Document 9o3eVakZB0M6RdOzx0QNEvO6

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Copy No. / l V-'4' - - NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Progress Report (*) The Phase Rule Study of the System 2a0~Cr03-H20 at 25C Period Covered: Rov, 1943- - July, 1942* \ >k FILE: DATE: 212 April 28, 194i % N39990 Serial Ho. KH-44-23 Copy Ho. l Copy tot ^ #1 - numerical File ^ 2 - Research Office (212) 3 - library File (212) 15 -,, Impaerial Chemical Industries9. ltd. 6 7 - Mr. C.H. Ruppreeht/I.C.I. File 96 -_ 0nr. 0**0. Patterson, Exwptl. St*,., Wlflm. 10- <* W'*' C ^ ^ Ay. &XU.-v.J a , -- ^ . u - stop* (Lt**. u>-i - 12 13 - * 14 - * BEMRK. PLJU3T PIGMtf COLOR RESEARCH REPORT Progress Report the Phase Rule Study of the System Zxt0~Cr0^a20 at 23SC Period Covered: 1941 - July 1945 DATE ISSUED: April 2*. i44 N39990.01 DUP050150348 2 - imiffiiu The following report covering the results of several months work was submitted substantially la its present form in August, 1943. A few minor points were clarified by Dr. Done at the time of his visit to Bewark shortly before his death. The only changes which have been made are of an editorial nature. Obviously, the area of the three component diagram of most interest to us is the one in which the solubility, expressed as concentration of CrO in solution, is relatively low and this region has been explored mere completely than the others. In fact, data are lacking at present to enable us to complete the three component phase diagram with certainty* the gaps are indicated in the discussion under "Summary and Conclusions*. B. R. DEBSLOW With the granting to the Pew Jersey Zinc Company of a patent, U.8.2,251,146'9'$ on "sine tetroxychromate* as a new chemical individual and a metal protective pigment, interest in the basic sine chromate* increased greatly. To obtain data on solubility and constitution of basic sine chromates, this phase rule study of the system ZnQ*-Cr03-B20 was undertaken, M. ftroger^ made a phase rule study of this system and did not report & *lne tetroxy chromate*. However, his data were very meager in this region and no conclusions as to the existence or non existence of "sine tetroxy chromate" 5ZnO.CrO3.xS29 could be drawn. In January 1942 a literature survey of the sine chromates was reported in KB-42-12 (Kef.7). Bo reference could be found in the literature concerning "zinc tetroxy chromate". Also, no phase rule study other than Oroger*s was found. By a variety of methods (see Experimental Details) mixtures of ZhQ, CrOv and 820 were prepared and allowed to come to equilibrium during agitation at constant temperature (25C.) Subsequent separation of liquid phase and solid phases wet with liquid phase ?reduced samples for analysis. The analytical results are shown in able 1, column* 5, 6, 10 and 11. The methods of the Phase Bale were applied as described in the section of this report entitled "The Phase Buie Applied to Three Component Systems". It was found that, while several definite compounds were clearly indicated, there was positive evidence of solid solution in the region of solid phase mole ratio of 4.9 to 3.1 DUP050150349 -3- and chromate solubility of 0.001 to 6.3J6 CrO*. This broad rang of chromate solubility includes the region or chromate solubility which, according to oar present belief is desirable for metal protective pigments. v * ' As pointed out in the section cm *Phase Bale*, additional data is the region of solid solution formation were needed In order to determine the mid points (composition of solid phase) of the divergent *tie lines*. Therefore, several dry powders were