J.S.C.I.
, 68, January, 1949 TAYLOR-THE
THE ACTIVATION OF ALUMINA
By R. J. TAYLOR
An 'investigation has been made of the physical transformations
. whkh occur whcn y aluminium trihydratc (gibbsite) is dchydmtcd
by heat trea'men', and the effect such rransforma ions have on the
adsorption activity and porosity of the material. Dehydntion
proceeds according to the scheme : trihydrate+ monohydntc
-+alumina, no dihydrate bcing formed. Between 225" and 500"
positions of equilibrium arc established bciwccn the monohydnte
.and alumina and thc adsorption activity is directly related to the
degree of conversion to y alumina. At 500" and higher tempera-
tures, thc material is converted wholly to y alumina. This, unWte
the tri- and monohydrates cannot be completely defined as it is a
transitional product in a heat-controlled sol d reaction, its state being
at first highly disordered but rearranging to an orderly state as thc
reaction proceeds. The odsorption activity of the material is
dircctly related to the stote of disorder. Thc particle size distribu-
tion of the material is unaffeacd by the heat treatment which it
receives, hence the porosity of thc final product can be controlled
by selection of the stnning materid. Aluminas covering a widc
rangc of activities can bc prepared by simple heat treatment of the
hydrate.
There are two principal methods of preparing activated
alumina. I n one method a colloidal or sub-crystalline tri-
hydrate is precipitated from sodium alumhate by controlled
acidification. It is coagulated by drying, broken down mech-
anically to a suitable particle size range and dried further at a
temperature between 3m0and 7m0. I n the other the crystal-
line -( trihydrate (gibbsite) is precipitated by seeding from a
sodium aluminate solution, and is then converted to an active
form by calcining. The activity can be modified empirically
by washing with lime water or by exposure to a moist atmo-
sphere. Additionally, activated alumina can be prepared from
aluminium salts in a number of ways but these have no practicai
value comparable with the other two.
The sub-crystalline type, with a combined water content of
about 12%~has been used extensively in air and gas humidifiers
since it has a very large adsorptive capacity for water vapour,
and yet can be reactivated simply by heating in a current of
dry air. This type of adsorption, however, is essentially non-
selective and is apparently unaffected by changes in adsorption
characteristics which Mutchl has shown to occur with changes
in the preci itation technique and, more significantly, with the
age of the aimina. Such changes are undesirable in a product
which is to be used for selective adsorption, where uniform
quality is essential for a reproducible technique. Thus of the
two main methods for preparing alumina, one is led to prefer
that using the seeded crystalline hydrate as the starting material.
Therefore the work which is described in this paper deals only
with the crystalline y trihydrate and its conversion to active
;* alumina j it was carried out with two objects in view : (I) to
investigate the mechanism of activation, (2) to develop an
improved method of preparing an alumina of predetermined
activity and porosity.
Review of Literature
The physical forms of alumina and its hydrates have been
studied by a number of investigators during the last twenty-five
years, but it is curious to observe that individual investigations
have been concerned with only two out of three related proper-
ties-dehydration equifbria, crystal structure, and activity-
and not with the integrated relationship between the three.
Thus, Achenbach? and Beletzkii3 have studied the thermal
decomposition of alumina trihydrate and have given tempera-
tures for the transition of one crystalline form to another.
Frickc4 has made an important X-ray study of aluminium oxide
and its hydrates and has stated that the X-ray patterns indicate
a crystalline structure ki certain forms which is not shown by
other physical methods of examination. VerweyGhas made a
similar study of y alumina only and suggests it to be an inter-
ACTIVATION OF ALUMINA 23
mediate case between the amorphous and the completely
arranged state. Milligan,O Fricke,' and Weisefl have studied
the dehydration curves of aluminium trihydrate and find no
isobars to indicate the formation of an intermediate crystalline
form. Weiser suggests that this is due to the formation of B
highly active anhydrous alumina which immediately adsorbs
some of the free water.
KriegerO has studied the effect of time and temperature on
the adsorption of nitrogen by alumina, and Jellineklo has
studied 'the relation between heat treatment and crystallite size.
Unfortunately in these two latter investigations prepared
aluminas were used without knowledge of the method of
preparation, and the interpretation of their results is thereby
limited.
No reference has been found to workon the relation between
the porosity of alumina and its method of preparation.
Analytical study methods
The character of a given alumina can be defined by its
activity, crystalline structure and porosity, the latter being
determined by the particle size distribution of the material.
Methods are available for assessing each of these propcnies,
and the problem is mainly one of selection of methods. In
the case of the activity, however, it was found that none of
the methods yielded, simply, a single figure index. The
classical method of Brockmannl' allows one to classify aluminas
only in terms of the relative rates of movement of a number of
dyes. Le Rosen'? has used a similar method using a single
dye and more rigidly defined constants in an attempt to make
the method quantitative. The method, however, is dependent
on the adsorbed zone maintaining a clear cut and sharply
defined boundary, a concept which is rarely realized in practice.
. M i i l l ~has
r ~ ~proposed a calorimetric method of standardizing
in which the heat of adsorption of water at o' is measured,
while KriegeP and others have used a method of adsorbing
helium or nitrogen. The two latter methods do yield the
required index of activity, the gas adsorption method being
particularly neat and attractive ; they are time-consuming
methods, however, and could be applied only to research of n
restricted nature.
Acfiwify.-A method was developed for use in the present
work, not so elegant as the gas adsontion method but having
the following advantages : it was Gmple and reproducible
it required no specialized apparatus, it was quick and
applicable to routine analysis. The method was to adsorb a
suitable dye (Waxoline Blue C.S.) from dry redistilled ligroin
(b.p. 4 ~ 6 0 " non-selectively
) on to alumina, wash the alumina
free from excess dye solution, remove the adsorbed dye with
alcohol, and determine the strength of the alcoholic solution.
The activity was then expressed as the weight (in mg.) of dye
adsorbed by unit weight of alumina.
Crystalline strticture.--Powder photographs were taken of the
various samples in a 12.5 cm.* camera and the lattice spacings
@ / t i ) were measured. In addition, a visual estimate was made
of the intensities of the various lines. Comparison was then
made with the known line spacings and intensities of the various
forms of alumina.
Parlicle size distribrition.-This was studied by means of a
combination of sieve and sub-sieve analysis. For the sieving
tests an automatic sieving machine was used and the results
were reproducible. The finest fraction (<3m mesh) was
submitted to further analysis by means of air elutriation.
Experimental
Five g. samples of a crystalline aluminium trihydrate (sup-
plied by the British Aluminium &.) were weighed into tared
silica dishes and transferred to a thermostatically controlled
* See Appendix
24 TAYLOR-THE ACTIVATION OF ALUMINA J.S.C.I., 68, January, 1949

