3. inorg, nuel. Chem., 1967, Vol. 29, pp. 1953 to 1961. Pergamon Press Ltd.

Printed in Northern Ireland

EQUILIBRIA BETWEEN BORATE ION AND SOME

POLYOLS IN AQUEOUS SOLUTION*
J. M. CONNEP,~" and V. C. BULGRIN
Department of Chemistry, University of Wyoming, Laramie, Wyoming

(Received 23 January 1967)

Abstract--The amount of complex formation between borate ion and some diols and polyols of
known stereochemistry has been measured by a pH method at four temperatures, allowing determina-
tion of values of K, AG°, AH ° and AS °. The major factors affecting complexing appear to be the ease
of attaining coplanarity of the hydroxyl carbons and oxygens entering the complex, and the degree of
substitution on the hydroxyl carbons.
INTRODUCTION
Tim FORMATIONof complexes between borate ion and organic polyhydroxy compounds
has long been established. In 1842, BIOTtl~ reported that the addition of sugars
caused b o d e acid solutions to become acid to litmus. In the years following, m a n y
workers tested series of compounds and reported quantitative data, the most notable
of these being BOESEKEN.(2-s) HERMANS(9) proposed the structural explanation of the
complexing which is still accepted. He postulated that 1,2- and 1,3-diols of c i s
configuration frequently formed two types of complexes, which while having the
structure of diesters were distinguished therefrom by the great speed of their formation.

r o 1
: 1 complex anion 2:1 complex anion
The first is formed by splitting out two molecules of water between a molecule of
polyol and a B(OH)4- ion, and the other by removal of four molecules of water from
two molecules ofpolyol and a borate ion. Since the oxygens are arranged tetrahedrally
about the b o r o n a t o m it is evident that optical isomers are possible in the case of the
2:1 complex, and indeed some of these have been isolated, c°~
Other studies of polyol-borate complexes include m a n y that give quantitative

* Taken from portions of the Ph.D. thesis (J. M. C.), University of Wyoming, 1966.
1" Present address: Regis College, Denver, Colorado 80221.
a~ M. BIOT, C.r. hg~bdS~anc Acad. Nci., Paris 14, 49 (1842).
~ J. B6~Erd~Nand A. VANROSSEM,.RecL tray. chim. 30, 392 (1911).
~3~j. B 6 ~ E ~ , Ber. ichw 46, 2612 (1913).
~4~j. B6~Er~N et aL, RecL cruv. chim. 34, 96 (1915).
~5~j. B~Erd~N and J. VANG ~ N , .RecL tray. chim. :39, 183 (1920).
~e~j. B6~EmBN, Chem. Zentr. 314, 2778 (1924).
~7~j. B6~F.~N, .RecL tray. chim. 45, 552 0926).
~s~j. B6~.sEg,~N,N. V ~ s , W. H. Z.~'~R and J. L. LEEFm~.S,.Reel. tray. ehim. 54, 853 (1935).
~s~ p. H. ~ . R ~ s , Z. ~ o r g . allg. Chem. 142, 83 (1925).
9 1953
1954 J . M . Co,,am and V. C. BUL~RtN

data, with widely varying a n d inconclusive results. T o d a t e m o r e w o r k with m a n n i t o l

has been p u b l i s h e d t h a n with a n y o t h e r polyol, a n d values o f Kx f r o m zero ~°) to
9160 ~]]) a n d o f K~ f r o m 51,000 t12) to 363,000 tx°) have been r e p o r t e d , all a t 25°C.

B - -f- P = B P - K~ = __[BP-] (1)

[B-I[P]
[BPz-]
B- q- 2P = BP2- K2 -- [B_][p]---~
- , (2)

where B= = borate ion and P = polyol.

Similarly, values of K~ for the glycerol complex from 14.8(xa) to 44 (]4) have been
r e p o r t e d a t r o o m t e m p e r a t u r e . T h e m o s t c o m p r e h e n s i v e recent p u b l i c a t i o n on t h e
subject o f b o r a t e - p o l y o l c o m p l e x e s is t h a t o f RoY et al. (x~) T h e y m e a s u r e d the equilib-
r i u m c o n s t a n t s for c o m p l e x f o r m a t i o n for fourteen p o l y o l s a t 25°C b y a p H m e t h o d
similar to t h a t used in the p r e s e n t w o r k , b u t m a d e no c o r r e c t i o n for the m e d i u m effect
on the solvent b y the polyol.