prepared and the analytical results shown In Table II were obtained. So special precautions were taken in drying the samples and it is probable that some were under- and some over-dried. However, an approximation of too composition of the solid phase in the region of solid solution was obtained by plotting in Fig.l the data of Table II and drawing the best straight lime among toe points and terminating it at toe point of convorganeo of toe next group of tie lines. Because of too low concentration of solute in toe liquid phase in toe region of solid solution formation, even large inaccuracies in placing the solid phase lino result in negligible change in toe calculated 2a0 t CrOj mole ratio in the solid phaoo. In Fig.l, the analytical results of Table I, columns 5* 6, 10, 11 and Table II, are plotted on a triangular diagram according to toe principles of the Phase Buie, ill intersections of tio lines, which points represent solid composition, were calculated by analytic geometry and toe results were converted to mole ratios and ere shown in Table I, column 12. From toe standpoint of metal protective pigments, the results in toe region of less than If CrOa in the liquid phase were considered of most interest* The triangular graph method is not suited for presenting data for such very dilute solutions, and another precede? ms therefore used for plotting the results which greatly magnifies the dilute mad of toe curve. Shown in Pig. 2 is the graph of toe leg of toe grams of r0 per liter of saturated solution (Table I, col.7) versus toe tndsGrChi mole retie In toe solid pheso (Table 1, eel. 12) Presented also in Fig.2 is too graph of too data (Table FIX) taken dlreetly from irogert8 peper vlJ. Other evidence of toe discontinuity in the curve (Fig. 2) at mole ratio 1*5 was obtained by preparing a series of mixtures in too region of retie 1.5 from sine oxide obtained from different sources. If toe displacement of the point of discontinuity from 1*0 (according to driger) to 1.5 were due due to presence of a fraction of *wnreaetive* ZnO, a discon tinuity at a different ratio should result for each typo of sine oxide because of probable different fractions of *unreeetlve" ZnO present, however, using resistance measure ments as a measure of composition of the liquid (See Fig.5 for graph of resistance versus composition), mixtures mad# from either a different lot of Reagent Quality sine oxide or DUP050150350 the commercial Kadox exhibited a discontinuity at the same Zn0tCrO3 mole ratio of 4*5. The results of these two series of experiments are shown in fables III and IT and Pigs. 4 end 5. The discontinuity at ratio 4*9 was reproduced, also, in conductlmetric titrations in which CrO* solution was added to ZnO slurry and vice versa. to present in convenient tabular form the information on the limits of the composition of the various combinations of phases in mutual equilibrium, fable T was compiled frost Figures 1 and 2. The results of mlerosoople examination of/the crystals in equilibrium mixtures are shown in fable TI. Qrogerw obtained the same type of crystals at mole ratio 4 and 3 as were obtained in this study In the range of solid solution. She 2*1 crystals be described as "eloudy, spherical crystallites", which description fits the 2<1 preduet found in the preswat study. Bo described the 111 compound as "small crystals", which also corresponds qualitatively with observations made in the present study. The following conclusions may be drawn regarding the system at 25*6. 