electric oven which had been preheated to a determined
temperature. Tests were made at 225' and 300-1000"in steps
of roo", and for temperatures up to 600" the dishes were
removed successively over a period of hours, cooled and
weighed under conditions which limited adsorption of water
vapour by the powder. No positive action was taken to remove
the water vapour released from the hydrate but it is reasonable
to assume that under the conditions of test it would be effec-
tively dispersed. For temperatures up to 600' this method
provided a satisfactory means of studying the water-loss/time
relationship. Above 600" there was a serious '' ebullition "
loss as the hydrate was introduced into the furnace but since,
at these temperatures, the loss of water was complete and
almost instantaneous the point was not significant ; the true
loss was determined independently by slow elevation of the
material to the specified temperature.
anhydrous y alumina line (d/n = I . 39)corresponds very closely
to one of the monohydrate lines and Mutch (loc. cit.), for
example, has commented on the apparently similar crystalline
(monohydrate) character of aluminas which had dissimilar
activities.. However, if Fig. 2 (c) and (d) are compared it
will be seen that an inversion has taken place in the rqlative '
-
intensities of the I -39and I 85 lines and it is logical to infer
that this is due to the presence of anhydrous alumina in Fig.
2 (d). In fact, there are two factors which raise some doubt ,
whether the 1.39 line and its weaker associate at 1.97 are
really monohydrate lines but rather represent a partial con-
version to anhydrous alumina ;one is the indeterminate nature
of the transition from one crystalline state to another which
is emphasized by the dehydration curves and which will

I I
Fxc. I. Dehydration ctipces for a l u i h i u ~ rrilg*drate
~i in rke tcn~peratirre $ I
130
.
105 197
range 22~-~00" FIG.2. Heat transfonttationof y altintinitftfttriiiydratc (Gibbiire)
(u) Trihsdrnte
Dehydration.-In Fig. I dehydration curves are given for ( b ) Ilcated 10 ZZS' for 4 hi. :trihydrote + monohydrate
{f) ,, ,, ZZS' ,, 8 hi. : rubstantially monohydrate
temperatures up to 500". Beletzkii (loc. cit.) gave the tempera- ,,,, ,,,, JDO' ,, 6 hr. :monohydrate -t. y alumina
600' ,, 6 hr. :y alumina
# ::.. ,.
ture of conversion to monohydrate as 225' and examination (e)
,, gooo ,, s min. :y nlumina
of our end product at the same temperatures showed it to ,, 900' 6 hi.: yalumina
I J W ~:: z hr. : alumina
contain combined water equivalent to a monohydrate. X-ray (I

