1822 Ind. Eng. Chem. Res.

2001, 40, 1822-1831

Kinetics and Mechanism of Cyclohexanol Dehydration in

High-Temperature Water
Naoko Akiya and Phillip E. Savage*
Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109-2136

We examined cyclohexanol dehydration in pure water at temperatures of 250, 275, 300, 350,
and 380 °C with water densities ranging from 0.08 to 0.81 g/cm3. Under these conditions,
cyclohexanol dehydrates readily in the absence of added catalysts to form cyclohexene as the
major product. The most abundant minor products are 1- and 3-methyl cyclopentenes. The
reaction rate and product distribution at 380 °C show a remarkable sensitivity to the water
density. At low densities, the reaction is slow, and cyclohexene is the only product. At high
densities, the reaction is nearly complete, and methyl cyclopentenes appear along with
cyclohexene. The experimental results implied a reaction mechanism that comprises two
pathways: (1) reversible cyclohexanol dehydration to form cyclohexene through an E2 mecha-
nism, and (2) subsequent cyclohexene protonation to form the cyclohexyl cation, which rapidly
rearranges to form methyl cyclopentyl cations, which then lose a proton to form methyl
cyclopentenes. A kinetics model based on the proposed mechanism was able to predict the striking
effect of the water density on the product yields at 380 °C and, thereby, to demonstrate that the
proposed mechanism captures the trends in the experimental data. An analysis of mechanistic
issues regarding cyclohexanol dehydration in high-temperature water (HTW) revealed three
roles for water. Water participates in elementary reaction steps as a reactant and as a product,
water is the source of the acid catalyst (H3O+), and water also drives the mechanism toward E2
by favoring, through solvation, the oxonium ion rather than the carbocation as the reaction
intermediate. This study provides further evidence that acid-catalyzed reactions can be
accomplished readily in HTW in the absence of added acid and that HTW has potential
applications in environmentally benign industrial chemistry.

Introduction temperature of 375 °C for 20 min, but that the addition

High-temperature water (HTW), including both liquid
water (T > ∼200 °C) and supercritical water (T > 374
°C, P > 218 atm), is attracting increased attention as a
medium for organic chemistry.1,2 Water near its critical
point exhibits many properties that are distinctly dif-
ferent from those of ambient liquid water, such as high
solubility for organic and gaseous compounds, high ion
product, low dielectric constant, and weak hydrogen
bonds. These and other properties of HTW vary over a
wide range of values as a function of temperature and
pressure. This strong temperature and pressure depen-
dence of the properties provides opportunities to tune
the reaction environment to optimal conditions for the
chemical transformation of interest.
The reactions of cyclohexanol and its products in
HTW provide an opportunity for the convenient exami-
nation of several different types of chemical transforma-
tions (dehydration, dehydrogenation, aromatization,
rearrangement) in HTW. As such, it is a good model
system. The goal of the study described herein is to
obtain kinetics data for cyclohexanol dehydration in
HTW and to use them to gain mechanistic insights. This
study of cyclohexanol dehydration is the first step
toward a better understanding of cyclohexanol chemis-
try in HTW.
Crittendon and Parsons3 reported that cyclohexanol
is unreactive in pure HTW at a nominal reaction
* Corresponding author. E-mail: psavage@umich.edu.
Phone: 734 764-3386. Fax: 734 763-0459.
10.1021/ie000964z CCC: $20.00 © 2001 American Chemical Society
Published on Web 03/27/2001
of a solid metal catalyst (PtO2), acid (HCl), or base (NH4-
OH) leads to a variety of products. Kuhlmann et al.,4
on the other hand, reported that the dehydration to
cyclohexene occurs readily at 300 °C after 60 min
without the deliberate addition of any catalysts. They
also reported that cyclohexene is the only product
observed in their experiments. They speculated that the
dehydration was acid-catalyzed, with H3O+ generated
from the dissociation of water being the likely catalyst.
This hypothesis is consistent with the work by Antal
and co-workers, who showed that tert-butyl alcohol
dehydration occurs in pure HTW at 250 °C without the
addition of any catalyst.5,6
Antal and co-workers have been very active in the
field of alcohol (but not cyclohexanol) dehydration in
HTW. They have reported mechanisms and kinetics for
the dehydration of ethanol, 1- and 2-propanol, and tert-
butyl alcohol to the corresponding alkenes.5-8 The
quantitative kinetics data have facilitated the concep-
tual design and economic evaluation of chemical pro-
cesses based on the new chemistry in HTW.9,10
In contrast to the kinetics and mechanistic informa-
tion available for the dehydration of the C2-C4 alcohols
in HTW, there are no kinetics or mechanisms available
for the dehydration of cyclohexanol in HTW. Moreover,
the limited data that are available are contradictory.
The present investigation of cyclohexanol dehydration
in HTW resolves this conflict and fills this gap in the
literature on alcohol dehydration in HTW.

Experimental Section
We performed experiments at different batch holding
times, temperatures, and water densities to determine
the effects of these variables on the product yields and
reaction rates. The conditions examined are tempera-
tures of 250, 275, 300, 350, and 380 °C, times ranging
from 15 to 180 min, and water densities ranging from
0.08 g/cm3 (4.7 mol/L) to 0.81 g/cm3 (45 mol/L). The
cyclohexanol concentration was 0.3 mol/L (at reaction
conditions) in all experiments.
We used batch reactors fashioned from nominal
1/ -in. stainless steel Swagelok tube fittings (one port
4 been measured to be 2-3 min,13 which is short com-
connector and two caps). The reactor volume is 0.59 cm3.