1, "Zinc tetroxy chromate" as described in B.S.2,251,846 does not exist. A solid phase containing rare than 4.5 moles ZnO to 1 rale Cr$3 is a mixture of sine oxide rad the limiting solid solution 4.5 ZnOiCrQ-j. (lotos X-Ray diffraction studies made by the Experimental Station on a pigment with the empirical composition 5 ZcOtCrOt stewed the pattern of free zinc oxide as veil as the ZnO-free pattern of the 4*5 Z&OtCrQj pigment. The latter pattern corresponded with the pattern presented by the U, Zine Co. in the patent on "Zinc tetroxy chromate".) 2. "Zine trlexy*(4 Ztod.CrOO and "sine dioxy chromate" (3 ZnO.CrO*) both reported by Groger'l'. do not exist as definite chemical compounds. Instead, a series of solid solutions varying in compo sition between the limits of ZmOtCrdj mole ratio of 4*5 to 3.1 exists, (lotes X-Ray diffraction studies by the Experimental Station Shewed that several lines of the 4*9 pattern disappear to fora the 3*1 pattern...This is a phsraasaon of crystalline solid solutions.) Idfoger'*' described both the 4*1 and 3*1 compounds as identical under the microscope.) The wide range (6,000-fold change) of chromate solubility of the solid solution allows the preparation of a pigment with a chromate solubility anywhere in this range. Although the points in the region of solid solution Show some tendency toward scattering (See flg2) It Is believed that a standardised method of manufacture would be reproducible. It is believed that equilibrium between the solution and the surface of crystals of sdlid solution is established readily, but that constancy of composition throughout the length, breadth, and thickness of a crystal is approached slowly, as the rate of diffusion of atomic groups Inside a crystal is naturally limited, me possible disadvantage to the use of this type of material as a DUP050150351 -5- metal protective pigment should he mentioned* namely, the amount of CrOj available la quite limited and its solubility is reduced quite rapidly by leaching. However, leaching merely produces the same combination of ingredients as is present In "sine tetroxy chromate#, which itself has shown premise as a metal protective pigment in tests conducted by the Sew Jersey Zinc Company. 3. the compounds 2ZaO.CrO3.2i20 and Za0.CrO3.2a2O **** clearly indicated* However, the nature of the solid phase of composition between the two is not clear* The existence of a 1*5 ZhQtOrOt compound (reported by Groger) is neither confirmed nor disproved* (Botes x-iay diffraction studies made by the Experimental Station showed dry material with a ZsO*Cr3 ratio of i.S to have the pattern of the 3,1 limiting solid solution and of a 2tl compound, Examination of 111 material showed a different pattern} (Hotel the compounds 2Za0~Cr03*l*5 BoQ and 2h0*Cr03*H2# reported by Grogeru; are believed to neve been the remit of his overdrying of the Silt2 sad lilt2 compounds of the liquid-solid equilibrium mixtures. (The dry powders of mole ratio 2.57 and 2*2$ (Ho.5 and 6, Table 1) were definitely overdried, as indicated by their positions In Fig.l.) 4* The dotted-line portico of the liquid curve (Fig.l) is the only portion which remains uncertain, It is believed that along mis lineo lies the varying liquid compositions Hwohfifcmhananrc\winreepqouritleibdriuthme with zinc compounds dichromate. (Hotel ZnO.ZCrOj and ZaO*2Cr03< 3fl2 5. The compound reported by Hoffmann(6) is dearrllyy indicated by mis phase rule study. 