Nov. 5, 1952 FREEZING P O I N T C U R V E S OF CONCENTRATED kIQUEUUS SULPUKIC .

i C I D 5271

causes a significant increase in basicity of alkoxide Effect of Solvent Changes on Relative Acidity.-
anions but appears to have little effect on the All values of K , are, of course, larger in isopropyl
basicity of amines may also suggest that there is an alcohol than in ethanol, but it is interesting to
opposing effect of “B-strain” which would be more relate the size of the change to the area over which
important in the latter equilibrium between tri- the negative charge is spread in the anion derived
valent and tetravalent nitrogen than in the former, from the various acids. From the data in Table V
between univalent and divalent oxygen.
The Relative Effect of Various “R”’s on the TABLEV
Acidity of Different Functional Groups.-This ef- EFFECTOF SOLVEXT
O N RELATIVE
ACIDI~Y
fect was studied by plotting values of log K (in K e in Iic(i-l’rOH)
-
Compound i-PrOH EtOH Ke(Et0H)
water)zgfor various RCOaH compounds against the
values of log K e for the corresponding RCH20H, I,l’-l)initrodiphenylamine 21600 43.4 500
RCHOHCH3, ROH, RCONH? and RCONHC6Hj 2,1-L)initrodiphenylamine 19600 26.68” 730
compounds. The values of K , have been suitably 2,1-Uinitroaniline 2700 4,773“ 570
corrected. For example, they have been divided Ethanol 0.95 0.058 16
by two in the case of symmetrical glycols. In Fig. Glycerol 175 5.ja 32
2, the RCHzOH plot, the data for the hydroxyl- 1-Sitrobenzamide 290 1 .I” 310
containing R groups have been ignored in drawing From the data of Steariis aiid Whclaiid.11
the best line, since it seems likely that the anions
of the glycols are stabilized by internal hydrogen it is seen that this change is smallest with ethanol,
bonding and hence that the equilibria measured where the negative charge is presumably almost
here are really not of the same type as with the entirely on one oxygen atom. It is somewhat
monohydroxy alcohols. It is seen that there is a larger with glycerol, perhaps indicating that the
close relation between the effect of an R group on the charge is somewhat dispersed by the hydrogen
acidity of -C02H and on -CHZOH, but that it is not bonding of an unreacted hydroxyl group to the
a perfect one. With the -CHOHCH3, -CONHz and alkoxide oxygen atom. The largest changes are
-CONHCsHb compounds plotted in Fig. 3, the situa- found with compounds in which the charge may be
tion appears to be similar, but here the number of spread over several atoms by resonance. These
compounds studied is more limited. The ROH plot data would be expected from the greater ability of
displayed very little correlation and is not shown. ethanol to solvate the anions with more concen-
trated charges, which are susceptible to stronger
(29) Better correlations may have been obtained Iiy using the ioniza- solvation.
tion c o n s l a n t s in isopropyl alcohul solution, but these were n u t avail-
able. ATLANTA,
GEORGIA

[CON~RIBUTIOS
FROM THE CHEMICAL
LABORATORY
OF THE UNIVERSITY 1
OF CALIFORNIA

The Freezing Point Curves of Concentrated Aqueous Sulfuric Acid’

AND W. F. GIAUQUE
BY J. E. KUNZLER
RECEIVEDMAY26, 1952

The freezing point composition curves for aqueous sulfuric acid have been investigated over the range H?SO4,2H20-
H2S04.H20 eutectic t o somewhat on the SO8 side of HzSOa. The regions near the melting points of H Z S Oand ~ HZSOI.H?O
have been considered in detail so t h a t the measurements can be used for calculating the change of free energy with composition.
Evidence has been presented t o show that maximum freezing sulfuric acid corresponds to absolute sulfuric acid within a few
thousandths of a wt. 70. On this basis we believe t h a t maximum freezing sulfuric acid is a more accurate standard of acidim-
etry than can be prepared by any other known method. I t has been shown that the relative compositions of maximum
freezing anhydrous sulfuric acid and the maximum freezing monohydrate correspond t o the theoretical H2S04:H?SO,.H20
ratio t o within 0.01 wt. % H2SOa. Thus maximum freezing H2SO,.H20 is a pure compound within 0.01 wt. % HzSOa.
The melting points of H2S04 and H&04*H20were found t o be 10.371 and 8.489’, respectively.

