TRANSACTIONS 2016, 22: 486-491

OF TIANJIN UNIVERSITY DOI 10.1007/s12209-016-2638-6

Equilibrium on the Hydrolysis of Boron Trifluoride

in Large Amount of Water*
Zhang Weijiang(张卫江)1，Liu Tianyu(刘天雨)1，Lang Wuke(郎五可)2, Xu Jiao(徐 姣)1
(1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
2. College of Chemistry and Life Science, Weinan Normal University, Weinan 714099, China)

© Tianjin University and Springer-Verlag Berlin Heidelberg 2016

Abstract：In order to clarify the equilibrium components in the hydrolysis solution of boron trifluoride(BF3-H2O),
the BF3-H2O was prepared by mixing BF3-CH3OH with large amount of water, in which the stoichiometric concen-
tration of BF3 is less than 0.1 mol/L. Two ionic equilibrium models were proposed to simulate the hydrolysis equi-
librium of BF3 and tested by special acid-base titration technique. The most accurate ion equilibrium constants were
determined. The model, which was assumed to have no HF, was proved to be more representative for the real sys-
＋
tem and used to simulate the hydrolysis equilibrium of BF3. The simulation suggested that H , BF4- , BF3OH- and
H3BO3 were the main species in the dilute hydrolysis solution, while BF2 (OH)-2 and F were insignificant species
-

whose concentrations were both in the order of 10-4 mol/L magnitude, and BF(OH)-3 could be omitted because its
concentration almost equaled zero. Meanwhile, the equilibrium constant of the overall ionic reaction at 25 ℃ was
obtained as 161.6.
Keywords：boron trifluoride; hydrolysis equilibrium; ionic equilibrium; simulation

Boron trifluoride(BF3)and its complex are a kind of
catalysts for esterification, polymerization, isomerization,
sulfonation and nitration, in which water is essential as
the co-catalyst for polymerization and isomerization[1].
Refs. [2]—[4] utilized the reaction between BF3 complex
and calcium carbonate or lithium carbonate to produce
boric acid in water. However, the mechanism of this reac-
tion was not studied particularly. The reaction of BF3
with inorganic salt in water contains two steps. The first
step is the hydrolysis of BF3 in water, and the second step
is the reaction of hydrolysis product with inorganic salt.
Thus, it is essential to study the hydrolysis of BF3 in de-
tails.
The reaction of BF3 with water is complicated. It
can produce the complexes BF3·H2O and BF3·2H2O when
the molar ratios of BF3/H2O are 1:1 and 1:2, respec-
tively[5]. When water was added continuously, the com-
plex would hydrolyze further. Wamser[6] claimed that the
hydrolysis product contained HBF 4 , HBF 3 OH,
HBF2(OH)2, HBF(OH)3 and H3BO3. Ball[7] regarded the
hydrolysis product as HF and H3BO3. Yan et al[8] re-
ported that the hydrolysis product mainly contained HF,
Accepted date: 2015-06-19.
* Supported by the Independent Innovation Fund of Tianjin University (No. 1307).
Zhang Weijiang, born in 1953, male, Dr, Prof.
Correspondence to Xu Jiao, E-mail: xujiaohh@163.com; and Lang Wuke, E-mail: lwktsg@163.com.
H3BO3, HBF4 and BFx(OH)3-x.
The hydrolysis product is different for different re-
searchers, and the greatest difference is the existence of
HF. In order to clarify the hydrolysis product of BF3 and
understand the reaction of BF3 with inorganic salt, two
hydrolysis equilibrium models that suggest the existence
and inexistence of HF respectively were built based on
Ref. [6]. A proper model was chosen through experimen-
tal test, and the equilibrium of the dilute hydrolysis solu-
tion of BF3 was simulated by this model.
1 Theory
1.1 BF3 source and the stoichiometric concentra-
tion of BF3
The hydrolysis solution of BF3 can be obtained by
mixing different BF3 derivatives with water. Wamser[6]
reported that the mixtures of BF 3 ＋ H 2 O,(BF 3 ·H 2 O,
BF3·2H2O)+H2O, B(OH)3+3HF+H2O or HBF2(OH)2+
HF+H2O were identical at equilibrium for equivalent
stoichiometric concentrations of BF3. Thus, BF3-CH3OH
was regarded as the valid source of BF3 to study the hy-
Zhang Weijiang et al: Equilibrium on the Hydrolysis of Boron Trifluoride in Large Amount of Water
drolysis of BF3 when it was mixed with abundant water.
Solid will precipitate from the hydrolysis solution
with the stoichiometric concentration of BF3 rising.
Wamser[6] reported that boric acid would precipitate at
3.17—12.2 mol/L. Maya[9] reported that boric acid was
the equilibrium solid phase at a high water concentration,
while metaboric acid was the equilibrium solid phase at a
low water concentration. Thus, the stoichiometric con-
centration of BF3 in this study was controlled under 0.1
mol/L.
1.2 Equilibrium modeling
1.2.1 Hydrolysis mechanism of BF3
Wamser[6] considered that it was oversimplified if
the hydrolysis of BF3 in water was written as Eq.(1). He
proposed a mechanism as Eqs.(2)—(6), where Eq.(2)is
a quick reaction, Eqs.(3)—(5)are a series of quick fluo-
rine removing reactions, and Eq.(6)is a slow reaction.
Our study is based on the above work.
4 BF3 + 3H 2 O 
 3HBF4 + B(OH)3 (1)
BF3 + H 2 O 
 HBF3 OH
HBF3 OH+ H 2 O 
 HBF2 (OH) 2 + HF
HBF2 (OH) 2 + H 2 O 
 HBF(OH) 3 + HF
HBF(OH)3 
 B(OH) 3 + HF
HBF3 OH+ HF 
 HBF4 + H 2 O
1.2.2 Modeling
The above equations indicated that the hydrolysis
solution of BF3 was a mixture of various acids and low
pH was predictable. Assume that the strong electrolyte
dissociated completely, while the weak electrolyte did
not dissociate at all, the possible equilibrium reactions for
the hydrolysis of BF3 could be presented as Eqs.(7)—
(12).
Wamser[6] reported that HBF4 was as strong as HCl,
and it cannot exist as pure HBF4 [10]. Hence, HBF4 was
reasonable to be denoted as H＋ and BF4- in dilute solu-
tion. In addition, Wamser[6] reported that HBF3OH and
HBF2(OH)2 were as strong as trichloroacetic acid(pK＝
0.7)and dichloroacetic acid(pK ＝ 1.48), respectively;
and Mesmer et al[11] proved that the concentrations of
HBF3OH and HBF2(OH)2 were less than 5% and 25% of
BF3OH- and BF2 (OH)-2 respectively, in which BF2 (OH)-2
was far less than BF3OH-. Thus, it is valid to regard
HBF3OH and HBF2(OH)2 as BF3OH- and BF2 (OH)-2
respectively in dilute solution. Since boric acid(pK ＝
9.24)is a kind of weak acid and orthoborate ion B(OH)-4
does not appear in appreciable amounts below pH 7, nor
do the polyborate ions at the low boron concentrations[12],
Trans. Tianjin Univ.
it is reasonable to consider boric acid as H3BO3 in dilute
acidic solution. In one word, it is valid to express the
equilibrium reactions in the dilute hydrolysis solution of
BF3 as Eqs.(7)—(12). In fact, Eq.(12)was excluded due
to the low concentration of F-.
B(OH)3  F 
K
BF(OH) 
1
3
(7)
B(OH)3  2F  H  BF2 (OH) 2  H 2 O
  K2
(8)
B(OH)3  3F  2H  
K3
BF3 (OH)   2H 2 O (9)
B(OH)3  4F  3H  
K4
BF4  3H 2 O (10)
F  H  
K5
HF (11)
  