EXPERIMENTAL
All inorganic chemicals used were reagent grade, with the exception that the arsenic(IH) oxide
used as the primary standard in the periodate analyses of the polyols was primary standard grade.
The water used in all reaction mixtures, solutions, and dilutions had been first distilled and then
passed through a deionizing column containing Crystalab "Deeminite" resin. All water which was
to be used in pH determinations had high purity dry grade nitrogen gas bubbled through it for 1 hr
just before use, to remove dissolved carbon dioxide.
2-Methoxyethanol, 1,2-ethanediol, 1,2,3-propanetriol, cyclopentene, D-mannitol, 1,2-benzenediol,
~-o-glucose, and phenol were reagent grade, and were used without further purification. 1,2-Propane-
diol was redistilled under the vacuum of a water aspirator and dried over P20~ before use. 1,3-
Propanediol was found by gas-liquid chromatography to be 96"0yo pure, the major contaminant
being water. L-2,3-Butanediol was prepared by the Aerobacilluspolymyxa fermentation of corn, (x6~
purified by fractional distillation, and just before use redistilled under the vacuum of a water aspirator
and dried over P~Os. meso-2,3-Butanediol was prepared by the Aerobacter aerogenes fermentation of
corn, c'e~twice recrystallized from dry isopropyl ether, and just before use distilled under atmospheric
pressure and dried over P205. 2-Methyl-2,3-butanediol was prepared by oxidation of the unsaturated
hydrocarbon with performic acid. c'vJ It was purified by fractional distillation using a Todd Scientific
Co. 40-plate column. 2,3-Dimethyl-2,3-butanediol (pinacol) was prepared through the magnesium
pinacolate by the condensation of acetone, c*s) It was purified by reerystallization from water and
dried by distillation followed by fractionation of the portion boiling above 165°C. The portion
boiling above 169° was then collected as anhydrous product, ct~-l,2-Cyclopentanediolwas prepared
by a method similar to that of WIBERGand SA~Grm~mTH,ct*~and the product distilled under a pressure

c~0~j. TUNG and H. CHANG,J. Chinese Chem. Soc. 9, 125 (1942).

(al) p. j. ~ N , Acta chem. scand. 9, 1008 (1955).
ix2) A. DEtrrsCH and S. OSOL~G, J. Am. chem. Soc. 71, 1637 (1949).
txa~R. SARO'~r and R. RmMAN,III, J. phys. Chem. 60, 1370 (1956).
c]4) p. j. ANnKAINEN,Soumen 30B, 185 (1957).
c~5~G. L. Roe, A. L. LAt~PaER~ and J. O. EDWAROS,J. inorg, nucl. Chem. 4, 106 (1957).
tts~ E. R. KooI, E. I. FULM~Rand L. A. UNDERKOrLLm,Ind. Engng Chem. 40, 1440 (1948).
uT~ A. ROEBUCKand H. ADraNS, Organic Syntheses, Collective, Vol. 3, p. 217. John Wiley, New York
(1955).
,~s~ R. ADAMS and E. W. ADAMS, Organic Syntheses, Collective, Vol. 1, p. 459. John Wiley, New York
(1941).
c~) K. B. WmER(~and K. A. SAV.,3,~aARTH,J. Am. chem. Soc. 79, 2822 (1957).
 Equilibria between borate ion and some polyols in aqueous solution 1955

of 12 mm Hg. c~-l,2-Cyclohexanediol was prepared by the method of CLARKandO w~s. '~°~ It was
recrystallized four times from CCI~, distilled under the vacuum of a water aspirator, and dried over
P206. trans-l,2-Cyclopentanediol and trans-l,2-cyclohexanediol were prepared by the method of
ROEBUCKand A o ~ s , '~7~and were dried over P~Os.
The concentrations of the stock solutions of 1,2,3-propanetriol and of all the diols except 1,3-
propanediol and 1,2-benzenediol were determined by periodate oxidation.`2~ Concentration of the
1,3-propanediol solution was calculated from the chromatographic purity, and that of the ~-o-
glucose solution was determined by polarimetry. The remaining polyols were assumed to be 100K
pure. Solutions of sodium tetraborate decahydrate (borax) were standardized by pH titration with
standard HC1.
All pH measurements were made with a Beckman Research model pH meter. It was equipped
with a Beckman #39166 probe electrode assembly (consisting of a glass electrode with silver-silver
chloride internal and a silver-silver chloride reference electrode), which permitted the use of quite
small solution volumes. The meter was standardized separately at each temperature, using the
"phosphate buffer E" of BATES.la2~
A Dewar flask containing melting ice in a well-stirred ice-water bath was used to give a constant
temperature of 0.00 4- 0.02°C. Mercury thermoregulators were used in a conventional water bath to
give the same 4-0.02°C control at 13.05, 25.00 and 34.98°C. Brooklyn Thermometer Co. thermom-
eters with 0-01°C scale markings and small ranges were used, and the temperatures corrected in
the usual manner.
The reactions were carried out in 100-ml giass-stoppered volumetric flasks. Twenty-five millitres
of 0.1 M borax solution and an amount of polyol stock solution were placed in the flasks to give a series
of solutions with polyol concentrations from zero up to the highest concentration practical for the
particular polyol (0.9 M or less). COs- free conductivity water was added to fill the flasks to the mark.
After thorough shaking, the flasks containing the solutions were placed in the constant temperature
bath for 45 min prior to standardization of the meter and measurement ofpH. For a given compound
the same set of solutions was used for all four temperatures. The measured pH was corrected as
discussed below, and then the corresponding [H +] values calculated.

