J O U R N A L O F M AT E R I A L S S C I E N C E L E T T E R S 1 7 ( 1 9 9 8 ) 1 8 3 9 1 8 4 2

Effect of reaction parameters on the hydrolysis of zirconium propoxide.

A study by infrared spectroscopy
F. RUBIO, J. RUBIO, J. L. OTEO
Instituto de Ceramica y Vidrio. (C.S.I.C.), Arganda del Rey, Madrid, Spain
E-mail: frubio@icv.csic.es

It has been well established that certain parameters

affect the morphology of zirconium oxides obtained
by hydrolysis and polymerization reactions of
zirconium alkoxides [1]. Yoldas has carried out an
important study of such parameters and concluded
that the type of alkyl group in the alkoxide,
water=alkoxide ratio, molecular separation of species
and the reaction temperature affect the particle size
and the morphology of such zirconium oxides, and
therefore these parameters affect the sintering
behavior and crystalline transformation [2].
The hydrolysis of zirconium alkoxides leads to
preferential formation of oxo and aquo groups rather
than true hydroxides [3]. It has been shown that the
oxide content of ZrO2 is close to 80% by weight,
regardless of the amount of water used during the
hydrolysis. This result is different than that of other
alkoxides such as silicon, aluminum and titanium
[1].
Zirconium alkoxides react rapidly with water in
accordance with these simplied reactions [4]:
Zr(OR)4 H2 O ! ZrO(OR)2 2R(OH)

(1)

2ZrO(OR)2 ! ZrO2 Zr(OR)4

(2)

where R is an alkyl group. Therefore, 1 mole Zr(OR)

reacts with 1 mole H2 O to give a half mole of ZrO2.
For a complete reaction, 2 moles of H2 O are
necessary [5]. Yoldas has shown the importance of
a controlled hydrolysis of zirconium alkoxides for
obtaining products with desired properties [2].
Zirconium alkoxides are used for obtaining ZrO2,
and they are widely used in conjunction with other
metal alkoxides (silicon, aluminum, titanium, etc.)
for obtaining glass bers, high-density refractory
bodies, thin lms, composites, catalysts and adsorbents [4]. In these cases, the hydrolysis of different
metal alkoxides are of different reaction rates, and
this result may allow precipitation of that hydroxide
at a faster reaction rate. Therefore, the hydrolysis
must not only be controlled, but it also must be
known. The infrared spectroscopy is a powerful
technique that allows one to follow the hydrolysis of
metal alkoxides [6, 7]. In this work, we used Fourier
transformation infrared (FTIR) spectroscopy to study
the hydrolysis of zirconium n-propoxide (ZrOPr),
the effects that produce different H2 O=alkoxides and
the alcohol=alkoxide ratios on such reactions.
The hydrolysis of ZrOPr was carried out in a
200 ml beaker coupled with a refrigerator, a mech0261-8028 # 1998 Kluwer Academic Publishers