Work in progress in this Laboratory on the ther- melting points of the several pure phases. I t was
modynamic properties of sulfuric acid requires the found desirable to supplement the data of G., B.
free energy of dilution. This can be determined and M. by very numerous measurements near the
from the freezing point curves of the several melting points of the anhydrous acid and the mono-
hydrates. Gable, Betz and Maron2 have recently hydrate. At the same time measurements of in-
published an excellent phase equilibrium diagram creased accuracy were obtained over the range from
of the sulfur trioxide-water system. However, the HzS04.2H20-HzS04.HzO eutectic to somewhat
these authors did not contemplate the use of their on the SOaside of the anhydrous acid.
data for the determination of free energy from the Apparatus.-The measurements were made in a one-liter
freezing point lowering. A calculation of this dewar which had a long narrow neck. I t was submerged,
’

type requires numerous precise values near to the except for about 2 in. of the neck, in a one-gallon dewar of
crushed ice. The sainple dewar was equipped with a motor
(1) This work wa5 iupported in part by the Office of Kdval Research driven stirrer and the tops of both dewars were protected by
United States S a v y Bakelite covers. Several small openings, with removable
(2) C \IGablc H r Betr and b €1 X I u o t i , l m b J O U K K A I 72, glass sleeves, were provided for the stirrer shaft, sampling,
I l l 2 (1030) ;ddiiig iiicremeiits of thc solution coinpoiieiits, and for a tcti-
 junction copper-constautail therinocouple. The acid was The therinocouple was coiiiparcd with a strain-frec plati-
purified by distillatio~i.~Samples were taken with a pipet num resistancc thcrinotneter calibrated at the U . S. Bureau
which withdrew solution by means of an evacuated bulb of Staiidards.
which could be opened to the pipet by means of a stopcock. The observations are given in Table I in chroiiological
The pipet has been described by Kunzler.3 Its special order.
featurc is an extension, in the form of it small chamber end-
itig iii a tip, attached to the pipet by nicans of a t:tpered TABLE I
ground glass joint. A sintered glass filter disk, with an FREEZISC,POIXTLOWERING I N AQUEOUSSULPURIC ACID
avenlge porc size of about 10 microns to csclutic the iinc
acid slurry, is sealcti across the iiiiddlc of the chuiiber. @ = freeziiig poiiit lowering
I )uring the pcriod bcfore cquilibriuin, a very small stream of TVt. '0
HzSO, 0 , oc.
iiitrogen bubbles prevented entry of solution so th;tt the
4iitered glass filter could not be containinatcd b!. liquitl. !10.288 16.07
Son-equilibrium liquid can bc produced bj- the melting of 89.!)26 14.07
solid when a pipet a t 25' is introduced, but any such liquid 80.482 11.7!)
88.8!)0 9 10 11zSOd.II20 crystals
could not enter or be produced in the pipet as used here.
S8.42 0 7 . 21 added
Method.-The dctermiiiatioii of free energy from freezing
point lowering measurcinents near the melting point ol the Serics ,5 76,643 26.51
acid, or that of onc of its hydrates, rcquirch it very accurate S7.718 z.01 i6.103 L'O.53
knowledge of the conipositioii in this range. \\~ithdra\virig 8 7 , 3:1X 0 . 80 73.990 30.9!1
sanli)lcs corresponding to cach tempcraturc o1,scrv;itioti is 8fi 8!1li 2 ,7I 7 5 .786 3:'
_.-
I,rborious aiitl uiiticccasarily inaccuratc. The iiictliotl tiset1 8ti. 54 2 1 . !IS.$ I J 2.3!! : { 3 87
ih soincwlmt similar to thosc usctl Iiy I ianiinctt a i i r l D C J T U1~ ) 8Ii.Trl1 I . ! !I
a i d Cillcspie,6 iri that thc variation of coiiipositioii \ v a s o b 8!i 1 1 3 I.
taincd by addition of wcighed amounts of niatcrial. 8;).:!I1 I) 7!l7
A known weight of some 2300 g. of acid, a little on thc ,188 , I!il
SO2 side of I I ? S 0 4 , was placed in the dewar. The coinposi- . 180 . 23:j
tion was kiiown only approximately. About 20'% of the
acid was in the form of solid at the beginning but t h e :tinoutit Series >.a
was known only w r y roughly. Thus iicithcr the ovcr-all 84,!l09 0.0871
composition iior the compositiou of the liquid portion werc 84.89; ,0821
known a t the start. 8t.880 ,0762
\Vater was added in the forin of small iiicrements of aque- 8 4 . 828 ,0362
ous acid, which was shown b>- analysis to havc a composi- 84.775 .01108
tion of 96.20 i 0.01%. This reduced heat introduction 84.723 ,0277
and gave increased accuracy with respect to the amount of 8 4 . 6 7 2 .0l68
water added. S e a r the melting point the temperature 84, A 2 0 ,0087