RESULTS AND DISCUSSION

T h e m e t h o d o f calculation o f e q u i l i b r i u m c o n s t a n t s d e p e n d s o n a k n o w l e d g e o f the
i o n i z a t i o n c o n s t a n t o f b o r i c acid at the given t e m p e r a t u r e a n d ionic strength. B o r a x
has a chemical c o m p o s i t i o n such t h a t its a q u e o u s solution is a half-neutralized s o l u t i o n
o f b o r i c a c i d j u s t as it is. Since the e q u i l i b r i u m c o n s t a n t s have b e e n s h o w n to be
i n d e p e n d e n t o f buffer c o n c e n t r a t i o n in solutions as dilute as were herein used, as)
t h e buffer c o n c e n t r a t i o n was k e p t c o n s t a n t for each polyol. T h e fifteen p o l y o l s
investigated were 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol,
L-2,3-butanediol, meso-2,3-butanediol, 2-methyl-2,3-butanediol, 2,3-dimethyl-2,3-
b u t a n e d i o l , cis- a n d trans-l,2-cyclopentanediol, cis- a n d trans-l,2-cyclohexanediol,
g-D-glucose, o - m a n n i t o l a n d 1,2-benzenediol. O f these only the two trans c o m p o u n d s
f o r m e d no complexes. A typical set o f d a t a is s h o w n in T a b l e 1 a n d f o u r sets are
p l o t t e d in Fig. 1.
W e have f o l l o w e d m o s t p r e v i o u s w o r k e r s in a s s u m i n g t h a t the p o l y o l s c o m p l e x
only with the a n i o n i c f o r m o f the buffer (the b o r a t e ion). Since there is n o change in
c h a r g e t y p e in the r e a c t i o n s studied, we a s s u m e d t h a t the c o m p l e x i n g constants d o
n o t d e p e n d u p o n ionic strength. Finally, a c c o r d i n g to KErn 't~a~ in solutions with
b o r a x c o n c e n t r a t i o n b e l o w 0.2 m only m o n o b o r a t e ions, B ( O H ) ~ , occur. I n this

~20~M. F. CLARKand L. N. OWEN,J. chem. Soc. 318 (1949).

t2x~F. R. DUKE and V. C. BULGRIN,J. Am. chem. Soc. 76, 3803 (1954).
iz2~R. G. BATES,J. Res. Natn. Bur. Stand. A66, 179 (1962).
t2s~p. H. KEMP, The Chemistry of Borates, Part I. Borax Consolidated Ltd., London (1956).
1956 J. M. CONNER and V. C, BULGRIN

TABLE I.--DATA FOR CALCULATION OF COMPLEXING CONSTANTS

(Example: 1,2=ethanediol,0.00°C, [Borate] = 0.05380 M )

pH [H +] × 101° [P]
[P]~otal pH corrected corrected K' free

0 9"490 9"490 3.236 -- --

0"1741 9"317 9"302 4"989 3"51 0"154
0.2611 9-245 9"223 5.984 3"59 0"236
0"3481 9-181 9"151 7.063 3-71 0-319
0-4352 9"118 9-081 8"299 3"89 0-402
0'5222 9'064 9"019 9"572 4"02 0"487
0"6092 9"021 8"969 10.74 4"06 0"572
0"6962 8.976 8"917 12.11 4-18 0"657
0"7833 8-935 8"868 13"55 4"29 0.742