anical stirrer, an addition burette and a hole for

sampling used for FTIR measurements. The total
volume used in all reactions was 100 ml. ZrOPr
(Fluka 70.0%), n-propanol (n-PrOH) (Fluka, 99.9%)
and water (distilled and deionized) were used as
starting materials. In this work, we studied the
inuence of both water:alkoxide molar ratio as a
function of alcohol:alkoxide molar ratios and
alcohol:alkoxide molar ratio as a function of
water:alkoxide molar ratios. Then, for a ratio of nPrOH:ZrOPr of 4:1, the ratios of H2 O:ZrOPr
studied were 1:1, 2:1, 3:1 and 4:1, and for a ratio of
H2 O:ZrOPr of 4:1, the ratios of n-PrOH:ZrOPr
studied were 4:1, 8:1, 16:1 and 32:1. In all cases, the
experimental procedure was identical: ZrOPr and
half of the corresponding volume of n-PrOH were
mixed in the reaction beaker, and the remaining nPrOH was mixed with the corresponding H2 O in a
different beaker; both solutions were stirred for 2 h
at the reaction temperature (25  0:2 8C). Both
beakers were sealed to avoid alcohol evaporation
as well as hydrolysis of ZrOPr due to room
humidity. After this time, the H2 O=n-PrOH solution
was transferred to the addition burette maintained
constantly at the reaction temperature, and for 2 h
this solution was added dropwise to the reacting
solution while a vigorous stirring was maintained.
We used the same parent alcohol (n-PrOH) to avoid
ester interchange reactions [3]. During the addition
process, small volumes of reactants were extracted
by a liquid microsyringe (50 l) and placed between
two infrared transparent crystals; the corresponding
spectra were recorded. Ten scans were used in each
measurement, and the background was subtracted in
all cases. An FTIR spectrophotometer (Perkin-Elmer,
Model 1760x) was used with a resolution of 2 cm1 .
The spectra were stored in a computer and then
deconvoluted in the corresponding IR bands assuming a Gaussian prole for each band; these bands
were characterized by the position (wave number),
half width and intensity.
FTIR spectra of ZrOPr, n-PrOH and a mixture of
ZrOPr=n-PrOH are shown in Fig. 1a. Because Zr
OPr is a crystalline solid, it is necessary to dissolve
it in a small amount of n-PrOH to obtain a liquid
[3]. The amount of this alcohol may be observed in
the purity of the ZrOPr used (70.0%). As can be
observed in Fig. 1a, this result is in accordance with
the presence of IR bands of n-PrOH in the spectrum
of ZrOPr. Three spectral regions may be observed
1839

TRANSMITTANCE (a.u.)

TRANSMITTANCE (a.u.)

n-PrOH

Zr-OPr

1153 cm21
4000
(a)

3400

2800

2200

1600

1000

400

WAVENUMBER (cm21)

1200
(b)

1150
1100
1050
WAVENUMBER (cm21)

1000

Figure 1 (a) Infrared spectra of raw materials in the spectral range of 4000400 cm1 where (1) ZrOPr; (2) n-PrOH; and (3) starting sol, (b)
infrared spectra of raw materials in the spectral range of 12001000 cm1 .

1840

(a)

1153 cm21

(b)
TRANSMITTANCE (a.u.)

in the ZrOPr spectrum. Between 40001400 cm1

OH and CH stretching and bending vibrations
occur. Both IR vibrations do not give any information about the hydrolysis of the zirconium alkoxide.
Between 1300800 cm1 , the ZrOC stretching in
ZrOPr and the CO stretching in n-PrOH occur.
Between 800400 cm1 , the corresponding bending
vibrations of ZrOC and CO bonds appear [8].
Because in this low wave number region the out-ofplane OH bending of n-PrOH appears, the 1300
800 cm1 region is the most important region in
which to study the hydrolysis of ZrOPr.
In the 1200800 cm1 spectral region, the IR
bands corresponding to ZrOPr appear and are
located at 1153, 1132, 1108, 1082 and 1006 cm1
(clearly shown in Fig. 1b in the spectral range 1200
1000 cm1 ); these bands are associated with the Zr
OC stretching. On the other hand, the n-PrOH
gives 8 IR bands lying at 1099, 1069, 1056, 1017,
970, 907, 888 and 860 cm1 . At 1127 cm1 there
also appears a slight shoulder. To obtain complete
information about the hydrolysis process, we rst
deconvoluted the spectra of ZrOPr, n-PrOH and a
mixture of ZrOPr=n-PrOH. In this step, the
unambiguously assigned IR bands of ZrOPr and
n-PrOH were obtained; such bands were characterized by the three parameters of a Gaussian band;
intensity, half-width and wave number. The error
between the deconvoluted and experimental spectra
was lower than 3% in all cases. The study of the
hydrolysis of ZrOPr was carried out by analyzing
the evolution of these three parameters, which are
used to obtain the integrated intensities of the
corresponding IR bands. Because the ZrOPr bands
located at 1132, 1108, 1082 and 1006 cm1 are very
close to those of n-PrOH, the band that can be
studied is the well-dened, very strong band lying at
1153 cm1 (Fig. 1b).
Spectra corresponding to the hydrolysis of ZrOPr
at different reaction times are shown in Fig. 2. It can

