Dec., 1953
SORPTION-DESORPTION STUDIES IN THE BeO-In203 SYSTEM
random, no coherent scattering of the X-rays would be expected, and hence new diffraction lines would not appear. The small radius of the beryllium ion compared to that of the oxygen and indium ions and the lack
885
of a detectable shift in the observed cubic In203 lines (Fig. 4) make this type of interstitial solid solution a likely explanation of the crystal structures giving rise to the X-radiograms obtained of the BeO-In20, system.
SORPTION-DESORPTION STUDIES IN THE SYSTEM BeO-In20a' BY W. 0. MILLIGAN AND C. R. ADAMS The Rice Institute, Houston, Texas Received March 9. 1868
Water vapor sorption-desorption isotherms a t 2 and 12" have been obtained for a series of eleven heat-treated (2-hour periods) gels selected a t every 10 mole per cent. in the system BeO-InzOs. Two zones of enhanced adsorption occur at compositions of about 40-60 and 90 mole per cent. BeO, in a plot of specific adsorptive capacity at constant p / p o as a function of composition. Plots of BET surface area as a function of composition lead to the same conclusion. The two zones of enhanced adsorptive capacit correspond to the zones of mutual protection against crystallization previously detected by X-ray diffraction methods. Losteric differential and integral heats of adsorption are likewise higher in the regions of mutual protection. The observed enhanced composition zones of amount of adsorption and the enhanced heats of adsorption confirm a prediction set forth in an earlier paper. The most frequent uncorrected Kelvin pore radii computed from the desorp, tion isotherms are 125 A. for pure In208 and 25 b. for pure BeO. As the amount of B e 0 is increased the pore radii decrease regularly, the greatest changes occurring at compositions of 10 and 90 mole per cent. BeO.
Introduction In a previous report from this Laboratory2 a systematic X-ray diffraction study of dual hydrous oxide gels in the system BeO-In203 demonstrated the existence of two composition zones of mutual protection against crystallization. In an earlier investigation3 the prediction was made that such zones of prot,ection may correspond to regions of maximum surface, and which, therefore, may exhibit enhanced adsorptive properties. The purpose of this present paper is to report the results of an extensive sorption-desorption study of gels in the system BeO-In20e which have been heat treated at 500 O. Experimental Preparation of Samples.-The samples employed in this investigation were prepared similarly to those previously used in X-ray diffraction experiments.2 Freshly prepared solutions of beryllium and indium nitrate (0.5 M with respect to the anhydrous oxides) in 0.01 N nitric acid were coprecipitated at a pH value of 9.4 in a rapid mixing device4 by the addition of a previously determined quantity of dilute freshly distilled ammonium hydroxide. The amounts of the beryllium and indium nitrate solutions were selected so that the eleven gels corresponded to 0, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100 mole per cent. InlOs. The carefully washed2 gels were dried in air at room temperature, and then were heat treated at 500' for a period of two hours. After the heat treatment the samples were allowed to attain equilibrium with water vapor in the atmosphere, in order that samples for sorption-desorption isotherms and aliquot portions for water analysis would be identical in composition. X-Ray Analysis.-In order to ensure that the samples were closely similar to the ones used earlier in X-ray diffraction studies,2 monochromatic X-radiograms were obtained, using chromium Ka X-radiation from a sodium chloride crystal monochromator. "No-Screen" X-ray film was employed, and the exposure time was 60 hours. (1) Preliminary results presented before the Division of Colloid Chemistry at the 122nd meeting of the American Chemical Society in Atlantic City, N. J., September 14-19, 1952. (2) L. M. Watt and W. 0. Milligan, THISJOURNAL, 57, 883 (1963). (3) H. B. Weiser, W. 0. Milligan and G. A. Mills, ibid., 52, 942 (1948). (4) H. B. Weiser and W. 0. Milligan, ibid., 40, 1075 (1936).