50

40

30

KI

2O

I0

I t i i i i, ! I I i

0 0.2 0.4 0.6 0.8 I.O

FIG. 1.--Plot of pseudo equilibrium constant vs. uncomplexed polyol for 1,2-ethane-
diol, 25-00°C, curve A; 1,2-propanediol, 0.00°C, curve B; 1,2,3-propanetriol, 34.98°C,
curve C; and 2,3-dimethyl-2,3-butanediol, 34.98°C, curve D.
 Equilibria betweenborate ion and some polyols in aqueous solution 1957

work the borax concentration has been maintained at about ~ this value, allowing
complications from polyborate ions to be neglected.
For each temperature, a solution containing no polyol was made and from its pH
the Ka of boric acid at that temperature and ionic strength was calculated. The pH of
a series of solutions of borax and non-complexing 2-methoxyethanol was measured
at each temperature and plotted vs. [2-methoxyethanol] in order to obtain a correction
for the medium effect. The pH dependence was linear with concentration, and
reached about 0.1 pH unit at 1 M at all four temperatures. Corrections were made
from these graphs equating polyol concentration to 2-methoxyethanol concentration.
In the single case of 1,2-benzenediol an additional problem arose. 1,2-Benzenediol
is itself an acid of strength comparable to that of boric acid, and thus would decrease
the pH of borax solutions appreciably even in the absence of complexing. Previous
workers have not taken account of this, and have reported very large complexing
constants for this compound. We were unable to determine correction factors with
2-methoxyphenol (analogous to 2-methoxyethanol) owing to its very limited solu-
bility in water, and used phenol instead. These corrections were obtained and used in
the same way as those from 2-methoxyethanol. The pH dependence here was about
ten times as large in the opposite direction, and was not linear with concentration.
Complexing constants for 1,2-benzenediol were calculated in two ways (see Table 2):
using only a 2-methoxyethanol correction, and using both corrections. The values of
K 2 using only the 2-methoxyethanol correction increased with increasing temperature,
providing further justification for the phenol correction. Using both corrections it
was not possible to detect any of the 2: 1 complex, but the values of K i were reasonable
and behaved properly with temperature.
In order to be certain that no complex involving two borate ions and one polyol
molecule was present in the mannitol solutions, an equation was derived corresponding
to Equation (7) below, but considering the two complexes 1 : 2 and 1 : 1 : mannitol:
borate. The low [mannitol] points were recalculated according to this scheme and
plotted. The result was a curve in which the new K' decreased sharply with increasing
[P], ruling out the possibility of a 1 : 2 complex.
Very good K'vs. [P] plots were obtained for all compounds which showed complex-
ing. For the series of methyl-substituted homologs of 1,2-ethanediol the K values
for complexing always increase with increasing molecular weight, with the exception
that the fourth methyl group seems to have little effect. Apparently the primary
consideration in this series is the degree of substitution of the hydroxyl carbons rather
than a steric effect. The order of size of/(2 is here (at 0.00°C): 2,3-dimethyl-2,3-
butanediol > 2-methyl-2,3-butanediol > L-2,3-butanediol > meso-2,3-butanediol >
1,2-propanediol > 1,2-ethanediol. For periodate at 0.00°C BULGRIN(~i) found the
order 1,2-propanediol > 1,2-ethanediol > L-2,3-butanediol > rneso-2,3-butanediol >
2-methyl-2,3-butanediol > 2,3-dimethyl-2,3-butanediol. There is a general reverse
correlation, and two major contributing factors are doubtless that borate ion is
tetrahedral whereas periodate is distorted octahedral, and the great difference in the
size of the two ions. In this connexion it should be noted that there are two pairs of
compounds where the order is the same for borate as for periodate, and these are
the two cases where the change in steric hindrance for the anion is least: 1,2-propane-
diol > 1,2-ethanediol and L-2,3-butanediol > meso-2,3-butanediol. Thus it appears
1958 J. M. CO~Sr.R and V. C. BLrt~RIN