Now rcvcrrnl of the rclative inrcnrities of the 1.38 and 1.85 linrs i n (c) and ( d )
examination substantially confirmed this but showed the indicaiivc of n panial convcrsinn to y niuminn; also tile cmcigcncc nnd development
material to contain traces of both trihydrate and anhydrous of y nlumina pattern from ( E ) 10 (s).
-{ alumina. .It is possible, in view of the gradual nature of obviously tend to obscure interpretation of the X-ray pattern,
the conversion at this temperature, that the true transitional and the other is the low angle X-ray scattering which gives the
temperature is slightly lower than 225" and the dehydration central white spot in the photographs reproduced in Fig. 2
period longer than 7 hours, but there are doubts whether the and indicates that small crystallites are present, although the
conv:rsion is clear cut at any temperature. well-defined character of the main monohydrate lines shows
Between 225' and 500" the material reached a state of that the monohydrate crystallites are large. Thus the photo-
equilibrium quickly in marked distinction to the slow change graphs can be fully explained if there is no intrinsic temperatuk
that took dace at 225', yet the end products contained hydrated for conversion of the monohydrate, so that some anhydrous
water in' percentages which did -not correspond to -known alumina is formed at all temperatures, and if the crystallite
crystalline forms. The equilibrium values lay on a smooth size of the anhydrous material thus formed is small in com-
curve, however, indicating that the conversion was systematic. parison with the monohydrate.
It is not easy to see why positions of equilibrium were estab- (iii) 500'' and higher-At these temperatures the conversion
lished, and particularly why they were established so quickly, to anhydrous alumina was complcte but the X-ray pattern of
as under the experimental conditions it is unlikely that the many of the samples differed significantly, the changes in
gaseous phase remained in contact with the solid material. It pattern being systematic both in relation to the temperature
may be, as Weiser (loc. cit.) has suggested, that the answer lies at which conversion was effected and the period of heating.
in the mechanics of crystal distortion at elevated temperatures. At 500" and 600"a sparse and diffuse pattern was formed which
X-ray study.-Esamination of the samples revealed impor- did not change with prolonged heating (Fig. 2 (e)). At goo"
tant modifications in crystal structure : (if At 2t5O the X-ray the sparse, diffuse pattern appeared after 5 minutes' heating
photographs showed a steady conversion from the trihydrate (Fig. 2 (f)),but with continued heating the pattern developed
to the monohydrate and this is illustrated in Fig. 2 (a), (b) and and the individual lines became progressively better defined
(c), which are photographs of the original trihydrate and the (Fig. 2 (g)). At intermediate temperatures the development
same material after 4 hours' and 8 hours' heating. There is was proportionately less. Even at IOOOO the y alumina pattern
no evidence of the formation of an intcrmediate dihydrate. was still developing and there was no cvidence of conversion
(ii) 300" and qoo"-The sequence of changes was similar at to OL alumina (corundum). The typical u alumina pattern
both these temperatures but more strongly developed at 400". shown in Fig. 2 (14) was obtained by heating the trihydrate
The trihydrate was converted rapidly to monohydrate and then to 1400"for 2 hours.
partially converted to anhydrous alumina. I t is important to Telliiek (foc. cit.) has suggested that such deveiodnz t at terns
establish
- ._ -..... the
.. validitv of such a conversion for the ... main are indicadve of a'growth-Gf crystallite size withiithi particle.
.___~..
~
J-S-Cb6% J n n u n r ~1919
~ TA YLOR-THE ACTlVATlON OF ALUMINA 25

