3 06
WILLIAM E. IHI3NDI3RSOX i\XD I).\VID R. KELLOGG.
[reattneiit. a t present; hiit insofar as interpretation is possible, the theory o f compressible atoms seems to apply. ?YOLCC,Ir (.;inns MEWJKIAL I.AROKI\TOKS, ! I . ~ K S A R i ~r s l v c R s I l Y , C I A ~ I B K I L x . I I . 31.\5.5.
. [ C O h l K i B l 1IOX FROht THE CHEMICAL
LABORATORY OP T H 6
OHIO STATE UNIVERblTY.]
THE HYDROLYSIS OF ETHYL ACETATE BY FSEUTRAL SALT SOLUTIONS. 131 \\ I L L I I Z ~ IE ~ I r \ n P l < ' W \A U L l D A V I D
K. k L L L O C G .
lZeLci\.ed J.inuari 2 Y . 1913
In the course of some previous work' one of us found that the reaction between ethyl acetate and water, represented in the equation CH,COOC,H, c €1,0 - CH,COOH + C,H,OH, is greatly accelerated by potassium chloride, bromide, or iodide. The results obtained a t that time seemed to be of sufficient interest to justify a further study of this neutral salt effect. Accordingly the investigation has been extended along two general lines, namely: ( I ) The catalytic effect of an additional number of salts has been studied a t 10'. (2) Conductivity and viscosity data have been obtained for these salts a t the concentrations and temperature employed in the hydrolysis experiments, and from these data the degree of ionization has been calculated.
Methods and Apparatus. Bleasureme?tt of Hydrwlysir.--The velocity of hydrolysis was determined in the manner described in the earlier work, using the same apparatus but with the following changes The sealing tubes were made with necks sufficiently wide to allow liquids to run in without the use of the capillary funnel. The ethyl acetate was measured with an automatic overflow pipet hich added materially to the accuracy of the measurements. (At 2 j o this pipet delivered in three experiments, 1 . 2 2 7 1 grams, 1.2283 grams, 1 . 2 2 7 0 grams, or a mean of 1.3274 grams.) The salts selected for study were the chlorides of sodium, lithium, calcium, strontium, barium, and cadmium, together with cadmium iodide. The halides of potassium were studied in the previous paper. Solutions of desired concentration were made by direct weighing of the dry salt except in the case oi the chlorides of calcium and lithium. These were made up to approsimately the concentration desired and their exact concentration determined by titration. The cadmium salts were crystallized several times, the others being taken from original packages of J. 7'. Baker's Analyzed Chemicals. Kahlbaum's ethyl acetate ( I zoo grams) was purified by washing with a sG{ solution of sodium carbonate, no effervescence being noted. I t was then washed three times with water,
' 'l'HI5 JOVRI\I !L
3 1 , 403, 886
HYDROLYSIS OF ETHYL ACETATE BY XEUTRAL SALT SOLUTIOKS.
397
dried for some hours over calcium chloride with frequent shaking, and finally distilled. The portion distilling between 7 5 . 5 O and 78'. (bar. 746) was retained for the work. Methods of Analysis.-Until measurements on the cadmium salts were begun no difficulties in analysis appeared, as simple titration in the tubes is very easy. Owing l o the insolubility of cadmium hydroxide, direct titration in the presence of cadmium salts is impracticable. Distillation i n vacuo was resorted to, and after many failures the following procedure was adopted : "ke usual arrangement of apparatus was modified by inserting a rather long, vertical distilling tube between the distilling flask and the condenser, the purpose of which was to stop the spray of cadmium salt which persisted in going over into the receiver as the distillation proceeded to dryness. I t was also necessary to insert a loose plug of absorbent cotton just below the exit of the distilling tube to render it entirely efficient. This tube was 35.0 cm. in length and 0.9 cm. in diameter, and was connected with a TOO cc., round-bottomed flask, air being admitted through a capillary extending the length of the distilling tube and almost to the bottom of the flask. The exit of the distilling tube was connected tightly with the condenser, and this in turn, by means of a long-stemmed adapter, with a 2m cc. plain cylinder. The latter-contained an excess of standard alkali, and was closed by a two-holed stopper. The stem of the adapter passed through one hole and extended below the surface of the alkali; the second hole provided for a connection with the water pump. A tall beaker of boiling water was used to heat the flask, and condensation in the distilling tube was prevented by providing the latter with a steam jacket. Each sealed tube as it came from the thermostat was cooled, opened, emptied into the distilling flask, and rinsed once. The flask was then connected with the distilling tube and distillation carried to dryness by means of the water bath. The flask was then disconnected, the tube twice rinsed into it, and water added to bring the total to 30 or 40 cc. On again distilling to dryness all acetic acid was shown to be over. Before this method was used in the analysis of samples of unknown composition, it was tested with known mixtures. A series of experiments showed: ( I ) that the acetic acid is quantitatively recovered; ( 2 ) that ethyl acetate is not appreciably hydrolyzed in the short time required by the operation; (3) that small quantities of hydrochloric acid come over with the acetic. A t first the total acidity found was corrected by deduction of the hydrochloric acid as determined by titration, using potassium chromate as an indicator. Later this correction was discontinued, ( a ) because it was always smaller than the unavoidable errors of experiment, and ( b ) because i t is uncertain how much of the correction is occasioned by hydrolysis of the cadmium salt, involving a real error, and what frac-
148
WXLI,IAM E. HENDERSO?: 4 x 1 DAVID R. K$LLOGC.