TABLE2.--EQUILmPatn~ CONSTANTSFOR POLYOL--BORATECOMPLEXES

0.00°C 13.05°C 25.00°C 34.98°C
Kx K1 K1 K1
Compound K~ K~ K~ Ks
1,2oEthanediol 3.29 2.90 2.15 1.87
1.38 1.19 1.15 0.893
1,2-Propanediol 6.35 4.35 4.05 3-40
8.29 6.06 3.85 2-36
1,3-Propanediol 2-81 1.77 1.27 0-95
0-20 0.12 0.I I 0.056
1,2,3-Propanetriol 23-0 17.5 14.0 12"5
97.0 68.6 57.9 41-7
L-2,3-Butanediol 62 43 37 25
399 281 164 125
meso-2,3-Butanediol 5.1 3'2 2-7 2"3
12"8 7-6 4-6 2"7
2-Methyl-2,3- 39 24 18 13
butanediol 579 336 210 124
2,3-Dimethyl-2,3- 24 19 11 5
butanediol 620 397 216 88
cis-l,2-Cyclopen- 45 31 26 21
tanediol 364 231 142 102
c/~-l,2-Cyclohex- 2 1 1 1
anediol 2 2 0-7 0.3
or-D-Glucose 215 175 135 125
880 880 870 880
D-Mannitol 4200 2300 1100 800
266,000 204,000 137,000 111,000
1,2-Benzenediol* 12,300 10,300 8000 6500
11,400 12,200 17,300 22,100
1,2-Benzenediolt 7300 5700 4950 4200
0 0 0 0
* Corrected by 2-methoxyethanol only.
t Corrected by both 2-methoxyethanol and phenol.

that in the absence of steric problems in the case of periodate, the order would be the
same for the two anions.
The smaller constants for meso-2,3-butanediol than for the laevo compound m a y
be explained by the greater crowding of the terminal methyls in the complexes with
the meso isomer. The constants for 1,3-propanediol are substantially lower than for
1,2-propanediol. N o doubt this is another case of a primary vs. a secondary alcohol
group, with an additional contribution from the greater loss of rotational freedom
caused by complexing with the 1,3 compound. The cyclopentanediols gave the
expected results from models: moderately strong complexing with the c/s isomer and no
complexing with the trans. Models indicated that complex formation in the case of
trans-l,2-cyclohexanediol (both conformations) was impossible, and none was ob-
served. For the cis-l,2-cyclohexanediol, models predicted that a complex was possible
only with the boat form, and indeed very little complexing occurred. It is thus believed
that the degree of complex formation here is indicative of the amount of boat f o r m
present.
~-D-Glucose solution was prepared and used quickly, being kept in a refrigerator at
 Equilibria between borate ion and some polyols in aqueous solution 1959

just above freezing when not in use, in order to keep the concentration of fl form to a
minimum. The fl configuration has no vicinal cis hydroxyls and by analogy to the
propanediols in this work and also according to AWnKAtN~rqt~a~is expected to complex
far more weakly (if at all) than the 0cconfiguration.
D-Mannitol has long been considered to present complications with regard to its
borate complexing. We submit that there are actually no complications at all, and
the problem has been the failure of previous workers to calculate self-consistent values
for the complexing constants and concentration of uncomplexed or free polyol,
preferring to make simplifying assumptions leading to explicit but erroneous equations.
The errors become unusually large for mannitol because of its unusually large com-
plexing constants.
The results obtained here with 1,2-benzenediol are not considered to be definitive,
but the suggestion of the need to correct for the acidity of the diol itself is felt to be the
valid approach.
APPENDIX
Calculation method
In the derivations of the working equations for calculation of the uncomplexed or free polyol, [P],
and of the overall pseudo-equilibrium constant, K', the assumption was made that the amount of
unionized boric acid does not change significantly with polyol concentration and remains equal to the
"initial" value, or the value it would have in the absence of polyol. Thus it is appropriate to first
prove the validity of this assumption, that [HB]0 = [HB]. Substitution of the equation for conserva-
tion of charge,
[B-] + [BP-] + [BP~-I = [H +1 + [Na +1 -- [OH-],
into the equation for conservation of boron,
[HB]0 + [B-]0 = [HB] -k [B-I + [BP-] + [BP~-],
in which the subscript zero denotes initial concentrations, leads to:
[HB]0 + [B-]o = [HB] -b [H +] + [Na +] -- [OH-],
[Na +] and [B-]0 are constants and are equal. All pH values encountered were between 4"5 and 9"5,
with the result that the quantity [H ÷] -- [OH-] never varied from zero by more than q-3 × 10-5 M.
Thus, at the boric acid concentration of 0.05 M used in the sample solutions of this work, it is a valid
assumption that [HB]0 = [HB].
The complexing constants are defined by Equations (1) and (2). The equation for conservation of
polyol is:
[P] = [P]~ -- [BP-] - - 2[BP2-], (3)
where [P]~ = total polyol. The equation for conservation of borate, which includes implicity the
assumption that [I-IB]o = [HB], is:
[B-]0 -- [B-] = [BP-] + [BPc]. (4)
Further, the ionization equilibrium for boric acid is given by"
[H+][B -] [H+][B -] [H+][B -]
[liB] = [H +1 + [B-I Ka . . . . . (5)
[HB] [HB]0 [B-J0
Making appropriate intersubstitutions of these five equations and solving for [P] leads to,
(2K, tB-1q
[PI~ - 2is-J0 + \ [H+I ]
[PI = (6)
1 ~ [H+I ]
(s4) p. i. ANTIKAINEN,Soumen 31B, 255 (1958).
1960 J.M. CONfeR and V. C. BULOarN