differencc was read to 0.0001", and nxas aceuratc to 0.000i'", 81,,570 ,0033
after cach addition. The laboratory i n which thc experi- 8 ) 518 ,000.1
inelit was performed was thcrinostated a t 2 3 " . The incre- 81. '$6') ,0002
ments of 96.20% acid were a t 25' when added and thus a t 81.I I ' I .(IO20
k n o \ \ ~ iheat content. The heat of stirring plus heat lcak 81,::71 .002!i
could be evaluated from the rate of change of melting point 8% :323 .011:
with tinic ovcr long periods. This caii be determined most 81 %i(i 020-I
accurately near the beginning and eiid of such :i series w1iei.c Series 5 fcoiit )
the ratc of change of temperature with the ;tinoutit of solid
melted is grcateit. The dewar vesscl ivaq treated :t< a cal- s I . 00G 0 , 100%
orimeter and a n accurate record of it5 change iii heat coritcirt 83.132 0.4!)7
was recorded from the beginning to the ciid of it serics of 82.821 1.23Ri
observations. When the cornposition of the acid had 82.412 1.022
reached about 99.79yo, four samples of the cquilibriuiii 81,;s:; :3,241
liquid werc withdrawn and analyzed to within 0 . 0 0 5 ~ o .
The data were treated bl- plotting a curve of iriclting
point against amount of 96.20% acid adticti. At the nielt-
ing point maximum the composition corresponded to purc
H&O, and this could be determincd to 0.0002% acid. 80.154 8.31
Since the amount of excess water between the melting point 7!!.446 11.19
iuaximum and the end of the scries was known to about
0.4%, the amount of solid a t the end of the series could be NzSOI.HZOcrystals
calculated. The heat of mixing of 96.209/0 acid in thc vari- added
ous solutions was available from the paftial specific heat Series 6 (cont.)
content measurements of Kunzler and G ~ a u q u e although ,~ 78.921 13.63
the calculations required one approximation before the final
result was obtained. Since the heat content \vas kiiorvn for " I:.]). \lightly high bccausc amount of solici was I I J U
each temperature mcasurenicnt, the amount of solid and
thus the composition of the liquid could bc calculated. The S c w inaterial was used a t thc start of cach iiuiiibercti
heat of fusion of H2S09,2560 cal. iiiole - I , was takcii from scries ill Table I . Some 30 to 10% of the sample was prcsciit
the iucasurenients of Rubin aut1 Giauqtrc.' as the equilibrium solid in the form of a slurry of fine crys-
The heat quantities were known with sullicicnt accuracy tals which were thoroughly and continuously stirred. Serics
80 that the accuracy at each point was essentially not in- 1 and 2 were measured in the order of descending teinpera-
fluenccd by the calculation of thc various :tniouiits of solid tures by adding 96.20% sulfuric acid. Series 3 , 4 and thc
during the experiment. first part of Series 5 were measured in order of ascending
I n regions farther removed from the melting points, the temperatures to take advantage of the heat capacity of the
temperatures were observed, and samples removed for system. In Series 3, acid with about 3070 excess SO3 was
analysis t o 0.005Yo. used to increase the concentration, and finely divided crys-
- ... . . tals of H2S04, cooled by means of solid carbon dioxide,
(3) J. E . Kunzler. work to be published were added where noted. I n Series 4 and 5, except 5a, ice at
(4) I.. P. H a r u m r t t artri A, J Deyrup. THISJ U I J H K A L , 66, I!lOO 0' was used for dilution, and on the one occasion noted,
(I!)?3J crystals of H&04.H20cooled by stoiing the container in
( 5 ) R.J. Cillespie, J . C h e m .Soc , 21!?3 (1930). solid carbon dioxide were added. In Series 6 and 7 , dilu-
( 6 ) J. E. Kurizlcr atid IV. F. Ci8irilue. TEIWJ o r i R N n l . . 7 4 , 3172 tion was with ice a t 0' or a t liquid nitrogen teinperaturc as
(l!)52). requirctl. \Vhrii it wits necessary to add crystals of €I&OI.
$ 7 ) T. IC. Rtibiri atid IV. 1 : . Gi8iit~iiie,i h L ,7 4 , 800 (I!J52J. 1 1 ~ or0 I I2SOI tlicsc wcrc adjustctl approximately to solutioii
temperature before addition. The portion of Series 5 TABLE I1
designated 5a and Series 8 covering the regions near the
compounds H&O4.H20 and H ~ S O I ,respectively, utilized MELTINGP O I N T DATA ON H,SOd CONTAININGA SMALL
the calorimetric accounting method of determining concen- AMOUNTO F HzS207
trations as described above. The dilution in Series 5a was
by means of water at 25" and in Series 8, 96.20% acid at 25' -A,
was used.
Equilibrium-One of the sources of error in freezing point ~~. .
measurements depends on the extent to which equilibrium
~