(c)

(d)

(e)
(f)

1200

1100

1000

900

800

WAVENUMBER (cm21)
Figure 2 FTIR spectra corresponding to the hydrolysis of ZrOPr
(molar ratio of H2 O:ZrOPr 1:1) at different reaction times where
(a) 2 min; (b) 10 min; (c) 30 min; (d) 60 min; (e) 90 min; and
(f) 120 min.

be clearly observed that the ZrOPr bands mentioned above disappear, and the long time spectrum
only shows the bands corresponding to n-PrOH.
Fig. 3 shows the evolution of the 1153 cm1 band as
a function of the hydrolysis time for different
H2 O:ZrOPr molar ratios. As the water:alkoxide
ratio decreases, the rate of hydrolysis also decreases,
as may be expected. It can be observed in Fig. 3 that
for H2 O:ZrOPr ratios of 4:1 and 3:1, the hydrolysis
of ZrOPr is completed in 2 and 24 h, respectively.
For H2 O:ZrOPr ratios of 2:1 and 1:1, it is possible
to extrapolate times from the experimental curve and
the obtained hydrolysis that are 238 and 23.106 days,
respectively.
In accordance with Reactions 1 and 2, 2 moles of
H2 O are needed for a complete hydrolysis of 1 mole

1:1

INTEGRATED AREA (a.u.)

1.10

2:1
3:1
0.08

4:1

0.06

0.04

0.02

0.00
0

ln (TIME (min.))

Figure 3 Time evolution of the integrated area for the 1153 cm1 band
during hydrolysis of ZrOPr for different molar ratios of H2 O:ZrOPr.

of ZrOPr. Therefore, the only H2 O:Zr-OPr ratio

used in this study that does not give such complete
hydrolysis is the 1:1 ratio. The obtained hydrolysis
times are in accordance with the ratios used. Bradley
and Carter [5] have shown that the hydrolysis of Zr
OPr gives three kinds of polymers: unsolvated
trimeric species, solvated dimeric species and
monomeric solvated species. For H2 O:alkoxide ratios
lower than one, trimeric and dimeric species are
present in the early stages of hydrolysis. For
H2 O:alkoxide ratios higher than one, solvation
becomes more effective and polymers based on
dimeric and monomeric species are present. Thereafter, polymers based in monomeric species become
increasingly signicant as the H2 O:alkoxide ratio is
increased. Bradley and Carter stopped their hydrolysis study for a water:alkoxide ratio of 1.814 due to
the presence of residual water in the system, which
also suggests the presence of ZrOH groups. A wide
range of water:alkoxide ratios are normally used
[1, 2], however, and it is necessary to study such
hydrolysis ratios. Fig. 3 shows that it is possible to
study the hydrolysis of ZrOPr even when ZrOH
groups are formed.
It is also observed in Fig. 3 that the higher
hydrolysis rate occurs during the addition of the
H2 O=alcohol solutions, i.e., the rst 2 h, and this
reaction rate increases as the H2 O:alkoxide ratio
increases. This result shows that, as is known, the
hydrolysis of the zirconium n-propoxide is instantaneous.
Yoldas [2] has shown the inuence of the
H2 O:alkoxide and alcohol:alkoxide ratios in the
properties of zirconium oxide materials obtained
from Zralkoxides. We have shown the different
hydrolysis rates found for different H2 O:alkoxide
ratios, and now we are going to study the effect of
the alcohol:alkoxide ratio or, in accordance with
Yoldas, the molecular separation [9]. When for a
given H2 O:alkoxide ratio, the alcohol:alkoxide ratio
decreases, the concentration of the solution in-