tion is due to a partition effect between the competing hydrochloric and acetic. acids, and not, therefore, to he counted as an error. Measurernewt of Conductzzzty. --The problem which next presented itself was that of determining at 100' the conductivity of salt solutions such as had been used in the hydrolysis experiments. It was not thought desirable to attempt the measurement of this property in the presence of the ethyl acetate, as i t was desired to find any peculiarities which might exist in the salt solution itself. A second reason for omitting the ethyl acetate is the fact that a t 100" the hydrolysis of the ester would give enough acetic acid to continually change the conductivity. The splendid work of A. A. Koyes on the electrical conductivity of aqueous solutions has shown that the conductivity of salt solutions can be determined with great accuracy at IOO', and affords conductivity data for potassium chloride a t that temperature which may be used in determining the cell constant of any form of apparatus employed. Of course, without the elaborate apparatus devised by him it is impossible to obtain results of equal accuracy. For the present purpose this was not necessaq ior extreme accuracy would have no particular value in this work. I t was hoped, however, that a relatively simple form of cell might be deyised which would give, a t this temperature, an accuracy about equal to that of ordinary laboratory measurements of this kind a t room temperature. This was accomplished by the construction of the two cells which will now be described. Conducttvztjr Cells. For the stronger solutions, tenth molar and upwards, a ti-tube arranged as shown in Fig. L served admirably, a G longitudinal section of one limb alone being represented. .4 loosely fitting brass collar, B, a-as set onto the glass tube A with plaster of Paris, after the end of the tube h a d b e e n slightly flared. When the. plaster of Paris had set, the projecting end of the tube A was ground off flush with B, using Fig. I. emery and water. The
HYDROLYSIS Ol? ETHYL ACI?l"l'TE BY NEUTRAL SALT SOLUTIONS.
399
glass electrode tube E passes through a rubber stopper, C. The latter is forced into place by the screws through D threaded into G. A brass collar is set onto the electrode tube, flush with D, with plaster of 'Paris to make sure that the electrode is always held a t the same height. D is always screwed entirely home so that the electrode is replaced in the same position after removing the stopper, electrode, and plate to fill the tube. About I cc. of air space was left above the liquid to provide for expansion. The cell was closed very tightly by the stopper, and loss of the solvent by volatilization was thus prevented. Upon long standing in the thermostat, drops of condensed solvent could be seen on the sides of the tube above the solution, but after mixing the solution again the 3ame conductivity values were obtained as had been read a t first. For'standardization of the cell, a 0.1 N solution of potassium chloride was used. According to Noyes' this has a specific conductance a t rooo of 3 ~ . 6 -mhos. ~ The cell constant, using this value for the specific conductance, was found to be 4.454. After the work had progressed somewhat it became necessary to change the position of the electrodes slightly. Redetermination of the constant gave the value 4.493, and a later adjustment gave 4.540. TP these standardizations the deviations from the mean of successive bridge readings, after emptying and refilling the cell, were 0.20%~ 0.27% and 0 . 2 7 % ~ respectively. This apparatus gave great satisfaction, and proved to be an excellent instrument for securing conductivities a t reasonably high temperatures. With the concentrated solutions no appreciable effect was produced by the solubility of the glass vessel. At greater dilutions, however, this became a very serious factor. Accordingly for use with dilute solutions another type of cell was employed (Fig. 2 ) . The vessel C is a platinum crucible. Electrode 'tubes E, E pass through the rubber stopper S. A brass plate, A, had two holes, slightly larger than the electrode tubes, drilled the same distance between centers as the holes in the stopper. A second piece of brass, B, had the same sized holes spaced a trifle farther apart, so that when it was screwed down on A it exerted a slight shearing stress and held the tubes firmly. Plaster of Paris was poured into the holes in B, and as an added precaution small guide Fig. 2. 1
"l!$lectrical Conductivity of Aqueous Solutions.'' p. 47
400
VVILLJAM E . HEKDERSOX AXD DAVID R . KELLOGG.
