NOTES
June, 1958
755
the saturated solution is the monohydrate8; ,8942 polymorphism reported by Vold, et al., for impure 1.000 soap samples, was not observed in this work. No change in the X-ray pattern of calcium oleate could be detected. The dihydrate has been re- 0.0000 ,1042 p~rted.~ The nature of hydration in this case inay .1560 be noli-coordinative lattice absorption. (8)IC. W. Gardiner, n4. J. Buwger and L. E. Smith, THISJOURNAL, 49, 417 (1945); IE. D. Vold, J. D. Grandine and M . J. Vold, J . Colloid Sei., 3, 339 (1948); M . J. Vold, G. S. Hattiangdi and R. D. Vold, ibid., 4, 93 (19.49). (9) F. Hoppler. Faltc'u. Seifen, 49, 700 (1942).
THE SYSTEM SODIUM CHLORATE-SODIUM CHLORIDE-WATER AT VARIOUS TEMPERATURES
.2600 .3917 .4702 .6158 ,7228 .7562 .8723 .9202 1.000
. 9696 ....
5.31 5.35
1.453 1.467
8.82 8.20 8.04 7.50 6.81 6.39 5.47 4.75 4.89 4.90 4.89 4.90
Temp. 45' 1.201 .... 1.226 0.0145 1.240 ,0232 1.267 ,0384 1.308 .0580 1.336 ,0807 1.398 ,1134 1.458 ,4510 1.462 ,9365 1.476 .9506 1.481 ,9756 1.491 ....
A A
1.42
..
..
I)
1.12. 1.15 1.09 0.98 1.07 1.01 1.22 1.20 1.52 1.61
B B B B B B B,A A A
A A
..
BYTHOMAS 5. OEY AND DONALD E. KOOPMAN Receaued January 1 8 , 1868
The available data2on the ternary system sodium chlorate-sodium chloride and water were found inadequate for use in the study of the yuateriiary system involving the three components of this system and sodium chlorite. The present work has been undertaken to re-examine this teriinry system over much wider ranges of temperatures and concentrations. TABLE I
',
s4 2 01
or
03
as
a4
a6
07
08
a9
X
Fig. 1.-The
NdIO,
system sodium chloride-sodium water a t 25'.
chlorate-
THETERNARY SYSTEMSODIUM CHLORATE, SODIUM CHLORIDE A N D
WATER
Solid phase: A, NaC103; B, Na41 2:
Compn. of s o h . 'W Sp. gr.
Compn. of wet residue X w
0.0000 ,1593 ,2142 .2696 ,3887 .4394 ,4722 .6175 ,6940 ,7478 ,8362 .9163 1.000
9.01 8.18 7.95 7.64 7.01 6.66 6.57 5.55 5.75 5.82 5.79 5.82 5.88
Temp. 25" 1.200 ,... 1.240 0.0165 1.255 ,0290 1.271 .0337 1.309 .0604 1.327 .0567 1.340 ,0548 1.402 .4689 1.408 ,9341 1.414 .9476 1.423 .9669 1.429 .9844 .... 1.440
0.0000 ,0948 ,1808 .2265 ,3333 ,4382 ,5932 .6754 .7060 ,8133 ,8659
8.96 8.48 8.03 7.79 7.22 6.62 5.67 5.14 5.18 5.26 5.29
Temp. 35" 1.201 .... 1.224 0.0130 1.246 ,0310 1.259 .0350 1.289 ,0497 1.325 ,0781 1.388 .1066 1.430 .6018 1.433 .9112 1.444 ,9466 1.451 .9599
Solid phase
.. 0.85 1.04 0.95 1.10 0.88 0.76 3.39 1.36 1.21 1.17 1.09
.. .
I
1.12 1.35 1.20 1.05 1.17 1.00 1.40 1.55 1.50 1.55
.