Sorption-Desorption Isotherms.-The isotherms were obtained in a multiple sorption-desorption apparatus, fully described elsewhere.6 The temperature was held constant during each isotherm to approximately f0.001'.~ At the same time that the adsorption samples were placed in the apparatus, aliquot portiones were weighed and then ignited to constant weight at 750 . The loss in weight upon ignition was attributed to the loss of water, inasmuch as these samples had previously been heated at 500°, a t which temperature essentially all of the possible foreign volatile matter would have been lost. Complete sorption-desorption isotherms were obtained at 1 2 O , employing water vapor as the adsorbate. Barium chloride dihydrate, carefully degassed at liquid nitrogen temperature, was used as the source of water vapor. Water vapor was made available to the samples, while the temperature was being lowered from that of the room to 12' in order to maintain true equilibrium, after which the apparatus was evacuated at mm. before the commencement of the isotherms. Upon completion of the isotherms at 12", the temperature was lowered to 2', again in the presence of excess water vapor. Complete sorption-desorption isotherms were then obtained at 2", following the same procedure as at 12".
Results and Conclusions X-Ray Analysis.-The results of X-ray diffraction analysis were similar to those obtained previously2 at a temperature level of 500 or 600". Samples in a wide region of composition were found to be amorphous t o X-rays: namely, the region lying between 70% 1n203-30% Be0 and 10% 1n2O3--9O% BeO. The samples containing 30% or less Be0 gave only the pattern of In203with a decrease in crystallinity as the amount of Be0 increased. The X-ray results will not be discussed in detail here. Isotherms.-The sorption-desorption isotherms are plotted in Figs. 1-22. All of the samples gave similarly shaped isotherms, with the exception of the sample consisting of pure BeO. The isotherms for the ten samples containing In203 show that a considerable amount of water vapor is taken up at low relative pressures and that only a small amount of water vapor is taken up thereafter, until the relative pressure reaches a rather high value. At (5) W. 0. Milligan, W. C. Simpson, G. L. Bushey, H. H. Rachford, Jr., and A. L. Draper, Anal. Chem., 23,739 (1951).
W. 0. MILLIGAN AND C.R. ADAMS
886
VOl. 57
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0.0 0.6 0.8 1 . 0 0 . 0 0.2 0.4 0.6 0 . 8 1.0 P/Po P/Po Figs. 1-11.-Sorption-desorption isotherms a t 12' and Kelvin pore distributions a t 2 and 12Ofor InzOa-BeO mixtures: 1 2 3 4 5 6 7 8 9 10 11 Fig. BeO, mole sln 10 20 30 40 50 60 70 80 90 100 .- 0 Fig. 12.-Sorption-desorption isotherms a t 2' and differential solid line) and integral (dashed line) heats of adsorption a t 7" for 100 mo e % InzOs.
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high relative pressures a large amount of vapor is adsorbed, and marked hysteresig QCGUTB~
The sample consisting of pure Be0 gives a decidedly different type of iwtherm, The amsunt ad-
SORPTION-DESORPTION STUDIES IN THE BeO-Inp03 SYSTEM
Dec., 1953
887
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0.4 0.6 0.8 1 . 0 0 . 0 0 . 2 0.4 0.6 0 . 8 1 . 0 0 . 0 0 . 2 0.4 0 . 6 0.8 1.0 P/Po PIP0 P/Po Figs. 13-21.-Sorption-desorption isotherms at 2 O and differential(solid line) and integral (dashed line) heats of rtdsorp tion at 7" for In20a-Be0 mixtures: Fig. 13 14 15 16 17 18 19 20 21 20 30 40 BeO, mole % 10 50 60 70 80 90 0.2
sorbed increases more rapidly in the middle pressure region than for the other ten samples. Also it is noted that, whereas hysteresis in the other ten samples continues up to the saturation pressure, there is a definite region near saturation where adsorption is reversible, and that the hysteresis occurs at a much lower relative pressure, indicating the the absence of large pores. The results bear out the conclusions reached from X-ray diffraction studies: namely, that the effect of Be0 upon the properties of InaOais not nearly equivalent to the effect of In203 upon the properties of BeO. The addition of a large amount of Be0 to has relatively little effect upon the properties of the latter, whereas only a small amount of Inz03 added to Be0 changes its characteristics drastically.