Preliminary experiments indicated that the use of new
reactors (as received) produced results that differ from
those obtained with reactors that have been used at
least once. New reactors led to higher cyclohexanol
conversions and the formation of additional (unidenti-
fied) byproducts. To eliminate these effects, we seasoned
the new reactors prior to use. The reactors were loaded
with water and heated in a sand bath at 300 °C for 30
min, after which they were cooled gradually at ambient
conditions. The reactors were then washed with acetone
and dried. All of the data reported herein were obtained
from seasoned reactors.
The reactors were loaded with a carefully measured
amount of cyclohexanol and placed in a glovebox filled
with purified helium. In the same glovebox, we vigor-
ously bubbled helium through distilled and deionized
water to eliminate dissolved oxygen and carbon dioxide,
gases that might influence the reactions. The reactors
were then loaded with a measured amount of deaerated
water and sealed under a stream of helium in the
glovebox. In some experiments, cyclohexene was the
reactant. Because cyclohexene is very volatile, it was
added to the reactor in the glovebox immediately after
the reactor was loaded with deaerated water. All
chemicals were obtained commercially in high purity
and used as received.
The amount of water added to the reactor set the
volume of the vapor phase at subcritical reaction tem-
peratures and the water density at supercritical reaction
temperatures. For experiments at subcritical tempera-
tures (250-350 °C), we chose water loadings that
ensured that the reactors would be nearly filled with a
single liquid phase. The required water loading for each
temperature was determined by taking the density of
the reactor contents to be that of pure liquid water at
the same temperature.11
Because cyclohexanol and cyclohexene are both in-
soluble in water at room temperature, we were con-
cerned with the possibility that two immiscible liquid
phases might be present in the reactor during experi-
ments at subcritical temperatures. Kuhlmann et al.4
ascertained experimentally the solubility of cyclohexanol
(and other organic reagents) in water up to 100 °C and
concluded that mixtures that are 0.3-0.5 M in organics
at room temperature are homogeneous at 300 °C. We
conducted our experiments at temperatures of 250-350
°C and cyclohexanol concentrations of 0.4-0.6 M at
room temperature. To probe further the solubility of
cyclohexanol and cyclohexene in HTW at the tempera-
tures and concentrations used in our experiments, we
performed calculations with the chemical process simu-
lator ASPEN PLUS.12 We used the RK-ASPEN ther-
mophysical properties model, which is suitable for a
mixture of polar and nonpolar compounds at high
Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001 1823
temperatures and pressures. Simulations of cyclohex-
anol in water and cyclohexene in water predicted a
single liquid phase at the experimental conditions.
Judging from these calculations and the experimental
results of Kuhlmann et al., we believe that the reactor
contents were always homogeneous under the reaction
conditions used.
The loaded and sealed reactors were placed in a
preheated, fluidized sand bath (Techne SBL-2) set at
the desired reaction temperature. The sand bath was
kept isothermal to within (1 °C with a temperature
controller (Techne TC-8D). The reactor heat-up time has
pared to the typical batch holding times used in this
study. Upon reaching the desired holding time, the
reactors were removed from the sand bath, and the
reaction was quenched immediately by immersing the
reactors in a cold water bath. The reactor temperature
dropped to room temperature in less than 1 min. The
reactors were further cooled in a freezer for up to 1 h to
condense any volatile components. The reactors were
opened, and the contents were recovered through the
addition of acetone. It was essential to complete this last
step quickly to minimize the loss of volatile compounds.
We used two Hewlett-Packard model 5890 gas chro-
matographs equipped with either a flame ionization
detector or a mass spectrometric detector to analyze the
reaction products. The sample constituents were sepa-
rated with a Hewlett-Packard HP-5 fused silica capillary
column. Product identification was accomplished by
comparing retention times with those of authentic
standards and by inspecting mass spectra. The number
of moles of each product present was obtained from the
chromatographic analyses with experimentally deter-
mined detector response factors for each component. We
used methyl cyclohexane as the standard. Product molar
yields were then computed by dividing the number of
moles of product formed by the number of moles of
cyclohexanol initially loaded into the reactor.
Experimental Results
Table 1 and Figures 1-7 present the experimental
product yields for cyclohexanol dehydration in pure
HTW. The uncertainties reported are 95% confidence
intervals determined from multiple (typically 5-10)
runs under nominally identical reaction conditions.