creases, and therefore the molecular separation also

decreases giving as a result a higher possibility of
encounters between reacting molecules. If these
molecules have hydroxyl groups in their terminal
bonds, a condensation reaction can take place where
H2 O is eliminated and a metaloxygenmetal bond
is formed [10]. On the other hand, when the terminal
bonds are alkyl groups, the encounters between
molecules cannot lead to chemical reactions. In
accordance with Reactions 1 and 2 in the case of
zirconium alkoxides, it is not necessary that terminal
groups be hydroxyls. To study the inuence of the
alcohol:alkoxide ratio in the hydrolysis rate of Zr
OPr, we only studied the H2 O:ZrOPr molar ratio of
4:1, and, as we have noted for this ratio, the
hydrolysis of ZrOPr is completed in 2 h. The nPrOH:ZrOPr ratios studied were 4:1, 8:1, 16:1 and
32:1.
Fig. 4 shows the FTIR spectra of the hydrolysis of
ZrOPr when the alcohol:alkoxide ratio is 32 as a
function of the reaction time. These spectra are very
close to those shown in Fig. 2, obtained for a lower
alcohol:alkoxide ratio. The spectral deconvolution
gave the results shown in Fig. 5 where the evolution
of the ZrOC band located at 1153 cm1 could be
observed. The evolution of this band has the same
behavior for the different n-PrOH:ZrOPr ratios
studied. This result shows that when an excess of
water is used for the hydrolysis of ZrOPr, the
hydrolysis rate does not depend on the dilution of
the solution. Yoldas [2] has also shown that for a
given water:zirconium alkoxide ratio, the ZrO2
powders obtained for different alcohol:alkoxide
ratios have similar densication curves due to a
high degree of resistance to monoclinic-tetragonal
transformation. The results obtained in this work are
in accordance with those of Yoldas.
In summary, this work has shown the possibility of
studying the hydrolysis of zirconium n-propoxide by
(a)

1153 cm21

(b)
TRANSMITANCE (a.u.)

1.12

(c)
(d)

(e)

(f)

1200

1100

1000

900

800

WAVENUMBER (cm21)
Figure 4 FTIR spectra corresponding to the hydrolysis of ZrOPr
(molar ratio of n-PrOH:ZrOPr 32:1) at different reaction times
where (a) 2 min; (b) 10 min; (c) 30 min; (d) 60 min; (e) 120 min; and
(f) 202 min.

1841

if a water-rich environment is used for the hydrolysis

of the zirconium n-propoxide, the hydrolysis does
not depend on the dilution of the alkoxide solution.

INTEGRATED AREA (a.u.)

0.30

0.25

4:1
8:1

0.20

16:1
32:1

Acknowledgments
The authors wish to thank the Comision Interministerial de Ciencia y Tecnologia of Spain for nancial
support under Project MAT96-0564.

0.15

0.10

References

0.05
0.00
0

10

12

ln (TIME (min.))

1. B . E . YO L D A S , J. Amer. Ceram. Soc. 65 (1982) 387.

2. Idem., J. Mater. Sci. 21 (1986) 1080.
3. D. C . B R A D L E Y and W. WA R D L AW, J. Chem. Soc. 73

(1951) 280.

4. K . S . M A Z D I YA S N I , C . T. LY N C H and J. S . S M I T H ,

J. Amer. Ceram. Soc. 48 (1965) 372.

Figure 5 Time evolution of the integrated area for the 1153 cm1 band
during hydrolysis of ZrOPr for different molar ratios of n-PrOH:Zr
OPr.

5. D. C . B R A D L E Y and D. G . C A RT E R , Con. J. Chem. 39

means of FTIR spectroscopy. By a conventional

deconvolution procedure, the evolution of the Zr
OC band is followed, and their integrated intensity
is used for determining the hydrolysis degree of the
zirconium alkoxide. The hydrolysis rate depends
strongly on the water:alkoxide molar ratio, being
higher as such ratio is increased. On the other hand,

7. M . C . M AT O S , L . M . I L H A R C O and R . M . A L M E I D A ,

1842

(1961) 1434.

6. F. R U B I O , J. R U B I O and J. L . O T E O , Spectroscopy Lett.

31 (1998) 199.

J. Non-Cryst. Solids. 147148 (1992) 232.

8. R . T. C O N L E Y, ``Infrared Spectroscopy'' Ed. Alhambra.

9. B . E . YO L D A S , J. Non-Cryst. Solids 51 (1982) 105.
10. Idem., ibid. 82 (1986) 11.

Received 9 July
and accepted 22 July 1998