rings G were set on with it also. The rubber stopper was forced tightly into the crucible by screwing down the yoke A by means of the nuts F F’ on the threaded uprights. By this use of platinum most of the troubles from solution oi foreign matter were eliminated, although very dilute solutions, upon long standing in this cell, did increase somewhat in conductivity, probably owing to material dissolved from the rubber stopper. ’Chis cell was standardized with a 0.02 .V solution of potassium chloride. Noyes gives the data for 0.01.V and for 0.08 iV potassium chloride, and from this the conductivity of 0.02 ;V was calculated, both by graphical interpolation, and by use of the formula, 1 -3, = I / & t K(CA)’L-’ in which n = 1.4. By the first method the value 7.346 X IO-^ was obtained and by the second the value 7.338 x IO-^. The latter value was adopted. A t various times in the work the electrodes were moved slightly, giving cell constants as follows: 0.2900, 0.2926, 0.2986. In these measurements the percentage accuracy was less than with the other cell, since the number by which the ratio is divided was so much smaller. Deviations from the mean of successive readings were 1 . 2 ~ 4 ,1.6% and 1 . 3 9 ‘ €or ~ ~ the three values of cell constant given. For all of the conductivity measurements a platinum-iridium bridge, calibrated according to Strouhal and Barus, was used. As the leads to the cell were rather long, their resistance was measured and an equal resistance was inserted in the other arm of the bridge. illeasiwement o j I’ucosity. - For use a t IOOO, where the vapor pressure of aqueous solutions is large, all types of open viscometers are unsuitable. -4 rotating disc might have been used, but both observations and calculation of results are extremely laborious with this type of instrument. Of the other iorms, that of l’horpe and Roger as modified by Bingham and White seemed best suited to the requirements of the problem. This form of apparatus is complicated, however, and calls for a rather extensive set-up. In view of these facts an effort was made to design an instrument which would be both simple and accurate, and would a t the same time form an entirely closed system. The results of these R efforts is the viscometer represented in Fig. 3. The glass bulb B is connected a t the lower end with the H capillary C, and above joins the large tube Cr which I:ig .; connects with the reservoir R. The capillary also empties into R. The side tube F permits of easy filling. The glass part just described is held in the frame by the spring clips H, and is mounted
HYDROLYSIS OF ETHYL ACETATE 131’ NEUTRAL SALT SOLUTIONS.
401
on a shaft, S, a t right angles to the plane of the glass part. The shaft carrying the viscometer is rotated by means of a bevel gear, actuated by the small head wheel a t the top. The liquid whose viscosity is to be determined is run in a t the side tube F, which may then be closed in any suitable manner. For the present work a rubber stopper was used, cut away so as to have a cylindrical piece to go inside F, and a square shoulder to rest on the end of F. This plug was held in place by a brass yoke that screwed down. Having introduced a quantity of liquid sufficient to half fill the reservoir, paying no attention to the exact amount, the viscometer is closed and completely immersed in the thermostat. To get the liquid into the small bulb, the instrument is rotated so that it stands point downward. When the bulb and capillary have filled, rotation is continued until the capillary is again vertical. There is sufficient volume above the mark a to give plenty of time for setting the capillary vertical by coincidence with some previously determined reference h e , and to snap the stopwatch as the meniscus passes the upper mark. I t will be noted from Fig. 3 that tlie receiver R is very large in comparison with the bulb B. This makes it unnecessary to measure the liquid to be examined, as the capillary drains into what is virtually an open space. This eliminates back pressure, since the connecting tube is large also and has no liquid standing in it; hence the accuracy of the experiment is independent of the quantity of liquid present, provided it does not more than about twothirds fill the receiver. Since the whole system is closed, there is no change in concentration by evaporation, and a given portion of liquid may be run through the capillary as many times as desired, each experiment requiring only a few minutes. The Thermostat.-For viewing the passage of the liquid in the capillary tube it is necessary to bave a thermostat regulated a t I O O O and large enough to permit of the rotation of the viscometer. I t is very desirable to have a glass-sided thermostat, and one was obtained from Fritz Kohler which was well adapted in dimensions, but proved to be unable to stand the temperature without leaking. For a portion of the work a metal tank was used, illumined with a bung-hole lamp slipped within a long test tube and immersed in the tank. The socket was dispensed with, the wires being soldered directly to the base of the lamp. While the liquid in the capillary is invisible under such illumination, the air column which follows i t is very bright and the readings are sharp. A large 880-watt “Quick-Hot” immersion heater was used as the main source of heat, supplemented by a smaller 44o-watt heater on the relay. The former, being a special order, was not well designed and quickly burned out, and some of the measurements had to be made by placing the thermostat on a gas stove using the relay heater to maintain a constant temperature.