B B B B B B B B,A A A A A A
' {
0.1
NaCi
a2
a3
a4
n
as
a6
a7
as
as
NaCI03
Fig. 2.-The
system sodium chloride-sodium water at 35".
cldorate-
Fig. 3-The
system sodium chloride-sodium water at 45'.
chlorate-
B B B B B B
-
6.4
A A A
(1) This investigation was made under a grant from the National Science Foundation (NSF-G2750). ( 2 ) F. Winteler, 2. Elektrochem., 1, 360 (1900); J. Billiter, Monatsh., 41, 287 (1920); C. DiCapua and U. Soaletti, G a m . chim. dd.,51, 391 (1927).
The system sodium chlorate-sodium chloride and water is a simple one; no double salts have been found within the temperature interval 25-45', the solid phases found in the equilibrium mixture being sodium chlorate arid sodium chloride. Materials.-The sodium chlorate and sodium chloride used were of the analytical reagent grade. The impurities
756
NOTES
present in this grade were deemed much too small to affect the results. Distilled water was used in all of the experiments. Experimental.-The experiments were carried out as is customary in equilibrium investigations. The apparatus and procedures for all of the experiments have been reported earlier.8 As in this earlier work, the Schreinemaker's wet reaidue method was used. The figures given in Table I are in moles of salts and moles of water. The x function is the moles of sodium chlorate divided by the sum of the moles of sodium chlorate and the moles of sodium chloride. The w function is the moles of water divided by the sum of the moles of sodium chlorate and the moles of sodium chloride. Analytical.-Procedures for the analysis of chlorate and chloride have been described by White.4 The solutions and wet residues in the various equilibrium mixtures were analyzed for chlorate ion and chloride ion. The water in the liquid phase and the wet residue was determined by difference.
The Ternary System Sodium Chlorate-Sodium Chloride-Water.-In this system three isotherms have been worked out: 25, 35 and 45". The data are summarized in Table I and shown in Figs. 1, 2 and 3. They show only sodium chlorate and sodium chloride as the solid phases present.
Vol. 62
Determination of the Oxygen.-The amount of combined oxygen as well as its disposition in each sample was estimated by evacuating 2-g. portions at 1200' in a resistance tube furnace, collecting water in calcium chloride tubes and analyzing the rest of the gasea evolved in Orsat-Lunge gas analysis apparatus in the usual way. Heat of Immersion.-Two to four g. samples were measured into thin-walled glass bulbs and outgamed for about 10 hours. Water (redistilled) and Merck extra pure methyl alcohol, ethyl alcohol, n-hexane and benzene thoroughly dried over magnesium turnings or sodium were used as the wetting liquids. The calorimeter and its technique were essentially the same as described by Boyd and Harkinsl and all the precautions were duly observed. The reproducibility varied from 1 to 2%. Isotherms and Surface Area.-Water and methyl alcohol adsorption isotherms were determined a t 25'.' Surface areas were calculated from the water isotherm^.^>^ Base Adsorption.-Base adsorption capacity was determined by mixing 0.5 g. of charcoal with 100 ml. of 0.1 N bariuni hydroxide solution, shaking the suspension for about 48 hours and titrating an aliquot of the clear supernatant liquid against a standard acid solution.