TABLE 3.--THERMODYNAMIC IrUNCTIONS FOR POLYOL--BORATE COMPLEk'L~ AT 25"00°C

AG1 ° AH1 ° ASi °

AG~° AH~ ° AS, °
Compound (cal)* (cal)t (cal/°C):~

1,2-Ethanediol --453 --2700 --7-5

--83.2 --1970 --6.3
1,2-Propanediol --830 --3020 --7.3
--800 --7220 --22
1,3-Propanediol -- 142 --4550 --15§
1300~ --6180 --16§
1,2,3-Propanetriol --1570 --2850 -4"3
--2140 -3880 --4"9
L-2,3-Butanediol --2140 --4300 --7-2
--3020 --5480 --8-2
meso-2,3-Butanediol -- 588 - 3430 - 9-5
--905 -7190 --21
2-Methyl-2,3- -- 1710 • -- 4900 -- 11
butanediol --3170 - 8000 -- 16
2,3-Dimethyl-2,3- -- 1420 -- 7090 -- 19
butanediol -- 3190 -- 9000 -- 20
c/s-1,2-Cyclopen- -- 1930 - 3530 - 5.4
tanediol --2940 -6060 -- 11
cis-l,2-Cyclohex- 0t --4000~ --1011
anediol 200"~ - - I 0,000~ --4011
~-o-Glucose --2910t -- 3520 --2"0
--4010 --149 13
D-Mannitol --4150 --8050 -- 13
--7010 --4450 8"6
1,2-Benzenediol¶ -- 5320 -- 3190 7"1
--5780 3770 32
1,2-Benzenediol** -- 5040 -- 2670 8.0

* Estimated error, -4-3~ o r less.

t Estimated error, q-10yo.
:~ Estimated error, q - 2 5 ~ .
§ Estimated error, : k 5 0 ~ .
II Estimated error, q-60~o.
¶ Corrected by 2-methoxyethanol only.
** Corrected by b o t h 2-methoxyethanol and phenol.

In this equation b o t h [P] and K1 are unknown. Since at large values o f [P]~ it is good to a first
approximation that [P] = [P]~, the larger values o f [P]~ may be substituted into the left side o f
Equation (7) below, and corresponding values o f K'calculated. Then a plot o f K ' v s . [P]~ leads to an
initial value o f Kx, which is used in Equation (6) to obtain better values o f [P]. This is repeated until
self-consistency is obtained. In the case where K2 was very large (the only example in the present w o r k
was D-mannitol), self-consistency was best approached from initially assuming all borate to be
complexed, so that for the first approximation [P] = [P]~ - - 2[-B-]0.
The equation for K ' was obtained by substituting for [BP-] and [BP2-] from (1) and (2) into (4) to
give:
[B-]. = [B-I + KI[B-I[P] + K~[B-I[PI'.
 Equilibria between borate ion and some polyols in aqueous solution 1961

Dividing through by [B-][P], rearranging and substituting from (5) gives:

Ka -- 1 ~ =K'=KI+K2P. (7)

Thus a plot of K'vs. [P] gives K1 as its intercept and K~ as its slope. However, it must be emphasized
that this equation is not exact, because in its derivation [BP¢] was assumed to be equal to 2[BPg-]. ~x~
The standard free energy change, A G ° , corresponding to each equilibrium constant value at
25°C was calculated from the equation:
AG ° ---- --2.303RTlog K, where R = the gas constant.
The values of the standard enthalpy change, A H °, were determined from the slope of a plot of log K
vs. 1 / T using the Gibbs-Helmholtz equation:
A H ° = --2"303R d(Iog K)
dOlT ) '
The values of the standard entropy change AS °, corresponding to the equilibrium constants at 25°C
were calculated from the equation:
AH o _ AG o
ASO=.
T

The values of these functions are given in Table 3.