402
WILLIAM E. HENDERSON AND DAVID R. KELLOGG.
HYDROLYSIS OF ETHYL ACETATE BY NEUTRAL SALT SOLUTIONS.
403
404
WILLIAM E. H E N D E R S O N A N D IIAVID R . KELLOGG.
HYDROLYSIS OF ETHYL ACETATE BY NEUTRAL SALT SOLUTIONS.
405
406
WILLIAM
E. H$NDERSON
AND DAVID R . KSLLOCG.
HYDROLYSIS OF I3THVI. ACETATE BY NEUTRAL SALT SOLUTIONS.
407
40s
WILLIAM
E.
HENDERSON AND DAVID R. KELLOGG.
This arrangement was difficult to control, which accounts for the raggedness of some results. A new thermostat was designed and constructed which admirably meets the requirements of the case, but it was finished too lake to be of use in this work. I t was also found that with care a glass battery jar may be used, a t least to temperatures approaching 100'. For work a t this temperature a solution of calcium chloride was employed within the thermostat. With continued use this becomes very turbid. As long as the turbidity was not too great, sharp readings could be made by using a square-ended glass tube (like a Nessler tube) as a submarine telescope. We are indebted to Mr. A. W. Davidson, A.M., for most of the measurements with this viscometer. Density Determinations.-Density determinations were made by means of an ordinary Ostwald-Sprengel pyknometer, parallels being run in every case. These checked to a percentage accuracy as good as that of the stopwatch and usually better than that. With the dilute solutions 100' was very near the boiling point and these solutions boiled out of the pyknometer or were thrown out by small bubbles of air and vapor, so that the determination of their densities had to be abandoned. However, this was not a matter of any great moment, as interpolation on the viscosity curves gave results near enough to the true values. At small concentrations, viscosities differ from that of water by a very small amount, and hence a slight error in reading from the curves would occasion only a minimum error in the ratio. Experimental Results. Hydrolytic Eflect of .4 lkali and A lkaline-Earth Chlorides.-The results of the experiments on the hydrolysis of ethyl acetate in the presence of the chlorides of the alkali and alkaline-earth metals are given in Tables I-VI and shown graphically on Plates 117-VIII. (For plates 1-111, representing the effect of the halides of potassium, see previous article.) Table I gives the data for the hydrolytic effect of pure water upon the acetate a t the concentration employed, and the curve derived from these data is traced as a heavy line on each of the plates for ready comparison. TablesVII andVIII, together with Plates I X and X, show the corresponding effect of the chloride and iodide of cadmium. These will be discussed more a t length latgr on. The most noticeable feature of these data is that all the salts employed, even a t concentrations as low as 0 . 1 molar, increase to a large extent the rate of reaction. This increasejs not, however, proportional to the concentration throughout a wide range : the ratio, acceleration +molar concentration, grows steadily smaller passing through zero and becoming negative in all cases where the molar solubility is sufficiently high. This negative value is shown wherever a curve lies below the water curve.
IIYDROI.1 SIS O F ETH\ .I ACETATE l31 NEUTRAIL SAbT SOLUTIONS.
409
Plates XI-XIV are derived curves, obtained by plotting as abscissas the molar concentration, and as ordinates the percentage of hydrolysis in z hours, 5 hours, and I O hours. Pl-tte S I shows the curves for the three halides of potassium, discussed in the former article. Plate XI1 shows the curve for sodium chloride and lithium chloride. I t will be noted that the two sets of curves resemble one another very closely. Calcium, strontium, and barium chlorides gave results very nearly t h e same, and the curve for calcium chloride (Plate XIII) was drawn as typical of the group. It will be seen that these curves are much like those for the alkali chlorides, but show a somewhat larger effect. TABLE HYDROLYSIS TATE BY P U R E
OF
ETHYI,A%ce- TABLE II.-HYDROL,YSIS OF E T r i Y L ACETATEBY SOI)IUM CHLORIDE.
\irAl'ER.
1 . 2 2 7 4 grams ethyl acetate. T Time. Hrs.
74hydrolysis.
3 .oo 3.75 3.75 3.87 3 .87
16.2 14.9 '3.7
j .OO
22.6
5 .oo 5 .oo 5.75 5 .75 5 75 6.00
21.4
6.00
7.91 7.91
10.0
I2
23
,!