couple therm. Av. liquid melted ih-f,

is attained between the solid phase and the bulk liquid which
is analyzed. Even when heat leak is reduced to a minimum 0.29 0.29 0.29 0.0052 0.15 0,0008
there will be a small amount of heat developed by the stir- ,155 ,145 .15 .0032 .22 .0007
ring which is essential to the attainment of uniform concen- ,127 ,128 ,128 ,0029 .30 .0009
tration. Thus prior t o and during the period of observa-
tion there will be a small amount of crystal melting. In ,081 ,079 ,080 ,0021 .37 .0008
these circumstances one cannot escape the conclusion t h a t ,058 .om . o m .ooi7 .44 . o m 7
the concentration in the immediate vicinity of the melting ,046 ,000 .053 .0016 .51 .0008
crystals will be rich with respect to the liquid resulting from .050 ,050 .050 .0016 .58 .0009
the solid phase. I n a n y two-component system this must
raise the temperature above the value which would result Average 0.0008 =k 0,0001
from true equilibrium between the solid and the bulk liquid.
The present measurements were made with a full apprecia-
tion of this difficulty and the conditions were such as to re- portant to realize t h a t the temperature composition data
duce it to a minimum. The finely ground crystals presented used as a basis for treating the data of R. and G. were ob-
it very large surface. After additions of liquid, equilibrium
tained by a method in which the amount of the solid changed
was established within two minutes a t the higher tempera- by only 1.6% during the investigation which has been men-
tures and within about 10 minutes at the lower tempera- tioned above. I t is also of interest to note that the ac-
tures. When cold solids, such as ice at liquid nitrogen tem- tivity of H~S201in the solution with 15% melted is about
peratures, were added, a long period was necessary to bring twice t h a t when 58% is melted. This ratio is readily cal-
them into equilibrium. Aside from this reason for slow- culable from the freezing point curve. We believe that the
ness, equilibrium was reached rapidly even in the more con- above facts support the conclusion t h a t H&07 is very in-
centrated regions and at lower temperatures where increased soluble in solid absolute sulfuric acid. There is no trend
viscosity would reduce the rate of diffusion. in the amount of H2S207 shown in the last column of Table
Comparison of Maximum Freezing Sulfuric Acid and 11.
Sulfuric Acid Monohydrate.-During the course of the Rubin and Giauque7 made measurements of heat capacity
present work the sulfuric acid content of maximum freezing below the melting point and evaluated the premelting heat
sulfuric acid and its monohydrate were compared. The calorimetrically. They give the result A = -0.0000 as
freezing point curve of the monohydrate is much flatter than compared to -0.0008 in Table 11. They expressed the
t h a t of the anhydrous acid but the maximum was located a t opinion that their results were low because insufficient
8.489" within a composition accuracy of 0.003 wt. 70. time was allowed for equilibrium. Such a situation will
The maximum at 10.371" for was determined to a n result in a low concentration of impurity a t the melting
accuracy of 0.0002 wt. %. The comparison showed that boundary and require a long time for equilibrium by diffu-
the two maxima were in agreement within 0.005% and i t is sion and heat conduction The results in Table I1 were
conservative to assume that the total possible error is withiti based on the two-hour equilibrium period mentioned above
0.01%. and if a substantial part of this time had been used for
Evidence that H2S04 Crystallizes as Absolute Acid to a equilibrium in the premelting heat measurements they
High Degree of Accuracy.-LichtyS mixed equimolal would probably have given agreement.
amounts of sulfur trioxide and water and proved t h a t the Rubin and Giauque? also estimated the amount of H & 0 7
maximum melting point corresponded to absolute acid impurity present in the liquid remaining a t the H&O4-H2-
S207 eutectic point as 0.0010 mole of H&O7 per mole of
within 0.01 wt. %.
Rubin and Giauque' made a considerable number of un- HaSO4 in the calorimeter. This estimate was based on a
published determinations of the melting point of sulfuric small amount of eutectic melting and is somewhat uncertain
acid as a function of the fraction melted. There was a due to the fact t h a t the heat of fusion of the H2S207 phase is
small excess of H~S207in their sample. These measurements known only roughly. The value 0.0010 may be taken as
were made after waiting long periods, of about two hours, comparable with the more reliable value of 0.0008 given in
for equilibrium. They were not used by R . and G . to in- Table 11. It may be shown that the activity of H&O,
vestigate the amount of impurity because i t was not pos- increases by a factor of about 150 between the melting point
sible to estimate the freezing point lowering with sufficient of HzSO, and the eutectic and despite this large increase the
accuracy, and also because related detailed measurements results indicate that the H2S04eutectic solid phase does not
as a function of composition were unavailable. The needed contain any appreciable amount of H&07. I n reaching
observations were obtained during the present research. this conclusion it is not assumed that the entire solid woultl