Discussion It is seen (Table I) that treatment of the degassed charcoals with oxygen as well as with nitrogen peroxide (cf. samples numbered 1, 9, 22 and 30) (3) G. L. Cunningham and T. S. Oey, 1. A m . Chem. Soc., 77, 799 results in the fixation of appreciable amount of (1955). oxygen which on evacuating a t 1200" is given out (4) J. F. White, A m . Dyestuf Reporter, 31, 484 (1942). as carbon dioxide, carkion monoxide and water in the case of sugar charcoal and as carbon dioxide T H E HEAT OF IMMERSION OF CHARCOAL and water in the case of coconut charcoal. The AS A FUNCTION OF ITS OXYGEN amount of chemisorbed oxygen decreases progressively on degassing these samples at increasing COMPLEXES temperatures. The oxygen contents of a few BY BALWANTRAI PURI, D. D. SINGHAND LEKH RAJ samples were determined by ultimate analysis as SHARMA well. These values are shown in the footnote to Department of Chemistry, Panjab University, Hoshiarpur, India I. Table Received January 16, 1865 Surface areas of the samples appear to remain Hydrophilic solids give higher heats of immersion about t h e same irrespective of their oxygen content. in water than hydrophobic solids.lJ Adsorbent This is in conformity with the observations of Arcarbons and charcoals provide interesting materials ne11 and Mc12ermotg and Emmett and Anderson.'O for such studies because even though they are However surface areas increase appreciably on basically hydrophobic solids, their surface be- activating the original samples of charcoal in steam havior can be modified appreciably on oxidation. 3-6 (samples numbered 17-21 and 38-42) a t increasing The present paper describes the measurements of temperatures up to 1000". But this treatment, a t heats of immersion of different samples of charcoal the same time, results in the progressive elimination associated with varying amounts of oxygen, in of the combined oxygen, disposed as COZ. water and a few organic liquids.. The immersional heats of wetting in water, expressed as ergs/cm.2, are seen to decrease appreExperimental Materials.-Two samples of charcoal prepared by the ciably when the samples treated with oxygen or carbonization of recrystallized cane-sugar and coconut nitrogen peroxide are subsequently subjected to shells were freed of ash and divided into several 10-g. por- evacuation a t gradually increasing temperatures tions. Some of these were activated in steam a t different temperatures varying from 400 to 1200' and some by heating up to 750". After this, the values remain more or in vacuo a t 1200' followed by treatment with oxygen or ni- less unchanged even though the oxygen content trogen peroxide at 4 O O o 8 ~ *in a rotating (35 revolutions/ goes on decreasing on further evacuation right up in. bore). The gas was led over the to 1200°, particularly in the case of sugar charcoal. min.) Pyrex tube material a t the rate of about 2 l./hr. for about 16 hours. The treatments with oxygen and nitrogen peroxide resulted A careful examination of the data shows that in the fixation of an appreciable amount of oxygen. Por- oxygen disposed as COZand HzO gets almost comtions from each sample were then subjected to evacuation pletely eliminated a t 750" but a certain amount of a t different temperatures varying from 450 to 1200' in combined oxygen, largely disposed as CO, remains order to remove increasing amounts of the chemisorbed even above 750°, a t least in the case of sugar charoxygen. coal. It appears, therefore, that oxygen disposed ( 1 ) G. E. Boyd and W. D. Harkins, J. A m . Chem. Soc., 6 4 , 1190 CO does not affect the value of heat of immersion as (1942). (2) F. H. Healey, J. J. Chessick, A. C. Zettlemoyer and G. J. Young, THIEJOURNAL, 68,887 (1954). (3) 6.Weller and T. F. Young, J. A m . Chem. Soc., 7 0 , 4155 (1948). (4) J. H. Wilson and T. R. Bolam, J . CooEEoid Sei., 6,550 (1950). ( 5 ) B. R. Puri, Y.P. Myer and L. R. Sharma, J. Ind. Chem. Soc., 33, 781 (1956). ( 6 ) F. H. Healey, Y. F. Yu and J. J. Chessick, T H I JOURNAL, ~ 59, 399 (1965).
__
(7) B. R. Puri, M. L. Lakhanpal and B. Verma, J. Ind. Chem. SOC., 29, 841 (1952). (8) S. S. Kistler, E. A. Fischer and I. R. Freeman, J . Am. Chem. SOC., 66, 1909 (1943). (9) H. L. McDermot and J. C. Arnell, THIS JOURNAL,58, 492 (1954). (IO) P. H. Emmett and R. B . Anderson, J . A m . Chem. Soc., 67, 1492 (1945).
1