.o
31.1 31.5 31.1 28,7
31.9 43 2 '
4.1 . 2
8.00
43.2
8.00 8.00
44.1
8.17 8.17
49.1
8.17
10.43 10.45 11.83 '5.42 1j.42
15.42
'7.45 17.45 17.45 17.45
50,7 47.3 48.4 61 . 2 64.5 69.5 81.9 80.3 78.2 82.7 84.7 85.9 85. I
=
ioo.o0.
1.22
Serial
74 grains ethyl acetate. T Solution.
=
70hy:
HIS. drolys1s.
25 c c .
NO.
Time.
mol. NnCl o . I mol. NaCl 0 . I inol. NaCl 0 . I mol. NaCl 0 , I i ~ i o l NaCl . 0 . I mol. NaCl 0 . I mol. S a C l
rj.8 30.3 -1.6.8 64,5 I I .on 7 5 . 5 12.33 8 1 . 1 13.33 83 .'I
o .j mol. mol. 0 . j mol. 0 . j mol.
NaCl NaCl NaCl NaCl
9.77 7 7 , 6 12.13 82 .') 1.1.00 8 9 , 9 2.32 14.9
mol. mol. 0 . 5 inol. 0 . j mol.
KaC1 NaCl NaCl NaCl
0 .I
0 .j
0 .j
0 .j
3 .oo 4 51 6.33 8.;;
4.16
37.2 6.16 57.6 7.66 6 8 . I 9 00 7 6 . 6
25.4 cc.
.omol. I .omol. I .o mol. I .omol. I .omol. I .amol. I .omol. I . o mol. I
XaCI NaCl NaCI NaCl NaCl NaCl NaCl KaCl
3.25
26.2
j .OO
46.0 67.7 77.4 S4.7 81.j 91.9 92.6
6.27 9.18
.oo 9.93 1j.68 I I
18.00
26.0 cc.
.omol. h'aC1 .omol. NaCl 2 . o mol. NaCl 2 . o mol. NaCl 2 . o mol. NaCl 2 2
3.25 2 4 . 2 5 .oo 42 .o 7.;7 55.6 9.17 7 1 . 4 I I .OQ
78.2
10o.o~.
WILLIAM E. HENDERSON AND DAVID R . KELLOGG.
410
TABLEI1 (continued). Time. YChy-
Solution. 26.0 cc.
Hrs.
z . o mol. NaCl 2 , o m o l . NaCl 2 . o mol. NaCl
drolysis.
12.93 8 1 . 5 15.68 8 9 . 1 18.00 90.7
TABLE111 (continued).
0100
0101
0102
26.6 cc.
3 . o mol. NaCl 3 . o mol. NaCl 3 .o mol. NaCl 3 . o mol. NaCl 3 .o mol. NaCl 3 .omol. NaCl 3 .omol. NaCl 3 .o mol. NaCl 3 .o mol. NaCl 3 .o mol. NaCl 3.0mol. NaCl 3 . 0 m o l . NaCl 3 . 0 mol. NaCl
3 . 0 6 12.36 0449 3 . 1 5 9.93 0450 6.02 23.23 "451 6 . 0 2 2 2 . 8 7 0452 8 . m 30.55 0454 10.00 38.95 0456 I2 .oo 54.31 045 7 I 2 .oo 57.09 0458 14.00 67 .oo 0459 14.00 72.50 0460 16.00 74.61 0461 18.00 80.76 0462 2o.00 8 3 , 0 8 0464
2 7 . 9 cc.
4 . 0 mol. NaCl 4 . 0 m o l . NaCl 4 . 0 m o l . NaCl 4 . 0 mol. NaCl 4.0mol. NaCl 4 . 0 m o l . NaCl 4 . 0 m o l . NaCl 4 . 0 mol. NaCl 4 . 0 mol. NaCl 4 . 0 m o l . NaCl 4 . 0 mol. NaCl 4 . 0 mol. NaCl 4 . 0 rnol. NaCl
20.00
18.00 16.00 16.00 14.00 14.00 12.00 10.00
i o ,00 8.00 8.00
3.13 2 .oo
61.82 58.54 j0.56 47. IO 41.81 42.52 37.70 30.37 33.77 28.05 26.50 8.04 4.64
0465 0466 046j 0468 0469 0470 0472 0473 0474 0475 0476 0479 0481
TABLEIII.-HYDROLYSISO F ETHYL ACETATEBY LITHIUMCHLORIDE. 1.2274 grams ethyl acetate. T = 1 0 0 . 0 ~ . Time.
Solution. 25.0 cc.
,0853 mol. o ,0853 mol. 0.0853 mol. 0.0853 mol. 0.0853 mol. 0.0853 mol. 0,0853 mol. 0.0853 mol. 0.0853 mol. 0
Hrs.