Specific Adsorptive Capacity.-In Fig. 23 the amount of water vapor adsorbed at two different relative pressures is shown as a function of composition. From these two curves it is noted that there are two major regions of increased specific adsorptive capacity, at a region corresponding to 40-60% Be0 and at a region corresponding to 90% BeO. These are the same composition regions where maximum mutual protection against crystallization has been observed. The enhanced adsorptive capacity may be explained on the basis of mutual protection against crystallization.s If one oxide acts as a protective colloid for another oxide in the solid state, the protective action serves to prevent growth in the solid phase into the ordered crystal state. It follows that if oxide A is adsorbed by oxide B, it will inhibit
W. 0 . MILLIGAN AND C. R. ADAMS
888
1 w
‘
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VOl. 57
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p / p o = 0.4
P/Po Fig. 22.-Sorption-desorption isotherm at 2’ and differential (solid line) and integral (dashed line) heats of adsorption at 7 O for 100 mole % BeO.
the crystallization of B, and if oxide B is adsorbed by oxide A, it will inhibit the crystallization of A. The mutual protective action of the two oxides on each other will result in two composition zones of maximum protection against crystallization (one in which oxide A is in excess, and a second in which oxide B is in excess) and three zones of maximum crystallization (in which B is in large excess, a second in which A is in large excess, and a third in which both A and B are present in proportionately large amounts). In the zones of protection, the gels are amorphous to X-rays or consist of extremely finely divided crystals which may correspondto regions of maximum surface and which, therefore, exhibit enhanced adsorptive properties.
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Fig. 23.-Specific
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adsorptive capacities and surface areas in the system BeO-InzOl.
The adsorption data mere converted to the BET function and were found to give good straight lines within the range of relative pressures from 0.05 to 0.3, where experience has shown that the BET equation is usually applicable. Surface areas, as calculated by fitting the data to the BET equation by means of the method of least squares, are shown as a function of composition in Fig. 23. They are pIotted with the x/m values corresponding t o monolayer coverage on the same scale as the x/m values at p / p o = 0.0 and 0.1. It is noticed that this curve parallels quite closely the curve of x/m vs. composition a t p / p o = 0.1. A discussion of the surface areas would lead to the same conclusions as those reached above in connection with enhanced specific adsorptive capacities.
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Fig. 24.-Differential (dashed line) and inte ral (solid line) heats of adsorption in the system Be%-InzOa.
Pore Size Distribution.-The hysteresis effects often observed in sorpt ion-desorp tion isotherms may be interpreted on the basis of the pore structure of the adsorbent.6 The curves in the insets of Figs. 1-11 give the uncorrected pore distribution for each of the samples as obtained by means of the Kelvin equation, assuming complete wetting.’ This assumption is justifiable, since the walls of the pores already are wetted by at least a monolayer of water. The maximum point of these curves represents the most frequent uncorrected pore radius. It will be noticed that the pore distributions at the two different temperatures agree closely. This internal consistency of the results supports the view that the Kelvin equation is applicable, inasmuch as several temperature dependent variables are involved. The most frequent pore radius for 100% Inz03is about 125 8. The addition of 10 mc$e per cent. Be0 decreases this value to about 80 A. The average gore radius does not change by more than h 1 0 A. upon the addition of more Be0 until a composition of 90% Be0 is reached. Here the average pore radius is about 64 8.)a decrease attributed to the effect of a high concentration of BeO. The pure Be0 shows a verv sharp distribution at) about 25 8. Differential and Integral Isosteric Heats of Adsorption.-The isostesc differential heats of adsorption at 7 O obtained by means of the classical Clausius-Clapeyron equation are given in the insets in Figs. 12-22. The integral heat of adsorption (6) W. 0.Milligan and H. H. Rechford, Jr., THISJOURNAL,51, 33 (1947). . 0. RIilligsn end H. H. Racliford, Jr., J . Am. Chem. Soc., 70, (7) W 2922 (1948).
Dec., 1953 ELECTRICAL CONDUCTIVITY OF HYDROCARBON-BASE SOLUTIONS OF “SOLUBLE OIL” TYPE 889 was also computed, at constant spreading pressure, employing methods described in the literature.8 The integral heats are also included in Figs. 12-22. The differential heats of adsorption at 7 ” obtained by means of the classical Clausius-Clapeyron equation are quite high at low p / p o values where the water vapor is being adsorbed on the bare oxide surface. However, by the completion of the second layer the heats have dropped off to approximately the heat of liquefaction of water. The integral heats of adsorption at 7 ” are of lower magnitude in the lower relative pressure regions and show a much smaller decrease with increasing pressure. This is probably due to the particular shape of the adsorption isotherm; there is very little increase in adsorption for a long increase of pressure after a value of O.lp/p, is reached. The integral heats hold practically constant until pressures of 0.6 to 0.7plp0, a t which point they progress regularly toward the heat of liquefaction of bulk water. (8) T. L. Hill, P. H. Emmett and L. G.Joyner, dbid., 73,5102 (1961).