6, The compound Cx-03 is clearly indicated as being the solid phase associated with the final segment of the liquid curve. fp mm mm rnm^mgfLsgKmm mmm (For the purpose of illustration Figure 7 is presented) The Phase Buie Is applicable only to systems all phasos of which are mutually at physical and chemical equilibrium. Mathematically, the Phase Buie is stated as PC-P 2 (Eg* 1) where F is the amber of degrees of freedom (independent variables, such as temperature* pressure, composition of a phase, which may be varied without the appearaaee of disappearance of a phase)j where C is the number of eompea- eats (smallest number of chemical species which may be used DUP050150352 6- to express the composition of each phase of the system) j where P is the number of phases present (one gaseous, one or more liquid, end one or more solid). Let us eon eider a three component system consisting of B|0 and solid compounds A and B In the presence of the atmosphere, air is a 4th component, but pressure of the system is maintained constant at one atmosphere and is thus eliminated as a variable. Thus, at constant pressure P (C - P 2)-l * 4-P+2-1 5 - P (Bq. 2) At constant pressure and temperature P * (5 - P)- 1 * 4 - P (Eq. 3) Prom equation 3 it may be calculated that presence of two solid phases, one liquid phase, and one vapor phase (at constant fressure and temperature) allows aero degrees of freedom, herofore each of the four phase# must maintain constant compo sition or one of the ptoses must disappear. to compositions of spaeh invariant mixtures lie in areas 2 1 IX, 3 ZXZ IV, 4 XV V Mixtures containing one solid phase and, therefore, possessing one degree of freedom lie In areas X 12, XX XXX 32, XV 34, V 45. the independent variable is the percentage of one of the components in the liquid phaset the other components are altered dependently in such a manner that the liquid compositions lie on the line 12345. In the area above line 12345 there is no solid phase present and a mixture there has two degrees of freedom, namely, the percentage composition of two of the component* in the liquid. Experlmentally, a Phase Buie graph of a real system is worked out by analysing the liquid phase of an equilibrium mixture and analysing a mixture of liquid and solid phases. Greater accuracy in graphing is obtained by removing as much liquid as possible before analysing the mixture, the salytlcal results for eaeb mixture are represented on the triangular composition diagram by a pair of points. She straight line thru the two points, when extended toward Mho region of loss liquid eontout will pass , through the composition of the solid ptoses, intersection of two or more tie lined from different liquid compositions in a single point determines the chemical composition of a compound, which constitutes the solid phase. Potato 1, IV, and V represent such compounds, (Bef.9). fie lines emanating from a point representing a single liquid composition lead to a solid phase composition consisting of a mixture of two phases. Such liquid compositions are the points 2, 3, and 4* Since points XV and V represent chemical DUP050150353 compounds, the tie lines from point A terminate in a straight line connecting points 17 and 7, which line represents mixtures of compounds XT and 7 in various proportions. However, complications arise for this "method of intersections" in regions of varying liquid, composition where the tie lines do not intersect in a point* Such a region is line 23, which represents a series of liquid solutions in equilibrium with a series of "solid solutions". Xt is impossible to determine the composition of the solid phases without securing additional data. Ingenious means of obtaining samples of the solid phases free of all liquid and without decomposition must be devised, and the samples analysed. Thus the line X XX XXX XT may be constructed, the