Riley15has discussed work on the heat treatment of magnesium 0 o

carbonate and of ferric hydroxide in which similar trends have
been noted, and he has shown how a crystalline body can $ 7 0
break down to a highly disordered transition state with modified
physical or chemical properties. One is led to the conclusion, t
therefore, that y alumina is not a completely defined entity like
the y monohydrate (boehmite) or a alumina (corundum), but
a transitional product in a heat-controlled solid reaction, at 5
first highly disordered but rearranging to an orderly state a: Hso
the reaction proceeds. On this basis the so-called " Kappa
and " Theta " aluminas listed in the A.S.T.M. X-ray diffraction
S
'
cards fall into the pattern of the transitional state, being of the g 4 0
same order of development as our product of z hours' heating a
at IOOO~.
Activity.-The distinctions noted in the previous baragraphs PERIOD OF ACTIVATION, h O W 8
were of particular importance in explaining changes in the FIG.3. Actiwirier of the lieat transfornratiorr products of y alrtnri~tirtttt
activity with heat treatment, shown by the various samples and triirydrare t i t tire reniperatitre rurrge 300-1000"
illustrated in Fig. 3. At zz5O the material was almxt wholly
in the monohydrate form and the activity was negligible. At Table I
300Oand 400Otherewas a marked increase in activity correspond- EJecr of iieat treatrrretit otr particle size of dunrinas
ing to the partial conversion to anhydrous material which took AIurnina*
place. It will be noted, moreover, that the order of activity Sample Hydrate A B C
of the final products was similar to that obtained immediately Sieve raJrgt Retaincd15omesh 2.1 2.2 1.0 2.0
at higher temperatures by a complete conversion to anhydrous Pass 150mesh ,, zOO ,, 47.9 48.6 43.8 46.0
alumina, from which it follows that the anhydrous phase of ,, ,, ,, 3m ,, 01 27.4 27.4 34.8 30.5
the mixture was extremely active and hence that the crystallites ,, 300 ,, 2 22-6 21.8 19.4 21.5
were extremely small. One would expect the X-ray pattern Sub sieve r a w
1%% -..
.. ..
of this active phase to be correspondingly diffuse, therefore,
.. .... 4.3
45 1'. (*"* * * * * * '4.' 13*' 14.6
30p. ( 4.8 3.6 3.6
and this would explain why Mutch (loc. cit). was able to Is p. ( ,, ,, ) 3 2.7 3.1 3.4 2.3
distinguish only a y monohydrate lattice in samples heated to
400' for several days and containing 4 4 % water, for one can
8 p. ( ,, ,, ) ,,, . . . . .. 0 . 5 0 . 2 1 . 8 0.7
A. Rnised to 700" in I hr. j maintained for I hr.
well understand the diffuse y alumina pattern being obscured 8. Raised to 700' in 7 hr. ;maintained for 9 hr.
by the sharply defined monohydrate pattern. C. Roiscd to gw" in & min. ;maintained for 3 min.
At 500" and higher, the increase in activity was immediate,
but with continued heating the activity decreased, the rate of hydrate from which it is produced. Thus by suitable choice .
decrease being greater and the final value lower as the tempera- of the starting product, one can be certain that the end product ,
ture was raised. These changes were in conformity with the is ~ $ ~ ~ ~ & ~ n ~ ~ ! ! $ a identity ~ ~ & of h cparticle size of
which suggests that when water Of the hydrate and of the is that since 35% of the of
hydration is driven out of the large monohydrate crystallites, each particle is expelled during conversion, the partick density
they break down fO an open spongelike mesh of very small of the oxide (1.6) is less than that of the hydrate (2.4) in this
crystallites within the panicle ;the material then has a large
available surface and is highly active, but with continued heat proPOrtiony whereas the true density (3.4) is greater'
treatment the crystallites grow and the available surface (and Practical applications
the activity) is reduced. This cannot be the complete explana- It follows from the foregoing that alumina of B given activity,
tion, however, for such transitions are not intrinsic to alumina ; within a wide range of activities, can be prepared from crystal-
magnesium carbonate, for example, breaks down to give line y aluminium trihydrate (gibbsitc) merely by heating it to
crystallites as small as those of alumina yet its activity is not a specified temperature for a specified time. This is in contrast
so great. It is more probable that activity is a function of both to the classical method of preparing a range of aluminas by
the surface area of the material and the atomic arrangement, taking a highly active, but unspecified alumina, and deactivating
within the surface, of,the incompletely developed crystalline it by exposure to a humid atmosphere or, as described in
structure. B.P.565,405, by mechanical admixture of water.
Parficle size.-The thermal conductivity of alumina is low, The advantages of the proposed method are :(a) the activity
therefore heating of the material during the initial stages of is a property of the alumina per se and is identifiable ;(6) no
activation will be non-uniform, the outer layers being raised conditions of storage need be enforced to maintain its proper-
to activation temperature much more quickly than the inner ties ;(c) the alumina can always be brought to a fixed activity
core. Such a condition will impose a mechanical strain on level by drying at 110'.
the panicles and it is important to know what effect this has
on the particle size distribution. In Table I the results are Appendi.
given of a number of experiments designed to study this point, The X-ray camera used in this work is a focusing camera
and covering the extreme conditions of slow and sudden based on the design of Frevel.10 It has, however, a larger
elevation to activation temperature, and it is interesting to note diameter and hence a higher resolution than Frevel's camera,
that in no case is there any significant change in particle size the probable error of single measurements being of the order
distribution. Thus there is not only an absence of disruptive of 1% at 20 A., and O - I at~ 2~ A. (uskg CuK. radiation).
effect on the particle, but the particle shape remains unaffected Therefore we feel it will be of interest to give our measurements
by the loss of 35% of its mass. This is an important conclusion of certain of the alumina compounds, together with visual
for it means that the production of active alumina of uniform estimates of the intensities of the lines relative to the strongest
particle size distribution can be maintained by control of the (= 100). These results are given in Tables 11, 111, IV and V.
.
26 DAVIS, Et AI.-METHYLENE DJCHLORIDE AND 1 2-DICHLOROETHANE . J.S.C.I., 68, January, 1 ~ 9

