn. and free from PoHy ., With dry Ca{OH)»2 and Ba(0H)p, S, Se, and P exhibit the same type of reaction as with Mg(OH)o except that (a) 8 and Se undergo oxidation to a lower stage, i.e., to sulfite and selenite, resp.; (b) the acidic hydrides evolved therefrom are largely esbsorbed back; and (c) the phosphine content of the evolved gases is low. | | CA U6, 98104 Process for Obtalning Sodium Hydrox1de Containing Small Amounts of Sofiium Chloride Tadeusz Ademski and Zycemunt Frankl Prace (lownego Inst. Chem. Przemysl. No. 2, l-h(l951)(Engllsh summary) Crufis, tech. NalOH obtained by diaphragnm electrolysls was freed from Nall by crystn. of Na hydrates. A soln. of tech. NaOH was dild. to 50% conen. and upon cooling to room temp. decanted or filtered. This soln. was then further 4ild. to 37% NeOH, cooled to about 140, and a paste of 3 parts cryst. NaOH to 5 parts HpO added. This was cooled to about ¢°. The . crystals were then collected on a Buchner funnel and washed with cold -HoO, the liguid being coned. by the ususal procedures to obbtain more NaOH. This method effectively decreased the Impurities except that of NapCOg. Ca b6, 9959f Catalytic Action of Copper Hydroxide in Hydrogen Peroxide and Peracetic Acid Solutions, as well as in the Raschig Hydrszine Synthesie and its Suppression by Magnesium Hydroxide J. d*Ans and J. Mattner {Tech. Univ., Berlin-Chsrlottenburg) Angew. Chem. 64, Whi8-52{1552) The decompn. of HzOs in alk. soln. by Cu(OH), is a lst-order reaction which 1s proportional to the sguars of the catalyst conen. Mg{OH)o (I) removes traces of hesvy metals, sspecially of Cu, from alk. solns. The exptl. part describes in detail: (1) fixation of Cu dissolved in N=OH by I, (2) prepn. of pure distd. Ho0, (3) stabilization of alk. HpOp solns. by purification with I, (4} catelytic action of Cu on HpOs in 1 N NaOH goln., (5) suppression of the action of Cu on alk. solns. of peracetic h acid by I, and (6) use of the I pptn. in the Raschig hydrazine synthesis. 25 refersnces. Ga b6, 10561f Device for Making Alkalil Hydroxides in Granular Form Spolek pro chemickou s hutni vyrcbu, narodni podnik (United Chemicsl and Metalliurgical Works, National Corp.). Auvstrian 171,687, Juns 25, 1952 The device consists of a dropping vessel and a plste for receiving and cooling the droplets of melten alksll hydroxide. The parts of the app. which come into contact with the molten alkalies are msds from metals of the Bth Group of the pericdic system, having a normal potential above =0.29v. ' ca 46, 10708a Apparatus for Continuous High-Temperature Reactions within Closs Limilts James F. Adams, Russell L. Bauer, and Geo. E. Taylor (to Monsanto Chemical Co.) U.5. 2,610,109, Sapt. 9, 1952 The app. designed for high heat transfer rate within cloge limits, such as + 5°, to operate at temps. of 350-450° without localized overheat- ing, is well adapted to continuous evapn.-concn. of ag. caustic sclns., a5 well as to fusion of ac alkall metal hydroxide with an aryl sulfonate and alkali wmetal phenolats in the presence of superheated steam to produce 1 or more phenols. “» 21 CA 46, 1080kh Absorptlon of Carbon Dioxide by Solutions of Sodium Hydroxide and Sadium Carbonate under Conditions of Intensive Mixing M. Kh. Kisbinevskii and A. V. Pamfilov (Inst. Industry, Gorkii) Zhur. Anal. Khim. 22, 1183- 90(19#9), Chem. Zentr. 