points XX and XXX are the limiting compo sitions in the series of solid solutions. The straight segment X XX represents mixtures of compound X mid limiting solid solution XX. the straight segment XXX XT represents mixtures of limiting solid solution XXX and compound XT. (For further discussion of this method of indirect analysis In relation to solid solution formation see Bancroft, Ref. f) Methods of Preparation Usually, mixtures containing three to five grams of solid phase per 100 cc were prepared, the following outline describes the various methods of preparation. Distilled water. Reagent quality ZnO (dry process) and Reagent quality CrOq were used and mixed during constant agitation. A. to a prepared slurry of sine oxide, chromium trioxide solution was added. B. |*o a saturated solution of ZnO and CrOj sine oxide slurry was;added. C. to a mixture prepared by Method A sine oxide slurry was added* D. to a mixture prepared by Method A water was added. E. to a sine oxide slurry a saturated solution of ZnO and CrO^ was added. F. Zinc oxide slurry was added to C1O3 solution. 0. Solid CrOj was added to a saturated ZnO, CrOj solution. H. Saturated solution of 2no and CrOj was evaporated in a desiccator over CaC12 P2O5. the resulting mixture was ground smooth in a mortar. DUP050150354 j Supersaturate solutions were prepared by adding zinc oxide (slurried or dry) to saturated solutions of ZnO and CrO-a. After stirring a few minutes the mixture was filtered. Upon standing for various lengths of time a precipitate usually formed* Excess liquid was decanted off and the resulting mixture was used* K. Supersaturated solution was prepared by filtering a ZnQ-CfrCj-HgO mixture at 0~3C. Upon warming, precipitate usually formed* Excess liquid was decanted off* I>* A large quantity of an equilibrium mixture of 2^$*Crd*2ggd and its saturated solution 5*2# ZhO, 12*2# CrOj was vat washed Id times. From time to time daring the washing process a sample cf the settled mixture was removed and placed in a shaking flask for attainment of equilibrium at 25C. Each mixture wes placed in an Brlanatyer flask of 125 m. capacity (500 c.e* site for some of the less soluble mixtures). The flasks ware fitted with ground-in glass stoppers lubricated with a small amount of inert grease and securely held in place while in the shaking apparatus in the thermostat by pressure from a half-inch thickness of sponge rubber. Agitation of the mixtures while attaining equilibrium was provided by means of a *ferris wheel* type of shaking apparatus with spaces fer 24 flasks* This ms purchased from the Arthur H. Thomas Co*(Catalog Item Ho.8910) and was operated in a water bath whose temperature was held at 25 0.01C. by means of a toluenemercury tharmercgulator and a vacuum tube relay controlling and Immersion heater* Changes in concentration of solutos in the mixtures while approaching equilibrium were conveniently followed by measuring the resistance of a dip-in conductance cell placed directly in the reaction mixtures from time to time. After equilibrium conditions were believed to have been reached the liquid phase was separated at constant temperature m& without evaporation by allowing the mixture to drain by gravity through the fritted glass plug of a Fyrex filtering crucible. A small beaker served to collect the filtrate, and both filter and beaker were contained in a wide-memth glass bottle tightly capped and submerged in the weter bath during filtration* For analysis, a sample of the liquid was transferred to a weighing bottle by means of a pipette of suitable size. Usually the volume in the pipette was