Under the conditions employed in this study, cyclohex-
anol readily dehydrates to form cyclohexene in HTW
without any added catalyst. The minor products include
1- and 3-methyl cyclopentene, with yields as high as 22
and 6%, respectively. Our identification of 3-methyl
cyclopentene remains tentative because the mass spec-
trum for this compound is also consistent with the
fragmentation pattern for 2-methyl cyclopentene. Nev-
ertheless, we are confident that this product is a methyl
cyclopentene. Methylene cyclopentane formed in some
experiments but in yields of less than 1%. The combined
yields of 1- and 3-methyl cyclopentene and methylene
cyclopentane appear as “methyl cyclopentenes” in the
figures and in Table 1. Cyclohexanone was also present
but in yields that were typically less than 1%. The
highest cyclohexanone yields (2-3%) were obtained at
380 °C and water densities of 0.20 g/cm3 and lower. The
carbon balance generally exceeded 90%, and the lowest
value was 79%. The carbon loss showed no notable trend
with changes in temperature or water density. Back-
ground experiments revealed that the failure to achieve
1824 Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001

Table 1. Experimental Molar Yields for Cyclohexanol Dehydration in Pure HTWa

T (°C) [H2O]0 (g/cm3) time (min) cyclohexanol cyclohexene methyl cyclopentenesb cyclohexanoneb
250 0.81 30 0.86 ( 0.15 0.077 ( 0.040 nd nd
60 0.70 ( 0.03 0.085 ( 0.043 nd nd
90 0.68 ( 0.08 0.20 ( 0.07 nd nd
120 0.70 ( 0.07 0.23 ( 0.07 nd nd
180 0.63 ( 0.11 0.24 ( 0.06 nd nd
275 0.76 15 0.71 ( 0.08 0.12 ( 0.04 nd nd
30 0.58 ( 0.09 0.27 ( 0.07 nd nd
45 0.43 ( 0.06 0.38 ( 0.06 nd nd
60 0.43 ( 0.08 0.41 ( 0.08 nd nd
90 0.40 ( 0.07 0.50 ( 0.07 nd nd
300 0.73 15 0.63 ( 0.08 0.33 ( 0.07 nd 0.001 ( 0.001
30 0.32 ( 0.07 0.59 ( 0.07 0.001 ( 0.001 0.001 ( 0.001
45 0.34 ( 0.08 0.64 ( 0.08 0.002 ( 0.001 0.001 ( 0.001
60 0.27 ( 0.07 0.67 ( 0.06 0.003 ( 0.001 0.002 ( 0.002
90 0.18 ( 0.03 0.71 ( 0.05 0.005 ( 0.001 0.002 ( 0.001
350 0.59 15 0.075 ( 0.015 0.80 ( 0.06 0.013 ( 0.003 0.004 ( 0.002
30 0.071 ( 0.006 0.80 ( 0.03 0.013 ( 0.003 0.003 ( 0.003
45 0.063 ( 0.023 0.82 ( 0.07 0.022 ( 0.012 0.002 ( 0.003
60 0.076 ( 0.013 0.76 ( 0.04 0.033 ( 0.006 0.004 ( 0.000
90 0.074 ( 0.019 0.78 ( 0.05 0.033 ( 0.014 0.003 ( 0.003
380 0.08 60 0.86 ( 0.07 0.070 ( 0.073 nd 0.021 ( 0.032
0.14 30 0.76 ( 0.08 0.12 ( 0.08 nd 0.004 ( 0.006
45 0.75 ( 0.08 0.14 ( 0.02 nd 0.011 ( 0.010
60 0.69 ( 0.09 0.15 ( 0.04 nd 0.020 ( 0.014
75 0.68 ( 0.06 0.17 ( 0.03 nd 0.007 ( 0.014
90 0.65 ( 0.08 0.28 ( 0.06 nd 0.021 ( 0.009
0.17 30 0.64 ( 0.05 0.23 ( 0.09 nd 0.007 ( 0.007
45 0.60 ( 0.10 0.28 ( 0.08 nd 0.010 ( 0.010
60 0.57 ( 0.07 0.34 ( 0.05 0.001 ( 0.001 0.009 ( 0.019
75 0.58 ( 0.08 0.38 ( 0.07 nd 0.011 ( 0.006
90 0.56 ( 0.07 0.34 ( 0.09 nd 0.012 ( 0.005
0.20 30 0.52 ( 0.06 0.35 ( 0.06 nd 0.006 ( 0.006
45 0.49 ( 0.09 0.46 ( 0.08 nd 0.012 ( 0.004
60 0.33 ( 0.09 0.58 ( 0.07 nd 0.028 ( 0.021
75 0.26 ( 0.05 0.68 ( 0.07 0.001 ( 0.002 0.009 ( 0.003
90 0.21 ( 0.05 0.71 ( 0.07 0.001 ( 0.002 0.011 ( 0.007
0.25 60 0.041 ( 0.055 0.91 ( 0.06 0.010 ( 0.003 0.010 ( 0.019
0.34 15 0.032 ( 0.004 0.87 ( 0.03 0.009 ( 0.001 0.005 ( 0.006
30 0.025 ( 0.010 0.87 ( 0.09 0.012 ( 0.003 0.004 ( 0.005
45 0.026 ( 0.004 0.86 ( 0.04 0.013 ( 0.002 nd
60 0.032 ( 0.016 0.87 ( 0.05 0.015 ( 0.013 0.013 ( 0.028
0.51 15 0.045 ( 0.010 0.80 ( 0.04 0.026 ( 0.011 0.008 ( 0.010
30 0.042 ( 0.006 0.81 ( 0.06 0.035 ( 0.046 0.004 ( 0.011
45 0.048 ( 0.016 0.84 ( 0.03 0.052 ( 0.024 0.008 ( 0.004
60 0.046 ( 0.006 0.82 ( 0.05 0.061 ( 0.032 0.009 ( 0.004
90 0.041 ( 0.009 0.74 ( 0.07 0.12 ( 0.05 0.006 ( 0.003
0.68 15 0.068 ( 0.007 0.82 ( 0.07 0.055 ( 0.014 nd
30 0.068 ( 0.013 0.74 ( 0.09 0.078 ( 0.025 nd
45 0.064 ( 0.010 0.70 ( 0.11 0.12 ( 0.04 nd
60 0.059 ( 0.007 0.60 ( 0.05 0.21 ( 0.01 0.005 ( 0.001
120 0.055 ( 0.018 0.48 ( 0.09 0.26 ( 0.08 0.006 ( 0.001
180 0.035 ( 0.013 0.48 ( 0.09 0.28 ( 0.04 0.001 ( 0.002
a [Cyclohexanol]0 ) 0.3 mol/L. b nd ) not detected.

Table 2. Molar Yields of Individual Methyl yields of methylene cyclopentane were always an order
Cyclopentenes at 380 °C and 0.68 g/cm3 of magnitude smaller than the yields of the 1- and
time 1-methyl 3-methyl methylene 3-methyl cyclopentenes.