LiCl LiCl LiCl LiCl LiCl LiCl LiCl LiCl LiCl
0,427 mol. IX1 0.427 mol. LiCl
II
.08
13,60 15.66 18 .oo 4.40 6.73 8.77 10.62 2 .43 II
,08
rj.66
Solution.
Serial No.
'$7~ h y - Serial drolysis. No.
ij . O
0299
83.9 88.7 92.6 29.5 55.6 70,I 79.' 11.8
0300 030: 0302 0303 0304 0305 0306 0307
9 6 . 6 0308 9 1 . 9 0310
Time.
2 5 . 0 cc.
0.427 mol. 0.427 mol. 0.427 mol. 0.42 7 mol. 0,427 rnol. 0.427 rnol.
Hrs.
LiCl LiCl LiCl LiCl LiCl LiCl
0.8868 mol. 0.8868 mol. 0.8868 mol. 0.8868 mol. 0.8868 mol. 0.8868 mol. 0,8868 mol. 0.8868 mol. 0,8868 rnol. ,034 mol. 2.034 mol. 2 ,034 mol. 2.034 mol. z ,034 mol. 2 034 mol. 2,034 mol. 2.034 mol. z ,034 mol. 2
LiCl LiCl LiCl LiCl LiCl LiCl LiCl LiCI Licl
LiCl LiCl LiC1 LiCl LiCl LiCl LiCl LiCl LiCl
% h y - Serial drolysis. No.
18.00 4.40 6.73 8.77 10.62 2.43
94.7 38.8 65.3 78.6 94.6 15.4
'4.75 17.08 19.50 21.72
90.6
0311 0312 03'3 0314 0315 0316
03'7 9 3 , 4 0318 9 4 . 3 03'9 9 4 . 6 0320 1z.00 8 8 . 8 0321 2 . 7 5 2 2 . 2 0322 5 . 0 8 5 1 . 1 0323 9 . 7 2 8 3 . 5 0324 7 . 5 0 7 3 . 4 0325
14.75 17.08 19.50 21.72
8g.1 90.6 93.1 93.4 12.00 8 5 , s 2 . 7 5 , 19.8 5 . 0 8 46 4 7 . 5 0 7'54 9.72 81.5
0326 0327 0328 0329 0330 0331 0332 0333 0334
3.00 1 4 , s 8.58 5 1 . 5 10.75 62.0 12.90 73.8 5.72 2 9 . 1 14.00 76.2 16.20 79.1 18.08 8 5 . 5 21.20 88.7
0335 0336 0337 0338 0339 0340 0341 0342 0343
3.00 8.58 10.75 5.72 14.00 16.20
0344 0345 0346 0348 0349 0350 0351 0352
26.5 cc.
3 . 1 3 mol. LiCl 3 . 1 3 mol. LiCl 3 . 1 3 mol. LiCl 3 . 1 3 mol. LiCl 3.13 mol. LiCl 3 . 1 3 mol. LiCl 3 . 1 3 mol. LiCl 3 . 1 3 mol. LiCl 3 . 1 3 mol. LiCl 27.6 c c .
mol. 5 . oj ~mol. 5 . 0 1 5 mol. 5.015 mol. j . 015 mol. 5 . 0 1 5 mol. 5 . oj ~mol. 5 .oxj mol. ,j ,015
LiCl LiCl LiCl IIC1 LiCl LiCl LiCl LiCl
33.1 cc.
10.81 mol. Licl 10.81 mol. LiCl 10.81 mol. LiCl
5.2
29.9 32.6 16.9 38.8 48.0 18.08 56.4 21.20 66.4
HYDROLYSIS
OF ETHYL ACETATE BY NEUTRAL SALT SOLUTIONS.
IV.-HYDROLYSIS O F ETHYL ACETATEBY BARIUMCHLORIDE. 1.2274 grams ethyl acetate. T = 100 o o . Solution. Serial Time. % hy;
TABLEV (continued).
TABLE
25.0 c c .
0 . 1 mol. 0 . 1 mol. 0 . 1 mol.
0 . 1 mol. 0 . 1 mol.
mol. 0 . 1 mol. 0 . 1mol. 0 .I
BaC1, BaCl, BaC1, BaC1, BaCl, BaC1, BaC1, BaC1,
Hrs.
drolysis.
No.