adjusted to the mark, and a measure of the density was thereby obtained* However, these density results are inaccurate to the extent of *drainago error" in transferring the more dense and viscous liquids* Densities obtained in this manner are shown in Table X and Fig* 4. DUP050150355 9 After the liquid had drained from It, the resulting paste was prepared for analysis in one of the following ways, M, ft sample was transferred to a weighing bottle, B, A sample of paste was placed between pieces of porous porcelain plate in a closed bottle at 25*C for further removal of mother liquor* A sample of the thickened paste was transferred to a weighing bottle* The filter containing the paste was removed fro the theraoatatted bottle mad was quickly subjected to veeuu filtration only to the extent that no air passed through the filter* A sample of the thickened paste was then transferred to a weighing bottle* After being veiled, the samples of liquid and of paste were transferred to velwaetrle flasks* A few drops of dilute sulfUric .acid were used to dissolve the paste* Water was added to bring to proper volume and aliquot portions of suitable sis# wore taken for sine and chromate analyses* Chromate was determined by the lodevetrlc method for sine yellow described In KCR #46, Unsatlsfactory results were obtained by the Hgft method for sine in sine yellow* Consequently, a method for sine was developed especially for this study* Standard methods (2,3,4) using 8-hydroxy quinoline as a quantitative precipitant for sine wore modified* Ammonium hydroxide and ammonium chloride were employed, producing an alkaline solution to prevent the reduction of the CrOi radical hr the organic reagent and producing a solution of eomplox sine salt to prevent precipi tation of basic sine compounds until addition of the reagent. This method was subsequently set up es KCR 133, Water was determined by the method described in KCR 46. Methods |f (felealafelng the Solid Phaaa lad of the Tie Lines. (These calculated points' are shown in Table I, column 12*5 A - The compositions of the dry powders shown in Table II wore plotted on Fig,l. The best straight line was drawn through the point K (2ZnO* Cr3* 2B3>0) and among the experimental points* Xt is emphasised that this resulting lino represents only an approximation of the course of the solid phase compo sition. Actually, at mole ratio 3.1 a break in the solid phase curve may be expected. The intersection of this line with the straight tie-line determined by the pair of liquid and paste points was calculated by Analytic Geometry, This involved using the % ZnO as the x-coordinate and the % Cr03 as the DUP050150356 -10- y~coordinate and thus obtaining an equation for the line through any pair of ##!***. The Analytic formula y - YXm^z ~ Fi X - X! X2 - tx was used* Here subscript 1 represents one point and subscript 2 represents the other point of the pair, for example the equation for the line through points (10# 2n0, 20# CrO*) and (16# ZnO, m Cr03) " H^-4- By solving two such equations simultaneously for X mod y the coordinates of their point of intersection are obtained with an accuracy unobtainable with a graphical method. B - As an arbitrary line upon which to calculate Inter sections with tie lines converging toward ZnO.CrO3.2H2O the straight line passing through the compositions CrO-j mod ZnO.CrQ3.2B2O was chosen. Intersections were calculated by Analytic Geometry. C - As the line upon which to calculate intersectiocs of tie lines In the vicinity of ZnO.3GrO3.lH9G. the line passing through ZnQ.3CrO3.3H2O and Cr03 was chosen. D - The intersection of the tie line with the ZnO-free axis waa calculated. From the data of Table X, Fig. 6 waa constructed in order to obtain, by Interpolation, the densities of solutions which were not determined directly. DUP050150357 ~n- 1. Kroger, 1., Z. Aaorg. Chesu 2SU 135-144 (1911) 2. Chiraslde, R.C., t al, Analyst j& 399-407 (1941) 3. Prodlager, W.P., "Organic Reagents Used la Qufaatitatlve inorganic*, Rev Jerk, Elsevier Pah. Co. (1940), page 106. 