(min) cyclopentene cyclopentene cyclopentane Figures 1-3 show the temporal variations of the
15 0.038 ( 0.012 0.016 ( 0.002 0.001 ( 0.001 product yields for cyclohexanol dehydration in HTW at
30 0.058 ( 0.021 0.020 ( 0.005 nd 250, 300, and 350 °C, respectively. At the lower tem-
45 0.092 ( 0.027 0.027 ( 0.009 0.001 ( 0.002
60 0.17 ( 0.01 0.037 ( 0.002 0.002 ( 0.001
peratures, the cyclohexanol yield decreases continuously
120 0.21 ( 0.06 0.045 ( 0.014 0.004 ( 0.003 with time, and this change is accompanied by a corre-
180 0.22 ( 0.04 0.057 ( 0.008 0.003 ( 0.002 sponding increase in the cyclohexene yield. At 250 °C,
cyclohexene is the only product, whereas at 300 °C,
100% carbon balance is most likely due to losses of methyl cyclopentenes appear in a low yield that in-
volatile products (cyclohexene and methyl cyclopentenes) creases with time. At 350 °C, the conversion of cyclo-
prior to analysis. hexanol is rapid and appears to reach an equilibrium
Table 2 shows the product yields for individual methyl value after no more than 15 min of reaction time. The
cyclopentenes at 380 °C and 0.68 g/cm3, the reaction cyclohexene yield, on the other hand, reaches 80% after
conditions for which the yields of these minor products 15 min but then gradually decreases at longer times.
were the highest. 1-Methyl cyclopentene always had the This decrease in the cyclohexene yield is accompanied
highest yield, followed by 3-methyl cyclopentene. The by a corresponding increase in the methyl cyclopentenes

Figure 1. Yields of cyclohexanol and cyclohexene at T ) 250 °C
and [H2O]0 ) 0.81 g/cm3.
Figure 2. Yields of cyclohexanol, cyclohexene, and methyl cyclo-
pentenes at T ) 300 °C and [H2O]0 ) 0.73 g/cm3.
Figure 3. Yields of cyclohexanol, cyclohexene, and methyl cyclo-
pentenes at T ) 350 °C and [H2O]0 ) 0.59 g/cm3.
yield. Taken collectively, Figures 1-3 show that in-
creasing temperature increases the rate of cyclohexanol
disappearance and the selectivity toward methyl cyclo-
pentenes.
Figures 4-7 show the temporal variations of the
product yields at 380 °C and water densities of 0.14,
0.20, 0.51, and 0.68 g/cm3, respectively. A remarkable
influence of the water density on the yields is evident.
At water densities of 0.14 and 0.20 g/cm3, cyclohexene
is the only product observed. The cyclohexanol yield
decreases continuously with time, and this decrease is
accompanied by a corresponding increase in the cyclo-
hexene yield. At water densities of 0.51 and 0.68 g/cm3,
we observe a low and nearly time-invariant cyclohexanol
yield, a maximum in the cyclohexene yield, and the
appearance of and a steady increase in the yield of
methyl cyclopentenes. These data show that higher
water densities facilitate the conversion of cyclohexanol
Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001 1825
Figure 4. Yields of cyclohexanol and cyclohexene at T ) 380 °C
and [H2O]0 ) 0.14 g/cm3.
Figure 5. Yields of cyclohexanol and cyclohexene at T ) 380 °C
and [H2O]0 ) 0.20 g/cm3.
Figure 6. Yields of cyclohexanol, cyclohexene, and methyl cyclo-
pentenes at T ) 380 °C and [H2O]0 ) 0.51 g/cm3.
and the formation of methyl cyclopentenes. At these
more liquidlike densities (0.51 and 0.68 g/cm3), the
methyl cyclopentenes yields at 380 °C are substantially
higher than those observed at lower temperatures. This
result is consistent with an increase in temperature
shifting the selectivity toward methyl cyclopentenes.
We also conducted experiments in the absence of
water at 300 and 380 °C for 60 min. The cyclohexanol
conversion was 8.2 ( 2.0% at 300 °C and 8.5 ( 1.3% at
380 °C. The low cyclohexanol conversion in the absence
of water confirms that water plays an important role
in the reaction of cyclohexanol. Cyclohexanone was the
major product at both temperatures, but small quanti-
ties of cyclohexene and methyl cyclopentenes were also
produced. At 300 °C, the product yields were 3.5 ( 0.6%
for cyclohexanone and 0.2 ( 0.1% for cycloalkenes. At
380 °C, the product yields were 9.5 ( 1.1% for cyclo-
hexanone and 0.5 ( 0.3% for cycloalkenes. Cyclohex-
1826 Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001
Figure 7. Yields of cyclohexanol, cyclohexene, and methyl cyclo-
pentenes at T ) 380 °C and [H2O]0 ) 0.68 g/cm3.
anone likely forms as a result of thermally activated
free-radical dehydrogenation of cyclohexanol. The much
lower yields of cyclohexanone from experiments in water
indicate that this pathway is either suppressed in HTW
or supplanted by the faster dehydration pathway.
Cyclohexanol dehydration and formation of methyl
cyclopentenes most likely occur by means of ionic
chemistry.
We conducted experiments with cyclohexene in HTW
to shed light on the fate of cyclohexene after its
formation via cyclohexanol dehydration. All experiments
were conducted for the batch holding time of 60 min.
The cyclohexene conversion was 21.6 ( 9.6% at 300 °C
and 39.3 ( 5.7% at 380 °C. At 300 °C, the product yields
were 14.3 ( 6.1% for cyclohexanol and 1.7 ( 1.6% for
methyl cyclopentenes. At 380 °C and 0.34 g/cm3 of
water, the product yields were 2.7 ( 0.5% for cyclohex-
anol and 15.3 ( 6.0% for methyl cyclopentenes. These
results indicate that two reaction pathways are avail-
able to cyclohexene in HTW. One pathway is hydration
to generate cyclohexanol, and the other pathway is
rearrangement to form methyl cyclopentenes. The ob-
served product distribution indicates that hydration is
the preferred pathway at 300 °C whereas rearrange-
ment is the preferred pathway at 380 °C and 0.34 g/cm3.