13.50 15.33 16.50 18.45 3.00 4.88 8.87 10.63
89.6 91.6 93.1 (11.9
0121
0123 0124
25.5
012.5
42.6 79.j 85.1
or26 0128
,0129
13.50 15.33 16.50 3.00 4.88
92.3 93.5 93.1 40.0 64. j 7 . 0 0 79.9 8 . 8 7 84.7 10.63 89. j
0130 0131 0132 0134 0135 0136 0137 0138
3.17 42.8 j . 4 2 7 1 .O 7.63 80.3 8.20 82. 7 11.58 89.9 11.58 9 0 . 3 '4.15 9 3 . 0 9.42 8 3 . 9
0139 0140 0141 0142 0143 0144 0145 0146
0122
25.4 cc.
mol. 0 . j mol. 0 . j mol. o 5 mol. o j mol. 0.. 5 mol. 0 . j mol. 0 . 5 mol. 0 .j
BaC1, BaC1, BaC1, BaC1, BaC1, BaC1, BaCl, BaCI,
25.6 cc. I
.o mol. BaC1,
.o'mol. BaC1, 1.omo1. BaC1, I . o mol. BaC1, I . o m o l . BaCl, I . o mol. BaC1, I . o mol. BaC1, I . o mol. BaC1, I
25.9 c c .
. 5 mol. I . 5 mol. I . 5 mol. I . 5 mol. I . j mol. I . 5 mol. I , j mol. I . j mol. I
BaC1, 2.57 BaCl, 4.18 BaC1, 6.22 BaC1, 8.10 BaC1, I O . 78 BaC1, '3.42 BaC1, 15.07 BaC1, 1 7 .40
2 7 .j
38.8 54.3 71.4 76.3 81.9 83.4 87.9
0148 0149 01.50
0151 0152 or54 0155 0156
TABLE V.-HYDROLYSIS O F ETHYL ACETATG B Y C.4LCIUM CHLORIDE. 1.22 74 grams ethyl acetate. T = 100.0~. Solution. 25.0 c c . 0 . 1mol.
mol. 0.I mol. 0 . 1 mol. 0 . 1 mol. 0 . 1 mol.
0 .I
CaC1, CaC1, CaC1, CalC, CaC1, CaCl,
Time. g% hy- Serial Hrs. drolysis. No.
4.70 48.0 0237 6 . 6 3 6 7 . 3 0238 9 . 1 3 81. j 0239 90.3 0240 12.01 3.00 24.6 0241 14.37 9 1 . 5 0242
411
Solution. 2 5 . 0 cc.
% hy- Serial. HIS. drolysis. No.
Time.
o .I mol. CaCl,
1 7 . IO
mol. CaC1, 0.489 mol. CaC1, n ,489 mol. CaCl, 0.489 mol. CaC1, 0.489mol. CaC1, 0.489 mol. CaC1, 0.489 mol. CaC1, 0.489mol. CaCl, 0 . 4 8 9 mol. CaC1, 0.489 mol. CaC1,
18.00 9 2 . 6
0 .I
3 .2 j 6.03 8,32 12.5j
13.2 15.00 18.10 17.08 IO.
15
9 2 . 3 0243 0244 43. j 0245 j j . o 0246 8 5 . I 0247 9 1 . 9 0248 42. o 0249 9 2 . 6 0250 92 6 0 2 5 1 93.0 0252 8 8 . j 0 2j 3
25.2 cc.
,023 mol. CaC1, ,023 mol. CaC1, I ,023 mol. CaC1, 1.023mol.CaC1, 1.023 mol. CaC1, I ,023 mol. CaCl, I ,023 mol. CaCl, I ,023 mol. CaC1, I ,023 mol. CaC1, I I
3.43 6.03 8.32 12.55
25.8
73,4 73.4 82.1 I j . O O 90.3 17.08 9 0 . 6 19.25 92.3 18.I O 91.5 I O . 15 8 1 . j
0254 OZjj
0256 ozjj 0258 0259 0260 0261
0262
26.6 cc.
,041 mol. CaC1,
2,j8
z ,041 mol. CaC1,
5,zz
7.I 33.6 2 ,041 mol. CaCl, 7 . j z 46.8 2.041 mol. CaC1, 1 2 . 2 j 67.6 2 . 0 4 1 mol. CaC1, 14.72 75.3 2 . 0 4 1 mol. CaC1, 17.08 81. j 2.041 mol. CaC1, 19.48 83.7 2.041 mol. CaCl, 9.47 48.4 2
0264 0265 0266 0267 0268
0269 0270
0271
27.6 cc.
3.026 mol. CaC1, 3.026 mol. CaC1, 3.026mol. CaC1, 3.026mol. CaC1, 3.026mol. CaC1, 3.026 mol. CaC1, 3.026 mol. CaC1, 3.026mol. CaCl, 3.026 mol. CaC1,
2.58 j .22
3.6 7.