4. Xellen, I, 'Organic Reagents in Inorganic Analysts*, Philadelphia, Blaklston (1941)7 page 610. 5. Lelsy, R.W. (The Hew Jersey Zlae Co.) U.S. 2,251,346 (Aug. 5, 1941) 6. Hofffeaan, BIexikon der anorgaolsChe ferhladungen*, vol.2, p, 498-499. 7. Literature Survey, Basic Sine Chromates SB-42-12, 1/12/42# Pile 150. 8. Bancroft, W.O., 3. Pfays. Chan. 6 . 17#, (1902). 9. Bill, A.E., fieterogealotts Equilibrium la Taylor's "Treatise on Physical Chemistry* fan Rostrand, 1925. 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Dri<t 3 toy *4 140*7. a *10 SB 66.2 20.9 12.92 3.89.1*3.43 ft** f 4001. 0S*t* 4 raa 4--IMWtw ***r ealiu efelorito. 0Fig %*Uw*4 4 0 ineoaplci dtltifc 4hJfc tAiljiA jikJP raMi abawrbei by 48 4*4fcc*nt, I 469 TD (44 22.4 13.3? 3.52*1*3.31 f*4 f 499*. 0rl6 at rn t*?. mmr leiaa *tlerl4. Drying Mtn4 4 b ia6pli 4U 4 lrg lUMMMKfc f *4r bawb< by 4eant. 4 410 7B 63*? 24.5 11.80 3.19*1*2.6? Paata of 4107. DrUAiuair t mm 4p. 4 11.0 W*0. Brjr- ing orayl4a<l **efrah alium blri4 4iceant. 5 313*0 60.68 28.88 (10.8) 1.5T1*2.0T f4 f 3H8 <ueb4 49y a fibl by filtratle. Filtar 4k UwA 4e dry at 149*7 for 3 toy. 6 USA 5I4( *UT4 (10.0) t.t5*l*l.T5 Bft4 f 313? B*Mi b4 9*m yl*4*. Brit a toy *4 140*7. ? ?2?-46A 8 927-468 66.91 4940 *0.4? (12.6) 4.01*1*3.31 | IT *16 (13.8) 4.94*1*4.46 ) 64* *1b*14*4 4 Inin slarry 4P Dri4 v*rlgb4 4 148*7. t fti-fli 69.3 20.TT (13.0) 3.98*1*3.4? VrS Mlttttaa 0<t6 4 alttrry f lagn4 S8. fftt4*p8 00B7 ftww#l fii*l4 rlgb4 4 14W, DUP050150364 It- RSSISTAttOB MEASORIMENTE OF A SERIES OF MIXTURES MADE BY ASMS* VMtYIBG a iq b b t s o f GrQa s o u j t io k t o a c o h s t a b t a mo u n t or a s l u r r y or c.p. b a k e r 's ANALYSED ZnO. (Aim 3 DAYS AOmfXOK AT 25C.) :i f k ITITTOT U28 A m 8ao 1.357 SSuCr*11* 0.26J 1128 B It .213 1128 0 it .283 1128 P II .309 1128 F l 321 ml * It .32? 1121 0 1128 H * it .333 341 1128 1 .355 1128 J .371 1128 X * .397 1128 1. at .40? 1128 H t .417 U28 H 41 .427- 1128 0 ft .450 x t o I f-- SMIHUTTM------------- SnOtGrOa nel* rftti* elms hog) 8.3 5000 (3.70) 6.1 5130 (3.71) 5.9 51BO (3.71) 5.4 5160 (3.71) 5.2 5200 (3.72) 5.1 5080 (3.71) 5.0 5000 (3.70) 4.9 9090 (3.71) 4.7 4840 (3.69) 4.4 3600 (3.56) 4.2 1150 (3.06) 4.1 680 (2.83) 4.0 480 (2.68) 3.9 350 (2.55) 3.7 20? (2.32) II MM ft* ftlurrjr 2.714 ga ZnO per 100 al. mm MM 7)1 *eluti* of OrOa/ Measured pouring ih* mixture int* a mall ceaduotirity cell* DUP050150365 -19- TABLB IT BE8ISTAHGI IEABUBEKE8TS OF A SERIES OP MIXTHRIS VASE TOOW A SLPftftY OP KADOX ZnO ATO 80LDTIOW Of 0*0*. (ATT! 3 SAYS A81TAY70K AY 25*0.) Deaig- Melee ZnO aatiea___ ..... nerlQG *,, 1231 A .0459 ... ::.....:......1 wmimmk ** Melee 0r0 ZnOtCrO* .. t>er IOO r ib. Mole retie ohms (1g b\ % .00804 5.71 3300 (3.52) 1831 B 1231 0 1231 B .0452 .0445 jwr .OO869 .00985 100975 5.20 4.80 4.50 3330 3260 2510 (3.52) (3.51) (3.40) 1231 B 1231 r .0432 .0427 01027 .01068 4.20 4.00 214 111.8 (2.33) (2.05) 1231 0 1231 H 0426 .0459 .01191 01482 3.67 3.10 59.1 28.6 (1.77) (1.46) 1231 I .0485 .01955 2.48 15.56 (1.19) 1231 J .0492 .02200 2.24 12.34 (1.09) 1231 K .0483 02273 2.12 12.05 (1.08) 1231 B .0473 .02355 2.02 10.49 (1.02) 1231 M .0571 .0432 1.32 3.985 (0.60) 1231 H .0633 .0555 1.14 3.62 (0.56) 1231 0 .0443 .00936 4.85 3125. (3.50) * Ye each Mixture me added eater te bring to a total net weight of 110 g. of Mixture. ** Measured by dlp-in conductivity cell. DUP050150366 -20 TABLE y.StnaiART RABGE OF C0MPG8ITJ0H OF lOOILlBtltJM HUTTOS LIJ5J15 * 2nd 0.0010 0.0010 2.8 P HAS 2 ... i l * CrOa . ,,~1j 5o " f ZnQ SOrOa 0.0012 99.998 ( \( 0 t 0.0012 .