In order to ensure uniformity in the temperature scales of continuously reconstitute itself along the freezing point
the two researches, which is particularly important when the curve. Even the assumption that a solid built up of layers
freezing point lowering, e, is the objective, the melting point deposited in equilibrium with the liquid during cooling
of sulfuric acid monohydrate, 281.649'K., was used as an should deplete the total available amount of 0.0008 mole
intermediate temperature reference. This melting point H ~ S Z Oby
? a n appreciable amount if much solubility existed.
is not very sensitive to composition and thus could be de- We believe t h a t the data as a whole indicate that maximum
termined rather accurately. We have applied corrections melting sulfuric acid corresponds to absolute H?SOI within
t o the melting point data of R . and G. to make them as a few thousandths of a per cent. and that this procedure for
accurate as possible for the present purpose. The results preparing absolute acid is more accurate than any other
are given in Table 11. The quantity - A , representing the known method. This is important in the present series of
moles deficiency of HnO or the excess SO3, per mole of HzSO4 researches on sulfuric acid in this Laboratory since analyti-
is calculated provisionally on the assumption t h a t the maxi- cal procedures have been based on this standard. The tle-
mum melting point corresponds t o pure sulfuric acid. It tails of these procedures will be published elsewhere. 3
should perhaps be emphasized that ideal solution laws were The fact that maximum melting sulfuric acid nionohy-
not assumed in a n y of these calculations. drate and maximum melting sulfuric acid have relative
It will be seen that the total amount of H&07 present in compositions which agree with the ideal composition ratio
the liquid does not change when the amou'nt of the solid for these compounds, taken with the fact that the latter is
melted changes from 15 t o 58%. It is evident t h a t the pure, also demonstrates that maximum melting H?S04.Hr0
solid does not have a n appreciable amount of HzS201 to con- corresponds to the pure compound with high accuracy.
tribute to the liquid produced by the melting. It is im- Comparison with Other Data.--Gillespieb cov-
( 8 ) D. M Lichty, THISJOURNAL, SO, 1845 (1908). ered the range 99.7% to 100.4% H$04 and Ham-
rnett and Deyrup' covered approximately the same absolute acid. The value obtained in the present
rmgc. Both of these researches were put ( 1 1 1 '111 rcsenrch is 10.371" (283.531 "K.j.
,ib~olutchas15 h v rcfrrcncc t o thr i r i r i \ i i i i i i i i i t rcc/irig I'hr Ijreseii 1 rcwlts diffrr c.oxisiderably Ircun thosf
Iioiiit. (hllcsl)~c c,tlciil,itccl Ihc rLit't ob I ) o t l i of (hhle, Bet/ antl M'iroii, cspeci'tlly a t tlic lowcr
researches to this b,isis for cotii~~arisoii. teiiiper,iturcs betweeii H2SO4 and IiaS04.Hs0
-1 wide investigation of the freezing point coiii- 'l'hcir results are high, soinetinies by as much as 2"
position diagram has been made by several ob- There is abundant evidence froiii melting and
servers but, except near the melting point of m- other fixed points i n other concentrations, even a t
hydrous acid, their work IS less accurate than that lower temperaturcs, to show that their temperature
oi Chble, Retz and hlaron? mho g i w references to measurements are substantially correct. Some of
most of the previous work. the difference could be attributed to errors in
I n the immediate vicinity [99.% to 100.0.5wt. sampling or analysis but it is not possible to explain
of absolute acid the present research is more ac- the difference in that way-. The results are high
curate than those of 1%. and D. or C,. Between 011 both sides of the eutectic, whereas systematic
00.7 and 99.9 wt. c( H2S04the present values of 0 analytical errors would be expected to raise the
lie about midway between the two previous re- results on one side and lower them on the other
searches in this region. 8 is smaller in the work of side of the H?SOd-HzSOI HzO eutectic. The only
Gillespie and larger in the work of Hammett and self consistent way of explaining the difference is in
Deyrup. Curves through the results of either terms of unattaiiied equilibrium in the boundary
observer lie just outside the estimated limit of region about the melting crystals. The viscosity
error of the present results. There is essentially no of sulfuric acid solutions is very high in this con-
error in the teniperature measurement but the centrated region which requires minimum heat
possible analytical error of +0.005 wt. 5; a t 99.8L?, leak, large crystal surface and thorough stirring
IS equivalent to 0.0:3@. The niethod used reduces to approach equilibrium.
error proportionally between the point of analysis The results of G., B. and M. on the dihydrate side
and the inaxiniutn melting point so that a t 1)9.9("b of the monohydrate agree much better and in the
the possible error WAS .t0.002.? wt. corresponding more dilute regions, beyond the rnono-dieutectic,
to about 0.01 2'". The accuracy of the present work it is expected that the results of G., B. and M. will
could have been iniproved by performirig the suffice for the free energy calculations which will he
:rnalysis on a sample taken a t a greater 8. presented in a later paper.
Gillespic gives 1 0 :W ;is the melting point of RERKEI E \ , c.il I T O R \ I 9