The higher yield of methyl cyclopentenes at higher
temperature is consistent with the results obtained with
cyclohexanol as the reactant.
Effect of Metal Surface. Even though the reactors
were treated hydrothermally prior to use, there remains
a possibility that the treated metal surfaces impose
some catalytic or surface effects on the reaction. We
investigated such wall effects by performing cyclohex-
anol dehydration experiments under nominally identical
conditions but in reactors with varying surface-to-
volume ratios. This variation was achieved by sepa-
rately adding 7 and 22 mg of stainless steel filings to
the reactors. Reactions were carried out at 380 °C, 0.34
g/cm3 of water, and 60 min of batch holding time. In
the absence of stainless steel filings, the product yields
were 3.2 ( 1.6% for cyclohexanol, 86.9 ( 5.0% for
cyclohexene, and 1.5 ( 1.3% for methyl cyclopentenes.
With 7 mg of stainless steel filings, the product yields
were 3.2% for cyclohexanol, 85.9% for cyclohexene, and
3.0% for methyl cyclopentenes. With 22 mg of stainless
steel filings, the product yields were 4.7% for cyclohex-
anol, 85.9% for cyclohexene, and 1.0% for methyl cyclo-
pentenes. It is clear that the product yields are insen-
sitive to the presence of the added stainless steel filings.
These results are consistent with negligible catalytic
effects due to the reactor walls.
Figure 8. Yields of cyclohexanol, cyclohexene, and methyl cyclo-
pentenes at T ) 300 °C and [H2O]0 ) 0.73 g/cm3 with deaerated
(solid line) and untreated (dashed line) water.
Effect of Dissolved Air. We also examined the
effects of dissolved air on the reaction rates at 300 °C.
Dissolved oxygen can oxidize the organic compounds,
and dissolved carbon dioxide forms carbonic acid, which
might catalyze dehydration. Reactors loaded with cy-
clohexanol and unsparged (hence not deaerated) water
were placed under a stream of purified helium and
sealed in the helium-filled glovebox to displace air from
the reactor headspace.
Figure 8 shows the product yields as functions of time
for reactions at 300 °C in deaerated and unsparged
water. The uncertainties from the experiments with
unsparged water are larger because fewer replicates
were done at each batch holding time. The cyclohexanol
conversion in Figure 8 is consistently higher in the
presence of dissolved air, and this rate-enhancing effect
appears to be stronger at shorter reaction times. For
example, the cyclohexanol conversions in the presence
of dissolved air are 66% at 15 min and 85% at 90 min,
whereas in deaerated water, they are 37% and 82%,
respectively.
The greater reaction rate is probably due to the lower
pH produced by the dissolved CO2. Regardless of the
cause of this effect, however, it is clear that distilled
and deionized water exposed to ambient air contained
sufficient quantities of dissolved gases to have measur-
able effects on the reaction kinetics. Therefore, for
kinetics and mechanistic studies, it is important to
remove dissolved air from water prior to use, even
though this necessity is not universally acknowledged
in the studies of acid-catalyzed reactions in HTW found
in the literature. From a practical point of view,
however, the presence of dissolved air might be desir-
able precisely because of this rate enhancement.
Comparison with Previous Experiments. The
experimental results in Table 1 are in apparent conflict
with those of Crittendon and Parsons,3 who reported
no reaction for cyclohexanol after 20 min in HTW (0.33
g/cm3) at 375 °C. We observed 97% conversion after 15
min for reaction in HTW (0.34 g/cm3) at 380 °C. This
difference in the observed cyclohexanol reactivity can
be easily explained, however. The reactor that Critten-
don and Parsons used had a much larger thermal mass
than did the reactors that we used. As a result, the time
required to heat their reactor from room temperature
to 375 ×bcC was much longer (>1 h). In fact, 20 min
after being placed in a tube furnace at 375 ×bcC, the
temperature inside their reactor was only 268 °C.14 Of
course, the average temperature of the reactor contents
during the experiments would be much lower than 268

°C. In contrast, the heat-up time is very short (2-3 min)
during our experiments. Another important distinction
is that, under the conditions employed by Crittendon
and Parsons, a large fraction of the reactor volume was
occupied by a vapor phase, so cyclohexanol could parti-
tion between the vapor and liquid phases. This phase
behavior could influence the reactivity. In contrast, we
conducted all of our experiments at subcritical temper-
atures in such a way that the reactor was nearly filled
with a single liquid phase. We speculate that the long
heat-up time and the partitioning of cyclohexanol
between the vapor and liquid phases contributed to the
apparent lack of reactivity of cyclohexanol in pure HTW
reported by Crittendon and Parsons.
The facile formation of cyclohexene that we observe
in the absence of added catalysts is consistent with the
results of Kuhlmann et al.,4 who reported that cyclo-
hexanol dehydration occurred readily in HTW at 300
°C. They reported a cyclohexene yield of 33% at 60 min,
which is lower, however, than the 67% yield listed in
Table 1 for the same conditions. Kuhlmann et al. did
not report the formation of any other products. Thus,
the present results, which identify 1-methyl cyclopen-
tene and 3-methyl cyclopentene as byproducts at 300
°C, albeit in small quantities, are also not in complete
accord with the results of Kuhlmann et al.
Recall from the Experimental Section that we cooled
the reactors in a freezer after the experiments and
completed the product recovery step quickly to minimize
the loss of volatile compounds, i.e. cyclohexene and
methyl cyclopentenes. Exploratory experiments con-
ducted without cooling the reactors in the freezer and
with a longer time (by ∼2 min) taken for the product
recovery step resulted in much lower cyclohexene yields
(30% after 45 min and 36% after 75 min) and no
recovery of methyl cyclopentenes. These results are fully
consistent with those reported by Kuhlmann et al.