02 j Z 0 2 53
7.52
21.0
0274
12.25
29.9 40.0 41.6 50.0 51.9 29.9
ozjj 0276
13.38 14.j z 17.08 19.48 9.47
0277 0278
0279 0280
28.8 c c .
4.094 mol. CaCl, 4.ogqmol. CaC1, 4.ogqmol. CaC1, 4.094mol. CaC1, 4.094 mol. CaC1, 4.094 mol. CaC1, 4.094 mol. CaC1, 4 .094 mol. CaC1,
2 . 47 0,; 9.27 1 2 . 1 12.51 18.2 16.38 2 5 . 0 24.18 4 0 . 8 27.95 5 5 . 6 20.35 29.5 5.69 I .5
028 I 0282
0283 0284 0285
0287 0288 0289
WILLIAM E. H E N D E R S O K .\KD DAVID R. KELLOGG.
412
TABLEV I ( c o n l i n u e d ) .
TABLEV ( c o n t i n u e d ) . Solution. 29.2 cc.
4.696 mol. CaC1, 1 . 6 9 6 mol. CaC1, 4.696mol. CaC1, 4.696 mol. CaC1, 4,696 mol. CaC1, 4.696 mol. CaC1, 4,696 mol. CaC1, 4.696 mol. CaC1, 4,696 mol. CaCI,
% hy-
Time.
Hrs. drolysis.
0.7
,47 9.33
.1.5
12.57
6.8
2
16.38 I O . j 20.3j 1 4 . 3 ,
Serial No.
0290 0291 0292 0293 0294 0295
19.4 2 8 , o 7 19.8 0296 30.83 23.4 0297 j .73 I .I 0298
24.27
TABLE VI.-HYDKOLYSIS
OP
mol. mol. mol. mol. mol. mol. mol. mol.
0 .I 0 .I 0 .I 0 .I 0 ,I
0 .I 0 .I 0 .I
SrC1, SrC1, SrC1, SrC1, SrC1, SrC1, SrCl, SrCI,
Hrs.
drolysis.
3.07 4 8.2 6.35 6.35 7.26
25.4 46, I 66.1 66.1
14. 1 2
89.9 81.3 93 . o
’
11.15
18.j O
70.I
2 . j
mol. SrC1, 0 , j mol. SrC1, 0 . j mol. SrC1, 0 . 5 mol. SrCi, 0 ,j mol. SrC1, 0 . 5 mol. SrC1, 0 . j mol. SrC1, 0 . j mol. SrC1, 0 . 5 mol. SrC1,
3.07 4.82 6.35 6.35 7.26
mol. SrC1, 2.jmol.SrC1, 2 . 5 mol. SrC1,
1.2274 grams ethyl acetate. T Solution. 2 5 . 0 cc. 0 ,I
0 .I 0 .I 0 .I 0 .I
0192
0 ,I
0193 0194 0195 0196 0197 0198
0 .I
75.8
0202
0200
0201
0203 77.8 1 1 , I j 0 8 . 3 ’ 0204 14.12 91.5 O Z O j 0206 11.15 89. I 18.00 9 3 . 5 0 2 0 7
2 5 . 4 cc.
.o mol. SrC1, I .o mol. SrC1, I .o mol. SrC1, I .o mol. SrC1, I . o mol. SrC1, I .o mol. SrC1, I .o mol. SeC1, I .o mol. SrC1, I
11,Ij
13.75 15.95 19.50 2.63 5.83 8.38 12.13
8 3 , 9 0208 8 3 . 5 0209 87 . 9 0 2 I O 91.1 0211 0212 21.8 0213 52.7 71 .8 0214 8 4 . 8 0 2 1j
I
.o mol. SrCl,
.o mol. SrC1, mol. SrC1, 2 . o mol. SrC1, 2 .o mol. SrC1, 2 . o mol. SrC1, 2 , o mol. SrC1, 2
2 .o
mol. CdCI, mol. CdC1, mol. CdCI, mol. CdC1, mol. CdC1, mol. CdC1, mol. CdCI,
jo ‘3.75 15.95 ‘9.50 2.63 5 .83 8.38 11.
43.2 56.8 j8.8 7 2 .6
0216
12.1
0220
27.5 36.8
0221
0217 0 2 I8
0219
0222
ETHYL
= 100.0’.
Serial Time. 7chy.. No. Hrs. drolysis.
0375 0376 0377 0378 0380 0381 84.80 0382
2.00
21.10
3.47 3.47 7.00 10.72 10.72 7.00
46.50 48.00 80.40 91.45 91.06
25.3 cc.
CdC1, 0 . 5 mol. CdCI, 0.5 mol. CdC1, 0 . j mol. CdC1, 0 ,