1950 II, 1202-3; cf. CA L6, 3835e The method described for the qtant. investigatian of the kinetics of absorption during intensive mixing (with the magnitude of the phase interface being unknown) is based on the maintenance of s const. phase interface by the choice of temps. and concns. that correspond to the const. phys. properties of the absorbent. If a high degree of turbu- lence is assumed, the following relations hold for the absorption of coz by NeOH and NapCO3 solns.: q = dw/e~. dt = 8p [KC + wn] / {KC + v, /H}] in which g = rate of 5bsmrption per unit of time per unit of interface surface; B = the hydrodynamic const. of the gas phase of the const. of the rate of diffusion in the gas phase; p = the partial pressure of C02; K = Kevy &7; Ko = const. of the velocity of the chem reaction; vn = the hydrodynamic const.; A7 = the period of renewal of the surface layer; C = the conen. of the chemically active component of the soln.; H = the soly. coeff. Exptl. results showed that at high turbulence the rate of absorption was proportional to the partial pressure and that the concn. of the absorbent had a slight effect on the rate of sbsorption. Under such conditions an increase in C result- ed in a reduction of q in those cases in which an sbsorption process and a slower chem. reaction were involved. It follows that the COp dissolved in the vol. of the ligquid phase does not react. ca 16, 10803 Tonizgtion Produced in Metallic Salts in Flames. III. Ionic Equilibrla in Hydrogen/Air Flames Containing Alkali Metal Salts. H. Smith and T. M. Sugden (Univ. Cambridge, Engl.) Proc. Roy. Soc. (London) A21l, 31-58(1952);'cf. CA b5, kghg The electron concn. wes examd. when alkali metal salts were added to H/air flames with excess H. The variation with respect to flame temp. and ionization potentlal differed from the theoretical prediction. Electron concus. were measured by attenuation of radio waves and temp. by Na D line reversal. The formation of neg. hydroxyl ions explains f some of the discrepancies observed. At. and mol. ions are measured by maintaining the flame in a parallel-sided condenser. This technique is described, and the way in which massive ions are detected is explained. There were some 20 times as many heavy ions as electrons, divided between 22 ca 46, 10803n (Contd) pos. alkall metal ions snd OH™. A value is calcd. for the 2lectron affinity of hydroxyl. IV. The Stability of Gaseous Alkali Hydroxides in Flames. Ibid. 58-T7k. Electron concn. was studied by centimetric wave attenuation. Devia- tions from predicted behavior was obaserved. For two flames of the same temp. on oppogite sides of stoichiometric compn. the air-rich one always shows lower attenuation, especially with Cs. The proposal of the produc- tion of OH ions independent of the metal can resolve the difficulties. CA b6, 10962¢ The Value of the Standard Potential of the Couple Nit*-Ni(OH)y and Properties of Nickel Hydroperoxide. S. I. Sobol (Gosudarst. Nauch-Issledovatel. Inst. Tsvetnykh. Metal "GINTsVetMet," Moscow) Zhur. Fiz. Khim. 26, 862-5(1952) From the new value (0.76 v., cf. Haissinsky and Quesney, CA 41, 4Ohhf) for the reaction Ni{OH)o + 2 OH™ = NiOp + 2 Ho0 + 2¢ and the new value for the goly. of Ni(OH)» (Gayer and Garret, CA 43, 8809n) the standard potential of Ni*t + 2 HyO = NiO2 + 4 H* + 2e is caled. to be 1.93 v. The o0ld value (1.75 v) should be abandoned. CA 46, 1099ke Several Compounds of Lithium and Oxygen. I. Alvin J. Cohen (U.S. Naval Ordnance Test Sta., China Lake, Calif.) J. Am. Chem. Soc. 7k, 3762-4(1952) A new method of prepg. LiOpH.H20 (LinOp.HpOs. 2 HpQ) by utilizing LiOEt and HoO2 in EtOH is described. The formula LinOp.HpOn.3 HpO for this compd. is discounted. Preliminary structure detns. are made from x-ray data. LiQpH.H2O crystals areorthorhpmbic, with possible space groups, Immm - Doy, 1212727 ~ D3, or Tmm - C5%; a = 7.92, b = 9.52, ¢ = 3.20 A.; d2> 1.69 indicates 4 mols./unit cell; np, 1.458 (a), 1.526 (7). LisOs is tetragonal with possible space groups, Ph/m - Cpy, Ph - CL, PUF - si, P42y - D, Ph2im - D3&, or P4/mmm - Dlh; a = 5.445 + 0.007, ¢ = 7.736 + 0.03% A.; d25 2.26 ifidicates 8 mols./*init cell. X-ray diffraction studies show that LiOoH and LipCOy do not exist at yroom temp. A dehydra- tion study proves that no fractional hydrate exists btetween LiOH.HpO and LiOH. | 23 CA 46, 11600g Evaporating Caustic Soda Solutions Francis M. Joscelyne and Imperial Chemical Industries Ltd. Brit. 670,726,Apr. 23, 1952 See U 8. 2,556, 185 (ca hs, 9818e)