Therefore, the likely source of the difference between
the present results and those of Kuhlmann et al. is the
possible loss of volatile components during their experi-
ments.
The paragraphs above provide a means of reconciling
the apparently contradictory results that had been
published for cyclohexanol dehydration in HTW. The
discrepancies can be traced to the different experimental
procedures and apparatuses that were used.
Reaction Mechanism
Previous studies have shown that HTW has a suf-
ficiently high concentration of H3O+ and OH- ions that
some acid- and base-catalyzed organic reactions occur
in the absence of any added catalysts.5,6,15-17 Figure 9
shows Kw, the ion product for water, as a function of
water density at 380 °C.18 The range of Kw is from 10-24
(mol/kg)2 at 0.08 g/cm3 to 10-11 (mol/kg)2 at 0.68 g/cm3.
This monotonic increase in the ion product, and hence
in the H3O+ concentration, with increasing water den-
sity at 380 °C might account for the strong influence of
the water density on the cyclohexanol conversion and
product yields at 380 °C. Interestingly, the dehydration
reaction occurs at 380 °C even at low water densities,
where Kw is many orders of magnitude smaller than its
value for ambient liquid water [Kw ) 10-14 (mol/kg)2].
This observation suggests that both thermal activation
and acid catalysis are important for the rate enhance-
ment of cyclohexanol dehydration in HTW. At temper-
atures and water densities used in the liquid-phase
Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001 1827
Figure 9. Ion product for water at T ) 380 °C.
experiments, Kw decreases from 10-11 to 10-12 (mol/kg)2
as the temperature increases from 250 to 350 °C,18 yet
the data show that the reaction rate increases with
temperature. Again, the role of thermal activation is
evident.
Alcohol dehydration is a classic organic reaction that
has been studied extensively. The established mecha-
nisms for alcohol dehydration are E1cB, E1, and E2.
These notations stand for elimination (“E”) with a rate-
limiting step that is either unimolecular (“1”) or bimo-
lecular (“2”). A given alcohol can undergo dehydration
by any one of these mechanisms, depending on the
reaction conditions. The dominant mechanism is deter-
mined by various factors, including the acid/base prop-
erties of the catalyst, the interactions of the reactant
and intermediate species with the reaction medium, the
reaction temperature, and the structural features of the
alcohol.19-22
The balance of the acidity and basicity of the catalyst
often determines the dominant mechanism. In the
presence of a strong base and a weak acid, alcohol
dehydration occurs primarily via a carbanion intermedi-
ate, which is formed when the base abstracts a proton
from the β carbon (E1cB mechanism). In the presence
of a strong acid and a weak base, alcohol dehydration
occurs primarily via a carbocation intermediate, which
is formed by the loss of the protonated hydroxy group
(-OH2+) as water (E1 mechanism). In the E1cB and E1
mechanisms, the (unimolecular) formation of the ionic
intermediate is the rate-limiting step, and the subse-
quent formation of the alkene is facile. In the E2
mechanism, alcohol dehydration occurs by β elimination,
in which the proton on the β carbon and the hydroxy
group are eliminated in a concerted fashion. The reac-
tion is bimolecular because a nucleophile is required to
initiate elimination. Although the E2 mechanism is
typically observed in the presence of an acid and a base
of balanced strength, the reaction is acid-catalyzed,
since the protonated hydroxy group is an excellent
leaving group.
In pure water, no base is present that is strong
enough to abstract a proton from the carbon backbone.
Therefore, the E1cB mechanism is highly unlikely. The
remaining candidates are acid-catalyzed E1 and E2
mechanisms, with H3O+ from water being the catalyst.
Figure 10 shows the reaction network for acid-catalyzed
cyclohexanol dehydration. Formation of the oxonium ion
is the necessary first step for both the E1 and E2
mechanisms. What distinguishes the two mechanisms
is that the carbocation is the key intermediate in the
E1 mechanism.
There is only one previously reported attempt to
1828 Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001
Figure 10. Reaction network for cyclohexanol dehydration in
HTW.
elucidate the reaction mechanism of cyclohexanol de-
hydration. Whittaker and co-workers performed deute-
rium-labeling studies for the gas-phase dehydration of
cyclohexanol over zirconium phosphate.23,24 Dehydration
experiments at 350 °C using 2,2′,6,6′-[2H4]cyclohexanol
as the starting material generated cyclohexene with
significant deuterium scrambling. The authors attrib-
uted this outcome to the reaction intermediate being a
carbocation with highly mobile positive charge, in which
case the dehydration mechanism would be E1.
There is some question, however, as to whether the
reaction mechanism observed for the gas-phase experi-
ments would also operate in HTW. Solvation can play
an important role in reactions in water, modifying the
reactivity of the species involved in ionic chemistry.19,25
There are numerous examples of direct observation of
carbocations by spectroscopic methods in (anhydrous)
superacids,26 but not in weaker acids such as sulfuric
acid solutions, because of the interactions of cations with
solvating molecules.25 This literature suggests, then,
that carbocations (R+) in water are solvated by water
molecules and exist largely as oxonium ions (ROH2+),25
in which case the dehydration mechanism should be
predominantly E2. This hypothesis is supported by a
recent ab initio study that showed that, in the presence
of room-temperature water, the oxonium ion is the
stable intermediate, even for secondary (i-propyl) and
tertiary (tert-butyl) alcohols.19 A recent 13C NMR study
also showed that, even in a moderately concentrated
solution of sulfuric acid, dehydration of tert-butyl alcohol
occurs via the oxonium ion intermediate and not the
carbocation intermediate.27
The spectroscopic evidences noted above were ob-
tained at room temperature, and there is always a
possibility that a different mechanism operates at
higher temperatures. Dabbagh and Mohammad Salehi28
observed a dramatic shift in the product distribution
with changes in temperature for the dehydration of 1,2-
diphenyl-2-propanol over alumina. At 200-260 °C, the
Hofmann (least branched) alkene is the major product,
whereas at 300 °C, the Saytzeff (most branched) alkene
is the major product. The authors attributed this result
to a shift in the dehydration mechanism from E2 to E1
as the reaction temperature increased. Carrizosa and
Munuera29 observed a similar shift in the product
distribution with temperature (at about 100 °C) for
t-pentanol dehydration over TiO2. Thomke30,31 found
that the mechanism of 2-butanol dehydration over ThO2
shifts from E1cB below 400 °C to E2 and even E1 above
400 °C. Although none of these studies was conducted
in aqueous environments, they suggested that the
formation of carbocations in water might also be favored
at higher temperatures.