[COSTRIDTJTIOS FROM HARPURCOI.I.EGl?,9 r A T E t!SIVERSITY 0 1 7 XBTY Y(IRK 1

The Solubilities of Naphthalene and Biphenyl in Aqueous Solutions of Electrolytes

Bs MARTINA. PAUL
RECEIVED
M . ~ Y13, 19.2

The solubilities of naphthalene and Iiiphenyl have been determined in aqueous solutions of several strong electrolytes a t
25' Iiy means of ultraviolet absorption. The data fit the Setchenow equation, in which the logarithm of the non-electrolyte's
activity coefficient is expressed as a linear function of the concentration of the particular electrolyte. The effects of different
electrolytes are generally similar t o those reported for other non-polar solutes. Comparison with published data for benzene
shows a progressive increase in the magnittide of the salting-out parameter for a given electrolyte from benzene to naphtha-
lene to biphenyl, apparently accompanying the increase in the molal liquid volume of the non-polar solute. The results nrr
discussed in terms of a theorv Dronosed hv 1IcT)evit antl Long in connection with their data for benzene. Data are reimrtrrl
?Iw for ~inphthaleneat 0'

The influence of various electrolytes on the solu- depend on the relative extents of interaction be-
bility of benzene in aqueous solutions has recently tween solvent and ions, as measured for example
been investigated by SlcDevit and Long1 and by by the contraction in volume accompanying dis-
Saylor, IYhitten, Claiborne and Gross. 1lcDevit solution of the electrolyte. This theory has the
arid Long have proposed a theory according to nierit of not only reproducing correctly the order
which the non-polar solute has the effect of modi- of effectiveness of various electrolytes in salting
fying the interaction between the solvent water out a particular non-polar solute but also account-
molecules and the ions of the electrolyte to a first ing for the salting in observed with perchloric acid
order of approximation merely by occupying and certain other electrolytes having large anions
\ olume. The salting-out parameter for a given or cations. It seemed desirable to obtain inforina-
electrolyte acting on a non-polar non-electrolyte tion for the larger non-polar molecules o€ naph-
should then be proportional in a first approxiination thalene and biphenyl. For polar non-electrolytes,
t o the non-electrolyte's own molal volume (in the of course, interactions of a more specific nature
liquid state), and for different electrolytes should niay be expected between the neutral solute niole-
cules and the ions on the one hand and the solvent
(1) n' 1 \rcIl?iit Jnd I 4 Ion: 'IIII> J o i ~ i 4 1 74, 1773 iiiolecules on the other, and this situation is indeed
f I [IX)
(2) J 11 Saylor, 4 I Wliittrn T ClAiImrne w d P I\.I Gro59 rbid , indicated by the nature of the experimental results
74, 1778 (10521 for such siibstances when contrasted with certain