( 99.998) - ee tc * 6.3 ) 90.9 ) ! to m 2.6 6.3 90.9 (- l C 54.5 'm u 33.5 2.8 11.8 6.3 tc 28.7 90.9 > > 59.5 ) 54.5 33.5 11.8 15.9 28 .T tc 39.2 59.5 ) ( 54.5 )( 44.9 ) ( 37.4 33.5 tc 44.0 15.9 20.4 39.2 tc 51.0 44.9 ) ) 28.6 ) 37.4 46.0 20.4 20.4 18.7 51.0 51.0 to ** 52.7 28.6 ( 37.4 ( (- 28.6 ) ( )( 28.5 ) ( 18.7 46.0 tc Cfr m tc 68.9 18.7 12.5 52 *T to 60.5 28.5 : 27.5 18.7 68.9 12.5 9.1 9.1 0 60.5 tc 60.2 60.2 tc 62.9 27.5 ) (18.7 |( 30.7 ) ( 0 30.7 32.1 )51\ 0 68.9 t 100 100 8:1 S % HaO 7 7 -.... Sweirieal Fcrmuin XnQ*7 HgO end 4.5 8n04?r0;7Hs0 7 4.5 ZnO^rOartHcO to* 7 3.1 fa0^r0.7IUS 7 12.0 12.0 3.1 2BO.OrOs*7B80 end 2 Xb0Ois .2H80 * 2 Zn0-0r0a-2H30 32.0 16.6 16.6 2 Zn0^3rOa*2RaO tc ** 2nO.0rOs.2BsO 2nO.CrO**2RaO 16.6 7 7 12.4 2nO*0rO8*2Ha0 end 2n0.2Cr0**7Ha0 2n0.2CrOs*7HeO tc* &>O.3OrOs.^0 12.4 12.4 0 2a0.30rOs*3BsO ZnO.3CrO8.3HgO end CrO 0 CrOg * Region of N valid nolutios". Region in which rent* of changing mgoiiilni In not certain. DU P050150367 -21- fmx n Oeslg----- nation 521 522 X 566 $ 506 2 506 2 506 0 330 V 507 F 316 0 SJXCROSOOPIC BfSCFIPTIOB OF CRYSTALS Hole Ratio 2O*0* - *..-..---.J^RflA.-or.fF*itlo.................. 4.1 Supersaturated solution was warmed te 25*6. Bsesrintisa Fellow needles. 0.003 to 0.01 na long. Between 4.1 * 4.5 Saturated solution from 521 0 aa heated te l80*F and allowed te settle at 1?GF. Telia* needles. 0.01 te 0.04 net long. 3.5 Supersaturated solution was Yella* needles. aliened te alt at room <0.001 mm long. temperature. 3*3 m Yellow needle#. 0.05 te 0.15 mm long. 3.1 ! Yellew needle#. 0.002 te 0.003 mm leng. 2.0 It Oleeterc of very smell orenge-yellow partlelee 2.0 CrOa solution addsS to 2nd slurry# tt 1.0 t Yery thin parollalegrana with a 45* newt# angle. Average dimensions 0.1 to 0.2 X 0.005 to .07 m.m. Red - Brews 1.0 Ad) elurry was added te a saturated solution Thin parallegrasw with 45* eeute angle, large variety of si too. DUP050150368 22- was v ii 04T4..02 gptomm or Bieie mm mmomnse % Anorg. Cham. j&t 135-144, (1911) (1) (2) Sxp.Ro. CrOs .--UAL.. (3) log (2) 1 o.eio 3.000? 2 0.010 3.ooo 3 0.010 3.000 4 0.404 1.781 5 2.14 0.330 6 4.19 I 11.4 11.5 9 22.2 10 31.4 0.422 1.057 l.o4o 1.344 1.497 n 43.1 12 5T.5 13 44.5 14 44.? 15 ?0.4 14 93.3 IT 101. 18 151. 19 192. 20 192. 21 285. 22 392. 23 450. 24 441. 25 443. 1.434 1.740 1.823 1.824 1.849 1.970 2.004 2.179 2.284 2.284 2.455 2.593 2.453 2.444 2.644 24 4?5. a? 574. 28 440. 29 749. 30 879 2.67? 2.759 2.820 2.884 2.944 31 970 2.987 (4) (5) 2n0ytr0s( molar) Co bo .So Iii. 32.2 16.7 6.90 3.98 4.00 3.97 3.50 3.31 2.99 3.00 2.98 2.99 2.43 '2220 1.990 1.076 1.970 1.972 1.720 1.611 1.444 1.4?0 1.44? 1.322 1.118 .951 .940 *952 .945 .952 .945 Constant a m Variable (9 Constant a Variable If 91 9 Constant Variable ft If 10 Coi3*tmt # Variable n Constant Variabla 40 # 41 t 91 (4) Solid nN| 2 2 2 1 1 1 2 2 1 1 1 1 2 2 1 1 1 1 2* 2 1 1 1 2 2 1 1 1 1 1 1 DUP050150369 DUP050150370 tu a .'n; ntiAKatiiAfi Co-on # * w u . * , A. DUP050150371 DUP050150372 DUP050150373 DUP050150374 s jL jm * n x 3 fV * * V K 'c t o o t t a o f j -d n i ` a m W w o s iio o a x 3 o o d , ' , *sM isA i<i a h o a i *aaausft"\*tiW 6 i e DUP050150375 DUP050150376 N * . 3 * 2 6 Y*U_)MKAlt. \ S tiS & K C O C IX BOOK CDW PANv , JNC. NORW