To summarize, this inspection of the relevant litera-
ture suggests that an oxonium ion intermediate (E2
mechanism) would be anticipated for dehydration in
HTW, but that the elevated temperature might admit
Figure 11. Proposed reaction mechanism for cyclohexanol dehy-
dration in HTW.
the formation of carbocations. The experimental data
in Table 1 support this hypothesis. Cyclohexene is the
major product under all reaction conditions examined
in this study. At 250 and 275 °C, cyclohexene is the only
product, but at higher temperatures, methyl cyclo-
pentenes are also produced, in a yield that increases
with increasing temperature. At 380 °C, the methyl
cyclopentene yield also increases with increasing water
density. If the secondary cyclohexyl carbocation is
generated during cyclohexanol dehydration, as required
in the E1 mechanism, it should quickly rearrange to the
tertiary methyl cyclopentyl carbocation, which is much
more stable.26 Thus, the absence of methyl cyclo-
pentenes at 250 and 275 °C suggests that the E2
mechanism operates at these temperatures. The forma-
tion of methyl cyclopentenes at higher temperatures
suggests that the formation of carbocations becomes
increasingly more favorable as the reaction temperature
increases. Because cyclohexene is consistently the major
product, however, the E2 mechanism probably remains
the dominant dehydration mechanism, even at temper-
atures of 300 °C and above.
On the basis of the experimental data reported herein
and supporting evidence from the literature as discussed
in the preceding paragraphs, we propose the following
scenario. Cyclohexanol dehydration to cyclohexene in
pure HTW occurs through the E2 mechanism. Some of
the cyclohexene molecules are then protonated to form
the secondary cyclohexyl carbocation. This carbocation
very quickly rearranges to form the tertiary methyl
cyclopentyl carbocation, which then loses a proton to
form 1-methyl cyclopentene. Charge migration within
the methyl cyclopentyl carbocation can yield structures
that deprotonate to form 3-methyl cyclopentene and
methylene cyclopentane, both of which were observed
experimentally. Both the increase in temperature and
the isothermal increase in water density favor the
carbocation formation. Figure 11 shows the detailed
reaction mechanism that we propose to account for
cyclohexanol dehydration in HTW. Species appearing
above the arrow in a reaction step are co-reactants, and
those appearing below the arrow are coproducts. The
mechanism described in Figure 11 is similar to the E2/
AdE3;E1/AdE3/Uni mechanism proposed by Antal et al.
to account for the reactions of 1- and 2-propanols in
HTW.7 This mechanism includes the conversion of
1-propanol to propylene via the E2 mechanism, followed
by the conversion of propylene to a secondary carboca-
tion, from which 2-propanol is formed.
The consideration of mechanistic issues related to

cyclohexanol dehydration in HTW reveals that the role
of water in this reaction is threefold. First, water
participates in the elementary reaction steps as a
reactant and as a product. Second, water is the source
of H3O+, which catalyzes the formation of both cyclo-
hexene and methyl cyclopentenes. Third, water drives
the reaction mechanism toward E2, rather than E1, by
favoring, through solvation, the oxonium ion (“OXO6”
in Figure 11) rather than the carbocation (“CAT6” in
Figure 11) as the reaction intermediate. We expect
water to make similar contributions to the dehydration
of other alcohols in HTW, although the extent to which
solvation influences the reaction mechanism should
depend on both the nature of the intermediate species
and the reaction conditions.
Mechanism-Based Model
Having proposed a mechanism for cyclohexanol de-
hydration in HTW, we next sought to demonstrate that
the mechanism was consistent with the experimental
results. Therefore, we constructed a detailed chemical
kinetics model based on the reaction mechanism shown
in Figure 11. The model equations, which apply to
reactions in a constant-volume batch reactor, are
d[NOL6]
) -k01[H3O+][NOL6] + k10[H2O][OXO6]
dt
(1)
d[OXO6]
) k01[H3O+][NOL6] -
dt
(k10 + k12)[H2O][OXO6] + k21[H2O][H3O+][ENE6]
(2)
d[ENE6]
) k12[H2O][OXO6] -
dt
(k21[H2O] + k23)[H3O+][ENE6] + k32[H2O][CAT6]
(3)
d[CAT6]
) k23[H3O+][ENE6] -
dt
(k32[H2O] + k34)[CAT6] + k43[CAT5] (4)
d[CAT5]
) k34[CAT6] - (k43 + k45[H2O])[CAT5] +
dt
k54[H3O+][ENE5] (5)
d[ENE5]
) k45[H2O][CAT5] - k54[H3O+][ENE5]
dt
(6)
We used a commercial modeling package, Scientist,32
to solve simultaneously the ordinary differential equa-
tions above (eqs 1-6) and perform parameter estima-
tions to obtain the rate constants k01, k10, k12, k21, k23,
k32, k34, k43, k45, and k54. The minimization algorithm
used by Scientist for parameter estimation is a Powell
variant of the Levenberg-Marquardt approach.33 We
used the experimental concentration profiles acquired
at 380 °C and water densities between 0.08 and 0.68
g/cm3 for parameter estimation. We fit the experimental
data at each density independently and found that k32
was consistently near zero (∼10-15-10-20 L mol-1sec-1).
Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001 1829
Table 3. Parameter Estimates for the Model in
Equations 7-9 Optimized for Experimental Data at 380
°C and 0.68 g/cm3
parameter value units
K1 2.05 × 106 L mol-1 s-1
K2 4.39 × 103 L2 mol-2 s-1
K3 4.51 × 101 L mol-1 s-1
This result suggests that the formation of the cyclohexyl
cation from cyclohexene is essentially irreversible. One
could rationalize this outcome by recognizing that the
formation of a more stable tertiary cation from a
secondary cation is highly favorable. It is likely that the
cyclohexyl cation rapidly rearranges to the tertiary
methyl cyclopentyl cation as soon as it is formed via
cyclohexene protonation.
Taking one of the steps to be irreversible greatly
simplifies the kinetics model. If one assumes that the
formation of the cyclohexyl cation is in fact irreversible
and, furthermore, employs the quasi-stationary state
approximation for the charged, reactive intermediates
(OXO6, CAT6, CAT5), one obtains the following system
of equations from the reaction mechanism:
( )
d[NOL6] k01k12
)- [NOL6][H2O] +
dt k10 + k12
( )
k10k21
[ENE6][H2O][H3O+] (7)
k10 + k12
) -K1[NOL6][H2O] +
K2[ENE6][H2O][H3O+]
d[ENE5]
) k23[ENE6][H3O+] ) K3[ENE6][H3O+]
dt
(8)
[ENE6] ) [NOL6]0 - [NOL6] - [ENE5] (9)
where K1, K2, and K3 are lumped parameters. As one
can see, the number of parameters in the model is
reduced from 10 to 3, which simplifies the parameter
estimation and reduces the likelihood that the data can
be fit simply because there are many parameters rather
than because the model is correct. We used Scientist to
solve simultaneously eqs 7-9 and perform parameter
estimation to obtain values for the parameters K1, K2,
and K3. We fit the model to a single concentration
profile, which was acquired at 380 °C and 0.68 g/cm3.
Table 3 lists the optimized values for K1, K2, and K3
under these conditions.
If the proposed mechanism is correct, then the model
in eqs 7-9 with the parameters in Table 3 should
provide reliable predictions of the product yields at 380
°C and all other water densities. To test this expectation,
we used the parameter estimates to predict the product
yields at other water densities at 380 °C. Figure 12
compares the experimental data and the model predic-
tions for reactions at 380 °C and 60 min as a function
of water density. The mechanism-based model is clearly
capable of predicting the strong water density effects
observed experimentally, even though the rate constants
were optimized at only one density (0.68 g/cm3). Note
that the model employs no empiricism to account for
the water density dependence. The reaction kinetics
depend on the water density in two ways. Water is both
a reactant and a product in different steps of the
mechanism, so the reaction rate is a direct function of
1830 Ind. Eng. Chem. Res., Vol. 40, No. 8, 2001
Figure 12. Comparison of experimental data and model predic-
tion for yields at T ) 380 °C and t ) 60 min.
the water concentration. Water is also the source of the
acid catalyst, H3O+, the concentration of which is a
function of both temperature and water density.18 It is
this latter effect that is the more important one in this
model. This kinetics modeling exercise clearly demon-
strates that the proposed mechanism is consistent with
the experimental data.
Conclusions
We studied cyclohexanol dehydration in HTW at
temperatures of 250-380 °C, reaction times of 15-180
min, and water densities of 0.08-0.68 g/cm3. Under
these experimental conditions, cyclohexanol dehydrates
readily in the absence of added catalysts to form
cyclohexene as the major product. The most abundant
minor products are 1-methyl cyclopentene and 3-methyl
cyclopentene. Increasing temperature and water density
increase the rate of cyclohexanol disappearance and the
selectivity toward methyl cyclopentenes over cyclohex-
ene. These results provide further evidence that acid-
catalyzed reactions can be accomplished readily in HTW
in the absence of added acid. The implications for
environmentally benign industrial chemistry are clear.
The reaction mechanism for cyclohexanol dehydration
in HTW comprises the following steps. Cyclohexanol
dehydrates reversibly to form cyclohexene by the E2
mechanism. Cyclohexene is then protonated irreversibly
to form the cyclohexyl cation. This cation rapidly rear-
ranges to form methyl cyclopentyl cations, which then
lose a proton to form methyl cyclopentenes. A detailed
chemical kinetics model based on this mechanism
captured the trends in the experimental data at 380 °C.
The model was able to predict the striking effect of the
water density on the product yields, thereby supporting
the proposed reaction mechanism.
We elucidated three roles for water in cyclohexanol
dehydration in HTW. First, water participates in the
elementary reaction steps as a reactant and as a
product. Second, water is the source of H3O+, which
catalyzes the formation of both cyclohexene and methyl
cyclopentenes. Third, water drives the reaction mech-
anism toward E2 by favoring, through solvation, the
oxonium ion rather than the carbocation as the reaction
intermediate. We expect water to make similar contri-
butions in the dehydration of other alcohols in HTW,
although the extent to which solvation influences the
reaction mechanism should depend on both the nature
of the intermediate species and the reaction conditions.
Acknowledgment
We thank Michelle Osinski for performing prelimi-
nary experiments and Jianli Yu for assistance in the
laboratory. Financial support from the National Science
Foundation (CTS-9985456), the donors of the ACS
Petroleum Research Fund (34644-AC9), and the U.S.
Environmental Protection Agency (STAR Fellowship for
N.A.) is gratefully acknowledged.
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Received for review November 13, 2000
Revised manuscript received February 15, 2001
Accepted February 20, 2001
IE000964Z