Table II Mutch, N., Quart. J. Pham. 1946, 19,490

Achenbach, H., Chcm. Erde 1g31,6,307
Spacjngs ajrd relative intensities of y aluminittm rri1iydrare Belctzkii, M. S., Legkic Metal. 1936,5, 16
d/it Intensity djn . Intensity dltr Intensity Frickc, R., Kolloid-2. 1934,69,312
4e.85 ..100 1.990 ..
18 1.399 ..
..
8 Verwey, E. J. W., J. Chmn. Physics 1935~3,592
4-37
3'37
..
.. 50
4
1.963
1'894
..
..1
15
1'377
1.360 .. 2
4
Milligan, L. H., J. Physical Chem. 1gzz,26, 247
' Fricke and Sevcrin, 2. anorg. Chcm. 1932,205,287
3.32 .. 8 ....
18 1*3# .. I Weiscr, H. B. and Milligan, W. O., J. Physical Chem. 1934~38,1175
3-18 .. 8
1.802
1.751 18 1.329 ..
.. 3 Kricger, K. A., J. Arncr. Chem. Soc. 1g41,63, 2712
3.11
2.71
..
.. 3 1.682
1.651
..
18
.. $
1.315
1.296 .. ? Jellinek, M. H. and Fankuchen, I., Ind. Eng. Chem. 1gq5,37, 158
I 1 Brockmann, H. and Schodder, H., Bcr. 1941,74B, 73
2.65 .. I
I 1.636 .. 1.273 ..
.. I Lc Rosen, A. L.,J. Amer. Chcm. Soc. 1 9 . p ~64, 1905
2'45
2-42
..
.. 25
3
1.590
1.572
..
..
4 1.263
1.245 .. I
3
IJ Miiller, P. B., Helv. C h m . Acta 1 g 4 , 2 7 , 4 0 4
I' Krieger, K A., Ind. Eng. Chem. (Anal.) 1 9 4 , 16, 398
2.38 .. 25 1.552 ..2
I 1.227 .. z I6 Rilcy, H. L., J. Oil Co!. CDcm. Assoc. 1946,29, 25
2.28
2.24
..
..
6
8
1.523
1.518
..
..I
I
1.210
1.191
.. 4
.. 3
FrevJ, L. K., Rev. SCI.Instr. 1 9 3 x 8 , 475
___ _ _ _ _ ~ _ _ _ . _-
-__
2.19
2.16 ......
I
10
1.504
1.484
1.456
..
..
I