2F  H  HF K6
2 (12)
HF was supposed to exist in the equilibrium, so
Model 1 was shown as Eqs.(7)—(11), while no HF was
supposed to exist in Model 2, as shown in Eqs.(7) —
(10). If the concentrations of H ＋ , F-, H3BO3 were as-
signed as x1, x2, x3 respectively, and the stoichiometric
(2) concentration of BF3 was assigned as Bt, two sets of
(3) equations could be established based on the mass balance
of B and F, and the charge balance of Model 1 and Model
(4)
2. The variables x1, x2, x3 could be solved by Newton
(5)
method if the equilibrium constants of Eqs.(7) —
(6) (11)and Bt were given, and the concentrations of all the
species could be obtained based on Eqs.(7)—(11).
1.3 Model test method
All the species in the equilibrium model could be
classified into four kinds of acids: HBF4, hy-
droxylfluoroboric, H3BO3 and HF if it existed, in which
hydroxylfluoroboric contained HBF3OH, HBF2(OH)2
and HBF(OH)3. The validity of models could be tested
by special acid-base titration technique based on the acid-
ity of different acids [13, 14]. HBF3OH was selected to de-
note the hydroxylfluoroboric because the other three
kinds of hydroxylfluoroboric could not be distinguished
and HBF3OH was the main species. The test equations
and component concentration equations of the two mod-
els are displayed in Tab. 1, where a, b, c and d denote the
concentrations of HBF4, hydroxylfluoroboric acid, free
H3BO3, and HF in the equilibrium solution respectively;
C0 denotes the concentration of NaOH solution; V1, V2,
V3, V4 denote the volume of NaOH solution consumed
each time; C is the concentration sum of the acids. The
titration for the solution of Model 1 was taken as an ex-
ample to explain the equations in Tab. 1.
When a certain volume of BF3-H2O test solution
was added, excessive CaCl2 and HBF4 would be con-
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