The pressures at which the integral heats of adsorption show an appreciable reduction correspond with the incidence of capillary condensation. In Fig. 24 are shown plots of the differential and integral heats of adsorption as a function of composition at various values of the relative pressure. Within the limits to which one would expect the surface properties of one sample to compare with those of another, the two types of curves show a great similarity. Two maxima exist, one between 30% Be0 and 60% BeO, the other between 80% Be0 and 90% BeO. These are essentially the same composition ranges in which there is mutual protection against crystallization2 and an increase in surface area and adsorptive capacity (Fig. 23). It will be noted that the two types of heat of adsorption curves cross, as is required.8 Although there appear to be some additional systematic small maxima, it is the opinion of the authors that they are not to be considered significant at the present time.
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THE STRUCTURE AND ELECTRICAL CONDUCTIVITY O F HYDROCARBON-BASED SOLUTIONS OF THE “SOLUBLE OIL” TYPE. A COMPARABLE AQUEOUS SYSTEM BY J. BROMILOW AND P. A. WINSOR Shell Pet,roleztna Co., Ltd., P . 0.Box 1, Chester, Great Britain Received March 6 , l 0 b S
The variations in electrical conductivity with gradual modification of the composition of a number of “soluble oils” based on Aerosol OT/undecane-3 sodium sulfate mixtures on monoethanolamine Iaurate or on monoethanolamine oleate have been examined. It has been found that a qualitative interpretation of the results obtained may be given on the basis of the intermicellar equilibrium indicated in Fig. 1 which has been used previously in interpreting the electrical conductivity and phase relationships shown by a ueous “solubilized systems” and in accounting for the X-ray diffraction patterns obtained from solutions of detergents. &e completely analogous form of the conductivity behavior and phase relationships of the “soluble oil” systems and of a series of wholly aqueous solutions in which t,he sodium ion of sodium hendecane-3 sulfate ie progressively re laced by the cyclohexylammonium ion has been demonstrated. It is concluded that an intermicellar equilibrium of tEe kind indicated in Fig. 1 is operative in all solutions of amphiphilic substances from the completely aqueous to those based completely on hydrocarbon.
Introduction Systems of the type discussed earlier but of lower water content, or even containing no water In a series of papers published el~ewherel-~ observations have been described of the phase at all, are technically of much importance as watertransitions and electrical conductivity changes dispersible or “soluble” oils for use in metal working which accompany variations of the composition and as textile assistants, etc. The present paper and temperature of a number of solubilized sys- describes an investigation of systems of this type. tems. In these systems, containing various amphi- It will be seen that the phase changes and conducphilic salts as “solubilizing agents” or “co-sol- tivity variations now recorded are analogous to vents,” water and organic liquid were usually those found earlier with the more aqueous systems. To complete the picture, analogous results obpresent in approximately equal proportions although in some cases water was the major con- tained with an aqueous system in the complete stituent. It was found that a consistent inter- absence of an organic liquid are given (Fig. 6). pretation of the results obtained could be given It thus appears that the intermicellar equilibria on the hypothesis of a very mobile intermicellar and the associated phase transitions shown in Fig. 1 equilibrium of the type illustrated by Fig. 1. may be realized over the entire range of solutions It was also shown4that such an equilibrium was in containing amphiphilic electrolytes from those agreement with the published X-ray measurements based completely on hydrocarbon, to t.hose based completely on water. on detergent solutions. Experimental (1) P. A. Winsor, Trans. Faraday Xoc., 44, 376 (1948). (2) P. A. Winsor, ibid., 44, 451 (1948). (3) P. A. Winsor, ibid., 46, 762 (1950). (4) P.A. Winsor. THIBJOURNAL,56,391 (1952)
Apparatus .-The apparatus and procedure used for the determination of the electrical conductivities were those described earlier.3