....
I
1.176
1.162
..
..
..
2
I METHYLENE DICHLORIDE AND 1 :2DI-
2.08
2.05
2.02
..
..
I
20
I
1.437
1.410
Is

..
6
8
1.151
1.140
1.117
.,
..
I
3
3
CHLOROETHANE. I. SOLURILITY ' OF
WATER. II. VAPOUR PRESSURE
Table III By W. DAVIES, .I. D. JAGGEH, and H. K. WHALLEY
Spacings arid relative iirtemities of y a1uinitiiuiii aroiroltydrarc T h e solubility of water in mcthylene chloride and I :2-dichloro-
d/ti Intensity d/ir . Intensity d/rr Intensity ethane over the temperature m g c - 20' to 4" and 80' respectively
6.10
3. t6
..
....
100
60
1.653
1.523
..
12
..
5
1.301
1.215
..
.. 22
I
has been determined. T h e vapour pressures of the solvents, alone
and in admixture, have been measured, and the composition of the
,
2.33
1.970 ..40
5
1.41
1.424
..
15
..
10
1.199
1-170
..
.. 1.
3
varour phases of the mixcd solvents determined at 10' intervals.
ovcr the range zo-so;.. Evidence of the formation of azcotmpes
1.853
1.840
..
..30
30
1.387
1.377
..
4
..
9
1.152
1.121
..
.. 3
7
with ~ a t eisr given; boihng point :composition and vapour pressure :
boiling point relationships arc derived. Mixtures of the two solvents
1.760 .. 8 we found closely to obcy Raoult's law. The results are discussed in
the light of Hildebrand's theory of liquids.
Table IV The use of methylene dichloride and I : 2-dichloroethane,
Spacings arid relative iirteirsities of y aluiniua separately or together, as industrial solvents is widely established,
(Effectof inmasing period of activation at 9") and for most applications some knowledge of the relevant
5 min. activation
d/n
4'439
4*1x0 ' *
2.397
2.276
2.086
..
..
..
..
SD
I
z
"'
Intensiw* d/lJ
4'429
4'092
3-475
3.022
2-864
5.r hr. activation
Intensity* d h
*.
..
"
80D
5oD
....I
I
3
I-985
1.907
1.871
1-794
**
Intensity*
..
..
..
..
10

2
I
I
thermodynamic data is required. For example, for certain
purposes where, because of corrosion risks, water must be
excluded, it is important to know the solubility of water in
these solvents at different temperatures. Further, the design
of processes for the efficient recovery of the solvents requires .
a knowledge of their vapour pressures, specific heats, etc.
2 . m
1.958)
..
IOD 2*802
2-715
**
.. 3
10
1.736
1.634
--
.. 2
I
A literature survey yielded the data summarized in Table I.

.... ..
2.566 gD 1-598 It was evident that the information available needed to be
:::o} ..
IwD 2.41
.. IOD 1.529 ..
..
2
I supplemented. In the account which follows, the work is
2-383 3D I a508 described and results reported on (a) the solubility of water ;
2*309 -.I 1.451
I
2 (6) the vapour pressures of the solvents, separately and in
2.116 * *
2*261
2.076 ..
..I
,
"433
::$$}
* * 5
100D
admixture; (c) the composition of the vapour phases of the
mixed solvents.
2.014 .. z
D denotes diffuse line I.-Solubility of water in the solvents
Experimental
Table V The solvents used for this section of the work were of
Spacings and relative intensities of a alrcwima commercial quality; their properties are described in detail
din Intensity dlli Intensity dllI ~~~~~~i~ in the second s e d o n and compared with those of the purified
.r1.63 .. 2 .1*929 .. I 1-371 .. solvents.
3.49
2.55
.. 50
70
1'739 .. 35
1.600 .. 100 1.234 . 10 . 2'4
1.373 .. T o determine the solubility of water, the solvent was agitated
with water until equilibrium was reached. The solvent and
2.38
2.08 .. '5
85 "553
1.511
* * '2 I*I85 * - waterwerecontainedinathree-neckedflask,fittedwithapower-
:::!! :: $
**
I .965 .. I I .402 :: 3: ful stirrer (so that the water was dispersed as very f k e droplets
in the solvent), a thermometer, and a pipette (10ml. or 25 ml.),
.Acknowledgements by which the lower solvent layer could be removed after equi-
librium had been obtained. The apparatus was contained in a
1 wish to thank Dr. V. Vand and his colleagues for their water thermostat. Equilibrium usually in less than
belP in PreFanng the X-ray photographs and hterprethg the .I min., but 20-jo
.data. -.
was, for safety, &wed. I. ml. of
the solvent layer was titrated with Fischer iodine solution,
which had been directly standardized against water dissolved
Research Department, in abEolute methyl alcohol. Before removing the solvent
Lever Brothers and Unilever Limited, layer for analysis, the mixture was allowed to stand, after
Port Sunlight, agitation, until it had become completelyclear at the temperature
Cheshire at which the solubility was to be measured. At low temperatures
~ = d , dM~~I,, 1 9 4 ~ (room temperature and below) this separation was not rapid,